Proton reduction, electrocatalysts

The reduction of protons is one of the most fundamental chemical redox reactions. Transition metal-catalyzed proton reduction was reviewed in 1992.6 The search for molecular electrocatalysts for this reaction is important for dihydrogen production, and also for the electrosynthesis of metal hydride complexes that are active intermediates in a number of electrocatalytic systems. 

Only a limited number of true metal complex electrocatalysts have been proposed for proton reduction due to the difficulty inherent in the bielectronic nature of this reaction. It is obvious that the design of such electrocatalysts must take into account the lowering of the overpotential for proton reduction, the stability of the catalytic system, and the regeneration of the starting complex. 

Electrocatalysis of proton reduction by metal complexes in solution has been widely studied [106-111] and confinement of molecular electrocatalysts for this process in polymeric films has also received some attention [111, 112]. This area has received much impetus from biochemical and structural studies of the iron-only... 

Pyridinium and its substituted derivatives are effective and stable homogeneous electrocatalysts for the aqueous multiple-electron, multiple-proton reduction of... 

Scheme 4 Ligand-centered reduction in electrocatalytic proton reduction mediated by a nickel(II) bisaryliminopyridine electrocatalyst...

The phthalocyanine containing polymer films were electrochemically investigated for their electrochromic reductions and reoxidations [406,411]. Under irradiation the reduction of O2 to water was studied in photoelectrochemical cells [407,409,412]. Especially Zn(II)-phthalocyanine in poly(vinylidene fluoride) shows high cathodic photocurrents. Also the electrochemical carbox dioxide and proton reduction by Co(II)-phthalocyanines in a low concentration monomolecular in a polyvinylpyridine matrix were investigated as part of a photoenergy systems [413,414]. As an active catalyst for proton reduction also a bipyridyl platinum complex in a polymer Nafion membrane was found [415]. In order to construct such a photochemical energy conversion system, the research in this field was extended for the electrocatalytic water oxidation to O2 [416-419]. The Ru-complexes cj5-[Ru(bpy)2Cl2] and especially Ru-red ([(NHsjs Ru >-Ru(NH3)4-0-Ru(NH3)5] ) are active as electrocatalysts. 

Since 1994, pyridinium and its substituted derivatives have been identified as effective and stable homogeneous electrocatalysts for the aqueous multiple-electron, multiple-proton reduction of CO2 to various products, such as formic acid, formaldehyde and methanol. Particularly high Faradaic yields were reached in the reduction of CO2 to methanol in both electrochemical and photoelectrochemical systems under energetically advantageous conditions [149]. 

In this section, we summarize the kinetic behavior of the oxygen reduction reaction (ORR), mainly on platinum electrodes since this metal is the most active electrocatalyst for this reaction in an acidic medium. The discussion will, however, be restricted to the characteristics of this reaction in DMFCs because of the possible presence in the cathode compartment of methanol, which can cross over the proton exchange membrane. 

Fernandez JL, Raghuveer V, Manthiram A, Bard AJ. 2005a. Pd-Ti and Pd-Co-Au electrocatalysts as a replacement for platinum for oxygen reduction in proton exchange membrane fuel cells. J Am Chem Soc 127 13100-13101. 

Several other polypyridyl metal complexes have been proposed as electrocatalysts for C02 reduction.100-108 For some of them HCOO- appears as the dominant product of reduction. It has been shown for instance that the complexes [Rhin(bpy)2Cl2]+ or [Rh n(bpy)2(CF3S03)2]+ catalyze the formation of HCOO- in MeCN (at —1.55 V vs. SCE) with a current efficiency of up to 80%.100,103 The electrocatalytic process occurs via the initially electrogenerated species [RhI(bpy)2]+, formed by two-electron reduction of the metal center, which is then reduced twice more (Rlr/Rn Rh°/Rh q. The source of protons is apparently the supporting electrolyte cation, Bu4N+ via the Hoffmann degradation (Equation (34)). 

A cathodic electrocatalyst, which uses the protons and electrons produced in the anodic section for the electrocatalytic reduction of C02. 

The features of the electrode used in this gas-phase electrocatalytic reduction of C02 are close to those used in PEM fuel cells [37, 40, 41] (e.g. a carbon cloth/Pt or Fe on carbon black/Nafion assembled electrode, GDE). The electrocatalysts are Pt or Fe nanoparticles supported on nanocarbon (doped carbon nanotubes), which is then deposited on a conductive carbon cloth to allow the electrical contact and the diffusion of gas phase C02 to the electrocatalyst. The metal nanoparticles are at the contact of Nation, through which protons diffuse. On the metal nanoparticles, the gas-phase C02 reacts with the electrons and protons to be reduced to longer-chain hydrocarbons and alcohols, the relative distributions of which depend on the reaction temperature and type of metal nanoparticles. Isopropanol forms selectively from the electrocatalytic reduction of C02 using a gas diffusion electrode based on an Fe/N carbon nanotube (Fe/N-CNT) [14, 39, 40]. Not only the nature of carbon is relevant, but also the presence of nanocavities, which could favor the consecutive conversion of intermediates with formation of C-C bonds. 

Raghuveer, V., Manthiram, A., and Bard, A.J., Pd-Co-Mo electrocatalyst for the oxygen reduction reaction in proton exchange membrane fuel cells, J. Phys. Chem. B, 109, 22909, 2005. 

Electrocatalysts One of the positive features of the supported electrocatalyst is that stable particle sizes in PAFCs and PEMFCs of the order of 2-3 nm can be achieved. These particles are in contact with the electrolyte, and since mass transport of the reactants occurs by spherical diffusion of low concentrations of the fuel-cell reactants (hydrogen and oxygen) through the electrolyte to the ultrafine electrocatalyst particles, the problems connected with diffusional limiting currents are minimized. There has to be good contact between the electrocatalyst particles and the carbon support to minimize ohmic losses and between the supported electrocatalysts and the electrolyte for the proton transport to the electrocatalyst particles and for the subsequent oxygen reduction reaction. This electrolyte network, in contact with the supported electrocatalyst in the active layer of the electrodes, has to be continuous up to the interface of the active layer with the electrolyte layer to minimize ohmic losses. 

In the case of [Os(bpy)2(CO)II] as an electrocatalyst of the reduction of carbon monoxide in AN and in the presence of tetra- -butylammonium hexafluorophosphate as a supporting electrolyte, the main product is carbon monoxide under anhydrous conditions and formate anion in the presence of water (88OM238, 92IC4864). In the catalytic cycle for tr6z 5-[Os(bpy)(PPh3)2(CO)H] reversible protonation to f/ /7,s-[Os(bpy)(PPh3)(CO)(II)2] occurs and the product was characterized as the dihydrido cation (87IC1247). 

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