# Patent

## Title
Porous catalytic matrices for elimination of toxicants found in tobacco combustion products

## Abstract

Described herein are compositions and methods for capturing carbonylic or phenolic toxicants, or converting these toxicants into less volatile compounds. The toxicants, which may be a component of cigarette smoke, may be captured by physical or chemical adsorption, absorption, or entrapment.

## Background
BACKGROUND
Cigarette smoking is believed to contribute to or cause roughly 30% of all cancer deaths. Cigarette smoke contains more than 3500 chemicals, at least 50 of which are carcinogens. Carbonyls, including acetaldehyde, acrolein (propenal), formaldehyde, and others, are formed through the pyrolysis of tobacco. Accordingly, these compounds are among the compounds present at high levels in cigarette smoke. In fact, acetaldehyde and acrolein are present in international brands of cigarettes at concentrations of 860 and 83 μg/mg of nicotine, respectively. The Scientific Basis of Tobacco Product Regulation, WHO Technical Report Series 951, World Health Organization, Geneva, Switzerland, 2008. Long-term exposure to formaldehyde, acrolein, and acetaldehyde is known to increase the risk of asthma and cancer.
Cigarette smoke and tar also contain other carcinogens, such as polycyclic aromatic alcohols, which initiate the formation of cancer. Co-carcinogens in cigarette smoke, such as phenols, have also been identified; co-carcinogens accelerate the production of cancer by other initiators. Many phenols, naphthols and other co-carcinogens are also irritants.
The World Health Organization (WHO) has recommended mandated lowering of allowable levels of these toxicants in cigarettes. Current methods of reducing the amount of a toxicant in cigarette smoke include incorporation of transition metal oxide clusters, such as clusters of scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, and oxides and mixtures thereof. The nano-sized clusters or nanopoarticles of metal oxide are capable of catalyzing the conversion (oxidation) of carbon monoxide (CO) to carbon dioxide (CO2), or adsorbing carbon monoxide itself. The clusters are incorporated into a component of a smoking article, wherein the component is selected from the group consisting of tobacco cut filler, cigarette paper and cigarette filter material. See U.S. Pat. No. 7,712,471, incorporated herein by reference in its entirety. However, this reference not disclose any methods for reducing the levels of toxicants other than CO in the cigarette smoke.
Another method of reducing toxicants in cigarette smoke is disclosed in U.S. Pat. No. 6,615,843, hereby incorporated by reference in its entirety. This patent discloses a tobacco smoke filter synergistic composition comprised of antioxidants, such as ascorbic or citric acid, butylparaben, glutathione, melatonin, resveratrol, selenium, ubiquinones, or green tea, and adsorptive “minerals,” such as activated carbon, clinoptilolite, cuprous chloride, and ferrite. The antioxidants are effective as scavengers in reducing free radicals from the cigarette smoke, while activated carbon or similar adsorbent ‘minerals’ adsorb substantial levels of volatiles. However, U.S. Pat. No. 6,615,843 does not disclose any catalytic conversion of the volatile carbonylic compounds or phenols into less volatile chemicals. No catalytic condensation reactions of phenols and aldehydes found as toxicants in the cigarette smoke were disclosed.
Separately, metal-organic frameworks (MOF), constituted by metal ions or metal ion clusters occupying nodal framework positions coordinated with di- or multi-podal organic ligands, are rapidly emerging as an important family of crystalline materials to be utilized as catalysts in organic reactions. Some of these MOFs are crystalline materials with the lowest framework densities and the highest pore volume known to date. Among over 10,000 MOF materials, there are several transition-metal MOFs that are stable under liquid-phase reaction conditions. These include mesoporous chromium (III) terephthalate (MIL-101), which possesses acceptable resistance to water, common solvents, and temperatures (up to 320° C.). MIL-101 has a rigid zeotype crystal structure, consisting of 2.9 and 3.4-nm quasi-spherical cages accessible through windows of ca. 1.2 and 1.6 nm, respectively. Due to the high stability, MIL-101 exhibits no detectable leaching of chromium into solutions, allowing its safe use in different applications. In addition, MIL-101 possess a high density of chromium ions (three per elementary cell) with Lewis acid properties, which can be stable under reaction conditions. The open-pore structure of MIL-101 can be further functionalized by Pd or Au nanoparticles and polyoxometalate (POM) anions. The resulting composite materials are effective catalysts for hydrogenation reactions and oxidation reactions. Another POM material that can be utilized to functionalize the MIL-101 framework is phosphotungstic acid (PTA). PTA is the strongest known heteropolyacid. MIL-101/PTA composite materials (MIL101/PTA) have been shown to catalyze (i) the oxidation of alkenes using molecular oxygen and aqueous hydrogen peroxide as oxidants. (ii) H2O2-based alkene epoxidations, (iii) the Knoevenagel condensation of benzaldehyde and ethyl cyanoacetate, (iv) liquid and gas-phase acid-catalyzed esterifications (acetic acid with n-butanol, methanol dehydration), and (v) and carbohydrate dehydration.
SUMMARY OF THE INVENTION
In certain embodiments, the invention relates to a method of reducing the quantity of a toxicant in a fluid, comprising
contacting the fluid with a MOF matrix,
wherein
the MOF matrix comprises metal ions or clusters coordinated to polydentate organic ligands;
the fluid is a gas; and
the toxicant is a carbonylic compound or a phenolic compound.
In certain embodiments, the invention relates to any one of the aforementioned methods, wherein the fluid is tobacco smoke.
In certain embodiments, the invention relates to a method of adsorbing or absorbing a carbonylic compound or a phenolic compound, comprising
contacting the carbonylic compound or phenolic compound with a MOF matrix, wherein the MOF matrix comprises metal ions or clusters coordinated to polydentate organic ligands.
In certain embodiments, the invention relates to a method of catalyzing the conversion of a carbonylic compound to a non-carbonylic product, comprising
contacting the carbonylic compound with a MOF matrix for an amount of time, wherein the MOF matrix comprises metal ions or clusters coordinated to polydentate organic ligands, thereby forming the non-carbonylic product.
In certain embodiments, the invention relates to a method of catalyzing the conversion of a phenolic compound to a non-phenolic product or a polymeric product, comprising
contacting the phenolic compound with a MOF matrix for an amount of time, wherein the MOF matrix comprises metal ions or clusters coordinated to polydentate organic ligands, thereby forming the non-phenolic product or the polymeric product.



BRIEF DESCRIPTION OF THE FIGURES
FIG. 1 depicts typical BET nitrogen adsorption isotherms for MIL-101 and MIL101/PTA hybrid material at 77 K. P/P0 is the ratio of gas pressure (P) to saturation pressure (P0), with P0=746 torr.
FIG. 2 depicts equilibrium acrolein uptake by exemplary porous matrices and exemplary compounds of the present invention at room temperature.
FIG. 3 depicts a schematic of acrolein polymerization in the presence of the strong bases or acids of exemplary matrices of the present invention.
FIG. 4 depicts equilibrium acetaldehyde uptake by exemplary porous matrices of the present invention and phosphotungstic acid (PTA) at room temperature.
FIG. 5 depicts typical MALDI-TOF spectrum of the liquid condensed over MIL101/PTAja matrix after 2 days of exposure to acetaldehyde vapors at room temperature (peaks have no indicator). Also shown is a spectrum of α-cyano-4-hydroxycinnamic acid (ACHCA) matrix (indicated by *). For the measurement, 1 μL of the liquid was lyophilized, reconstituted in 1 μL of ACHCA matrix solution, spotted and analyzed.
FIG. 6 depicts a schematic showing a reaction between benzaldehyde and 2-naphthol catalyzed by a porous matrix of the present invention.
FIG. 7 tabulates properties of MIL-101 (Cr) particles synthesized in deionized water at pH 2.6. a Yield is calculated using chromium content in purified particles vs initial chromium content set in the synthesis. b Measured in particle suspension in methanol. c Determined from nitrogen adsorption isotherms. d Computed using instrument's built-in software using Barrett, Joyner & Halenda method.
FIG. 8 tabulates properties of MIL101/PTA hybrid materials synthesized by joint autoclaving of the MIL-101 components and PTA in deionized water (MIL101/PTAja) or by impregnation of MIL-101 by PTA in water. aDetermined from nitrogen adsorption isotherms. bObtained from elemental analysis and calculations based on Keggin structure (H3PW12O40)
FIG. 9 tabulates Baeyer condensations of aldehyde and b-naphthol catalyzed by MOF MIL-101 and its polyoxometalate composites and PTA. aIn all cases, except for catalysis with phosphotungstic acid (PTA), the catalyst loading is given in wt %. The loading is calculated as 100×catalyst weight/sum of weight of all componentsin the initial reaction mixture. bPTA loading is given in wt %/mol %. The content in mol % is calculated as 100×mols of catalyst/sum of mols of each component in the initial reaction mixture. cMW is the time of microwaving, wherein specified temperature is held within the reaction tube. dSeries of independent experiments conducted in triplicate demonstrated standard deviations of the yield determination to be within ±5 wt %. eMIL-101 samples prepared using autoclaving method are used throughout.
FIG. 10 tabulates properties of MIL-101 metal organic framework and MIL101/PTA composite materials synthesized by impregnation of MIL-101 by PTA in water (MIL101/PTAimp) or by joint autoclaving of the MIL-101 components and PTA in deionized water (MIL101/PTAja). aObtained from elemental analysis and calculations based on Keggin structure (H3PW12O40). bMeasured by dynamic light scattering in particle suspension in methanol. cDetermined from nitrogen adsorption isotherms.
FIG. 11 depicts a scheme showing acid-catalyzed aldol condensation of acetaldehyde.
FIG. 12 depicts typical 1H NMR spectra representing the kinetics of the acetaldehyde and phenol condensation reaction catalyzed by MIL-101/PTAja in THF-d8 at 25° C. Ca0/Cp0=2:1 (mol/mol). Numbers stand for time in minutes since the reaction commencement. Letters A and P indicate the aldehyde (substrate) and product signals, respectively.
FIG. 13 depicts the Baeyer condensation of acetaldehyde and phenol.
FIG. 14 depicts acetaldehyde conversion (F) vs time in the acetaldehyde-phenol (A-P) condensation reaction in deuterated THF. Initial acetaldehyde and phenol concentrations were Ca0=Cpi=0.33 M. T=25° C. For F definition, see equation (1).
FIG. 15 depicts a plot of the initial kinetics of acetaldehyde conversion in the Baeyer acetaldehyde-phenol condensation expressed in terms of




  P
  =
  
    
      
        ln
        ⁢
        
          
        
        ⁢
        
          C
          a
        
      
      
        q
        +
        
          C
          
            a
            ⁢
            
              
            
            ⁢
            0
          
        
      
    
    -
    
      
        ln
        ⁢
        
          
        
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          C
          a
        
      
      
        q
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          C
          a
        
      
    
  




vs time (equation (2)).

FIG. 16 tabulates effective catalyst concentration (Ccat), reaction half-life (t1/2), kinetic rate constant, and turnover frequency (TOF) of the acetaldehyde-phenol condensation conducted in THF-d8 at 25° C. and Ca0−Cpi=0.33 M. aConcentration of PTA in solution, bConcentration of PTA in the MIL101/PTA calculated per L of the suspension. cTotal concentration of the Brønsted and Lewis acid cites per L of the suspension. dCalculated from the expression TON=Ca0×F/Ccat. Here, F (equation (1)) is measured at 10 h after the reaction commencement.
FIG. 17 depicts a schematic showing the reaction between benzaldehyde and methanol.
FIG. 18 depicts typical 1H NMR spectra illustrating the kinetics of the reaction of benzaldehyde acetalization by methanol catalyzed by MIL101/PTAja at 25° C. Initial concentrations of methanol and benzaldehyde are Cmi=23.5 and Cb0=0.474 M, respectively. Samples of the reaction mixture withdrawn at timepoints indicated were dissolved in CDCl3 at 2:5 vol/vol ratio after catalyst separation. Numbers stand for time in minutes since the reaction commencement. Letters A and P indicate the aldehyde (substrate) and product signals, respectively.
FIG. 19 depicts a kinetic plot of benzaldehyde conversion in its acetalization by methanol catalyzed by MIL-101, MIL101/PTAja, MIL101/PTAimp and PTA at 25° C. The straight lines illustrate the initial reaction rates and are shown to guide the eye only.
FIG. 20 tabulates the effective catalyst concentration (Ccat), observed rate constant (kobs), reaction half-life (t1/2), and turnover frequency (TOF) of the acetalization of benzaldehyde with methanol conducted at 25° C. and Cb0=0.474 M,Cmi=23.5 M. aConcentration of PTA in solution. bConcentration of PTA in the MIL101/PTA calculated per L of the suspension. cTotal concentration of the Brønsted and Lewis acid cites per L of the suspension. dCalculated from the expression t1/2=ln(2)/kobs. eCalculated from the expression TON=Cb0×F/Ccat. Here, F (eqn (4)) is measured at 24 h after the reaction commencement.
FIG. 21 tabulates total catalyst recovery, Keggin ion content, Cr content and kinetic rate constants measured in 4 cycles of catalyst reuse. Each cycle consisted of 1 day of the catalytic reaction at 25° C., catalyst recovery, workup and reuse as described. aCalculated as 100×mass of catalyst in n-th cycle/initial mass of catalyst. bMeasured by elemental analysis in each cycle. cRate constants k and kobs are measured in the acetaldehyde-phenol and benzaldehyde-methanol reactions, respectively.



DETAILED DESCRIPTION
Overview
In certain embodiments, the present invention relates to materials and methods for filtering tobacco smoke. In certain embodiments, the present invention relates to materials and methods for filtering cigarette smoke. In certain embodiments, the materials are capable of capturing toxicant vapors and particles, and tar and other health-damaging materials, arising from the combustion of tobacco.
In certain embodiments, the invention relates to a method of capturing and converting carbonylic compounds into less volatile compounds. In certain embodiments, the capturing occurs via physical or chemical adsorption, absorption, or entrapping toxicant components of the cigarette smoke and smoke constituents.
In certain embodiments, the invention relates to a filter to be used by persons smoking tobacco, wherein the filter is capable of reducing the amount of contaminants in smoke passing through the filter (i.e., into the person's mouth).
In certain embodiments, the invention relates to a method of filtering tobacco smoke. In certain embodiments, the method combines absorption and catalytic reduction of the noxious components of the smoke.
Exemplary Matrices of the Invention
Overview
In certain embodiments, the invention relates to a metal-organic framework (MOF) matrix. In certain embodiments, the invention relates to any one of the aforementioned MOF matrices, wherein the MOF matrix comprises metal ions or clusters coordinated to organic ligands. In certain embodiments, the invention relates to any one of the aforementioned MOF matrices, wherein the MOF matrix comprises metal ions or clusters coordinated to polydentate organic ligands.
In certain embodiments, the invention relates to a ny one of the aforementioned MOF matrices, wherein the MOF matrix comprises at least one, at least bidentate, organic ligand bound by coordination to at least one metal ion. In certain embodiments, the invention relates to any of the MOF matrices described in U.S. Pat. No. 5,648,508 or U.S. Pat. No. 7,842,827, both of which are hereby incorporated by reference in their entireties.
In certain embodiments, the invention relates to any one of the aforementioned MOF matrices, wherein the MOF matrix comprises MIL-101 or MIL101/PTA. MIL-101 is a chromium terephthalate-based mesoscopic metal-organic framework and one of the most porous materials reported to date.
In certain embodiments, the invention relates to any one of the aforementioned MOF matrices, wherein the MOF matrix comprises MIL-101, strongly acidic MIL-101, or MIL101/PTA. In certain embodiments, the invention relates to any one of the aforementioned MOF matrices, wherein the MOF matrix is MIL-101, strongly acidic MIL-101, or MIL101/PTA.
In certain embodiments, the invention relates to any one of the aforementioned MOF matrices, wherein the MOF matrix is selected from the group consisting of MOF-177, MOF-178, MOF-74, MOF-235, MOF-236, MOF-69 to 80, MOF-501, MOF-502, and MOF-101. In certain embodiments, the invention relates to any one of the aforementioned MOF matrices, wherein the MOF matrix is selected from the group consisting of MOF-2 to 4, MOF-9, MOF-31 to 36, MOF-39, MOF-69 to 80, MOF103 to 106, MOF-122, MOF-125, MOF-150, MOF-177, MOF-178, MOF-235, MOF-236, MOF-500, MOF-501, MOF-502, MOF-505, IRMOF-1, IRMOF-61, IRMOP-13, IRMOP-51, MIL-17, MIL-45, MIL-47, MIL-53, MIL-59, MIL-60, MIL-61, MIL-63, MIL-68, MIL-79, MIL-80, MIL-83, MIL-85, CPL-1 to 2, and SZL-1.
Exemplary Metal Components of Matrices of the Invention
In certain embodiments, the invention relates to any one of the aforementioned MOF matrices, wherein the metal ion or cluster comprises a metal atom of group Ia, IIa, IIIa, IVa to VIIIa, or Ib to VIb. In certain embodiments, the invention relates to any one of the aforementioned MOF matrices, wherein the metal ion or cluster comprises Mg, Ca, Sr, Ba, Sc, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ro, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, TI, Si, Ge, Sn, Pb, or Bi. In certain embodiments, the invention relates to any one of the aforementioned MOF matrices, wherein the metal ion or cluster comprises Zn, Cu, Ni, Pd, Pt, Ru, Rh, or Co. In certain embodiments, the invention relates to any one of the aforementioned MOF matrices, wherein the metal ion or cluster comprises Cr, Fe, Zn, Al, Ni, or Cu.
In certain embodiments, metal ions or clusters are described in U.S. Pat. No. 5,648,508, hereby incorporated by reference in its entirety.
Exemplary Organic Ligands of the Invention
In certain embodiments, the invention relates to any one of the aforementioned MOF matrices, wherein the polydentate organic ligand is an organic ligand that is attached to a central metal ion by bonds from two or more donor atoms. In certain embodiments, the polydentate organic ligand is bidentate, tridentate, or tetradentate.
In certain embodiments, the invention relates to any one of the aforementioned MOF matrices, wherein the term “at least bidentate organic compound” designates an organic compound that comprises at least one functional group that is able to form, to a given metal ion, at least two coordinate bonds, or to two or more metal atoms, in each case one coordinate bond. In certain embodiments, the organic compound is able to form three coordinate bonds to one metal atom. In certain embodiments, the organic compounds is able to form one coordinate bond to each of three metal atoms.
In certain embodiments, the invention relates to any one of the aforementioned MOF matrices, wherein the organic ligand comprises a functional group selected from the group consisting of —COOH, —NO2, —B(OH)2, —SO3H, —Si(OH)3, —Ge(OH)3, —Sn(OH)3, —Si(SH)3, —PO3H, —CH(RNH2)2, —C(RNH2)3, —CH(ROH)2, —R(OH)3, —CH(RCN)2, —C(RCN)3,




and R is an alkylene group having 1, 2, 3, 4, or 5 carbon atoms, or an arylene group comprising 1 or 2 aromatic nuclei. In certain embodiments, the invention relates to any one of the aforementioned MOF matrices, wherein R is methylene, ethylene, n-propylene, i-propylene, n-butylene, i-butylene, tert-butylene, or n-pentylene. In certain embodiments, the invention relates to any one of the aforementioned MOF matrices, wherein R comprises two phenylene rings. In certain embodiments, the invention relates to any one of the aforementioned MOF matrices, wherein R comprises a heteroarylene group, wherein the heteroatom is N, O, or S. In certain embodiments, the invention relates to any one of the aforementioned MOF matrices, wherein R is substituted by at least in each case one substituent. In certain embodiments, R is not present. In certain embodiments, the invention relates to any one of the aforementioned MOF matrices, wherein the organic ligand comprises a functional group selected from the group consisting of —CH(SH)2, —C(SH)3, —CH(NH)2, —C(NH2)3, —CH(OH)2, —C(OH)3, —CH(CN)2 and —C(CN)3.

In certain embodiments, the invention relates to any one of the aforementioned MOF matrices, wherein the organic ligand is derived from a saturated or unsaturated aliphatic compound, an aromatic compound, or a compound that is both aliphatic and aromatic.
In certain embodiments, the invention relates to any one of the aforementioned MOF matrices, wherein the organic ligand is trans-muconic acid, fumaric acid, or phenylenebisacrylic acids.
In certain embodiments, the invention relates to any one of the aforementioned MOF matrices, wherein the organic ligand is an optionally at least monosubstituted mono-, di-, tri-, tetranuclear, or higher nuclear aromatic, di-, tri- or tetracarboxylic acid. In certain embodiments, the invention relates to any one of the aforementioned MOF matrices, wherein any of the aromatic nuclei is a heteroaromatic nuclei. In certain embodiments, the invention relates to any one of the aforementioned MOF matrices, wherein the organic ligand is a mononuclear dicarboxylic acid, mononuclear tricarboxylic acid, mononuclear tetracarboxylic acid, dinuclear dicarboxylic acid, dinuclear tricarboxylic acid, dinuclear tetracarboxylic acid, trinuclear dicarboxylic acid, trinuclear tricarboxylic acid, trinuclear tetracarboxylic acid, tetranuclear dicarboxylic acid, tetranuclear tricarboxylic acid, or tetranuclear tetracarboxylic acid. In certain embodiments, the invention relates to any one of the aforementioned MOF matrices, wherein any of the aromatic nuclei is a heteroaromatic nuclei. In certain embodiments, the invention relates to any one of the aforementioned MOF matrices, wherein any of the aromatic nuclei is a heteroaromatic nuclei; and the heteroatom is N, O, S, B, P, Si, or Al. In certain embodiments, the invention relates to any one of the aforementioned MOF matrices, wherein any of the aromatic nuclei is a heteroaromatic nuclei; and the heteroatom is N, S or O. In certain embodiments, the invention relates to any one of the aforementioned MOF matrices, wherein the organic ligand is substituted; and the substituent is —OH, —NO2, amino, alkyl, or alkoxy.
In certain embodiments, the invention relates to any one of the aforementioned MOF matrices, wherein the organic ligand is a dicarboxylic acid, including but not limited to asoxalic acid, succinic acid, tartaric acid, 1,4-butanedicarboxylic acid, 4-oxopyran-2,6-dicarboxylic acid, 1,6-hexanedicarboxylic acid, decanedicarboxylic acid, 1,8-heptadecanedicarboxylic acid, 1,9-heptadecanedicarboxylic acid, heptadecanedicarboxylic acid, acetylenedicarboxylic acid, 1,2-benzenedicarboxylic acid, 2,3-pyridinedicarboxylic acid, pyridine-2,3-dicarboxylic acid, 1,3-butadiene-1,4-dicarboxylic acid, 1,4-benzenedicarboxylic acid, p-benzenedicarboxylic acid, imidazole-2,4-dicarboxylic acid, 2-methylquinoline-3,4-dicarboxylic acid, quinoline-2,4-dicarboxylic acid, quinoxaline-2,3-dicarboxylic acid, 6-chloroquinoxaline-2,3-dicarboxylic acid, 4,4′-diaminophenylmethane-3,3′-dicarboxylic acid, quinoline-3,4-dicarboxylic acid, 7-chloro-4-hydroxyquinoline-2,8-dicarboxylic acid, diimidodicarboxylic acid, pyridine-2,6-dicarboxylic acid, 2-methylimidazole-4,5-dicarboxylic acid, thiophene-3,4-dicarboxylic acid, 2-isopropylimidazole-4,5-dicarboxylic acid, tetrahydropyran-4,4-dicarboxylic acid, perylene-3,9-dicarboxylic acid, perylenedicarboxylic acid, Pluriol E 200-dicarboxylic acid, 3,6-dioxaoctanedicarboxylic acid, 3,5-cyclohexadiene-1,2-dicarboxylic acid, octadicarboxylic acid, pentane-3,3-carboxylic acid, 4,4′-diamino-1,1′-diphenyl-3,3′-dicarboxylic acid, 4,4′-diaminodiphenyl-3,3′-dicarboxylic acid, benzidine-3,3′-dicarboxylic acid, 1,4-bis(phenylamino)benzene-2,5-dicarboxylic acid, 1,1′-dinaphthyl-S,S′-dicarboxylic acid, 7-chloro-8-methylquinoline-2,3-dicarboxylic acid, 1-anilinoanthraquinone-2,4′-dicarboxylic acid, polytetrahydrofuran-250-dicarboxylic acid, 1,4-bis(carboxymethyl)piperazine-2,3-dicarboxylic acid, 7-chloroquinoline-3,8-dicarboxylic acid, 1-(4-carboxy)phenyl-3-(4-chloro)phenylpyrazoline-4,5-dicarboxylic acid, 1,4,5,6,7,7-hexachloro-5-norbornene-2,3-dicarboxylic acid, phenylindanedicarboxylic acid, 1,3-dibenzyl-2-oxoimidazolidine-4,5-dicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, naphthalene-1,8-dicarboxylic acid, 2-benzoylbenzene-1,3-dicarboxylic acid, 1,3-dibenzyl-2-oxoimidazolidine-4,5-cis-dicarboxylic acid, 2,2′-biquinoline-4,4′-dicarboxylic acid, pyridine-3,4-dicarboxylic acid, 3,6,9-trioxaundecanedicarboxylic acid, O-hydroxybenzophenonedicarboxylic acid, Pluriol E 300-dicarboxylic acid, Pluriol E 400-dicarboxylic acid, Pluriol E 600-dicarboxylic acid, pyrazole-3,4-dicarboxylic acid, 2,3-pyrazinedicarboxylic acid, 5,6-dimethyl-2,3-pyrazinedicarboxylic acid, 4,4′-diaminodiphenyletherdiimidodicarboxylic acid, 4,4′-diaminodiphenylmethanediimidodicarboxylic acid, 4,4′-diaminodiphenylsulfonediimidodicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,3-adamantanedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 8-methoxy-2,3-naphthalenedicarboxylic acid, 8-nitro-2,3-naphthalenecarboxylic acid, 8-sulfo-2,3-naphthalenedicarboxylic acid, anthracene-2,3-dicarboxylic acid, 2′,3′-diphenyl-p-terphenyl-4,4′′-dicarboxylic acid, diphenyl-ether-4,4′-dicarboxylic acid, imidazole-4,5-dicarboxylic acid, 4(1H)-oxothiochromene-2,8-dicarboxylic acid, 5-tert-butyl-1,3-benzenedicarboxylic acid, 7,8-quinolinedicarboxylic acid, 4,5-imidazoledicarboxylic acid, 4-cyclohexene-1,2-dicarboxylic acid, hexatriacontanedicarboxylic acid, tetradecanedicarboxylic acid, 1,7-heptadicarboxylic acid, 5-hydroxy-1,3-benzenedicarboxylic acid, pyrazine-2,3-dicarboxylic acid, furan-2,5-dicarboxylic acid, 1-nonene-6,9-dicarboxylic acid, eicosenedicarboxylic acid, 4,4′-dihydroxydiphenylmethane-3,3′-dicarboxylic acid, 1-amino-4-methyl-9,10-dioxo-9,10-dihydroanthracene-2,3-dicarboxylic acid, 2,5-pyridinedicarboxylic acid, cyclohexene-2,3-dicarboxylic acid, 2,9-dichlorofluororubin-4,11-dicarboxylic acid, 7-chloro-3-methylquinoline-6,8-dicarboxylic acid, 2,4-dichlorobenzophenone-2′,5′-dicarboxylic acid, 1,3-benzenedicarboxylic acid, 2,6-pyridinedicarboxylic acid, 1-methylpyrrole-3,4-dicarboxylic acid, 1-benzyl-1H-pyrrole-3,4-dicarboxylic acid, anthraquinone-1,5-dicarboxylic acid, 3,5-pyrazoledicarboxylic acid, 2-nitrobenzene-1,4-dicarboxylic acid, heptane-1,7-dicarboxylic acid, cyclobutane-1,1-dicarboxylic acid 1,14-tetradecanedicarboxylic acid, 5,6-dehydronorbornane-2,3-dicarboxylic acid, and 5-ethyl-2,3-pyridinedicarboxylic acid.
In certain embodiments, the invention relates to any one of the aforementioned MOF matrices, wherein the organic ligand is a tricarboxylic acid, including but not limited to 2-hydroxy-1,2,3-propanetricarboxylic acid, 7-chloro-2,3,8-quinolinetricarboxylic acid, 1,2,4-benzenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 2-phosphono-1,2,4-butanetricarboxylic acid, 1,3,5-benzenetricarboxylic acid, 1-hydroxy-1,2,3-propanetricarboxylic acid, 4,5-dihydro-4,5-dioxo-1H-pyrrolo[2,3-F]quinoline-2,7,9-tricarboxylic acid, 5-acetyl-3-amino-6-methylbenzene-1,2,4-tricarboxylic acid, 3-amino-5-benzoyl-6-methylbenzene-1,2,4-tricarboxylic acid, 1,2,3-propanetricarboxylic acid, and aurintricarboxylic acid.
In certain embodiments, the invention relates to any one of the aforementioned MOF matrices, wherein the organic ligand is a tetracarboxylic acid, including but not limited to 1,1-dioxidoperylo[1,12-BCD]thiophene-3,4,9,10-tetracarboxylic acid, perylenetetracarboxylic acids such as perylene-3,4,9,10-tetracarboxylic acid or perylene-1,12-sulfone-3,4,9,10-tetracarboxylic acid, butanetetracarboxylic acids such as 1,2,3,4-butanetetracarboxylic acid or meso-1,2,3,4-butanetetracarboxylic acid, decane-2,4,6,8-tetracarboxylic acid, 1,4,7,10,13,16-hexaoxacyclooctadecane-2,3,11,12-tetracarboxylic acid, 1,2,4,5-benzenetetracarboxylic acid, 1,2,11,12-dodecanetetracarboxylic acid, 1,2,5,6-hexanetetracarboxylic acid, 1,2,7,8-octanetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 1,2,9,10-decanetetracarboxylic acid, benzophenonetetracarboxylic acid, 3,3′,4,4′-benzophenonetetracarboxylic acid, tetrahydrofurantetracarboxylic acid, and cyclopentane-1,2,3,4-tetracarboxylic acid.
In certain embodiments, the invention relates to any one of the aforementioned MOF matrices, wherein the organic ligand is acetylenedicarboxylic acid (ADC), benzenedicarboxylic acids, naphthalenedicarboxylic acids, biphenyldicarboxylic acids (for example, 4,4′-biphenyldicarboxylic acid (BPDC)), bipyridinedicarboxylic acids (for example, 2,2′-bipyridinedicarboxylic acids like 2,2′-bipyridine-5,5′-dicarboxylic acid), benzenetricarboxylic acids (for example, 1,2,3-benzenetricarboxylic acid or 1,3,5-benzenetricarboxylic acid (BTC)), adamantanetetracarboxylic acid (ATC), adamantanedibenzoate (ADB), benzenetribenzoate (BTB), methanetetrabenzoate (MTB), adamantanetetrabenzoate, or dihydroxyterephthalic acids (for example, 2,5-dihydroxyterephthalic acid (DHBDC)).
In certain embodiments, the invention relates to any one of the aforementioned MOF matrices, wherein the organic ligand is terephthalic acid, isophthalic acid, 2-aminoterephthalic acid, 2,5-dihydroxyterephthalic acid, 1,2,3-benzenetricarboxylic acid, 1,3,5-benzenetricarboxylic acid, or 2,2′-bipyridine-5,5′-dicarboxylic acid.
In certain embodiments, the invention relates to any one of the aforementioned MOF matrices, wherein the organic ligand comprises a polydentate organic ligand and a monodentate organic ligand.
In certain embodiments, organic ligands are described in U.S. Pat. No. 5,648,508, hereby incorporated by reference in its entirety.
Exemplary Dopants
In certain embodiments, the invention relates to any one of the aforementioned MOF matrices, wherein the matrix further comprises a dopant, thereby forming a hybrid MOF matrix, or a MOF composite matrix. In certain embodiments, the dopant is a functional material. In certain embodiments, the dopant is of a shape and size sufficient to fit into the porous structure of MOF matrix. In certain embodiments, the dopant is acidic or basic. In certain embodiments, the dopant is a polyoxometalate (POM) or a supernucleophilic amine.
In certain embodiments, the invention relates to any one of the aforementioned MOF matrices, wherein the MOF matrix comprises a polyoxometalate; and the polyoxometalate is a heteropoly acid or isopoly acid. In certain embodiments, the invention relates to any one of the aforementioned MOF matrices, wherein the MOF matrix comprises a polyoxometalate; and the polyoxometalate is phosphotungstic acid (PTA), phosphomolybdic acid, silicomolybdic acid, silicotungstic acid, phosphotungstomolybdic acid, phosphovanadomolybdic acid, or a heteropoly acid comprising tungsten or molybdenum and at least one other element having a positive valence from 2 to 7. In certain embodiments, the invention relates to any one of the aforementioned MOF matrices, wherein the MOF matrix comprises a polyoxometalate; and the polyoxometalate is phosphotungstic acid (PTA) or PTA modified by inclusion of metal ions. In certain embodiments, the invention relates to any one of the aforementioned MOF matrices, wherein the MOF matrix comprises a polyoxometalate; and the polyoxometalate is PTA modified by inclusion of Ti, Cr, Co, or Cu.
In certain embodiments, the invention relates to any one of the aforementioned MOF matrices, wherein the MOF matrix comprises a supernucleophilic amine; and the supernucleophilic amine is a 4-aminopyridine. In certain embodiments, the invention relates to any one of the aforementioned MOF matrices, wherein the supernucleophilic amine is 4-N,N-dimethylaminopyridine (DMAP).
Exemplary Properties of Matrices of the Invention
In certain embodiments, the invention relates to any one of the aforementioned MOF matrices, wherein the MOF matrix is crystalline
In certain embodiments, the invention relates to any one of the aforementioned MOF matrices, wherein the MOF matrix is one-, two-, or three-dimensional.
In certain embodiments, the invention relates to any one of the aforementioned MOF matrices, wherein the MOF matrix is porous. In certain embodiments, the invention relates to any one of the aforementioned MOF matrices, wherein the MOF matrix comprises a plurality of pores. In certain embodiments, the invention relates to any one of the aforementioned MOF matrices, wherein the MOF matrix comprises nanopores or mesopores. In certain embodiments, nanopores are defined as pores having a diameter from about 0.1 nm to about 2 nm. In certain embodiments, mesopores are defined as pores having a diameter in the range from about 2 nm to about 50 nm. In certain embodiments, the presence of nanoropores or mesopores can be studied using sorption measurements, these measurements determining the MOF uptake capacity for nitrogen as specified in DIN 66131 and/or DIN 66134.
In certain embodiments, the invention relates to any one of the aforementioned MOF matrices, wherein the MOF matrix comprises pores that range in diameter from about 0.1 nm to about 30 nm. In certain embodiments, the invention relates to any one of the aforementioned MOF matrices, wherein the MOF matrix comprises pores that range in diameter from about 0.1 nm to about 4 nm. In certain embodiments, the invention relates to any one of the aforementioned MOF matrices, wherein the MOF matrix comprises pores that have an average diameter of about 0.1 nm to about 30 nm. In certain embodiments, the invention relates to any one of the aforementioned MOF matrices, wherein the MOF matrix comprises pores that have an average diameter of about 0.1 nm to about 4 nm. In certain embodiments, the invention relates to any one of the aforementioned MOF matrices, wherein the MOF matrix comprises pores that have an average diameter of about 0.1 nm, about 0.2 nm, about 0.3 nm, about 0.4 nm, about 0.5 nm, about 0.6 nm, about 0.7 nm, about 0.8 nm, about 0.9 nm, about 1.0 nm, about 1.5 nm, about 2.0 nm, about 2.5 nm, about 3.0 nm, about 3.5 nm, about 4 nm, about 4.5 nm, about 5.0 nm, about 6 nm, about 7 nm, about 8 nm, about 9 nm, about 10 nm, about 12 nm, about 14 nm, about 16 nm, about 18 nm, about 20 nm, about 22 nm, about 24 nm, about 26 nm, about 28 nm, or about 30 nm.
In certain embodiments, the invention relates to any one of the aforementioned MOF matrices, wherein the specific surface area of the MOF matrix, calculated according to the Langmuir model (DIN 66131, 66134) for a MOF in powder form, is greater than about 5 m2/g, greater than about 10 m2/g, greater than about 50 m2/g, greater than about 500 m2/g, greater than about 1000 m2/g, or greater than about 1500 m2/g. In certain embodiments, the invention relates to any one of the aforementioned MOF matrices, wherein the specific surface area of the MOF matrix, calculated according to the Langmuir model (DIN 66131, 66134) for a MOF in powder form, is less than about 10,000 m2/g.
In certain embodiments, the invention relates to any one of the aforementioned MOF matrices, wherein the MOF matrix catalyzes aldehyde-alcohol reactions at ambient temperature.
In certain embodiments, the invention relates to any one of the aforementioned MOF matrices, wherein the MOF matrix catalyzes the Baeyer condensation of aldehydes and phenols.
In certain embodiments, the invention relates to any one of the aforementioned MOF matrices, wherein the MOF matrix catalyzes aldehyde or ketone acetalizations.
In certain embodiments, the invention relates to any one of the aforementioned MOF matrices, wherein the MOF matrix catalyzes aldehyde self-condensation.
In certain embodiments, the invention relates to any one of the aforementioned MOF matrices, wherein the MOF matrix captures and catalyzes reactions of acetaldehyde, acrolein, formaldehyde, butyraldehyde, crotonaldehyde, benzyl aldehyde, propionaldehyde, phenol, m-cresol, p-cresol, o-cresol, α-naphthol, or β-naphthol.
In certain embodiments, the invention relates to any one of the aforementioned MOF matrices, wherein the MOF matrix chemically or physically adsorbs, absorbs, entraps, catalyzes, or chemically reacts with a product of tobacco combustion or pyrolysis. In certain embodiments, the invention relates to any one of the aforementioned MOF matrices, wherein the MOF matrix adsorbs, absorbs, or converts at least one product of tobacco combustion or pyrolysis.
In certain embodiments, the invention relates to any one of the aforementioned MOF matrices, wherein the MOF matrix catalyzes condensation reactions such as polycondensation reactions of aldehydes that lead to (i) increasing the product molecular weight making is less volatile relative to the initial aldehyde, and (ii) consumption of toxic aldehyde groups. In certain embodiments, the invention relates to any one of the aforementioned MOF matrices, wherein the MOF matrix catalyzes condensation reactions between aldehydes and phenols (Baeyer reactions), leading to the consumption of both aldehyde and phenol toxicant families.
Exemplary Filter Elements of the Invention
In certain embodiments, the invention relates to a filter element comprising any one of the aforementioned MOF matrices.
In certain embodiments, the invention relates to any one of the aforementioned filter elements, wherein the filter element has a filter rod structure. In certain embodiments, the filter rod structure means a structure (a filter structure) formed by arranging a given number of mono-filaments (for example, about 3,000 to about 100,000 mono-filaments) in the flow direction of mainstream smoke.
In certain embodiments, the invention relates to any one of the aforementioned filter elements, wherein the filter element is capable of reducing the quantity of contaminants in smoke.
Exemplary Smoking Articles of the Invention
In certain embodiments, the invention relates to a smoking article comprising any one of the aforementioned filter elements. In certain embodiments, the invention relates to any one of the aforementioned smoking articles, wherein the smoking article comprises any one of the aforementioned filter elements attached to a tobacco rod.
In certain embodiments, the invention relates to any one of the aforementioned smoking articles, wherein the smoking article is a cigarette, a cigar, or a pipe.
Popular smoking articles, such as cigarettes, have a substantially cylindrical rod-shaped structure and include a charge, roll or column of smokable material such as shredded tobacco (e.g., in cut filler form) surrounded by a paper wrapper thereby forming a so-called “smokable rod” or “tobacco rod.” Normally, a cigarette has a cylindrical filter element aligned in an end-to-end relationship with the tobacco rod. Typically, a filter element comprises cellulose acetate tow plasticized using triacetin, and the tow is circumscribed by a paper material known as “plug wrap.” A cigarette can incorporate a filter element having multiple segments, and one of those segments can comprise activated charcoal particles. Typically, the filter element is attached to one end of the tobacco rod using a circumscribing wrapping material known as “tipping paper.” It also has become desirable to perforate the tipping material and plug wrap, in order to provide dilution of drawn mainstream smoke with ambient air. A cigarette is employed by a smoker by lighting one end thereof and burning the tobacco rod. The smoker then receives mainstream smoke into his or her mouth by drawing on the opposite end (e.g., the filter end) of the cigarette.
In certain embodiments, the invention relates to any one of the aforementioned smoking articles, wherein the filter element is inserted into the smoking article.
Exemplary Methods of the Invention
In certain embodiments, the invention relates to a method of capturing carbonylic compounds or converting carbonylic compounds into less volatile compounds. In certain embodiments, the capturing occurs via physical or chemical adsorption, absorption, or entrapping toxicant components of the cigarette smoke and smoke constituents.
In certain embodiments, the invention relates to a method of adsorbing or absorbing a carbonylic compound or a phenolic compound, comprising contacting the carbonylic compound or phenolic compound with any one of the aforementioned MOF matrices.
In certain embodiments, the invention relates to a method of catalyzing the conversion of a carbonylic compound to a non-carbonylic product, comprising contacting the carbonylic compound with any one of the aforementioned MOF matrices for an amount of time, thereby forming the non-carbonylic product.
In certain embodiments, the invention relates to any one of the aforementioned methods, wherein the non-carbonylic product is a ketal, an acetal, a polyketal, a polyacetal, or an organic heterocycle.
In certain embodiments, the invention relates to a method of catalyzing the conversion of a phenolic compound to a non-phenolic product or a polymeric product, comprising contacting the phenolic compound with any one of the aforementioned MOF matrices for an amount of time, thereby forming the non-phenolic product or the polymeric product.
In certain embodiments, the invention relates to any one of the aforementioned methods, wherein the non-phenolic product is an organic heterocycle.
In certain embodiments, the invention relates to a method of catalyzing an alcohol-aldehyde condensation, comprising contacting an alcohol and an aldehyde with any one of the aforementioned MOF matrices for an amount of time. In certain embodiments, the invention relates to any one of the aforementioned methods, wherein the alcohol is phenol. In certain embodiments, the invention relates to any one of the aforementioned methods, wherein the alcohol is phenol from cigarette smoke. In certain embodiments, the invention relates to any one of the aforementioned methods, wherein the alcohol is naphthol. In certain embodiments, the invention relates to any one of the aforementioned methods, wherein the aldehyde is formaldehyde. In certain embodiments, the invention relates to any one of the aforementioned methods, wherein the aldehyde is acetaldehyde. In certain embodiments, the invention relates to any one of the aforementioned methods, wherein the aldehyde is benzaldehyde. In certain embodiments, the invention relates to any one of the aforementioned methods, wherein the alcohol or the aldehyde is adsorbed onto the MOF matrix.
In certain embodiments, the invention relates to a method of acetylizing an aldehyde with an alcohol, comprising contacting the aldehyde and the alcohol with any one of the aforementioned MOF matrices.
In certain embodiments, the invention relates to any one of the aforementioned methods, wherein the aldehyde is benzaldehyde.
In certain embodiments, the invention relates to any one of the aforementioned methods, wherein the alcohol is methanol.
In certain embodiments, the invention relates to any one of the aforementioned methods, wherein the carbonylic compound or phenolic compound is a product of tobacco combustion or pyrolysis.
In certain embodiments, the invention relates to a method of substantially reducing the quantity of a toxicant in a fluid, comprising contacting the fluid with any one of the aforementioned MOF matrices.
In certain embodiments, the invention relates to a method of substantially removing a toxicant from a fluid, comprising contacting the fluid with any one of the aforementioned MOF matrices.
In certain embodiments, the invention relates to any one of the aforementioned methods, wherein the fluid is a gas. In certain embodiments, the invention relates to any one of the aforementioned methods, wherein the fluid is an aerosol. In certain embodiments, the invention relates to any one of the aforementioned methods, wherein the fluid is tobacco smoke. In certain embodiments, the invention relates to any one of the aforementioned methods, wherein the fluid is cigarette smoke. In certain embodiments, the invention relates to any one of the aforementioned methods, wherein the fluid is mainstream cigarette smoke or sidestream cigarette smoke. Smoking articles, such as cigarettes or cigars, produce both mainstream smoke during a puff, and sidestream smoke during static burning.
In certain embodiments, the invention relates to any one of the aforementioned methods, wherein the toxicant is a carbonylic compound or a phenolic compound.
In certain embodiments, the invention relates to any one of the aforementioned methods, wherein the carbonylic compound comprises acetaldehyde, acrolein, formaldehyde, butyraldehyde, crotonaldehyde, benzyl aldehyde, or propionaldehyde.
In certain embodiments, the invention relates to any one of the aforementioned methods, wherein the phenolic compound comprises phenol, m-cresol, p-cresol, o-cresol, α-naphthol, or β-naphthol.
In certain embodiments, the invention relates to any one of the aforementioned methods, wherein the quantity of toxicant in the fluid is reduced.
In certain embodiments, the invention relates to any one of the aforementioned methods, wherein the toxicant is adsorbed onto or absorbed into the MOF matrix. In certain embodiments, the invention relates to any one of the aforementioned methods, wherein the toxicant is chemically converted into a less volatile substance. In certain embodiments, the less volatile substance is a ketal, an acetal, a polyketal, a polyacetal, a polymer, or an organic heterocycle.
In certain embodiments, the invention relates to a method of making any one of the aforementioned MOF matrices. In certain embodiments, the MOF matrices may be made in a solvent selected from the group consisting of ethanol, dimethylformamide, toluene, methanol, chlorobenzene, diethylformamide, dimethyl sulfoxide, water, hydrogen peroxide, methylamine, sodium hydroxide solution, N-methylpolidone ether, acetonitrile, benzyl chloride, triethylamine, ethylene glycol, and mixtures thereof. In certain embodiments, solvents for making any one of the aforementioned MOF matrices are described in U.S. Pat. No. 5,648,508, hereby incorporated by reference in its entirety.
In certain embodiments, the invention relates to a method of making any one of the aforementioned MOF matrices. In certain embodiments, the invention relates to any one of the aforementioned methods, comprising contacting an aqueous PTA solution with MIL-101. In certain embodiments, the invention relates to any one of the aforementioned methods, comprising autoclaving aqueous Cr(III) nitrate and terephthalic acid solutions. In certain embodiments, the invention relates to any one of the aforementioned methods, comprising autoclaving Cr(NO3)3, terephthalic acid, and PTA in water. In certain embodiments, the invention relates to any one of the aforementioned methods, further comprising the step of evaporating the solvent.
In certain embodiments, the invention relates to any one of the aforementioned methods, wherein the pore size of the resulting MOF matrix may be controlled. In certain embodiments, the invention relates to any one of the aforementioned methods, the pore size of the MOF matrix is controlled by selection of the organic ligand. While not wishing to be bound by any particular theory, in certain embodiments, the larger the organic ligand, the larger the pore diameter in the resulting MOF matrix.
EXEMPLIFICATION
The invention now being generally described, it will be more readily understood by reference to the following, which is included merely for purposes of illustration of certain aspects and embodiments of the present invention, and is not intended to limit the invention.
EXAMPLE 1
Synthesis of Porous Catalytic Matrices
Materials
Chromium (III) nitrate nonahydrate (99%), terephthalic acid (≧99%), aluminum chloride hexahydrate (AlCl3 6H2O, 99%), acetaldehyde (≧99.5%), 2-amino terephthalic acid (99%), N,N-dimethylformamide (>99.9%), 2-naphthol (99%), benzaldehyde (purified by redistillation, ≧99.5%), β-caryophyllene (≧98.5%, sum of enantiomers, GC), methanol (anhydrous, 99.8%), phenol (≧99%) and acetamide (≧99.0%) were all obtained from Sigma-Aldrich Chemical Co. and were used as received. Hydrated 12-tungstophosphoric acid (H3PW12O40,PTA) (Sigma-Alrich, >99%) was dried at 70° C. for 8 h to obtain H3PW12O40.6H2O. All other chemicals and solvents used were obtained from commercial sources and were of highest purity available.
Porous MIL-101 (Cr) Matrix Synthesis
Particles of metal-organic framework (MOF) MIL-101 were synthesized hydrothermally, utilizing either microwave (MW) or autoclave oven heat supply. In the autoclave method, Cr(NO3)3.9H2O (2.0 g, 5 mmol), terephthalic acid (0.83 g, 5 mmol) and deionized water (20 mL) were blended and briefly sonicated resulting in a dark blue-colored suspension with a pH of 2.58. The suspension was placed in a Teflon®-lined autoclave bomb and kept in an oven at 218° C. for 18 h without stirring. After the synthesis and equilibration at room temperature, pH 0.5 was recorded in the suspension.
In the MW synthesis, Cr(NO3)3.9H2O (1 mmol, 400 mg), terephthalic acid (166 mg, 1 mmol) and deionized water (4500 mg, 250 mmol) were blended and briefly sonicated, resulting in a suspension with the initial pH 2.60. In a separate series of experiments, the pH was adjusted as needed using 1 M aqueous NaOH. A sample (1 mL) was withdrawn from the suspension, placed it in a glass tube and microwaved using CEM Discover MW oven (CEM Corp., Matthews, NC) at 220° C. for 15 min using 300 mW power under constant stirring.
After either synthesis, the MOF solids were separated from water using centrifuge (5,000 g, 10 min) and washed with water, methanol and acetone. The suspension in acetone was centrifuged and separated, the solids were placed in N,N-dimethylformamide (20 mL) and the suspension was sonicated for 10 min and then kept at 70° C. overnight. The resulting solids were separated by centrifugation, repeatedly washed with methanol and acetone, dried at 75° C. overnight and then under vacuum (10−5 Torr) at ambient temperature for 2 days. Total yield of dry MIL-101 particles based on chromium was 54-63 wt %. Typical elemental analysis, wt %: C, 48.1; Cr, 10.3.
Synthesis of MIL-101 (Cr)-Phosphotungstic Acid (PTA) Hybrid Materials (MIL101/PTA)
The hybrid materials were synthesized by either autoclaving chromium nitrate, terephthlaic acid and phosphotungstic acid mixtures in water or by impregnating already prepared MIL-101 by aqueous solution of phosphotungstic acid in water. In a typical “joint autoclaving” synthesis (resulting MOF designated MIL101/PTAja), Cr(NO3)3.9H2O (2.0 g, 5 mmol), terephthalic acid (0.83 g, 5 mmol), phosphotungstic acid (2 g, 0.7 mmol), and deionized water (20 mL) were blended and briefly sonicated resulting in a dark blue-colored suspension with a pH of 2.58. The suspension was placed in a Teflon®-lined autoclave bomb and kept in an oven at 218° C. for 18 h without stirring. The resulting MIL101/PTAaj solids were separated by centrifugation and washed with water, methanol, acetone and then dried under vacuum until constant weight. Elemental analysis (wt %): C, 33.1; Cr, 7.58; W, 21.8.
In the “impregnation” method, 1 g of dry MIL-101 synthesized in autoclave as described above was suspended in aqueous solution of phosphotungstic acid (1.0 g in 20 mL). The suspension was sonicated and shaken at 300 rpm at ambient temperature for 2 days. The solids were separated by centrifugation and dried under vacuum. The resulting MOF was designated MIL101/PTAimp. Elemental analysis (wt %): C, 33.5; Cr, 9.23; W, 19.9.
Based on the elemental analysis and molecular weight of the Keggin structure (H3PW12O40, 2880 Da), we estimated the PTA content of the MIL101/PTAaj and MIL101/PTAimp materials to be approximately 31 wt %.
EXAMPLE 2
Synthesis and Properties of NH2-MIL-101 (Al) Porous Material and NH2-MIL-101 (Al) Doped with Dimethlaminopyridine (DMAP)
A solution of aluminum chloride hexahydrate (0.97 g, 4.0 mmol) and 2-aminoterephthalic acid (1.09 g, 6.0 mmol) in 30 mL of DMF was placed in a Teflon®-lined autoclave and kept there at 130° C. for 72 h. The resulting yellow powder was separated by centrifugation (10,000 g, 15 min), washed with acetone, separated and suspended in 200 mL methanol at 75° C. for 24 h. The resulting powder was recovered from methanol by centrifugation and dried under vacuum. MOF surface area and pore parameters were measured using a Micromeritics' ASAP® 2020 Accelerated Surface Area and Porosimetry Analyzer (Micromeritics Corp., Norcross, Ga.). The compound's BET and Langmuir surface area values were measured to be 2080 and 2880 m2/g, respectively, and the average pore diameter was 2.2 nm.
For doping by DMAP, a solution of DMAP (1 g) in 30 mL methanol was added to 1 g of NH2-MIL-101 (Al) and the suspension was briefly sonicated and then shaken at room temperature for 48 h. The solid particles were then separated by centrifugation (10,000 g, 15 min), washed by methanol and dried under vacuum at room temperature.
EXAMPLE 3
Synthesis and properties of MIL-89 porous material and MIL-89 doped with dimethyaminopyridine (DMAP)
First, μ3-oxo-triaquohexakis(acetato)triiron(III)perchlorate dihydrate was prepared as follows: Electrolytic iron metal powder (11.2 g, 0.2 mol) was stirred with 100 mL of water and 51.6 mL (0.6 mol) of 70% HClO4. The mixture was warmed to 50° C. until all of the iron had reacted. A small amount of insoluble matter was removed by centrifugation. After the solution was cooled to 10° C., an excess (30 mL) of a 15% H2O2solution was added. The solution was cooled to 5° C., and anhydrous sodium acetate (32.8 g, 0.4 mol) was slowly added with stirring. The reaction mixture was placed in a stream of air. After 5 days the majority of the solution evaporated, leaving large red-brown crystals; yield 7.99 g (30.0%). The crystals were collected, washed with two 25-mL portions of chilled water, and blotted with filter paper. The crystals were further dried for 24 h under vacuum at room temperature.
Secondly, MOF Fe(III) acetate-muconic acid 1:5 (MIL-89) was synthesized as follows: Oxo-triaquohexakis(acetato)triiron(III) (400 mg) was dissolved in absolute ethanol (20 mL) and some amount remained undissolved, which was removed by centrifugation, dried and weighed. The dissolved fraction weighed 341 mg (0.277 mmol). To that solution, 200 mg (1.4 mmol) of trans,trans-muconic acid was added. The mixture was kept in a sealed vial at 75° C. for 1 week, resulting in orange particulates. The MOF was purified by DMF, hot methanol (3 times) and dried at 75° C. for 24 h and then under vacuum (10−5 Torr) for 1 week.
MOF surface area and pore parameters were measured using a Micromeritics' ASAP® 2020 Accelerated Surface Area and Porosimetry Analyzer (Micromeritics Corp., Norcross, Ga.). The compound's BET and Langmuir surface area values were measured to be 1880 and 2650 m2/g, respectively.
For doping by DMAP, a solution of DMAP (1 g) in 30 mL methanol was added to 1 g of MIL-89 and the suspension was briefly sonicated and then shaken at room temperature for 48 h. The solid particles were then separated by centrifugation (10,000 g, 15 min), washed by methanol and dried under vacuum at room temperature.
EXAMPLE 4
Properties of Porous Matrices Based on MIL-101 (Cr)
MOF surface area and pore parameters were measured using a Micromeritics' ASAP® 2020 Accelerated Surface Area and Porosimetry Analyzer (Micromeritics Corp., Norcross, Ga.). Thermogravimetric Analysis (TGA) was conducted using a Q5000IR thermogravimetric analyzer (TA Instruments, Inc.). Samples were subjected to heating scans (20° C./min) in nitrogen atmosphere and in a temperature ramp mode. 1H, 31P and 13C NMR spectra were collected at 25±0.5° C. using a Bruker Avance-400 spectrometer operating at 400.01, 161.9 and 100 MHz, respectively. Particle size distribution in MOF suspensions in methanol was measured using a ZetaPALS instrument (Brookhaven Instruments Corp.). The melting points were determined with a Mel-Temp II apparatus (Laboratory Devices USA) and are uncorrected. Elemental analysis was conducted in a commercial laboratory using an ICP apparatus.
The properties of the MIL-101 (Cr) particles synthesized in deionized water at pH 2.6 are collected in FIG. 7, whereas the properties of the MIL101/PTA matrices are shown in FIG. 1 and FIG. 8.
EXAMPLE 5
Capture and Conversion of Acrolein
Acrolein (also known as 2-propenal) is the persistent toxicant found in cigarette smoke. Acrolein can cause DNA damage that is similar to the damage seen in lung cancer patients. Since smoke contains up to 1,000 times more acrolein than other DNA-damaging chemicals, it could be a major cause of lung cancer. Acrolein also stops human cells from repairing DNA damage. And, like hydrogen cyanide, it kills the hairs that normally clean our lungs of other toxins. Its reactivity is due to the presence of its two reactive functions, vinyl and aldehyde, which can react individually or together. Acrolein is volatile, with boiling point at 53° C. and vapor pressure of 286 mbar at 20° C. In this example, we observed that acrolein is captured by and readily polymerized in the presence of basic and acidic MOF to give insoluble polymers (polyacroleins).
For acrolein capture, glass vials, each containing a weighed amount of dry powder of MIL-101, MIL101/PTAja, MIL101/PTAimp, PTA, NH2-MIL-101 (Al), NH2-MIL-101 (Al) doped with DMAP, and MIL-89 and MIL-89 doped with DMAP were placed in a desiccator next to an open Petri dish containing 10 g of liquid acrolein. The open vials were kept in the sealed desiccator for 5 days at room temperature, while weighing the uptake periodically by withdrawing the vials, rapidly sealing them and measuring weight. Equilibrium weight uptake was reached after 3 days, at which point no further weight increase of the vials was observed. The samples were prepared and measured in triplicate. The weight uptake was calculated as WU, %=100×(Sample weight after equilibration−Initial sample weight)/Initial sample weight.
The results of the weight uptake of acrolein are given in FIG. 2. As is seen, over 420 wt % acrolein uptake was observed by MIL-101 (Cr), which is the matrix with the highest pore volume and surface area. The uptake was significantly reduced by doping the MIL-101 (Cr) matrix with phosphotungstic acid (PTA), despite of the fact that PTA itself caused rapid polymerization of the vapors (see uptake of PTA exceeding 530%). The formation of transparent or yellowish polymeric layers was observed in all of the samples, but was most prevalent in the case of PTA. Phosphotungstic acid is the most potent acid of the known heteropolyacids, which causes polymerization of acrolein. It may be hypothesized that rapid polymerization of acrolein around PTA embedded into the pores of the MIL-101 prevented further uptake of the acrolein vapors in the cases of MIL-101(Cr)/PTA matrices, which reduced the overall acrolein uptake. Matrices MIL-101 (Al) and MIL-89 possessed much lesser surface area than MIL-101(Cr) and thus captured lesser amounts of acrolein. The ability of these matrices to uptake acrolein dramatically, 4.5-6.5-fold, increased by their modification with DMAP, which is an efficient catalyst of acrolein polymerization. In certain embodiments, the matrices of the present invention are capable of capturing acrolein vapors up to 5-fold of the matrix weight. The captured acrolein is rapidly converted into non-volatile polymeric species. Without being bound by any theory, polymerization of acrolein by an exemplary catalytic matrix of the present invention is shown in FIG. 3.
EXAMPLE 6
Capture and Conversion of Acetaldehyde
Acetaldehyde (CH3CHO) is a saturated aldehyde with a pungent and suffocating odor, but at more dilute concentrations the odor is fruity and pleasant, despite being irritant and lacrymator. Acetaldehyde is extremely volatile, with a boiling point of 20.16° C. and vapor pressure at 20° C. of 0.97 atm. Acetaldehyde concentration in cigarettes is 0.5-1.2 mg/cigarette, and 98% of the compound is found in the vapor phase/smoke. We conducted experiments illustrating the capture of acetaldehyde from vapor phase and its catalytic conversion into less volatile products as follows.
For acetaldehyde capture, borosilicate glass vials, each containing a weighed amount of dry powder of MIL-101, MIL101/PTAja, MIL101/PTAimp, or PTA were placed in a desiccator next to an open Petri dish containing 10 g of liquid acetaldehyde, initially poured into the dish at −20° C. Acetaldehyde rapidly evaporated from the Petri dish at room temperature, with the vapors contained inside of the sealed desiccator. The open vials were kept in the sealed desiccator for 7 days at room temperature, while weighing the uptake periodically by withdrawing the vials from the desiccator, immediately sealing them and measuring weight. Liquid acetaldehyde was added into the Petri dish within the desiccator each time the desiccator was open for samples withdrawal, to maintain the saturated vapor atmosphere inside the dessiccator. Equilibrium weight uptake was reached after 2 days, at which point no further weight increase of the vials was observed. Small samples (0.1 mL) of liquid formed in the vials were withdrawn intermittently after 2 days. Rapid change of color from white to yellow to brown to black was observed in the liquid condensed in the vials. The samples were prepared and measured in triplicate. The weight uptake was calculated as WU, %=100×(Sample weight after equilibration−Initial sample weight)/Initial sample weight.
The results of the weight uptake of acetaldehyde are given in FIG. 4. As is seen, over 200 wt % acetaldehyde uptake was observed by porous MIL-101 (Cr) matrix. The uptake was dramatically, over 4- to 5-fold, enhanced by doping the MIL-101 (Cr) matrix with phosphotungstic acid (PTA), resulting in MIL101/PTAja and MIL101/PTAimp matrices being filled with black liquid. The solid PTA powder completely dissolved in the black condensate liquid formed around it, with the uptake exceeding 2780%. It appeared that we unexpectedly discovered that PTA and PTA-loaded matrices are powerful condensing agents for acetaldehyde. The liquid condensed over the (initially) solid samples of the study was analyzed for composition by Matrix Assisted Laser Desorption/Ionization Time of Flight (MALDI-TOF) mass spectrometry using an Applied Biosystems Model Voyager DE-STR instrument, with α-cyano-4-hydroxycinnamic acid (ACHCA) as a matrix. A typical MALDI-TOF spectrum overlapped with the ACHCA spectrum is shown in FIG. 5.
As is seen in FIG. 5, initial acetaldehyde (m/z=44, b.p.=20° C.) is almost entirely (over 97%) converted to crotonaldehyde (m/z=70, b.p.=104° C.) (see FIG. 11), ethyl acetate (m/z=88, b.p.=77.1° C.), 2-methyl-2-pentenal (m/z=98, b.p.=133-134° C.), 3-hydroxy-2-methylpentanal (m/z=116, b.p.=180.5° C.), unsaturated aldehyde products of metaldehyde (aldehyde tetramer) dehydration (m/z=158, b.p.>170° C.) and other products of higher molecular weight. Over the time of measurements, molecular weight of the products further increased. Notably, the boiling points of aldol condensation products and their dehydration show that these products are a lot less volatile than the initial acetaldehyde. Eventually, polymerization of acetaldehyde catalyzed by matrices was observed to produce viscous polymeric liquids.
EXAMPLE 7
Catalysis of Reactions Between Aldehyde and Naphthol
Aldehydes and phenols such as naphthol are both carcinogenic products of the tobacco pyrolysis occurring during smoking and are found in tar and smoke (both vapors and particulates). In certain embodiments, the present invention discloses matrices that catalyze reactions between aldehydes and naphthols with the formation of non-volatile products. In the present Example, reactions between exemplary benzaldehyde and carcinogenic 2-naphthol catalyzed by porous matrices of the present invention are disclosed. Without being bound by any theory, the reaction is illustrated in FIG. 6.
The reaction was conducted as follows: A finely powdered aliquot of 2-naphthol (144 mg, 1.0 mmol) was mixed with 53 mg (0.5 mmol) of benzaldehyde and a measured amount of catalyst powder and the mixture, in a sealed stirred glass vial, was microwaved at a given temperature ranging from 60 to 90° C. for 2 to 10 min using 300 mW power under constant stirring. A rapid dissolution of 2-naphthol in benzaldehyde was observed at T≧60° C. At a given time, the contents of the vial were placed on dry ice and dissolved in 2 mL of deuterated THF or methanol, centrifuged at 15,000 g for 30 s and the supernatant solutions were kept on dry ice until 1H NMR spectra were recorded. The separated catalyst was rinsed with methanol three times, dried under vacuum and weighed. No side reactions such as hemiacetal or hemiketal formation with CD3OD were detectable under, these conditions. For the reaction yield measurement, the product separated from the solid catalyst in THF was dried under vacuum, dissolved in ethanol at 75° C. and the solution was chilled to 0° C. The ensued crystals of the dibenzoxanthene product were dried under vacuum and weighed to afford the reaction yield, which was calculated as a ratio of the actual product yield to the calculated one, based on the stoichiometry of the reaction.
Product Characterization after Recrystallization.
1H NMR (400 MHz, THF-d8) δH: 5.0 (1H, —CH), 7.08 (2H, naphthalene), 7.21-7.31 (5H, benzene), 7.47 (4H, naphthalene), 7.75 (2H, naphthalene), 7.81 (2H, naphthalene), 8.17 (2H, naphthalene). 13C NMR (100 MHz, CDCl3) δc: 45.3, 115.5, 118.8, 123.2, 126.7, 127.2, 128.4, 129.7, 133.5, 138.6, 153.6. Melting temperature, 181° C. Anal. Calcd. for C27H18O: C, 90.47; H, 5.06. Found: C, 90.35; H, 5.07.
The results of catalysis are shown in FIG. 9.
As is seen in FIG. 9, porous matrices of MIL101 containing PTA almost completely and rapidly converted benzaldehyde and 2-naphthol into non-volatile (solid, mp. 183° C.) product.
EXAMPLE 8
Condensation of Acetaldehyde and Phenol
The reactions between acetaldehyde and phenol in deuterated THF (THF-d8) were followed by 1H NMR spectroscopy, with the reactions conducted in triplicate at 25° C. Initial concentrations of phenol and acetaldehyde were Cpi=0.165 or 0.33 M and Ca0=0.33 M, respectively. In a typical experiment, phenol (188 mg, 2 mmol) and 10 mg of powdered catalyst were dissolved/suspended in THF-d8 (2 mL), and 38 μL of acetaldehyde (previously chilled at 0° C.) were injected into the reaction mixture through a syringe. By varying MIL101/PTA concentration, we conducted a series of control measurements to establish an optimum catalyst concentration. Addition of 5 mg MIL101/PTAimp or MIL101/PTAja into the initial acetaldehyde/phenol/THF-d8 reaction mixture resulted in 1.1- to 1.6-fold lower conversion within 30 to 60 min than with 10 mg of the corresponding catalyst species, whereas addition of 20 mg did not change the reaction rate under otherwise identical conditions. Therefore, all further studies, except for stability studies, were conducted with 10 mg catalyst addition. All catalysts were kept under vacuum (10−5 Torr) prior to the reactions. The reaction mixture was kept at 25° C. in a sealed 7-mL glass vial vigorously stirred at 800 rpm by a small magnetic bar. While phosphotungstic acid completely dissolved in THF, thus resulting in a homogeneous catalytic reaction, particles of MIL-101 and MIL101/PTA formed suspensions and therefore, in these cases the catalysis was heterogeneous. Samples (350 μL) were withdrawn from the vials intermittently, diluted 2-fold by THF-d8 and centrifuged for 30 s at 14,000×g to remove the catalyst. The catalyst was returned to the vial. 1H NMR spectra of the clear supernatant were then recorded. The timepoint was taken as a median of the measurement duration. In the catalyst stability/reuse studies, the reactions were performed with 20 mg catalyst. The catalyst was removed from the reaction mixture by centrifugation (14,000 g, 30 s), the resulting tablet was dispersed in 3 mL THF with brief sonication and the particles were again separated by centrifugation. The procedure was repeated twice and the resulting particles were separated and dried under vacuum. The recycled catalyst was weighed and analyzed for W or Cr content by elemental analysis, conducted in duplicates. The catalyst recovery (wt %) was measured as 100×mass of catalyst in n-th cycle/initial mass of catalyst. The performance of the catalyst in each cycle was measured as described above.
EXAMPLE 9
Reaction Between Benzaldehyde and Methanol
The reactions between benzaldehyde and methanol were conducted in triplicate at temperatures ranging from 25 to 55° C. Initial concentrations of methanol and benzaldehyde were Cmi=23.5 and Cb0=0.474 M, respectively. In a typical experiment, dry powdered catalyst (10 mg) was suspended in a mixture of methanol (6.7 mL, 166 mmol) and benzaldehyde (340 μL, 3.34 mmol) and the reaction commenced. All catalysts were kept under vacuum (10−5 Torr) prior to the reactions. The reaction mixture was kept at 25° C. in a sealed 7-mL glass vial vigorously stirred at 800 rpm by a small magnetic bar. While phosphotungstic acid completely dissolved in methanol, particles of MIL-101 and MIL101/PTA were insoluble and no organic product such as terephthalic acid was detected to leach out. Samples (200 μL) were withdrawn from the vials intermittently and centrifuged for 30 s at 14,000 g to remove the catalyst. The catalyst was returned to the vial. CDCl3 was added to the clear supernatant and 1H NMR spectra of the resulting solutions were then recorded. In cases when the samples could not be measured immediately after withdrawal from the reaction vials, they were placed into NMR tubes immediately after separation of the catalyst and dilution by CDCl3; the tubes were kept on dry ice prior to the spectra measurement to quench the reaction fully. In the control experiment, no measurable change was observed in NMR spectra for 2 days in samples kept under such consitions. As in the case of acetaldehyde-phenol reaction, by varying MIL101/PTA concentration, we attempted to establish an optimum catalyst concentration. Addition of 5 mg MIL101/PTAimp or MIL101/PTAja into the initial benzaldehyde/methanol reaction mixture resulted in 1.5- to 1.8-fold lower conversion within 30 to 60 min than with 10 mg of the corresponding catalyst species, whereas addition of 20 mg did not change the reaction rate under otherwise identical conditions. Therefore, all further studies were conducted with 10 mg catalyst addition, except for stability studies wherein 20 mg of the catalyst were used. For recycling, the catalyst removed by centrifugation from the reaction mixture was washed with THF and chilled methanol twice, dried under vacuum and weighed. Other stability parameters were measured as described above for the acetaldehyde-phenol reactions.
Benzaldehyde dimethyl acetal obtained in reaction catalyzed by MIL101/PTAja followed by the product purification by flash chromatography on silica gel was observed to be a brownish paste material. 1H NMR (CDCl3): d=3.37 (s, 6H), 5.42 (s, 1H), 7.34-7.42 (m, 3H), 7.47-7.49 (m, 2H). 13C NMR (CDCl3): d=52.3, 102.7, 126.2, 127.8, 128.0, 137.6.
EXAMPLE 10
Characterization of Catalysts
MOF surface area and pore parameters were measured using a Micromeritics' ASAP® 2020 Accelerated Surface Area and Porosimetry Analyzer (Micromeritics Corp., Norcross, Ga.). Thermogravimetric Analysis (TGA) was conducted using a Q5000IR thermogravimetric analyzer (TA Instruments, Inc.). Samples were subjected to heating scans (20° C./min) in nitrogen atmosphere and in a temperature ramp mode. 1H and 13C NMR spectra were collected at 25±0.5° C. using a Bruker Avance-400 spectrometer operating at 400.01 and 100 MHz, respectively. Particle size distribution in MOF suspensions in methanol was measured using a ZetaPALS instrument (Brookhaven Instruments Corp.). Elemental analysis was conducted in a commercial laboratory.
In the present study, MIL-101 framework was synthesized solvothermically in deionized water, without addition of toxic and corrosive hydrofluoric acid that is typically present in the MIL-101. Férey, G. et al. Science 2005, 309, 2040-2042. Despite of the absence of HF, the crystal structure of MIL-101 in the present work corresponds to the one previously published. Doping of the MIL-101 porous structure with PTA ions results in robust particles that possess 4- to 5-fold lesser surface area than the original MOF; a significant portion of the pores is occupied by the PTA. Kegginanion of PTA possesses relatively large size (ca. 1.3 nm diameter and 2.25 nm3 volume), so only the large cages of MIL-101 (3.6-nm diameter, FIG. 10) can host it. Férey, G. et al. showed that each cage can accept up to five Keggin ions, representing 50% of the volume of the cage. Crystals grown as a result of joint autoclaving of the MIL-101 components and PTA resulted in particles sized 5- to 25-fold larger than those of the original MIL-101 or MIL101/PTA. Despite of the larger particle size, as shown below, the catalytic activity of the MIL101/PTAja was virtually the same as the one of the MIL101/PTAimp with its smaller particles, indicating that the mass transport through the MOF pores was not limiting the activity.
EXAMPLE 11
Reaction Between Acetaldehyde and Phenol
Kinetics of the condensation reaction between acetaldehyde and phenol at room temperature was studied by 1H NMR. Acetaldehyde is readily miscible with most organic solvents as well as phenol at ambient temperatures. However, in the presence of the catalyst, the exothermic aldehyde-phenol condensation is extremely rapid. The rise of temperature causes further increase in the reaction rate, which in turn causes a further temperature rise. As in the industrial processes of novolak resin production, we needed to utilize a non-reactive diluent as a means of cooling. Deuterated tetrahydrofuran (THF-d8), which also served as an NMR lock, appeared to be an efficient diluent under chosen conditions, which afforded no detectable spike of temperature upon addition of acetaldehyde into the reaction mixture.
Typical 1H NMR spectra representing the kinetics of the acetaldehyde and phenol condensation reaction catalyzed by MIL101/PTAja in THF-d8 at 25° C. are shown in FIG. 12. As is seen in FIG. 12, in the course of the reaction, the signal of the aldehyde group proton (—HC═O) at 9.7 ppm disappeared, while a strong signal of the methyl groups belonging to the ethylidene links between phenolic rings of the condensate product (—CHCH3) appeared at 1.34 ppm and grew. These signals were a good reference for calculation of the aldehyde conversion (F), which was obtained from the expression




  
    
      
        F
        =
        
          
            0.33
            ⁢
            
              
            
            ⁢
            
              I
              1.3
            
          
          
            
              I
              9.7
            
            +
            
              0.331
              1.3
            
          
        
      
    
    
      
        (
        1
        )
      
    
  




where I1.3 and I9.7 are relative integrations of the corresponding methyl and aldehyde protons, respectively, measured at time t.

The positions of the triplet centered at 7.2 ppm (two meta-position protons in phenol and products) and multiplet centered at 6.9 ppm (two ortho- and one para-positioned protons in phenol rings) were independent of the solvents used in the present study and did not change as the reaction proceeded. It is interesting to observe that the positions of the signals corresponding to the phenolic hydroxyl groups in the areas 7.9-8.3 and 5 ppm were labile, depending on the extent of the reaction. Previous studies of the model phenol-aldehyde oligomers documented that the chemical shifts of the phenol hydroxyls are highly sensitive of the formation of intramolecular complexes, wherein phenolic and forming methylolic hydroxyls form hydrogen bonds, resulting in changes of chemical shifts (δOH) of up to 3 ppm. Formation and dissociation of such complexes explains the observed changes in δOH.
The overall reaction of the acetaldehyde-phenol condensation is shown in FIG. 13.
In the FIG. 13, we deliberately did not specify the position of the methylene bridges between the phenol rings, as both ortho- and para-positions of the aromatic phenol ring possess the same reactivity in acid-catalyzed reactions. It is possible, however, to obtain all-ortho phenol-acetaldehyde novolac resins with uniform constitution in other catalytic reactions such as bromomagnesium ion mediated reaction of phenol with acetaldehyde derivatives.
From the formal definition of a reaction rate, we can define the rate of the condensation (FIG. 13) as

r=kCpαCaβ,

where Cp and Ca is the phenol and acetaldehyde concentration, respectively. Assuming that —OH group does not react, the change in the aldehyde concentration with time is as follows:





  
    -
    
      
        d
        
          C
          a
        
      
      
        d
        t
      
    
  
  =
  
    
      
        k
        1
      
      ⁢
      
        C
        pp
      
    
    +
    
      
        k
        2
      
      ⁢
      
        C
        po
      
      ⁢
      
        C
        a
      
    
  




where Cpp and Cpo is the total number of the para- and ortho positions, respectively, available for reaction.

Approximating k1=k2=k, we obtain




  
    -
    
      
        d
        
          C
          a
        
      
      
        d
        t
      
    
  
  =
  
    
      k
      ⁡
      
        (
        
          
            C
            pp
          
          +
          
            C
            po
          
        
        )
      
    
    ⁢
    
      C
      a
    
  




The concentration of reacted aldehyde at a given time is Ca0−Ca, where Ca0 is the initial aldehyde concentration. The total concentration of the remaining ortho- and para-positions of phenol are then found from the expression Cpp+Cpo=3Cpi−Cao+Ca. Herein, Cpi is the initial phenol concentration.

The rate expression can then be written as follows:




  
    -
    
      
        d
        
          C
          a
        
      
      
        d
        t
      
    
  
  =
  
    
      k
      ⁡
      
        (
        
          
            3
            ⁢
            
              
            
            ⁢
            
              C
              pi
            
          
          -
          
            C
            
              a
              ⁢
              
                
              
              ⁢
              0
            
          
          +
          
            C
            a
          
        
        )
      
    
    ⁢
    
      C
      a
    
  




Denoting q=(3Cpi−Ca0), the above expression becomes





  
    
      
        dC
        a
      
      
        
          (
          
            q
            +
            
              C
              a
            
          
          )
        
        ⁢
        
          C
          a
        
      
    
    =
    
      -
      kdt
    
  
  ,




which after integration results in the following relation:





  
    ln
    ⁢
    
      
        C
        a
      
      
        q
        +
        
          C
          a
        
      
    
  
  =
  
    
      ln
      ⁢
      
        
          C
          a
        
        
          q
          +
          
            C
            
              a
              ⁢
              
                
              
              ⁢
              0
            
          
        
      
    
    -
    
      kqt
      .
    
  




Thus, by expressing the initial reaction results as the time-dependent acetaldehyde concentration function P vs time, where





  
    
      
        
          P
          =
          
            
              
                ln
                ⁢
                
                  
                
                ⁢
                
                  C
                  a
                
              
              
                q
                +
                
                  C
                  
                    a
                    ⁢
                    
                      
                    
                    ⁢
                    0
                  
                
              
            
            -
            
              
                ln
                ⁢
                
                  
                
                ⁢
                
                  C
                  a
                
              
              
                q
                +
                
                  C
                  a
                
              
            
          
        
        ,
      
    
    
      
        (
        2
        )
      
    
  




we will obtain a straight line with a slope proportional to kq and, hence, arrive at an estimate of the reaction rate constant, k.

As is seen in FIG. 14, the reaction catalyzed by PTA, MIL101/PTA and MIL101 proceeded with considerable rates in the first 30 min, at which point over 50% of the initial acetaldehyde were reacted. Complete conversion of acetaldehyde in the catalyzed reactions was reached within approximately 5 days. Spontaneous reaction without any catalyst added resulted in only ca. 5% conversion after 5 days at room temperature. The rate constant of the initial reaction was measured by expressing the time-dependent acetaldehyde concentration function (P) vs time (equation (2)) as shown in FIG. 15.
The slope of the linear fits (R2>0.96 in all cases) yielded the acetaldehyde-phenol condensation rate constants, k, values of which are collected in FIG. 16, along with the catalyst turnover number (TON) and frequency (TOF) values. The TOF was obtained from the initial slope of the time-dependent concentration of the converted aldehyde Cca/t=Ca0−Ca0F)/t and effective catalyst concentration (Ccat):

TOF=(Ca0/Ccat)(ΔF/Δt)  (3)

Similarly, the reaction half-life was calculated from the expression t1/2=ln(2)/(ΔF/Δt).

In the case of MIL-101 without PTA, we assumed that total concentration of the Brønsted and Lewis acid sites ( ̃2 mmol/g), rather than the concentration of coordinatively unsaturated cites in MIL-101 (0.7 mmol/g), provides an adequate estimate of the catalytic sites concentration. This value was used in Ccat calculation.
EXAMPLE 12
Acetalization of Benzaldehyde with Methanol
The reaction of acetalization of benzaldehyde (FIG. 17) using excess methanol with the formation of benzaldehydedimethyl acetal was readily followed by 1H NMR, which enabled measurement of the reaction kinetics (FIG. 18).
As is seen in FIG. 18, in the course of the reaction, the signal of the benzaldehyde proton (—HC═O) at 9.9 ppm disappeared, while signals at 5.3 ppm of the methine group located α to both —C—O— as well as benzyl group and 6 protons of the methyl groups of the dimethyl acetal at 3.3 ppm (—CH—O—CH3) appeared and grew. The aldehyde conversion (F) in this reaction was obtained from the expression




  
    
      
        
          P
          =
          
            
              I
              5.3
            
            
              
                I
                9.9
              
              +
              
                I
                5.3
              
            
          
        
        ,
      
    
    
      
        (
        4
        )
      
    
  




where I5.3and I9.9 are relative integrations of the corresponding methylene and aldehyde protons, respectively, measured at time t.

While the position of the signals of the methyl groups of methanol (3.38 ppm) remained constant throughout the course of the reaction, the position of the hydroxyl group signals varied in the range 3.7-4.3 ppm (FIG. 18). The δOH of the hydroxyl groups of methanol is known to depend strongly on the extent of the hydrogen bond formation, which depends of the solvent. In particular, the chemical shift of the —OH signal in the methanol-chloroform mixtures varies with the solvent composition in the 1.5-4.6 ppm range due to the hydrogen bonding between the methanol and the solvent. Slight variations of the methanol concentration in CDCl3 and appearance of water, with its strong propensity for H-bonding, in the course of the reaction, lead to the changes of the methanolic —OH chemical shift.
The kinetics and thermodynamics of the reaction of aldehyde with alkanols over solid acid, heterogeneous catalysts, such as zeolites, clays and ion exchange resins, have been studied. A reaction mechanism for the alkanol-aldehyde reaction involving heterogeneous catalysis was proposed, consisting of three elementary steps: (i) hemiacetal formation from the adsorbed aldehyde and the alcohol; (ii) formation of water (a limiting step), and (iii) formation of the acetal. Detailed studies involving the monitoring of the time-dependent activities of all reactants in the synthesis of acetaldehyde dimethylacetal on the acid resin Amberlyst-15 in a batch reactor revealed a kinetic law and rate constants of the reaction, and accounted for the acetaldehyde volatility. However, to the best of our knowledge, no rate constants have been reported in the case of arylaldehyde acetals, despite the reports on the formation of dimethyl acetals using trimethyl orthoformate as reagent and indium-layered MOF as catalysts and from benzaldehyde and methanol using Cu(II), Fe(II) and Al benzene di- and tricarboxylate MOFs as catalysts.
In the present work, we set out to evaluate the kinetics of the overall benzaldehyde dimethyl acetal formation reaction catalyzed by MIL-101 and its composites with PTA and compare the performance of these materials with those of the previously reported MOF catalysts. We avoided the description of the (unknown) elementary steps.
Considering the 50-fold molar excess of methanol over benzaldehyde, the change of benzaldehyde concentration (Cb) with time can be described by a pseudo-first order rate equation:




  
    -
    
      
        d
        
          C
          b
        
      
      
        d
        t
      
    
  
  =
  
    
      k
      obs
    
    ⁢
    
      C
      b
    
  




From the integrated form of the above equation being

ln(Cbt/Cb0)=ln(1−F)=−kobst,  (5)

we can obtain kobs using experimental 1H NMR results such as F vs time data, wherein F is obtained from eqn (4). The kinetics shown in FIG. 19 depict rapid conversion of benzaldehyde to its dimethyl acetal in the presence of PTA and its composites with MIL-101. The data points obtained within the first 60 min appeared to be straight lines (R2>0.98 in all cases) in coordinates of eqn (5), enabling estimates of kobs, the reaction half-time t1/2=ln(2)/kobs, and the turnover frequency TOF=Cb0kobs/Ccat. These parameters are collected in FIG. 20. Importantly, a very low (<5 mol %) benzaldehyde conversion was observed without the catalysts, while a complete conversion was observed within 48 h in the presence of all catalysts and 93-95 mol % conversion within 24 h in reactions catalyzed by the MIL101/PTA composites as well as PTA. With MIL-101, the conversion reached 80 mol % after 24 h. The catalytic turnover number (TON═Cb0×Conversion/Ccat) can be calculated. Calculated per total concentration of the Bronsted and Lewis acid cites per L of the suspension, at 80% conversion after 24 h we obtain TON of ca. 140 with MIL-101 (FIG. 16). The above estimates of TON indicate that MIL-101 is at least 10-fold more efficient a catalyst compared to Cu3(BTC)2 MOF. Importantly, the reaction rates were 5-fold and TON values were 20-fold higher with the MIL101/PTA composites compared to the unmodified MIL-101, indicating that the presence of a strong heteropolyacid in these composites enhanced the catalysis efficiency drastically.

EXAMPLE 13
Catalyst Recovery and Reuse
From the practical standpoint, maximum catalyst productivity, or kg of product produced per kg of catalyst, is the measure of a catalyst's performance merit. Highly stable catalysts that do not become deactivated easily during the reaction exhibit high productivity and many kg of product can be produced per kg of catalyst. Productivity data using MOFs as catalysts that are necessary to determine the economics of the process and the possibility to develop industrial processes based on MOF catalysis are available in only a few reports. In the present work, we accessed the stability of the MIL-101 and MIL101/PTA catalysts within four cycles of the alcohol-aldehyde reactions. The stability parameters were (i) overall catalyst recovery by mass, (ii) structural stability in terms of PTA (Keggin ion) content in the MIL101/PTA composites or Cr content in MIL-101, and (iii) performance in terms of kinetic rate constants in each cycle. The results of the recovery and reuse studies are collected in FIG. 21. As is seen, the loss of the catalyst mass over 4 cycles was approximately 10 wt % for all tested catalysts. This loss is attributable to the incomplete recovery of the catalyst after separation by centrifugation, due to minute fraction dissolving in methanol in the process of catalyst washing and some small catalyst quantities staying on the walls of the centrifuge tubes. These losses essentially stopped after the third cycle, and so did the losses of the PTA leaching out of the MIL-101 framework. We have previously demonstrated by XRD methods that prolonged and repeated exposure of the MIL-101 and its composites with PTA to organic solvents such as methanol, THF and some others in the temperature range from ambient to 90° C. did not induce any changes to the framework crystal structure. These data, along with essentially unchanged reaction rate constants (FIG. 21) demonstrate outstanding stability of the MOF catalysts. In 4 cycles, 20 mg of the MIL/PTA catalyst converted approximately 750 mg of phenol and 140 mg of acetaldehyde, or 1.35 g of benzaldehyde. This finding indicates high catalyst performance merit.
INCORPORATION BY REFERENCE
The contents of the articles, patents, and patent applications, and all other documents and electronically available information mentioned or cited herein, are hereby incorporated by reference in their entirety to the same extent as if each individual publication was specifically and individually indicated to be incorporated by reference. Applicants reserve the right to physically incorporate into this application any and all materials and information from any such articles, patents, patent applications, or other physical and electronic documents.
EQUIVALENTS
The invention has been described broadly and generically herein. Those of ordinary skill in the art will readily envision a variety of other means and/or structures for performing the functions and/or obtaining the results and/or one or more of the advantages described herein, and each of such variations and/or modifications is deemed to be within the scope of the present invention. More generally, those skilled in the art will readily appreciate that all parameters, dimensions, materials, and configurations described herein are meant to be exemplary and that the actual parameters, dimensions, materials, and/or configurations will depend upon the specific application or applications for which the teachings of the present invention is/are used. Those skilled in the art will recognize, or be able to ascertain using no more than routine experimentation, many equivalents to the specific embodiments of the invention described herein. It is, therefore, to be understood that the foregoing embodiments are presented by way of example only and that, within the scope of the appended claims and equivalents thereto, the invention may be practiced otherwise than as specifically described and claimed. The present invention is directed to each individual feature, system, article, material, kit, and/or method described herein. In addition, any combination of two or more such features, systems, articles, materials, kits, and/or methods, if such features, systems, articles, materials, kits, and/or methods are not mutually inconsistent, is included within the scope of the present invention. Further, each of the narrower species and subgeneric groupings falling within the generic disclosure also form part of the invention. This includes the generic description of the invention with a proviso or negative limitation removing any subject matter from the genus, regardless of whether or not the excised material is specifically recited herein.

## Claims

1. A method of reducing the quantity of a toxicant in a fluid, comprising:
contacting the fluid with a hybrid MOF matrix,
wherein:
the hybrid MOF matrix comprises (i) an MOF matrix, wherein the MOF matrix comprises metal ions or clusters coordinated to polydentate organic ligands, and the metal ions or clusters comprise Cr, Fe, Zn, Al, Ni, or Cu, and (ii) a dopant, wherein the dopant is a supernucleophilic amine;
the fluid is a gas; and
the toxicant is a carbonylic compound or a phenolic compound.

2. The method of claim 1, wherein the fluid is tobacco smoke.

3. The method of claim 1, wherein the fluid is mainstream cigarette smoke or sidestream cigarette smoke.

4. The method of claim 1, wherein the toxicant is a carbonylic compound selected from the group consisting of acetaldehyde, acrolein, formaldehyde, butyraldehyde, crotonaldehyde, benzyl aldehyde, and propionaldehyde.

5. The method of claim 1, wherein the toxicant is a phenolic compound selected from the group consisting of phenol, m-cresol, p-cresol, o-cresol, α-naphthol, and β-naphthol.

6. The method of claim 1, wherein the toxicant is adsorbed onto or absorbed into the MOF matrix.

7. The method of claim 1, wherein the toxicant is chemically converted into a less volatile substance.

8. The method of claim 7, wherein the less volatile substance is a ketal, an acetal, a polyketal, a polyacetal, a polymer, or an organic heterocycle.

9. The method of claim 1, wherein the organic ligand is terephthalic acid, isophthalic acid, 2-aminoterephthalic acid, 2,5-dihydroxyterephthalic acid, 1,2,3-benzenetricarboxylic acid, 1,3,5-benzenetricarboxylic acid, or 2,2′-bipyridine-5,5′-dicarboxylic acid.

10. The method of claim 1, wherein the dopant is dimethylaminopyridine.

11. The method of claim 1, wherein the metal ions or clusters comprise Cr.

12. The method of claim 1, wherein the metal ions or clusters comprise Al.

13. The method of claim 1, wherein the metal ions or clusters comprise Fe.

14. The method of claim 1, wherein the dopant is dimethylaminopyridine; and the metal ions or clusters comprise Al.

15. The method of claim 1, wherein the dopant is dimethylaminopyridine; and the metal ions or clusters comprise Fe.

16. A method of adsorbing or absorbing a carbonylic compound or a phenolic compound, comprising
contacting the carbonylic compound or phenolic compound with a hybrid MOF matrix, wherein the hybrid MOF matrix comprises (i) an MOF matrix, wherein the MOF matrix comprises metal ions or clusters coordinated to polydentate organic ligands, and the metal ions or clusters comprise Cr, Fe, Zn, Al, Ni, or Cu, and (ii) a dopant, wherein the dopant is a supernucleophilic amine.

17. A method of catalyzing the conversion of a carbonylic compound to a non-carbonylic product, comprising
contacting the carbonylic compound with a hybrid MOF matrix for an amount of time, wherein the hybrid MOF matrix comprises (i) an MOF matrix, wherein the MOF matrix comprises metal ions or clusters coordinated to polydentate organic ligands, and the metal ions or clusters comprise Cr, Fe, Zn, Al, Ni, or Cu, and (ii) a dopant, wherein the dopant is a supernucleophilic amine, thereby forming the non-carbonylic product.

18. A method of catalyzing the conversion of a phenolic compound to a non-phenolic product or a polymeric product, comprising
contacting the phenolic compound with a hybrid MOF matrix for an amount of time, wherein the hybrid MOF matrix comprises (i) an MOF matrix, wherein the MOF matrix comprises metal ions or clusters coordinated to polydentate organic ligands, and the metal ions or clusters comprise Cr, Fe, Zn, Al, Ni, or Cu, and (ii) a dopant, wherein the dopant is a supernucleophilic amine, thereby forming the non-phenolic product or the polymeric product.

19. A method of reducing the quantity of a toxicant in a fluid, comprising: contacting the fluid with a hybrid MOF matrix, wherein:
the hybrid MOF matrix comprises (i) an MOF matrix, wherein the MOF matrix comprises metal ions or clusters coordinated to polydentate organic ligands, and the metal ions or clusters comprise Cr, Fe, Zn, Al, Ni, or Cu, and (ii) a dopant, wherein the dopant is phosphotungstic acid;
the fluid is a gas; and
the toxicant is a carbonylic compound or a phenolic compound.

20. The method of claim 19, wherein the metal ions or clusters comprise Cr.

21. The method of claim 19, wherein the fluid is tobacco smoke.

22. The method of claim 19, wherein the fluid is mainstream cigarette smoke or sidestream cigarette smoke.

23. The method of claim 19, wherein the toxicant is a carbonylic compound selected from the group consisting of acetaldehyde, acrolein, formaldehyde, butyraldehyde, crotonaldehyde, benzyl aldehyde, and propionaldehyde.

24. The method of claim 19, wherein the toxicant is a phenolic compound selected from the group consisting of phenol, m-cresol, p-cresol, o-cresol, α-naphthol, and β-naphthol.

25. The method of claim 19, wherein the toxicant is adsorbed onto or absorbed into the MOF matrix.

26. The method of claim 19, wherein the toxicant is chemically converted into a less volatile substance.

27. The method of claim 26, wherein the less volatile substance is a ketal, an acetal, a polyketal, a polyacetal, a polymer, or an organic heterocycle.

28. The method of claim 19, wherein the organic ligand is terephthalic acid, isophthalic acid, 2-aminoterephthalic acid, 2,5-dihydroxyterephthalic acid, 1,2,3-benzenetricarboxylic acid, 1,3,5-benzenetricarboxylic acid, or 2,2′-bipyridine-5,5′-dicarboxylic acid.

29. The method of claim 19, wherein the metal ions or clusters comprise Al.

30. The method of claim 19, wherein the metal ions or clusters comprise Fe.

31. A method of reducing the quantity of a toxicant in a fluid, comprising contacting the fluid with MIL-101, strongly acidic MIL-101, or MIL101/PTA, wherein
the fluid is a gas; and
the toxicant is a carbonylic compound or a phenolic compound.

32. The method of claim 31, wherein the fluid is contacted with MIL-101 or strongly acidic MIL-101; the MIL-101 or strongly acidic MIL-101 further comprises a dopant; and the dopant is a polyoxometalate or a supernucleophilic amine.