Membrane-based catalysts

The inefficiency of the platinum/hydrogen reduction system and the dangers involved with the combination of molecular oxygen and molecular hydrogen led to a search for alternatives for the reduction of the manganese porphyrin. It was, for example, found that a rhodium complex in combination with formate ions could be used as a reductant and, at the same time, as a phase-transfer catalyst in a biphasic system, with the formate ions dissolved in the aqueous layer and the manganese porphyrin and the alkene substrate in the organic layer [28]. 

Several additional studies were carried out to obtain information about the precise behavior of the various components in the model system. The interplay between the manganese porphyrin and the rhodium cofactor was found to be crucial for an efficient catalytic performance of the whole assembly and, hence, their properties were studied in detail at different pH values in vesicle bilayers composed of various types of amphiphiles, viz. cationic (DODAC), anionic (DHP), and zwitterionic (DPPC) [30]. At pH values where the reduced rhodium species is expected to be present as Rh only, the rate of the reduction of 13 by formate increased in the series DPPC DHP DODAC, which is in line with an expected higher concentration of formate ions at the surface of the cationic vesicles. The reduction rates of 12 incorporated in the vesicle bilayers catalyzed by 13-formate increased in the same order, because formation of the Rh-formate complex is the rate-determining step in this reduction. When the rates of epoxidation of styrene were studied at pH 7, however, the relative rates were found to be reversed DODAC DPPC DHP. Apparently, for epoxidation to occur, an efficient supply of protons to the vesicle surface is essential, probably for the step in which the Mn -02 complex breaks down into the active epoxidizing Mn =0 species and water. Using a-pinene as the substrate in the DHP-based system, a turnover number of 360 was observed, which is comparable to the turnover numbers observed for cytochrome P450 itself. 

---

V.M. Linkov and R.D. Sanderson, Carbon membrane-based catalysts for hydrogenation of CO, Catal. Lett. 27 97 (1994). 

In the literature, few studies have focused on performance improvement and mitigation of high-temperature catalyst layers. For LT-PEMFCs, materials used in the catalyst layer preparation are commercially available. For HT-PEMFCs, materials are not only different from those in LT-PEMFCs but also differ from study to study. For example, in PBI membrane-based MEAs, Pt/C catalyst and PBI ionomer were used in the catalyst layer [80-83]. However, in a CSH2PO4 membrane-based catalyst layer, no ionomer was used [22]. It is expected that improvement and mitigation of a high-temperature catalyst layer should depend on the materials used, and the catalyst layer structures should be optimized according to the materials employed. 

Catalytic testings have been performed using the same rig and a conventional fixed-bed placed in the inner volume of the tubular membrane. The catalyst for isobutane dehydrogenation [9] was a Pt-based solid and sweep gas was used as indicated in Fig. 2. For propane oxidative dehydrogenation a V-Mg-0 mixed oxide [10] was used and the membrane separates oxygen and propane (the hydrocarbon being introduced in the inner part of the reactor). 

GP 1] [R 10] By proper heater design, membrane-based reactors with internal heaters allowed one to reach quasi-uniform temperatures at the membrane, which determines the catalyst temperature [19]. This thermal uniformity was checked during reaction, i.e. when large heats were released in the oxidation of ammonia and needed to be transferred out of the reaction zone (Figure 3.29). Thin-film-coated temperature sensors in the center and at the edges of the membrane served to monitor the lateral temperature difference. 

Such bimetallic alloys display higher tolerance to the presence of methanol, as shown in Fig. 11.12, where Pt-Cr/C is compared with Pt/C. However, an increase in alcohol concentration leads to a decrease in the tolerance of the catalyst [Koffi et al., 2005 Coutanceau et ah, 2006]. Low power densities are currently obtained in DMFCs working at low temperature [Hogarth and Ralph, 2002] because it is difficult to activate the oxidation reaction of the alcohol and the reduction reaction of molecular oxygen at room temperature. To counterbalance the loss of performance of the cell due to low reaction rates, the membrane thickness can be reduced in order to increase its conductance [Shen et al., 2004]. As a result, methanol crossover is strongly increased. This could be detrimental to the fuel cell s electrical performance, as methanol acts as a poison for conventional Pt-based catalysts present in fuel cell cathodes, especially in the case of mini or micro fuel cell applications, where high methanol concentrations are required (5-10 M). 

The application of whole-cells or enzyme-based catalysts was protected in two different bioprocess patents ([56] and [57], respectively). The patent specifies the process [57] involving a sulfur-specific reactant with membrane fragments, an enzyme, or a composition of enzymes having the ability to selectively react with sulfur by cleavage of organic C—S bonds, derived from R. rhodochrous strain ATCC No. 53968 or B. sphaericus strain ATCC No. 53969. 

A continuous cross-flow filtration process has been utilized to investigate the effectiveness in the separation of nano sized (3-5 nm) iron-based catalyst particles from simulated Fischer-Tropsch (FT) catalyst/wax slurry in a pilot-scale slurry bubble column reactor (SBCR). A prototype stainless steel cross-flow filtration module (nominal pore opening of 0.1 pm) was used. A series of cross-flow filtration experiments were initiated to study the effect of mono-olefins and aliphatic alcohol on the filtration flux and membrane performance. 1-hexadecene and 1-dodecanol were doped into activated iron catalyst slurry (with Polywax 500 and 655 as simulated FT wax) to evaluate the effect of their presence on filtration performance. The 1-hexadecene concentrations were varied from 5 to 25 wt% and 1-dodecanol concentrations were varied from 6 to 17 wt% to simulate a range of FT reactor slurries reported in literature. The addition of 1-dodecanol was found to decrease the permeation rate, while the addition of 1-hexadecene was found to have an insignificant or no effect on the permeation rate. 

Another way of retaining the catalyst is to create dendrimer-supported ligands, thereby allowing separation of the product and catalyst by membranes. Based on the readily modified BICOL backbone, two dendrimer-Hgands 43 were prepared that had performance comparable to that of MonoPhos 29 a in the hydrogenation of methyl N-acyl dehydrophenylalanine [81]. 

Another key part of a PEM membrane is the thin layer of platinum-based catalyst coating that is used. It makes up about 40% of the fuel cell cost. The catalyst prepares hydrogen from the fuel and oxygen from the... 

Since CO acts as a poison to the proton exchange membrane fuel cell in the 50 ppm range, it has to be removed before feeding the H2 enriched gas to the fuel cell. This CO removal occurs in the PROX reactor, where Pt/Al203 catalysts are common, even though some interest in Au-based catalysts is growing due the lower cost of the active phase [48]. 

There is a need for low-cost methane steam reforming catalysts that are active at low temperature and resistant to coke formation under membrane reactor conditions. Low-cost (Ni-based) catalysts are also needed that can withstand regeneration conditions in a sorption-enhanced reformer. 

Kamarajugadda, S., and Mazumder, S. Numerical investigation of the effect of cathode catalyst layer structure and composition on polymer electrolyte membrane fuel cell performance. Journal of Power Sources 2008 183 629-642. Krishnan, L., Morris, E. A., and Eisman, G. A. Pt black polymer electrolyte-based membrane-based electrode revisited. Journal of the Electrochemical Society 2008 155 B869-B876. 

This chapter gives an overview of the state of affairs in physical theory and molecular modeling of materials for PEECs. The scope encompasses systems suitable for operation at T < 100°C that contain aqueous-based, proton-conducting polymer membranes and catalyst layers based on nanoparticles of Pt. 

The previous discussion asserts that design, fabrication, and implementation of stable and inexpensive materials for membranes and catalyst layers are the most important technological challenges for PEFC developers. A profound insight based on theory and modeling of the pertinent materials will advise us how fuel cell components with optimal specifications can be made and how they can be integrated into operating cells. 

Most of the catalysts employed in PEM and direct methanol fuel cells, DMFCs, are based on Pt, as discussed above. However, when used as cathode catalysts in DMFCs, Pt containing catalysts can become poisoned by methanol that crosses over from the anode. Thus, considerable effort has been invested in the search for both methanol resistant membranes and cathode catalysts that are tolerant to methanol. Two classes of catalysts have been shown to exhibit oxygen reduction catalysis and methanol resistance, ruthenium chalcogen based catalysts " " and metal macrocycle complexes, such as porphyrins or phthalocyanines. ... 

The concept presented in Fig. 6 could use also other type of ordered mesoporous membranes, based on silica for example. As discussed before, oxides such as Ti02 provide better multi-functionalities for the design of such a type of nanofactory catalysts. Worth to note is that in the cover picture of the recent US DoE report Catalysis for Energy a very similar concept was reported. This cover picture illustrates the concept, in part speculative, that to selectively convert biomass-derived molecules to fuels and chemicals, it is necessary to insert a tailored sequence of enzyme, metal complexes on metal nanoparticles in a channel of a mesoporous oxide. 

A commercial Cu based catalyst supplied by Haldor-Topsoe was applied to the water-gas shift reaction. At 210 °C, a permeating flux of 4.5 Ndm3 nT2 s 1 was determined for pure hydrogen at a very low pressure drop of 0.2 bar. Then the membrane reactor was coupled with a conventional water-gas shift reactor. At 260-300 °C reaction temperature and a GHSV of 2 085 h 1, the maximum conversion achievable due to the thermodynamic equilibrium could be exceeded by this new technology by 5-10%. 

A.F.Y. Al-Shammary, I T. Caga, J.M. Winterbottom, A.Y. Tate and I.R. Harris, Palladium-Based Diffusion Membranes as Catalysts in Ethylene Hydrogenation , J. Chem. Tech. Biotech., 52 571-85 (1991). 

The choice of the catalyst is of large influence on the behaviour of the reforming process. Ni-based catalyst are most common, but recently more advanced catalysts have been developed as well. As indicated before, one of the advantages of a membrane reactor is that it can be operated at much lower temperatures but with the consequence that state-of-the-art catalysts might not be sufficiently active anymore. In this paragraph, an overview is provided on commonly used catalysts and some of the problems that may be encountered [7],... 

An important possible future use for pure hydrogen is in proton-exchange-membrane fuel cells (PEMFCs) the basic source for the hydrogen could be either a hydrocarbon or an alcohol, either of which can be steam-reformed to produce water-gas.16,17 As explained above, the equilibrium concentration of carbon monoxide decreases as the temperature falls (Figure 10.1), but as little as 1% is detrimental to the operation of platinum-based catalysts in a fuel cell. Excess water, which is commonly used,18 serves to move the... 

Recent results on isobutane dehydrogenation have been reported, and a conventional reactor has been compared with membrane reactors consisting of a fixed-bed Pt-based catalyst and different types of membrane [51]. In the case of a mesoporous y-AKOi membrane (similar to those used in several studies reported in the literature), the observed increase in conversion could be fully accounted for simply by the decrease in the partial pressures due to the complete mixing of reactants, products and sweep gas. When a permselective ultramicroporous zeolite membrane is used, this mixing is prevented the increase in conversion (% 70%) can be attributed to the selective permeation of hydrogen shifting the equilibrium. 

---