Carbon monoxide electrooxidation

Corrigan DS, Weaver MJ. 1988. Mechanisms of formic acid, methanol, and carbon monoxide electrooxidation at platinum as examined by single potential alteration infrared spectroscopy. J Electroanal Chem 241 143-162. 

Edens GJ, Hamelin A, Weaver MJ. 1996. Mechanism of carbon monoxide electrooxidation on monocrystalline gold surfaces Identification of a hydroxy carbonyl intermediate. J Phys Chem 100 2322-2329. 

Gasteiger HA, Markovic N, Ross PN Jr, Cairns EJ. 1994. Carbon monoxide electrooxidation on well-characterized platinum-mthenium alloys. J Phys Chem 98 617-625. 

Wang, K. et al.. On the reaction pathway for methanol and carbon monoxide electrooxidation on Pt-Sn alloy versus Pt-Ru alloy surfaces, Electrochim. Acta, 41, 2587, 1996. 

FIGURE 2.4 Adsorbed carbon monoxide electrooxidation on Pt(lll) run at 0.05 V s-1 in 0.1 M perchloric acid at room temperature. The voltammetric profile of Pt(lll) in the supporting electrolyte is superimposed. The adsorption of the residue was performed at 0.35 V for 5 min from a carbon monoxide saturated acid solution. 

Shubina, T.E. and Koper, M.T. (2002) Quantum-chemical calculations of CO and OH interacting with bimetallic surfaces. Electrochim. Acta, 47, 22—23. Gasteiger, H.A., Markovic, N.M., and Ross, P.N. (1995) Electrooxidation of CO and H2/CO mixtures on a well-characterized PtjSn electrode surface./. Phys. Chem., 99, 16757-16767. Wang, K., Gasteiger, H.A., Markovic, N.M., and Ross, P.M. (1996) On the reaction pathway for methanol and carbon monoxide electrooxidation on Pt-Sn alloy versus Pt-Ru alloy surface. Electrochim. Acta, 41, 2587-2593. 

Gasteiger, H.A., Markovic, N., Ross, P.N., et al. Carbon monoxide electrooxidation on weU-characterized platinum-ruthenium alloys. /. Phys. Cltem. 98 617-25. 

Crabb E M, Marshall R, and Thompsett D (2000), Carbon monoxide electrooxidation properties of carbon-supported FISn catalysts prepared using surface organometaUic chemistry , J. Electrochem. Soc., 147, 4440-4447. DOI 10.1149/ 1.1394083. 

Wang, K., Gasteiger, H., Markovic, N., etal. (1996). On the Reaction Pathway for Methanol and Carbon Monoxide Electrooxidation on Pt-Sn Alloy Versus Pt-Ru Alloy Surfaces, Electrochim. Acto, 41, pp. 2587-2593. 

Chang SC, Hamelin A, Weaver MJ. 1991. Dependence of the electrooxidation rates of carbon monoxide at gold on the surface crystallographic orientation A combined kinetic-surface infrared spectroscopy study. J Phys Chem 95 5560-5567. 

Gomez R, Orts JM, Feliu JM, Clavilier J, Klein LH. 1997. The role of surface crystalline heterogeneities in the electrooxidation of carbon monoxide adsorbed on Rh(lll) electrodes in sulphuric acid solutions. J Electroanal Chem 432 1 -5. 

Kizhakevariam N, Weaver MJ. 1994. Structure and reactivity of bimetaUic electrochemical interfaces Infrared spectroscopy studies of carbon monoxide adsorption and formic acid electrooxidation on antimony-modified Pt(lOO) and Pt(lll). Surf Sci 310 183-197. 

Gasteiger HA, Markovic NM, Ross PN Jr. 1996. Structural effects in electrocatalysis Electrooxidation of carbon monoxide on Pt3Sn single-crystal surfaces. Catal Lett 36 1-8. 

Leung L-WH, Wieckowski A, Weaver MJ. 1988. In situ infrared spectroscopy of well-defined single-crystal electrodes Adsorption and electrooxidation of carbon monoxide on plati-nuk(lll). J Phys Chem 92 6985-6990. 

Chang SC, Hamelin A, Weaver MJ. 1990. Reactive and inhibiting adsorbates for the catal34ic electrooxidation of carbon-monoxide on gold (210) as characterized by surface infrared-spectroscopy. Surf Sci 239 L543-L547. 

Two examples of the application of SERS and potential-difference IRRAS methods to the identification of adsorbed intermediates and reaction mechanism elucidation are also described, involving the catalytic electrooxidation of carbon monoxide and small organic molecules on transition-metal surfaces. 

Electrooxidation of carbon monoxide to carbon dioxide at platinum has been extensively studied mainly not least because of the technological importance of its role in methanol oxidation in fuel cells [5] and in poisoning hydrogen fuel cells [6]. Enhancing anodic oxidation of CO is critical, and platinum surfaces modified with ruthenium or tin, which favor oxygen atom adsorption and transfer to bound CO, can achieve this [7, 8]. 

Over the past 35 years, much has been learned about the electrooxidation of methanol on the surface of noble metals and metal alloys, in particular platinum and ruthenium [2, 4, 6, 7]. Significant overpotential losses occur in the reaction due to poisoning of the alloy catalyst surface by carbon monoxide. Yet, Pt-based metal alloys are still the most popular catalyst materials in the development of new fuel cell electrocatalysts, based on the expectation that a more CO-tolerant methanol catalyst will be developed. The vast ternary composition space beyond Pt-Ru catalysts has not been adequately explored. This section demonstrates how the ternary space can be explored using the high-throughput, electrocatalyst workflow described above. 

Vqq, of adsorbed carbon monoxide against electrode potential at gold electrodes, for CO-saturated (ca. ImM) solutions. Electrolytes were ( , ) 0.1 M HCIO, ( ) 0.1 M NaClO, and (A) 0.1 M KF. The arrowed dashed curves represent the sequential peak frequencies obtained upon potential excursions from 100 mV to 500 mV and return, into the region where CO electrooxidation, occurs. The solid straight line, drawn through the points obtained at potentials (< 100 mV) where adsorbed CO is stable towards electrooxidation, has a slope of about 50 cm l V. ... 

Other electrocatalysts were considered for the electrooxidation of ethanol, such as rhodium, iridium or gold, " " leading to similar results in acid medium. The oxidation of ethanol on rhodium proceeds mainly through the formation of acetic acid and carbon monoxide. Two types of adsorbed CO are formed, i.e., linearly-bonded and bridge-bonded, in a similar amount, at relatively low potentials, then leading rapidly to carbon dioxide when the rhodium surface begins to oxidize, at 0.5-0.7 V/RHE. On gold in acid medium the oxidation reaction leads mainly to the formation of acetaldehyde. " " ... 

Narayanasamy, J., Anderson, A. (2003). Mechanism for the electrooxidation of carbon monoxide on platinum by HjO. Density functional theory calculation. /. Electroanalytical Chem. 554-555,35-40. 

Different electron-conducting polymers (polyaniline, polypyrrole, polythiophene) are considered as convenient substrates for the electrodeposition of highly dispersed metal electrocatalysts. The preparation and the characterization of electronconducting polymers modified by noble metal nanoparticles are first discussed. Then, their catalytic activities are presented for many important electrochemical reactions related to fuel cells oxygen reduction, hydrogen oxidation, oxidation of Cl molecules (formic acid, formaldehyde, methanol, carbon monoxide), and electrooxidation of alcohols and polyols. 

Carbon monoxide is a key molecule in the electro-oxidation of Cl compounds and of many alcohols, since it is always produced by the dissociative chemisorption of the molecule, and since it may block the active catalytic sites. Therefore, its electrooxidation on platinum-based metals dispersed in an electron-conducting polymer, such as PAni, was investigated for a long time in our laboratory [8,28,34]. 

On the basis of the scheme described by Eq (24), Eqs. (30) and (31) represent the steady-state catalyst surface balance of adsorption, desorption, and electrooxidation fluxes of carbon monoxide and of hydrogen. If the intermediate hydrogen step is second order in catalyst sites, as was assumed on the basis of the nature of process (25) [66], then, in Eq. (31), n = 2. Equations (30) and (31) determine 0co, the fraction of catalyst sites with adsorbed CO,... 

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