Source: https://patents.google.com/patent/US7968191?oq=7%2C346%2C545
Timestamp: 2018-03-24 07:32:29
Document Index: 123975328

Matched Legal Cases: ['§119', 'Application No. 60', 'Application No. 60', 'Application No. 60', 'Application No. 60', 'Application No. 60', 'Application No. 2006136378', 'Application No. 2006136378']

US7968191B2 - Modified carbon products and their applications - Google Patents
Modified carbon products and their applications Download PDF
US7968191B2
US7968191B2 US11081771 US8177105A US7968191B2 US 7968191 B2 US7968191 B2 US 7968191B2 US 11081771 US11081771 US 11081771 US 8177105 A US8177105 A US 8177105A US 7968191 B2 US7968191 B2 US 7968191B2
US11081771
US20050244644A1 (en )
B01J2231/4261—Heck-type, i.e. RY + C=C, in which R is aryl
Modified carbon products including a metal group attached to the modified carbon product. The modified carbon products are particularly useful for various applications such as catalysis, electronic conduction, ionic conduction, absorbents, heat transfer and luminescence.
Pursuant to 35 U.S.C. §119(e), this patent application claims a priority benefit to: (a) U.S. Provisional Patent Application No. 60/553,612 entitled “Modified Carbon Products and Their Use in Gas Diffusion Layers” filed Mar. 15, 2004; (b) U.S. Provisional Patent Application No. 60/553,413 entitled “Modified Carbon Products and Their Use in Electrocatalysts and Electrode Layers” filed Mar. 15, 2004; (c) U.S. Provisional Patent Application No. 60/553,672 entitled “Modified Carbon Products and Their Use in Proton Exchange Membranes” filed Mar. 15, 2004; (d) U.S. Provisional Patent Application No. 60/553,611 entitled “Modified Carbon Products and Their Use in Bipolar Plates” filed Mar. 15, 2004; and (e) U.S. Provisional Patent Application No. 60/555,888 entitled “Modified Carbon Products and Their Applications” filed Mar. 24, 2004. Each of the above referenced provisional patent applications is incorporated herein by reference in its entirety.
A method for the functionalization of carbon products has been described in U.S. Pat. No. 5,900,029 by Belmont et al., which is incorporated herein by reference in its entirety. The process described therein is referred to herein as the Belmont process. It was shown by Belmont et al. that a wide variety of organic functional groups can be chemically bonded to the surface of almost any form of carbon using diazonium salt chemistry. To date, applications of these “surface modified carbons” or “modified carbon products” have focused on improving the dispersion characteristics of the carbon products in other media such as inks, pastes and polymers.
According to one embodiment of the present invention, the metal functionalization of surface modified carbon is provided where the functional organic groups are used to bind metal species that lead to a wide variety of functionality based on the presence of the metal species bound to the surface of the carbon products. In one embodiment, the metal is bonded to bulk carbon material for applications such as electrodialysis, electrocatalysis and electrical swing adsorption. In other embodiments, the carbon is only present at the surface of or otherwise combined with another phase such that the bulk properties of the material are less influenced by the presence of the carbon.
FIG. 1 illustrates various applications for modified carbon products and metal-functionalized modified carbon products according to the present invention.
The present invention relates to the use of modified carbon products in applications ranging from ion conduction membranes to electronics, as illustrated in FIG. 1. As used herein, a modified carbon product refers to a carbon material having an organic group attached to the carbon. A method for the production of such modified carbon products is described in U.S. Pat. No. 5,900,029 by Belmont et al., which is incorporated herein by reference in its entirety. The process for fabricating the modified carbon product includes the step of reacting at least one diazonium salt with a carbon material, preferably in the absence of an externally applied electric current sufficient to reduce the diazonium salt. Another process includes the step of reacting at least one diazonium salt with a carbon product in a protic reaction medium. The diazonium salt can include the organic group to be attached to the carbon. For example, the organic group can be an aliphatic group, a cyclic organic group or an organic compound having an aliphatic portion and a cyclic portion. The organic group can be substituted or unsubstituted and can be branched or unbranched.
FIG. 2 illustrates the surface modification of a carbon particle according to the Belmont process.
Types of Functional Groups Examples
(Y) (RY)
Proton conductivity (C6H4)CO2H or (C10H6)PO3NaH
Hydrophobic, Hydrophilic (C6H4)CF3, (C6H4)SO3H
Metal coordinating (C10H6)CO2H or (C6H4)NH2
Other examples of specific organic groups are listed in U.S. Pat. No. 5,900,029 by Belmont et al. and some are illustrated in FIG. 3.
Other preferred functional groups include electron donors or electron acceptors. Particularly preferred groups for the metal functionalized groups according to the present invention include those that are both ionically charged and are coordinating, such as —SO3H(—SO3 −), —NR3 + (where R=an alkyl or aryl group or hydrogen or any combination thereof), —NR2 (where R=an alkyl or aryl group or hydrogen or any combination thereof), —PR2 (where R=an alkyl or aryl group or hydrogen or any combination thereof), —CO2H(—CO2 −), —CONR 2 and —PO3H2. In addition, chelating ligands with multiple functionality are preferred in order to bind metal species more strongly. Examples of preferred chelating ligands include polyamines, polyphosphines, polycarboxylates and ligands with mixed functionality such as aminoacids, EDTA and prochiral ligands to create optically active metal complexes (see FIG. 3).
i) the binding of a covalent metal-containing molecule to the surface of the modified carbon product;
ii) the binding of an ionic metal-containing species to the surface of the modified carbon product; or
iii) the presence of a metal-containing species on the surface or derived from the surface of the modified carbon product where the metal species may be a pure metal, a metal oxide, metal halide, metal sulfide, metal boride, metal nitride, metal carbide or other inorganic metal-containing compound.
The modified carbon products according to the present invention can be manufactured in accordance with the Belmont process.
Ultrasonic transducers are generally submerged in a liquid and the ultrasonic energy produces atomized droplets on the surface of the liquid. Two basic ultrasonic transducer disc configurations—planar and point source—can be used. Deeper fluid levels can be atomized using a point source configuration since the energy is focused at a point that is some distance above the surface of the transducer. The scale-up of submerged ultrasonic transducers can be accomplished by placing a large number of ultrasonic transducers in an array. Such a system is illustrated in U.S. Pat. No. 6,103,393 by Kodas et al. and U.S. Pat. No. 6,338,809 by Hampden-Smith et al., the disclosure of each of which is incorporated herein by reference in its entirety.
In addition, two spray dryer designs are particularly useful for the production of modified carbon products. A co-current spray dryer is useful for production of modified carbon products that are sensitive to high temperature excursions (e.g., greater than about 350° C.) or that require a rotary atomizer to generate the aerosol. Mixed-flow spray dryers are useful for producing modified carbon powders that require relatively high temperature excursions (e.g., greater than about 350° C.) or require turbulent mixing forces. According to the present invention, co-current spray-drying is preferred for the manufacture of modified carbon black products.
In a co-current spray dryer, the hot gas is introduced at the top of the unit where the droplets are generated with any of the atomization techniques mentioned above. The maximum temperature that a droplet/particle is exposed to in a co-current spray dryer is the temperature of the outlet. Typically, the outlet temperature is limited to about 200° C., although some designs allow for higher temperatures. In addition, since the particles experience the lowest temperature in the beginning of the time-temperature curve and the highest temperature at the end, the possibility of precursor surface diffusion and agglomeration is high.
These conditions are advantageous for modified carbon particle synthesis at a wide range of diazonium salt (surface functional group) loadings, such as up to about 5 μmol/m2 surface functional groups on carbon. For co-current spray dryers the reaction temperatures can be high enough for the reaction of the diazonium salt (e.g., between 25° C. and 100° C.).
The highest temperature in these spray dryers is the inlet temperature (e.g., 180° C.), and the outlet temperature can be as low as 50° C. Therefore, the modified carbon particles reach the highest temperature for a relatively short time, which advantageously reduces migration or surface diffusion of the surface groups. This spike of high temperature can quickly convert the diazonium salt and is followed by a mild quench since the spray dryer temperature quickly decreases after the maximum temperature is achieved. Thus, the spike-like temperature profile can be advantageous for the generation of highly dispersed modifying groups on the surface of the carbon.
In general, the outlet temperature of the spray dryer determines the residual moisture content of the powder. For example, a useful outlet temperature for co-current spray drying according to one embodiment of the present invention ranges from about 50° C. to about 80° C. Useful inlet temperatures, according to the present invention, range from about 130° C. to 180° C. The carbon solids loading can be up to about 50 wt. %.
In one embodiment of the present invention, where the metal species to be bound are required to exist in an ionic form, the surface functional group is typically easily ionizable. Examples of these groups include sulfonic acids, e.g. —SO3 −, —PO3 2− and —NH3 +. The metal group may be in the form of a discrete or hydrated metal ions such as Li+, K+, Na+, Ca2+ or Mg2+ as depicted FIG. 3. In the case where the metal is bound in a stronger covalent state to form a coordination compound, the surface functional group should contain an electron pair donor such as —NR2, —CO2 − or —SR. In this case, the metal group formed is a coordination complex where the surface functional group may be neutral (e.g., —NR2, —SR) or may be charged such as —CO2 −. Other ligands may also be present in the coordination sphere of the metal ion to satisfy the coordination number of the species such as nitrogen donors (e.g., amines), phosphorus donors (e.g., phosphines), sulfur donors (e.g., thiols), or oxygen donors such as alcohols, ketones, aldehydes and carboxylic acids. In addition, combinations of these two situations may occur where coordination compounds may be bound to the carbon surface via the organic functional moiety which are also charged, either anionically or cationically, or an ionic species may be more covalently bonded.
The more covalently bonded metal species, are those that are typically bound strongly to the surface modified carbon and the ligand environment of that metal group is controlled to be either: highly static—to achieve, for example, chiral catalysis; or highly dynamic—to achieve reversible adsorption of specific molecules (ligands). These metal functionalized carbon species can be used for a variety of applications that vary from catalysis, molecular imprinting, specific gas adsorption and reversible gas storage, where the metal species remains intact on the surface. They can also be used in applications where the metal group acts as a precursor to metal or metal-containing (e.g., metal oxide, nitride, halide or sulfide) materials by conversion at relatively low temperatures. These metal-functionalized materials are valuable in applications where highly dispersed metal or metal-containing nanoparticles are required to be dispersed over a high surface area support or a continuous phase derived from conversion of the metal species is required in the final product. Application areas of these materials according to the present invention include heterogeneous catalysts and electrocatalysts, as well as electronic conductors.
As a further embodiment of the present invention, the metal-functionalized carbons can be converted to zero valent metallic phases at low temperatures. This low temperature conversion enables the printing or coating of substrates such as papers and plastics (such as polyester and the like) that are temperature sensitive. In this embodiment of the invention, the organic moiety should be chosen such that it can lead to conversion (reduction) of the coordinated metal species at low temperature through thermal, photochemical or chemical means. As an example of chemical conversion, it is well known that carboxylate derivatives of silver(I) can be thermally converted to silver metal at relatively low temperatures such as between 50° C. and 150° C. The metal-functionalized carbon product should be thermally stable under ambient conditions to avoid premature conversion to silver prior to being printed onto a surface. Other types of chemical reactions can be thermally induced. For example, copper metal can be formed from the disproportionation of copper(I) complexes to form copper metal and copper(II). The copper(II) can be removed from the system or can be further converted into copper metal by reduction.
According to another embodiment of the present invention, the modified carbon products are used in electrodialysis and other membrane applications. Electrodialysis is an ion separation process that relies on the transport of ions through ion permeable membranes under the influence of an electrical potential gradient. It finds a variety of applications including water desalination and deionization, production of chlorine, acids and bases, and chemical syntheses involving ions selectively transported through the ion-exchange membranes (see, for example, Grebenyuk et al., Russ. J. Electrochem., 38, pp. 806-809 (2002)). Additional information on the application of electrodialysis in the purification of wastewaters from ionic impurities such as the demineralization of whey, and the clean-up of electroplating wastewater can be found in Bodzek, “Water Management, Purification & Conservation in Arid Climates”, Lancaster, pp. 121-183.
The process has various shortcomings, which are mostly related to the membrane properties. Some of the requirements for electrodialysis membranes are listed in “Perry's Chemical. Engineering Handbook”, pp. 22-42 to 22-48. The membranes should have physical and mechanical stability, should be inert to changes in the ionic strength of the solution and should tolerate thermal stresses. In addition they should be stable to pH extremes and be capable of withstanding the entire pH range between pH 0 and pH 14. The membranes should also have low electrical resistance since they operate inside an electric field.
1. Increase the base electrical and thermal conductivity of the membrane since the base carbon particles are inherently electrically and thermally conductive.
2. Increase the mechanical stability of the membrane by incorporating carbonaceous rigid structures, such as carbon black particles, carbon fibers, carbon cloths and graphite flakes. Functional groups can be attached to the carbonaceous particles that improve their compatibility with the polymer constituents of the membrane enabling better dispersion of the particles in the membrane composite.
3. Increase the chemical stability of the membrane with respect to aggressive acidic or basic chemical environments by including surface modified carbonaceous compounds that are pH stable.
4. Reduce membrane swelling by substituting rigid modified carbon products such as carbon particles that have one or more ionic groups attached to the particles for the swellable polymer ion-exchange groups. Surface modified carbonaceous particles can be prepared with one or more anionic groups, e.g., benzenesulfonic acid, benzoic acid, etc. or cationic groups (phenyl pyridinium, phenethylamine, etc.) attached to the surface to have flexible chemistry that can be applied to both cation and anion exchange electrodialysis membranes.
5. Enhance the selectivity of the membrane by incorporating modified carbon products with functional groups that promote selective adsorption or transport. The choice of surface group can impact the mobility of the ions that are transported through the membrane. For example, acidic groups with chelating properties can be used to immobilize or decrease the mobility of multivalent metal cations, while selectively permitting the transport of monovalent cations through the membrane. Also, groups can be attached to the surface to selectively immobilize other ionic components that may need to be separated from the bulk of the ions, thus leading to concentrated acids and bases.
6. Enhance the catalytic activity of the membrane by incorporating modified carbon products with surface modification that includes metals with the desired catalytic activity.
7. Allow flexibility in the formulation of the membrane composition. Current membranes have most of the chemically selective functionality built into the polymer that is the major component of the membrane. The utilization of modified carbon products in the membrane decouples the functionality of the membrane from the polymer and can enable different combinations of functions that have not been achieved in the past.
None of the known approaches for improving membrane performance can combine the performance enhancements that can be accomplished by incorporating modified carbon products in accordance with the present invention.
Metallic nanoparticles supported on carbon black particles or other thermally conductive supports (e.g., fumed alumina or silica, colloidal alumina or silica, etc.) with a surface that can be surface modified, have been found to have thermal conductivity that is significantly better than that expected from the theory of composites put forth by Maxwell, as is described in Choi et al. (2003). According to the present invention, modified carbon particles can advantageously be dispersible in a variety of coolants by proper surface modification of the carbon support, as compared to the nanoparticles in heat transfer fluids known in the art. For example, particles containing Pt deposited on carbon black can be made dispersible in ethylene glycol/water mixtures by the attachment of a benzenesulfonic group on the carbon surface of the composite particle. As a consequence, these materials can provide enhanced rheological properties in addition to enhanced thermal conductivity. The viscosity of the heat transfer fluid is equally important in its heat transfer performance in convective applications, as is well known in the art. See, for example, Holman, “Heat Transfer”, 8th edition, McGraw-Hill (1997).
1. The metal particles are fixed on the support and cannot agglomerate. In FIG. 9 a transmission electron microscopy (TEM) photomicrograph of a carbon black aggregate with deposited Pt is illustrated. It is evident from FIG. 9 that the Pt nanoparticles have dimensions significantly smaller than that of the carbon black aggregate and are evenly dispersed on the surface of the carbon black aggregate, so they can not agglomerate.
2. The metal particle formation conditions and the amount of metal on the support can be manipulated to control the size and distribution of the metal particles and to consequently optimize the thermal properties of the dispersion. The Pt nanoparticles shown in FIG. 9 are an example of a 20 wt. % loading of Pt on C. The total loading of metal on the support can be increased or decreased according to the desired performance.
3. The particles will not coat or deposit on the surfaces that are in contact with the dispersion because they will be supported by the surface modified support. This property will enhance the applicability of metallic nanoparticle dispersions by expanding the range of applications.
4. The particles will be more stable because the stabilization of the dispersion will be performed via the surface modification of the support, which is more flexible than that of the metal nanoparticles. The particles shown in FIG. 9 are supported on carbon black, which is subsequently surface modified with benzenesulfonic groups. These groups in turn help stabilize the dispersion of these particles in water/ethylene glycol mixtures that are typical of heat transfer fluids. In general, stabilized dispersions have better rheological properties (e.g., viscosity, etc.) than unstable dispersions. Stabilized dispersions have a positive impact on the heat transfer fluid's heat transfer properties.
The enhanced performance of these materials can also be extended to other applications, where improved thermal conductivity is important, such as the enhancement of the properties of thermal pastes used as thermal interface materials for the dissipation of heat from microelectronics. Carbon black based dispersions have been reported (Leong et al., Carbon, 41, pp. 2459-2469, (2003)) to have enhanced performance in such applications. The materials that are used in the interface between a heat source and a heat sink should have low contact resistance, should conform to the surface topography of the surfaces that they join and also should have good thermal properties. The materials of the present invention can combine the thermal conductivity of the underlying carbonaceous materials with the enhanced thermal properties associated with the well-dispersed metallic nanoparticles on their surface and the excellent dispersion and compatibility with the matrix that arises from the surface modification of the carbonaceous surface.
The advantages of using carbon as a catalytic support have been explored by many, as reported by the variety of applications for these materials that are listed in Radovic et al. Specifically, carbon-based catalysts have found applications in the area of petroleum refining. Another area of application is that of hydro-desulfurization and/or hydro-denitrogenation where state-of-the-art catalysts include Mo, Co, Co—Mo or Ni—Mo supported on γ-alumina. There are reports that replacing or coating the alumina with carbon can lead to enhanced catalyst performance. Many applications are also described in Radovic et al. and its references. For example, hydrogenation reactions where Pd/C. (i.e., palladium on carbon), Pt/C, Fe/C, Ni/C, Ru/C, Pt—Ru/C, and various alkali metal promoted combinations of metals supported on carbon can be used for reactions as diverse as the reduction of nitroaromatics to ammonia production. In oxidation reactions, especially liquid phase oxidations of alcohols to aldehydes, ketones, or carboxylic acids, catalytic transition metals, such as Pt, Pd, Ru, Ir, and others alone, in mixtures/alloys, or enhanced by addition of selected elements (e.g. bismuth) supported on carbon have demonstrated increased activity and selectivity. There are a wide variety of other applications, including environmental applications, for the removal/reduction of SOx, NOx and other acid gas pollutants.
1. the morphology of the constituent carbon blacks.
2. the concentration and type of binder used to bind the carbon black aggregates
3. the conditions for curing and/or carbonizing the binder; and
4. the incorporation of reverse templating materials with desired morphologies that can be removed from the particles after the particle formation by dissolution, acid or base treatment, or other techniques known in the art.
The materials of the present invention can also have tailored surface chemistry that allows control over the design of the catalyst particle at the molecular level. This ability can enhance several aspects of the catalyst from its manufacturing processes to its final performance. For example, tailoring the surface before the deposition of the catalyst metal by attaching functional groups that have high affinity for the metal can enable a more uniform distribution of the metal particles. Modifying the surface with groups (e.g., ionic groups or hydrophilic polymer groups) that enable the starting carbon black particles to fully disperse in the precursor solution can enhance the uniformity of deposition of metal particles because the entire surface of the particle will be wetted and accessible. The modification of the surface with custom groups can also occur after the metal deposition depending on the intended application. This may facilitate processes such as the application of catalytic coatings on membranes, monoliths or other devices that may benefit from the presence of a carbon-supported catalyst.
The current art focuses almost exclusively on oxygenated groups that are either present on the carbon surface or can be incorporated by a variety of oxidation techniques as the only way to influence the carbon surface chemistry (see for example Radovic et al., in “Chemistry and Physics of Carbon: A Series of Advances, Vol. 25”, Marcel Dekker, (1997), pp. 243-358, and all references within). The present invention expands the range of functionalities that are possible on the carbon surfaces to a broad spectrum of organic and inorganic groups. The ability to surface modify carbon coated on inorganic oxides, enables the combination of unique surface chemistries of materials such as alumina or silica with the enhanced metal dispersion on the carbon fraction of the surface.
1. Metal-containing catalysts supported on carbon black aggregates that are surface modified to become dispersible in the reaction medium, thus enabling better contact and transport and yielding higher activity. Because of the submicron size of the particles this system is expected to behave as a quasi-homogenous system, showing enhanced performance.
2. The surface modification enables the preparation of totally new catalytic materials. Trends in catalysis are moving towards immobilized homogeneous catalysts that are easily removable from the reaction matrix and help improve productivity by reducing costs associated with product purification and precious metal loss and recovery (see for example S. Buckley, “Innovations in Catalysis” in Manufacturing Chemist, Jan. 19, 2002). The carbonaceous materials of the present invention can be surface modified with groups that either contain or can be reacted further to incorporate homogenous catalysts. Examples of such catalysts include: a) carbon supported Pd—P(Ph)3 containing catalysts used in Suzuki or Heck reactions in organic synthesis, b) carbon supported Rh—P(Ph)3 containing catalysts used in hydrogenation reactions, c) carbon supported Pt-complex containing hydrosilation catalysts. Virtually any organometallic complex that can act as a homogeneous catalyst can be supported on a carbonaceous support using the methods of this invention. The improved carbon supported homogeneous catalysts are expected to match the performance of the original homogeneous catalysts. Other supported homogeneous catalysts that are known in the art utilize polymer supports to anchor the homogeneous catalyst. The homogeneous catalyst is covalently bonded to inert polymer fibers that then swell to allow for diffusion of reagents to and from the active sites. This is why these materials are known to have comparable activity to homogenous catalysts, but suffer in that the reaction times are longer. The rigidity of the carbon support and the flexibility in terms of the morphology of the carbonaceous particles provide distinct advantages. The ability to create homogeneous supported catalysts on sub-micron carbon black aggregates combined with dispersion allow for ease of contact of the reagents with the active sites.
According to another embodiment of the present invention, the homogeneous catalysts are strongly bonded to the surface of the modified carbon products (including particle and fiber-based materials), and therefore the separation of the catalytic species from the reaction medium can be very efficiently achieved. This separation is a problem in many cases in which the products of the reaction may be contaminated by the presence of residual catalytic species, which also leads to loss of often expensive precious metal based catalytic reagents.
One type of hydrogen storage material is a metal alloy or intermetallic compound that includes a mixed metal, often referred to as a mixed metal hydride. Typical mixed metal compositions include AB, AB2, AB3, AB5 and A2B, where A can be selected from lanthanide elements (e.g., La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Th, Yb and Lu) as well as Mg, Ti and Zr, and B can be selected from the transition elements (e.g., Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Rh, Ru, Pd, Ag, Cd, La, Ce and the like). See Zuttel, Materials Today, September 2003, pp. 24-33 which is incorporated herein by reference. Preferred examples of such materials include LaNi5, Mg2Ni, Mg2Fe, TiFe, and ZrMn2 (Argonne National Laboratories Report “Basic Research needs for the Hydrogen Economy”, 2003). For example LaNi5 forms a species with the empirical formula LaNi5H6.5 and is the material of choice for nickel/metal-hydride batteries. Other examples are given in G. Sandrock, Journal of Alloys and Compounds, 293-295 (1999) 877-888, which is incorporated herein by reference. These materials currently have the most reliable reversible hydrogen uptake and are currently in use in nickel-metal hydride batteries. They are also the material most commonly used for hydrogen storage, but are not optimal because their gravimetric hydrogen uptake capacity is relatively low, between 1 and 3 wt. %. In addition, these materials typically decrepitate after the first adsorption/desorption cycle to form a powder that is pyrophoric when exposed to air.
In general it is believed that the addition of dopants or catalysts can enhance the storage capacity, kinetics, and regenerability of most chemical hydrides. For example, in the case of complex metal hydrides, the addition of a Ti Catalyst to sodium alanate (NaAlH4) described by Bogdanovic and Sandrock (MRS Bulletin, September 2002, pp. 712-716) led to a reversible capacity of >4 wt. % at 150° C., conditions not too far from ambient. In the case of simple metal hydrides, Barkhordian et al. (Scripta Materialia, 49, (2003), pp. 213-217) have shown that the incorporation of Nb2O5 and other metal oxides into Mg can have a significant effect on the adsorption and desorption kinetics of MgH2.
The most promising of these materials include carbon particles, carbon nanotubes or fullerenes and may also have present other hetero atoms which enhance the hydrogen uptake. These carbon-based materials can also have surface funtionalization groups that enhance the capacities and kinetics of hydrogen storage. High surface area active carbons have long been known to physisorb molecular hydrogen, but only at low temperatures due to the weak nature of the physisorption interaction. At the other extreme, chemical reaction of hydrogen with carbon (chemisorption) in the form of fullerenes to form hydrocarbons, e.g., C60H48, results in the formation of covalently bonded hydrogen that requires too high a temperature for desorption of the hydrogen. To resolve this dichotomy, a number of solutions have been explored. A reduction in the chemical stability of the “carbon hydrides” can be conceived to bring the adsorption/desorption kinetics closer to room temperature. Single wall carbon nanotubes have dimensions that are close to that required for capillary condensation of hydrogen molecules and may offer an alternative strategy. Finally, the incorporation of metal particles into the structure of the carbon particles could provide another mechanism to bring the reaction conditions closer to more commercially relevant conditions. A recent example was described in U.S. Patent Application Publication No. 2002/0096048 by Cooper et al., which is incorporated herein by reference in its entirety.
Modified carbon products may also be used as adsorbents or “getters” for volatile species present in electronic devices such as displays. In this application, a high surface area material that irreversible binds volatile species that may be present is desired to avoid a reduction in device performance caused by the reaction of the volatile species with an active component in the display. Furthermore, because the modified carbon products, such as modified carbon black is also a black pigment that can be used to construct the black matrix in a flat panel display, the modified carbon material may now exhibit a dual functionality of the black matrix and a getter for unwanted materials.
X—R1—Y
21. The method as recited in claim 20, wherein said functional group is —SO3H, —CO2H, —PO3H2, —PO3NaH, —CF3, —CONR2, —NR3 +, —NR2, —PR2, where R is alkyl, aryl, hydrogen, or any combination thereof.
30. The method of claim 29, further comprising adding a metal containing species that is silver, copper, nickel, europium, iron, aluminum, rhodium, cobalt, ruthenium, magnesium, calcium, or platinum, to the liquid precursor suspension prior to said atomizing.
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