# Patent

## Title
Process for preparing hydrogen peroxide from the elements

## Abstract

The present invention relates to a process for the preparation of hydrogen peroxide from oxygen or oxygen-delivering substances and hydrogen or hydrogen-delivering substances in the presence of at least one catalyst containing a metal-organic framework material, wherein said framework material comprises pores and a metal ion and an at least bidentate organic compound, said bidentate organic compound being coordinately bound to the metal ion. The invention further relates to a novel material consisting of said metal organic framework material wherein the material is brought in contact with at least one additional metal.

## Background
BACKGROUND AND SUMMARY OF THE INVENTION
1. Field of the Invention
The present invention relates to a process for preparing hydrogen peroxide from the reaction of oxygen and/or oxygen-delivering substances with hydrogen and/or hydrogen-delivering substances in the presence of a catalyst.
2. Discussion of the Background
Most hydrogen peroxide produced commercially is obtained via the anthraquinone process involving the oxidation of an anthra-hydroquinone in the presence of air (yielding the hydrogen peroxide) and the recycling reaction of reducing the resulting anthraquinone to anthra-hydroquinone in the presence of a noble metal catalyst, most commonly Pd. A catalyst free of noble metals is described in WO 97/01113. The formation of hydrogen peroxide from the elements is not of significant commercial importance at this point. However, for specific applications, e.g. in electronics, ultrapure hydrogen peroxide is required. In this context, producing hydrogen peroxide from the elements may be cost-effective over working-up and cleaning hydrogen peroxide obtained by the anthraquinone process.
In a promising novel and alternative strategy to create micro- and/or mesoporous catalytically active materials in general, metal ions and molecular organic building blocks are used to form so-called metal-organic frameworks (MOFs). The metal-organic framework materials as such are described, for example, in. U.S. Pat. No. 5,648,508, EP-A-0 709 253, M. O'Keeffe et al., J. Sol. State Chem., 152 (2000) p. 3–20, H. Li et al., Nature 402 (1999) p. 276 seq., M. Eddaoudi et al., Topics in Catalysis 9 (1999) p. 105–111, B. Chen et al., Science 291 (2001) p. 1021–23.
Among the advantages of these novel materials, in particular for applications in catalysis, are the following:

    
    
        (i) larger pore sizes can be realized than for the zeolites used presently;
        (ii) the internal surface area is larger than for porous materials used presently;
        (iii) pore size and/or channel structure can be tailored over a large range;
        (iv) the organic framework components forming the internal surface can be functionalized easily;
        (v) the metal-organic framework according to the invention is stable even if no host, solvent or any other additional substance is present, i.e. the framework does not collapse and/or interpenetrate and/or change its shape and dimension. This puts the material according to the invention in contrast to other metal-organic materials that maybe used as catalysts.
    
    


However, these novel porous materials have only been described as such. The use of these catalytically active materials for the reaction of hydrogen and oxygen to form hydrogen peroxide has not been disclosed yet. In related applications, the use of these novel porous materials as shaped bodies (U.S. application Ser. No. 10/157,182) and for epoxidation reactions (U.S. application Ser. No. 10/157,494) has been described.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide a process and a catalyst for the reaction of oxygen and/or oxygen-delivering substances with hydrogen and/or hydrogen-delivering substances, wherein the catalyst for said reaction contains a novel material, in addition to, or instead of, catalytic materials according to the prior art.
This object is solved by providing a process for the reaction of oxygen and/or oxygen-delivering substances with hydrogen and/or hydrogen-delivering substances in the presence of a catalyst, wherein said catalyst contains a metal-organic framework material comprising pores and at least one metal ion and at least one at least bidentate organic compound, which is coordinately bound to said metal ion, and wherein said framework material retains its dimension and shape even while no other materials are present.


DETAILED DESCRIPTION OF THE INVENTION
As has been mentioned above, metal-organic framework materials as such are described in, for example, U.S. Pat. No. 5,648,508, EP-A-0 709 253, M. O'Keeffe et al., J. Sol. State Chem., 152 (2000) p. 3–20, H. Li et al., Nature 402 (1999) p. 276 seq., M. Eddaoudi et al., Topics in Catalysis 9 (1999) p. 105–111, B. Chen et al., Science 291 (2001) p. 1021–23. An inexpensive way for the preparation of said materials is the subject of DE 10111230.0. The content of these publications, to which reference is made herein, is fully incorporated in the content of the present application.
The catalyst used in the present invention contains at least one metal-organic framework material, for example one of the materials described below.
The metal-organic framework materials, as used in the present invention, comprise pores, particularly micro- and/or mesopores. Micropores are defined as being pores having a diameter of 2 nm or below and mesopores as being pores having a diameter in the range of above 2 nm to 50 nm, respectively, according to the definition given in Pure Applied Chem. 45, p. 71 seq., particularly on p. 79 (1976). The presence of the micro- and/or mesopores can be monitored by sorption measurements for determining the capacity of the metal-organic framework materials to take up nitrogen at 77 K according to DIN 66131 and/or DIN 66134.
For example, a type-I-form of the isothermal curve indicates the presence of micropores {see, for example, paragraph 4 of M. Eddaoudi et al., Topics in Catalysis 9 (1999)}. In a preferred embodiment, the specific surface area, as calculated according to the Langmuir model (DIN 66131, 66134) is above 5 m2/g, preferably above 10 m2/g, more preferably above 50 m2/g, particularly preferred above 500 m2/g and may increase into the region of to above 3000 m 2/g.
As to the metal component within the framework material that is to be used according to the present invention, particularly to be mentioned are the metal ions of the main group elements and of the subgroup elements of the periodic system of the elements, namely of the groups Ia, IIa, IIIa, IVa to VIIIa and Ib to VIb. Among those metal components, particular reference is made to Mg, Ca, Sr, Ba, Sc, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, Al, Ga, In, Tl, Si, Ge, Sn, Pb, As, Sb, and Bi, more preferably to Zn, Cu, Ni, Pd, Pt, Ru, Rh and Co. As to the metal ions of these elements, particular reference is made to: Mg2+, Ca2+, Sr2+, Ba2+, Sc3+, Y3+, Ti4+, Zr4+, Hf4+, V4+, V3+, V2+, Nb3+, Ta3+, Ta3+, Cr3+, Mo3+, W3+, Mn3+, Mn2+, Re3+, Re2+, Fe3+, Fe2+, Ru3+, Ru2+, Os3+, Os2+, Co3, Co2+, Rh2+, Ir2+, Ni2+, Ni+, Pd2+, Pd+, Pt2+, Pt+, Cu2+, Cu+, Ag+, Au+, Zn2+, Cd2+, Hg2+, Al3+, Ga3+, In3+, Tl3+, Si4+, Si2+, Ge4+, Ge2+, Sn4+, Sn2+, Pb4+, Pb2+, As5+, As3+, As+, Sb5+, Sb+, Bi5+, Bi3+, and Bi+.
With regard to the preferred metal ions and further details regarding the same, particular reference is made to: EP-A 0 790 253, particularly to p. 10, 1. 8–30, section “The Metal Ions”, which section is incorporated herein by reference. In the context of the present invention, Zn is particularly preferred as the metal component.
In addition to the metal salts disclosed in EP-A 0 790 253 and U.S. Pat. No. 5,648,508, other metallic compounds can be used, such as sulfates, phosphates and other complex counter-ion metal salts of the main- and subgroup metals of the periodic system of the elements. Metal oxides, mixed oxides and mixtures of metal oxides and/or mixed oxides with or without a defined stoichiometry are preferred. All of the above mentioned metal compounds can be soluble or insoluble and they may be used as starting material either in form of a powder or as a shaped body or as any combination thereof.
As to the at least bidentate organic compound, which is capable to coordinate with the metal ion, in principle all compounds can be used which are suitable for this purpose and which fulfill the above requirements of being at least bidentate. Said organic compound must have at least two centers, which are capable to coordinate with the metal ions of a metal salt, particularly with the metals of the aforementioned groups. With regard to the at least bidentate organic compound, specific mention is to be made of compounds having

    i) an alkyl group substructure, having from 1 to 10 carbon atoms,
    ii) an aryl group substructure, having from 1 to 5 phenyl rings,
    iii) an alkyl or aryl amine substructure, consisting of alkyl groups having from 1 to 10 carbon atoms or aryl groups having from 1 to 5 phenyl rings,

said substructures having bound thereto at least one at least bidentate functional group “X”, which is covalently bound to the substructure of said compound, and wherein X is selected from the group consisting of CO2H, CS2H, NO2, SO3H, Si(OH)3, Ge(OH)3, Sn(OH)3, Si(SH)4, Ge(SH)4, Sn(SH)3, PO3H, AsO3H, AsO4H, P(SH)3, As(SH)3, CH(RSH)2, C(RSH)3, CH(RNH2)2, C(RNH2)3, CH(ROH)2, C(ROH)3, CH(RCN)2, C(RCN)3, wherein R is an alkyl group having from 1 to 5 carbon atoms, or an aryl group consisting of 1 to 2 phenyl rings, and CH(SH)2, C(SH)3, CH(NH2)2, C(NH2)2, CH(OH)2, C(OH)3, CH(CN)2 and C(CN)3.



Particularly to be mentioned are substituted or unsubstituted, mono- or polynuclear aromatic di-, tri- and tetracarboxylic acids and substituted or unsubstituted, aromatic, at least one hetero atom comprising aromatic di-, tri- and tetracarboxylic acids, which have one or more nuclei. Preferred bidendate organic compounds in the context of the present invention are alkyl group substructures with at least two carboxy groups and/or aryl groups with one or two phenyl rings having at least two carboxy groups.
A preferred ligand is 1,3,5-benzene tricarboxylate (BCT). Further preferred ligands are ADC (acetylene dicarboxylate), NDC (naphtalen dicarboxylate), BDC (benzene dicarboxylate), ATC (adamantane tetracarboxylate), BTC (benzene tricarboxylate), BTB (benzene tribenzoate), MTB (methane tetrabenzoate) and ATB (adamantane tribenzoate).
Besides the at least bidentate organic compound, the framework material as used in accordance with the present invention may also comprise one or more mono-dentate ligand(s), which is/are preferably selected from the following mono-dentate substances and/or derivatives thereof:

    a. alkyl amines and their corresponding alkyl ammonium salts, containing linear, branched, or cyclic aliphatic groups, having from 1 to 20 carbon atoms (and their corresponding ammonium salts);
    b. aryl amines and their corresponding aryl ammonium salts having from 1 to 5 phenyl rings;
    c. alkyl phosphonium salts, containing linear, branched, or cyclic aliphatic groups, having from 1 to 20 carbon atoms;
    d. aryl phosphonium salts, having from 1 to 5 phenyl rings;
    e. alkyl organic acids and the corresponding alkyl organic anions (and salts) containing linear, branched, or cyclic aliphatic groups, having from 1 to 20 carbon atoms;
    f. aryl organic acids and their corresponding aryl organic anions and salts, having from 1 to 5 phenyl rings;
    g. aliphatic alcohols, containing linear, branched, or cyclic aliphatic groups, having from 1 to 20 carbon atoms;
    h. aryl alcohols having from 1 to 5 phenyl rings;
    i. inorganic anions from the group consisting of: sulfate, nitrate, nitrite, sulfite, bisulfite, phosphate, hydrogen phosphate, dihydrogen phosphate, diphosphate, triphosphate, phosphite, chloride, chlorate, bromide, bromate, iodide, iodate, carbonate, bicarbonate, and the corresponding acids and salts of the aforementioned inorganic anions,
    j. ammonia, carbon dioxide, methane, oxygen, ethylene, hexane, benzene, toluene, xylene, chlorobenzene, nitrobenzene, naphthalene, thiophene, pyridine, acetone, 1-2-dichloroethane, methylenechloride, tetrahydrofuran, ethanolamine, triethylamine and trifluoromethylsulfonic acid.

Further details regarding the at least bidentate organic compounds and the mono-dentate substances, from which the ligands of the framework material as used in the present application are derived, can be taken from EP-A 0 790 253, whose respective content is incorporated into the present application by reference.



Within the present application, framework materials of the kind described herein, which comprise Zn2+ as a metal ion and ligands derived from terephthalic acid as the bidentate compound, are particularly preferred. Said framework materials are known as MOF-5 in the literature.
Further metal ions and at least bidentate organic compounds and mono-dentate substances, which are respectively useful for the preparation of the framework materials used in the present invention as well as processes for their preparation are particularly disclosed in EP-A 0 790 253, U.S. Pat. No. 5,648,508 and DE 10111230.0.
As solvents, which are particularly useful for the preparation of MOF-5, in addition to the solvents disclosed in the above-referenced literature, dimethyl formamide, diethyl formamide and N-methylpyrollidone, alone, in combination with each other or in combination with other solvents may be used. Within the preparation of the framework materials, particularly within the preparation of MOF-5, the solvents and mother liquors are recycled after crystallization in order to save costs and materials.
The pore sizes of the metal-organic framework can be adjusted by selecting suitable organic ligands and/or bidendate compounds (=linkers). Generally, the larger the linker, the larger the pore size. Any pore size that is still supported by a the metal-organic framework in the absence of a host and at temperatures of at least 200° C. is conceivable. Pore sizes ranging from 0.2 nm to 30 nm are preferred, with pore sizes ranging from 0.3 nm to 3 nm being particularly preferred.
In the following, examples of metal-organic framework materials (MOFs) are given to illustrate the general concept given above. These specific examples, however, are not meant to limit the generality and scope of the present application.
By way of example, a list of metal-organic framework materials already synthesized and characterized is given below. This also includes novel isoreticular metal organic framework materials (IR-MOFs), which may be used in the context of the present application. Such materials having the same framework topology while displaying different pore sizes and crystal densities are described, for example in M. Eddouadi et al., Science 295 (2002) 469, whose respective content is incorporated into the present application by reference.
The solvents used are of particular importance for the synthesis of these materials and are therefore mentioned in the table. The values for the cell parameters (angles α, β and γ as well as the spacings a, b and c, given in Angstrom) have been obtained by x-ray diffraction and represent the space group given in the table as well.




















Ingredients











molar ratios







Space


MOF-n
M + L
Solvents
α
β
γ
a
b
c
Group
























MOF-0
Zn(NO3)2.6H2O
ethanol
90
90
120
16.711
16.711
14.189
P6(3)/



H3(BTC)







Mcm


MOF-2
Zn(NO3)2.6H2O
DMF
90
102.8
90
6.718
15.49
12.43
P2(1)/n



(0.246 mmol)
toluene



H2(BDC)



0.241 mmol)


MOF-3
Zn(NO3)2.6H2O
DMF
99.72
111.11
108.4
9.726
9.911
10.45
P-1



(1.89 mmol)
MeOH



H2(BDC)



(1.93 mmol)


MOF-4
Zn(NO3)2.6H2O
ethanol
90
90
90
14.728
14.728
14.728
P2(1)3



(1.00 mmol)



H3(BTC)



(0.5 mmol)


MOF-5
Zn(NO3)2.6H2O
DMF
90
90
90
25.669
25.669
25.669
Fm-3m



(2.22 mmol)
chloro-



H2(BDC)
benzene



(2.17 mmol)


MOF-38
Zn(NO3)2.6H2O
DMF
90
90
90
20.657
20.657
17.84
14cm



(0.27 mmol)
chloro-



H3(BTC)
benzene



(0.15 mmol)


MOF-31
Zn(NO3)2.6H2O
ethanol
90
90
90
10.821
10.821
10.821
Pn(−3)m


Zn(ADC)2
0.4 mmol



H2(ADC)



0.8 mmol


MOF-12
Zn(NO3)2.6H2O
ethanol
90
90
90
15.745
16.907
18.167
Pbca


Zn2(ATC)
0.3 mmol



H4(ATC)



0.15 mmol


MOF-20
Zn(NO3)2.6H2O
DMF
90
92.13
90
8.13
16.444
12.807
P2(1)/c


ZnNDC
0.37 mmol
chloro-



H2NDC
benzene



0.36 mmol


MOF-37
Zn(NO3)2.6H2O
DEF
72.38
83.16
84.33
9.952
11.576
15.556
P-1



0.2 mmol
chloro-



H2NDC
benzene



0.2 mmol


MOF-8
Tb(NO3)3.5H2O
DMSO
90
115.7
90
19.83
9.822
19.183
C2/c


Tb2(ADC)
0.10 mmol
MeOH



H2ADC



0.20 mmol


MOF-9
Tb(NO3)3.5H2O
DMSO
90
102.09
90
27.056
16.795
28.139
C2/c


Tb2(ADC)
0.08 mmol



H2ADB



0.12 mmol


MOF-6
Tb(NO3)3.5H2O
DMF
90
91.28
90
17.599
19.996
10.545
P21/c



0.30 mmol
MeOH



H2(BDC)



0.30 mmol


MOF-7
Tb(NO3)3.5H2O
H2O
102.3
91.12
101.5
6.142
10.069
10.096
P-1



0.15 mmol



H2(BDC)



0.15 mmol


MOF-69A
Zn(NO3)2.6H2O
DEF
90
111.6
90
23.12
20.92
12
C2/c



0.083 mmol
H2O2



4,4′BPDC
MeNH2



0.041 mmol


MOF-69B
Zn(NO3)2.6H2O
DEF
90
95.3
90
20.17
18.55
12.16
C2/c



0.083 mmol
H2O2



2,6-NCD
MeNH2



0.041 mmol


MOF-11
Cu(NO3)2.2.5H2O
H2O
90
93.86
90
12.987
11.22
11.336
C2/c


Cu2(ATC)
0.47 mmol



H2ATC



0.22 mmol


MOF-11


90
90
90
8.4671
8.4671
14.44
P42/


Cu2(ATC)








mmc


dehydr.


MOF-14
Cu(NO3)2.2.5H2O
H2O
90
90
90
26.946
26.946
26.946
Im-3


Cu3(BTB)
0.28 mmol
DMF



H3BTB
EtOH



0.052 mmol


MOF-32
Cd(NO3)2.4H2O
H2O
90
90
90
13.468
13.468
13.468
P(−4)3m


Cd(ATC)
0.24 mmol
NaOH



H4ATC



0.10 mmol


MOF-33
ZnCl2
H2O
90
90
90
19.561
15.255
23.404
Imma


Zn2(ATB)
0.15 mmol
DMF



H4ATB
EtOH



0.02 mmol


MOF-34
Ni(NO3)2.6H2O
H2O
90
90
90
10.066
11.163
19.201
P212121


Ni(ATC)
0.24 mmol
NaOH



H4ATC



0.10 mmol


MOF-36
Zn(NO3)2.4H2O
H2O
90
90
90
15.745
16.907
18.167
Pbca


Zn2(MTB)
0.20 mmol
DMF



H4MTB



0.04 mmol


MOF-39
Zn(NO3)2.4H2O
H2O
90
90
90
17.158
21.591
25.308
Pnma


Zn3O(HBTB)
0.27 mmol
DMF



H3BTB
EtOH



0.07 mmol


NO305
FeCl2.4H2O
DMF
90
90
120
8.2692
8.2692
63.566
R-3c



5.03 mmol



formic acid



86.90 mmol


NO306A
FeCl2.4H2O
DEF
90
90
90
9.9364
18.374
18.374
Pbcn



5.03 mmol



formic acid



86.90 mmol


NO29
Mn(Ac)2.4H2O
DMF
120
90
90
14.16
33.521
33.521
P-1


MOF-0 like
0.46 mmol



H3BTC



0.69 mmol


BPR48A2
Zn(NO3)2.6H2O
DMSO
90
90
90
14.5
17.04
18.02
Pbca



0.012 mmol
toluene



H2BDC



0.012 mmol


BPR69
Cd(NO3)2.4H2O
DMSO
90
98.76
90
14.16
15.72
17.66
Cc


B1
0.0212 mmol



H2BDC



0.0428 mmol


BPR92A2
Co(NO3)2.6H2O
NMP
106.3
107.63
107.2
7.5308
10.942
11.025
P1



0.018 mmol



H2BDC



0.018 mmol


BPR95
Cd(NO3)2.4H2O
NMP
90
112.8
90
14.460
11.085
15.829
P2(1)/n


C5
0.012 mmol



H2BDC



0.36 mmol


Cu C6H4O6
Cu(NO3)2.2.5H2O
DMF
90
105.29
90
15.259
14.816
14.13
P2(1)/c



0.370 mmol
chloro-



H2BDC(OH)2
benzene



0.37 mmol













M(BTC)
Co(SO4).H2O
DMF
Same as MOF-0





MOF-0 like
0.055 mmol



H3BTC



0.037 mmol
















Tb(C6H4O6)
Tb(NO3)3.5H2O
DMF
104.6
107.9
97.147
10.491
10.981
12.541
P-1



0.370 mmol
chloro-



H2(C6H4O6)
benzene



0.56 mmol


Zn (C2O4)
ZnCl2
DMF
90
120
90
9.4168
9.4168
8.464
P(−3)1m



0.370 mmol
chloro-



oxalic acid
benzene



0.37 mmol


Co(CHO)
Co(NO3)2.5H2O
DMF
90
91.32
90
11.328
10.049
14.854
P2(1)/n



0.043 mmol



formic acid



1.60 mmol


Cd(CHO)
Cd(NO3)2.4H2O
DMF
90
120
90
8.5168
8.5168
22.674
R-3c



0.185 mmol



formic acid



0.185 mmol


Cu(C3H2O4)
Cu(NO3)2.2.5H2O
DMF
90
90
90
8.366
8.366
11.919
P43



0.043 mmol



malonic acid



0.192 mmol


Zn6(NDC)5
Zn(NO3)2.6H2O
DMF
90
95.902
90
19.504
16.482
14.64
C2/m


MOF-48
0.097 mmol
chloro-



14 NDC
benzene



0.069 mmol
H2O2


MOF-47
Zn(NO3)2.6H2O
DMF
90
92.55
90
11.303
16.029
17.535
P2(1)/c



0.185 mmol
chloro-



H2(BDC[CH3]4)
benzene



0.185 mmol
H2O2


MO25
Cu(NO3)2.2.5H2O
DMF
90
112.0
90
23.880
16.834
18.389
P2(1)/c



0.084 mmol



BPhDC



0.085 mmol


Cu-Thio
Cu(NO3)2.2.5H2O
DEF
90
113.6
90
15.4747
14.514
14.032
P2(1)/c



0.084 mmol



thiophene



dicarboxylic



0.085 mmol


C1BDC1
Cu(NO3)2.2.5H2O
DMF
90
105.6
90
14.911
15.622
18.413
C2/c



0.084 mmol



H2(BDCCl2)



0.085 mmol


MOF-101
Cu(NO3)2.2.5H2O
DMF
90
90
90
21.607
20.607
20.073
Fm3m



0.084 mmol



BrBDC



0.085 mmol


Zn3(BTC)2
ZnCl2
DMF
90
90
90
26.572
26.572
26.572
Fm-3m



0.033 mmol
EtOH



H3BTC
base



0.033 mmol
added


MOF-j
Co(CH3CO2)2.4H2O
H2O
90
112.0
90
17.482
12.963
6.559
C2



(1.65 mmol)



H3(BZC)



(0.95 mmol)


MOF-n
Zn(NO3)2.6H2O
ethanol
90
90
120
16.711
16.711
14.189
P6(3)/



H3(BTC)







mcm


PbBDC
Pb(NO3)2
DMF
90
102.7
90
8.3639
17.991
9.9617
P2(1)/n



(0.181 mmol)
ethanol



H2(BDC)



(0.181 mmol)


Znhex
Zn(NO3)2.6H2O
DMF
90
90
120
37.1165
37.117
30.019
P3(1)c



(0.171 mmol)
p-xylene



H3BTB
ethanol



(0.114 mmol)


AS16
FeBr2
DMF
90
90.13
90
7.2595
8.7894
19.484
P2(1)c



0.927 mmol
anhydr.



H2(BDC)



0.927 mmol


AS27-2
FeBr2
DMF
90
90
90
26.735
26.735
26.735
Fm3m



0.927 mmol
anhydr.



H3(BDC)



0.464 mmol


AS32
FeCl3
DMF
90
90
120
12.535
12.535
18.479
P6(2)c



1.23 mmol
anhydr.



H2(BDC)
ethanol



1.23 mmol


AS54-3
FeBr2
DMF
90
109.98
90
12.019
15.286
14.399
C2



0.927
anhydr.



BPDC
n-



0.927 mmol
propanol


AS61-4
FeBr2
pyridine
90
90
120
13.017
13.017
14.896
P6(2)c



0.927 mmol
anhydr.



m-BDC



0.927 mmol


AS68-7
FeBr2
DMF
90
90
90
18.3407
10.036
18.039
Pca21



0.927 mmol
anhydr.



m-BDC
Pyridine



1.204 mmol


Zn(ADC)
Zn(NO3)2.6H2O
DMF
90
99.85
90
16.764
9.349
9.635
C2/c



0.37 mmol
chloro-



H2(ADC)
benzene



0.36 mmol


MOF-12
Zn(NO3)2.6H2O
ethanol
90
90
90
15.745
16.907
18.167
Pbca


Zn2(ATC)
0.30 mmol



H4(ATC)



0.15 mmol


MOF-20
Zn(NO3)2.6H2O
DMF
90
92.13
90
8.13
16.444
12.807
P2(1)/c


ZnNDC
0.37 mmol
chloro-



H2NDC
benzene



0.36 mmol


MOF-37
Zn(NO3)2.6H2O
DEF
72.38
83.16
84.33
9.952
11.576
15.556
P-1



0.20 mmol
chloro-



H2NDC
benzene



0.20 mmol


Zn(NDC)
Zn(NO3)2.6H2O
DMSO
68.08
75.33
88.31
8.631
10.207
13.114
P-1


(DMSO)
H2NDC


Zn(NDC)
Zn(NO3)2.6H2O

90
99.2
90
19.289
17.628
15.052
C2/c



H2NDC


Zn(HPDC)
Zn(NO3)2.4H2O
DMF
107.9
105.06
94.4
8.326
12.085
13.767
P-1



0.23 mmol
H2O



H2(HPDC)



0.05 mmol


Co(HPDC)
Co(NO3)2.6H2O
DMF
90
97.69
90
29.677
9.63
7.981
C2/c



0.21 mmol
H2O/



H2(HPDC)
ethanol



0.06 mmol


Zn3(PDC)2.
Zn(NO3)2.4H2O
DMF/ CIBz
79.34
80.8
85.83
8.564
14.046
26.428
P-1


5
0.17 mmol
H2O/ TEA



H2(HPDC)



0.05 mmol


Cd2
Cd(NO3)2.4H2O
methanol/
70.59
72.75
87.14
10.102
14.412
14.964
P-1


(TPDC)2
0.06 mmol
CHP H2O



H2(HPDC)



0.06 mmol


Tb(PDC)1.5
Tb(NO3)3.5H2O
DMF
109.8
103.61
100.14
9.829
12.11
14.628
P-1



0.21 mmol
H2O/



H2(PDC)
ethanol



0.034 mmol


ZnDBP
Zn(NO3)2.6H2O
MeOH
90
93.67
90
9.254
10.762
27.93
P2/n



0.05 mmol



dibenzylphosphate



0.10 mmol


Zn3(BPDC)
ZnBr2
DMF
90
102.76
90
11.49
14.79
19.18
P21/n



0.021 mmol



4,4'BPDC



0.005 mmol


CdBDC
Cd(NO3)2.4H2O
DMF
90
95.85
90
11.2
11.11
16.71
P21/n



0.100 mmol
Na2SiO3



H2(BDC)
(aq)



0.401 mmol


Cd-mBDC
Cd(NO3)2.4H2O
DMF
90
101.1
90
13.69
18.25
14.91
C2/c



0.009 mmol
MeNH2



H2(mBDC)



0.018 mmol


Zn4OBNDC
Zn(NO3)2.6H2O
DEF
90
90
90
22.35
26.05
59.56
Fmmm



0.041 mmol
MeNH2



BNDC
H2O2


Eu(TCA)
Eu(NO3)3.6H2O
DMF
90
90
90
23.325
23.325
23.325
Pm-3n



0.14 mmol
chloro-



TCA
benzene



0.026 mmol


Tb(TCA)
Tb(NO3)3.6H2O
DMF
90
90
90
23.272
23.272
23.372
Pm-3n



0.069 mmol
chloro-



TCA
benzene



0.026 mmol


Formate
Ce(NO3)3.6H2O
H2O
90
90
120
10.668
10.667
4.107
R-3m



0.138 mmol
ethanol



Formaic acid



0.43 mmol



FeCl2.4H2O
DMF
90
90
120
8.2692
8.2692
63.566
R-3c



5.03 mmol



Formic acid



86.90 mmol



FeCl2.4H2O
DEF
90
90
90
9.9364
18.374
18.374
Pbcn



5.03 mmol



Formic acid



86.90 mmol



FeCl2.4H2O
DEF
90
90
90
8.335
8.335
13.34
P-31c



5.03 mmol



Formic acid



86.90 mmol


NO330
FeCl2.4H2O
form-
90
90
90
8.7749
11.655
8.3297
Pnna



0.50 mmol
amide



Formic acid



8.69 mmol


NO332
FeCl2.4H2O
DIP
90
90
90
10.0313
18.808
18.355
Pbcn



0.50 mmol



Formic acid



8.69 mmol


NO333
FeCl2.4H2O
DBF
90
90
90
45.2754
23.861
12.441
Cmcm



0.50 mmol



Formic acid



8.69 mmol


NO335
FeCl2.4H2O
CHF
90
91.372
90
11.5964
10.187
14.945
P21/n



0.50 mmol



Formic acid



8.69 mmol


NO336
FeCl2.4H2O
MFA
90
90
90
11.7945
48.843
8.4136
Pbcm



0.50 mmol



Formic acid



8.69 mmol


NO13
Mn(Ac)2.4H2O
ethanol
90
90
90
18.66
11.762
9.418
Pbcn



0.46 mmol



Bezoic acid



0.92 mmol



Bipyridine



0.46 mmol


NO29
Mn(Ac)2.4H2O
DMF
120
90
90
14.16
33.521
33.521
P-1


MOF-0 like
0.46 mmol



H3BTC



0.69 mmol


Mn(hfac)2
Mn(Ac)2.4H2O
ether
90
95.32
90
9.572
17.162
14.041
C2/c


(O2CC6H5)
0.46 mmol



Hfac



0.92 mmol



Bipyridine



0.46 mmol


BPR43G2
Zn(NO3)2.6H2O
DMF
90
91.37
90
17.96
6.38
7.19
C2/c



0.0288 mmol
CH3CN



H2BDC



0.0072 mmol


BPR48A2
Zn(NO3)2.6H2O
DMSO
90
90
90
14.5
17.04
18.02
Pbca



0.012 mmol
toluene



H2BDC



0.012 mmol


BPR49B1
Zn(NO3)2.6H2O
DMSO
90
91.172
90
33.181
9.824
17.884
C2/c



0.024 mmol
methanol



H2BDC



0.048 mmol


BPR56E1
Zn(NO3)2.6H2O
DMSO
90
90.096
90
14.5873
14.153
17.183
P2(1)/n



0.012 mmol
n-



H2BDC
propanol



0.024 mmol


BPR68D10
Zn(NO3)2.6H2O
DMSO
90
95.316
90
10.0627
10.17
16.413
P2(1)/c



0.0016 mmol
benzene



H3BTC



0.0064 mmol


BPR69B1
Cd(NO3)2.4H2O
DMSO
90
98.76
90
14.16
15.72
17.66
Cc



0.0212 mmol



H2BDC



0.0428 mmol


BPR73E4
Cd(NO3)2.4H2O
DMSO
90
92.324
90
8.7231
7.0568
18.438
P2(1)/n



0.006 mmol
toluene



H2BDC



0.003 mmol


BPR76D5
Zn(NO3)2.6H2O
DMSO
90
104.17
90
14.4191
6.2599
7.0611
Pc



0.0009 mmol



H2BzPDC



0.0036 mmol


BPR80B5
Cd(NO3)2.4H2O
DMF
90
115.11
90
28.049
9.184
17.837
C2/c



0.018 mmol



H2BDC



0.036 mmol


BPR80H5
Cd(NO3)2.4H2O
DMF
90
119.06
90
11.4746
6.2151
17.268
P2/c



0.027 mmol



H2BDC



0.027 mmol


BPR82C6
Cd(NO3)2.4H2O
DMF
90
90
90
9.7721
21.142
27.77
Fdd2



0.0068 mmol



H2BDC



0.202 mmol


BPR86C3
Co(NO3)2.6H2O
DMF
90
90
90
18.3449
10.031
17.983
Pca2(1)



0.0025 mmol



H2BDC



0.075 mmol


BPR86H6
Cd(NO3)2.6H2O
DMF
80.98
89.69
83.412
9.8752
10.263
15.362
P-1



0.010 mmol



H2BDC



0.010 mmol



Co(NO3)2.6H2O
NMP
106.3
107.63
107.2
7.5308
10.942
11.025
P1


BPR95A2
Zn(NO3)2.6H2O
NMP
90
102.9
90
7.4502
13.767
12.713
P2(1)/c



0.012 mmol



H2BDC



0.012 mmol


CuC6F4O4
Cu(NO3)2.2.5H2O
DMF
90
98.834
90
10.9675
24.43
22.553
P2(1)/n



0.370 mmol
chloro-



H2BDC(OH) 2
benzene



0.37 mmol


Fe Formic
FeCl2.4H2O
DMF
90
91.543
90
11.495
9.963
14.48
P2(1)/n



0.370 mmol



Formic acid



0.37 mmol


Mg Formic
Mg(NO3)2.6H2O
DMF
90
91.359
90
11.383
9.932
14.656
P2(1)/n



0.370 mmol



Formic acid



0.37 mmol


MgC6H4O6
Mg(NO3)2.6H2O
DMF
90
96.624
90
17.245
9.943
9.273
C2/c



0.370 mmol



H2BDC(OH)2



0.37 mmol


Zn
ZnCl2
DMF
90
94.714
90
7.3386
16.834
12.52
P2(1)/n


C2H4BDC
0.44 mmol


MOF-38
CBBDC



0.261 mmol


MOF-49
ZnCl2
DMF
90
93.459
90
13.509
11.984
27.039
P2/c



0.44 mmol
CH3CN



m-BDC



0.261 mmol


MOF-26
Cu(NO3)2.5H2O
DMF
90
95.607
90
20.8797
16.017
26.176
P2(1)/n



0.084 mmol



DCPE



0.085 mmol


MOF-112
Cu(NO3)2.2.5H2O
DMF
90
107.49
90
29.3241
21.297
18.069
C2/c



0.084 mmol
ethanol



o-Br-m-BDC



0.085 mmol


MOF-109
Cu(NO3)2.2.5H2O
DMF
90
111.98
90
23.8801
16.834
18.389
P2(1)/c



0.084 mmol



KDB



0.085 mmol


MOF-111
Cu(NO3)2.2.5H2O
DMF
90
102.16
90
10.6767
18.781
21.052
C2/c



0.084 mmol
ethanol



o-BrBDC



0.085 mmol


MOF-110
Cu(NO3)2.2.5H2O
DMF
90
90
120
20.0652
20.065
20.747
R-3/m



0.084 mmol



thiophene



dicarboxylic



0.085 mmol


MOF-107
Cu(NO3)2.2.5H2O
DEF
104.8
97.075
95.206
11.032
18.067
18.452
P-1



0.084 mmol



thiophene



dicarboxylic



0.085 mmol


MOF-108
Cu(NO3)2.2.5H2O
DBF/
90
113.63
90
15.4747
14.514
14.032
C2/c



0.084 mmol
methanol



thiophene



dicarboxylic



0.085 mmol


MOF-102
Cu(NO3)2.2.5H2O
DMF
91.63
106.24
112.01
9.3845
10.794
10.831
P-1



0.084 mmol



H2(BDCCl2)



0.085 mmol


Clbdcl
Cu(NO3)2.2.5H2O
DEF
90
105.56
90
14.911
15.622
18.413
P-1



0.084 mmol



H2(BDCCl2)



0.085 mmol


Cu(NMOP)
Cu(NO3)2.2.5H2O
DMF
90
102.37
90
14.9238
18.727
15.529
P2(1)/m



0.084 mmol



NBDC



0.085 mmol


Tb(BTC)
Tb(NO3)3.5H2O
DMF
90
106.02
90
18.6986
11.368
19.721



0.033 mmol



H3BTC



0.033 mmol


Zn3(BTC)2
ZnCl2
DMF
90
90
90
26.572
26.572
26.572
Fm-3m


Honk
0.033 mmol
ethanol



H3BTC



0.033 mmol


Zn4O(NDC)
Zn(NO3)2.4H2O
DMF
90
90
90
41.5594
18.818
17.574
aba2



0.066 mmol
ethanol



14NDC



0.066 mmol


CdTDC
Cd(NO3)2.4H2O
DMF
90
90
90
12.173
10.485
7.33
Pmma



0.014 mmol
H2O



thiophene



0.040 mmol



DABCO



0.020 mmol


IRMOF-2
Zn(NO3)2.4H2O
DEF
90
90
90
25.772
25.772
25.772
Fm-3m



0.160 mmol



o-Br-BDC



0.60 mmol


IRMOF-3
Zn(NO3)2.4H2O
DEF
90
90
90
25.747
25.747
25.747
Fm-3m



0.20 mmol
ethanol



H2N—BDC



0.60 mmol


IRMOF-4
Zn(NO3)2.4H2O
DEF
90
90
90
25.849
25.849
25.849
Fm-3m



0.11 mmol



[C3H7O]2—BDC



0.48 mmol


IRMOF-5
Zn(NO3)2.4H2O
DEF
90
90
90
12.882
12.882
12.882
Pm-3m



0.13 mmol



[C5H11O]2—BDC



0.50 mmol


IRMOF-6
Zn(NO3)2.4H2O
DEF
90
90
90
25.842
25.842
25.842
Fm-3m



0.20 mmol



[C2H4]—BDC



0.60 mmol


IRMOF-7
Zn(NO3)2.4H2O
DEF
90
90
90
12.914
12.914
12.914
Pm-3m



0.07 mmol



1,4NDC



0.20 mmol


IRMOF-8
Zn(NO3)2.4H2O
DEF
90
90
90
30.092
30.092
30.092
Fm-3m



0.55 mmol



2,6NDC



0.42 mmol


IRMOF-9
Zn(NO3)2.4H2O
DEF
90
90
90
17.147
23.322
25.255
Pnnm



0.05 mmol



BPDC



0.42 mmol


IRMOF-10
Zn(NO3)2.4H2O
DEF
90
90
90
34.281
34.281
34.281
Fm-3m



0.02 mmol



BPDC



0.012 mmol


IRMOF-11
Zn(NO3)2.4H2O
DEF
90
90
90
24.822
24.822
56.734
R-3m



0.05 mmol



HPDC



0.20 mmol


IRMOF-12
Zn(NO3)2.4H2O
DEF
90
90
90
34.281
34.281
34.281
Fm-3m



0.017 mmol



HPDC



0.12 mmol


IRMOF-13
Zn(NO3)2.4H2O
DEF
90
90
90
24.822
24.822
56.734
R-3m



0.048 mmol



PDC



0.31 mmol


IRMOF-14
Zn(NO3)2.4H2O
DEF
90
90
90
34.381
34.381
34.381
Fm-3m



0.17 mmol



PDC



0.12 mmol


IRMOF-15
Zn(NO3)2.4H2O
DEF
90
90
90
21.459
21.459
21.459
Im-3m



0.063 mmol



TPDC



0.025 mmol


IRMOF-16
Zn(NO3)2.4H2O
DEF
90
90
90
21.49
21.49
21.49
Pm-3m



0.0126 mmol
NMP



TPDC



0.05 mmol

























ADC
Acetylene dicarboxylic acid



NDC
Naphtalene dicarboxylic acid



BDC
Benzene dicarboxylic acid



ATC
Adamantane tetracarboxylic acid



BTC
Benzene tricarboxylic acid



BTB
Benzene tribenzoate



MTB
Methane tetrabenzoate



ATB
Adamantane tetrabenzoate



ADB
Adamantane dibenzoate










Examples of the synthesis of these materials as such can, for example, be found in: J. Am. Chem. Soc. 123 (2001) pages 8241 ff or in Acc. Chem. Res. 31 (1998) pages 474ff, which are fully encompassed within the content of the present application.
The separation of the framework materials, particularly of MOF-5, from the mother liquor of the crystallization may be achieved by procedures known in the art such as solid-liquid separations, centrifugation, extraction, filtration, membrane filtration, cross-flow filtration, flocculation using flocculation adjuvants (non-ionic, cationic and anionic adjuvants) or by the addition of pH shifting additives such as salts, acids or bases, by flotation, as well as by evaporation of the mother liquor at elevated temperature and/or in vacuo and concentrating of the solid. The material obtained in this step is typically a fine powder and is not optimally suited for most practical applications, e.g. in catalysis, where shaped bodies are preferred. Therefore, the powder is pressed or granulated or formed by any process known to the expert in the art, in particular any process that results in forming a powder into a shaped body. Such a process is disclosed, e.g. in the U.S. application Ser. No. 10/157,182.
In a preferred embodiment, the metal-organic framework material catalyst used for the reaction of oxygen and/or oxygen-delivering substances with hydrogen and/or hydrogen-delivering substances contains at least one additional metal selected from the main groups and/or the subgroups of the periodic table of the elements. In a further preferred embodiment, in order to produce said catalyst, the metal-organic framework material as described above is brought in contact with a substance, preferably a powder, a solution or a suspension, containing at least one metal of the main groups or the subgroups of the periodic table of the elements.
The term “bringing in contact” in the context of the present invention refers to any procedure yielding a metal-organic framework catalyst as described above, containing, at least in parts, at least one additional metal component. As far as the methods of bringing the metal-organic framework in contact with an additional metal component, any method known to the expert in the field, in particular any method known in the context of charging a porous material, can be used. In a preferred embodiment, these methods include but are not limited to: dipping, coating, spraying, impregnating, soaking, applying, precipitating, co-precipitating, kneading, powder kneading.
The additional metal is selected form the group consisting of the main group or the subgroup metals of the periodic table of the elements, preferably form the group of the sub group metals, further preferred from the group of Cu, Ag, Au, Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt, particularly preferred from the group of Pd, Pt, Au. Mixtures of at least two of all of the aforementioned substances are included as well.
For the reaction to produce hydrogen peroxide, any substance that contains or delivers oxygen and any substance that contains or delivers hydrogen can be used, so long as, ultimately, hydrogen peroxide is formed in the presence of the catalyst according to the invention. In a preferred embodiment the molecular gases oxygen and hydrogen are used. Either or both gases may be mixed with other reactive gases and/or inert gases, preferably with inert gases.
The invention is now further described by way of the following examples, which are, however, not meant to limit the scope of the present application.
EXAMPLES
Example 1
Preparation of the Metal-Organic Framework Material
41 g of terephthalic acid are dissolved together with 193.5 g of ZnNO3.4 H2O in 5650 g of diethyl formamide in a container with a frit (HWS, 10 liters). The mixture is heated to 130° C. and kept at that temperature for 210 minutes. Subsequently, the mixture is cooled down and the solid formed is filtered off and washed three times with 1 liter of chloroform, respectively. The filter cake is blow dried with nitrogen.
The product thusly obtained is subsequently activated in several portions under high vacuum. The structure of MOF-5 is discernible in the x-ray diffraction pattern.
Example 2
Preparation of the Catalyst
The preparation of the metal-organic framework material containing Pd and used as a catalyst was performed as described in the following: 1.0 g of Pd Acetate (4.45 mmol) are dissolved in 91.5 g of diethyl formamide and 33 g of acetonitrile in a beaker. The brownish solution is filled into a four neck flask containing 5.0 g of the MOF-5 from Example 1. The suspension is cooked in an oil bath at 60° C. for 7 h while being stirred. Subsequently the mixture is transferred into a beaker and the mother liquor is decanted off after the crystals have settled.
The crystals are over-layered with chloroform and, after 12 hours, washed with chloroform until the chloroform solution hardly shows any coloring, then transferred into a flask and dried at room temperature under high vacuum (turbo molecular pump). The yield was 5.7 g. Elemental analysis resulted in a Pd content of 1.6% by weight next to 29.2% by weight of Zn and a residual content of Cl of 220 ppm.
Example 3
Activation of the Inventive Catalyst
54.3 g of the catalyst prepared as described above are transferred into a glass reactor that is fed with 10% by volume of hydrogen in Ar at a flow rate of 30 ml/min. In a temperature-controlled reduction (Autochem II 2920, Micromeritics), the reactor is heated to 250° C. using a ramp of 5 K/min. At a temperature of 92° C., 3.67 ml STP of gas per gram of catalyst are activated in the presence of hydrogen, corresponding to approx. 1.7% by weight of Pd in the catalyst that can be reduced.
Example 4
Preparation of H2O2 Using the Inventive Catalyst
4 g of the material from Example 3 are mixed with 120 mg of Graphite and pressed into tablets of 4.75 mm over 3 mm using a tabletting apparatus (Korsch).
10 ml of these tablets are exposed to the following feed in a designated pressure container with a basket-like insert: 89 g/h of methanol containing 120 ppm of NaBr, 8 STDl/h of hydrogen and 37.4 STDl/h of oxygen. The liquid medium is stirred at 1500 rpm. A space-time yield of 16 g/l/h with respect to the formation of hydrogen peroxide was measured by means of titration at a temperature of 40° C., a pressure of 50 bar and a running time of 91 hours.

## Claims

1. A process for preparing hydrogen peroxide comprising:
reacting oxygen or an oxygen-delivering substance with hydrogen or a hydrogen delivering substance, in the presence of a catalyst,
wherein the catalyst comprises a metal-organic framework material having pores and comprising at least one metal ion and at least one at least bidentate organic compound coordinately bound to the metal ion and wherein the metal-organic framework material further comprises at least one additional metal selected from the group consisting of metals of groups Ia, IIa, IIIa, IVa to VIIIa and Ib to IIIb of the periodic table.

2. The process of claim 1, wherein the metal ion of the metal-organic framework catalyst comprises an ion selected from group consisting of Mg2+, Ca2+, Sc3+, Y3+, Ti4+, Zr4+, Hf4+, V4+, V3+, V2+, Nb3+, Ta3+, Cr3+, Mo3+, W3+, Mn3+, Mn2+, Re3+, Re2+, Fe3+, Fe2+, Ru3+, Ru2+, Os3+, Os2+, Co3+, Co2+, Rh2+, Rh+, Ir2+, Ir+, Ni2+, Ni+, Pd2+, Pd+, Pt2+, Pt+, Cu2+, Cu+, Ag+, Au+, Zn2+, Cd2+, Hg2+, Al3+, Ga3+, In3+, Tl3+, Si4+, Si2+, Ge4+, Ge2+, Sn4+, Sn2+, Pb4+, Pb2+, As5+, As3+, As+, Sb5+, Sb3+, Sb+, Bi5+, Bi3+, and Bi+.

3. The process of claim 2, wherein the metal ion is Zn2+.

4. The process of claim 1, wherein the at least bidentate organic compound has a substructure bound to at least one bidentate functional group, said substructure is selected from the group consisting of alkyl groups, an aryl group having 1 of 2 phenyl rings, and combinations thereof, and said bidentate functional group has at least 2 carboxy groups.

5. The process of claim 1, wherein the at least one additional metal is selected from the group consisting of Pd, Pt, and Au.

6. The process of claim 1, wherein the at least bidentate organic compound is selected from the group consisting of 1,3,5-benzene tricarboxylate, acetylene dicarboxylate, naphtalen dicarboxylate, benzene dicarboxylate, adamantane tetracarboxylate, benzene tricarboxylate, benzene tribenzoate, methane tetrabenzoate, and adamantane tribenzoate.

7. The process of claim 1, wherein said catalyst further comprises at least one monodentate ligand.

8. The process of claim 7, wherein the monodentate ligand is selected from the group consisting of alkyl amines having linear, branched, or cyclic aliphatic groups of from 1 to 20 carbon atoms, and alkyl ammonium salts thereof; aryl amines having from 1 to 5 phenyl rings, and aryl ammonium salts thereof; alkyl phosphonium salts, having linear, branched, or cyclic aliphatic groups of from 1 to 20 carbon atoms; aryl phosphonium salts having from 1 to 5 phenyl rings; alkyl organic acids having linear, branched, or cyclic aliphatic groups of from 1 to 20 carbon atoms, and alkyl organic anions and salts thereof; aryl organic acids having from 1 to 5 phenyl rings, and aryl organic anions and salts thereof; linear, branched, or cyclic aliphatic alcohols having from 1 to 20 carbon atoms; aryl alcohols having from 1 to 5 phenyl rings; inorganic anions of the group consisting of sulfate, nitrate, nitrite, sulfite, bisulfite, phosphate, hydrogen phosphate, dihydrogen phosphate, diphosphate, triphosphate, phosphate, chloride, chlorate, bromide, bromate, iodide, iodate, carbonate, bicarbonate, and acids and salts thereof; and ammonia, carbon dioxide, methane, oxygen, ethylene, hexane, benzene, toluene, xylene, chlorobenzene, nitrobenzene, naphthalene, thiophene, pyridine, acetone, 1-2-dichloroethane, methylenechloride, tetrahydrofuran, ethanolamine, triethylamine and trifluoromethylsulfonic acid.

9. The process of claim 1, wherein the metal ion is Zn2+.

10. The process of claim 1, wherein the metal-organic framework material is MOF-5.

11. The process of claim 1, wherein the catalyst has a pore size of from 0.2 to 30 nm.