Electrocatalysis of formic acid and

Climent V, Herrero E, Eehu JM. 1998. Electrocatalysis of formic acid and CO oxidation on antimony-modified Pt(lll) electrodes. Electrochim Acta 44 1403-1414. 

SAUER ET AL. Electrocatalysis of Formic Acid and Carbon Monoxide 285... 

Chang SC, Ho Y, Weaver MJ. 1992. Applications of real-time infrared spectroscopy to electrocatalysis at bimetallic surfaces. I. Electrooxidation of formic acid and methanol on bismuth-modified platinum (111) and platinum (100). Surf Sci 265 81-94. 

The good coincidence between the model and the experimental data depicted in Fig. 7.14 supports the idea that this model captures the essential aspects of the effect of different adatoms on the electrocatalysis of formic acid oxidation. 

Adzic RR, Tripkovic AV, Markovic NM. 1983. Structural effects in electrocatalysis oxidation of formic acid and oxygen reduction on single-crystal electrodes and the effects of foreign metal adatoms. J Electroanal Chem 150 79-88. 

Electrodes modified by underpotential deposition of metal were subjected as electrocatalysts to reduction of oxygen,oxidation of formic acid, and other processes in which polycrystalline metal substrates were used (see review in Ref. 151). Electrocatalysis of single-crystal electrodes modified by underpotential deposition was also investigated, as reviewed by Ad2iC. ... 

Electrocatalysis of formic acid (FA) oxidation reactions has been intensively studied for two main reasons (1) FA is an attractive chemical fuel for fuel cell applications due to its high energy density (1,740 Wh/kg, 2,086 Wh/L) and easy storage [1], and (2) FA is the smallest molecule that has four most common chemical bonds in organic compounds (C—H, C=0, C—O, O H), making FA an ideal model molecule for studying electrooxidation reactions. 

Chang SC, Leung LWH, Weaver MJ. 1990. Metal crystallinity effects in electrocatalysis as prohed hy real-time ETIR spectroscopy electrooxidation of formic acid, methanol, and ethanol on ordered low-index platinum surfaces. J Phys Chem 94 6013-6021. 

Vielstich W. 2003. CO, formic acid, and methanol oxidation in acid electrol3ftes—mechanisms and electrocatalysis. In Bard AJ, Stratmann M, Calvo EJ, eds. Encyclopedia of Electrochemistry. Volume 2. New York Wiley, p 466-511. 

Methanol is the typical fuel with one carbon (Cl) atom for fuel cells. Methanol was one of the first small molecules chosen to study the oxidation on platinum group metals in the very early beginning of electrocatalysis. In that time, the oxidation of other Cl molecules such as formic acid and formaldehyde (interest in CO oxidation came latter with the oxidation of reformatted gases) were investigated as a model oxidation because their elementary steps were supposedly present in the mechanism of methanol oxidation. From the point of view of CO2 emission, methanol has, among the other small molecules, the highest energy production per unit of produced... 

Tian M, Conway BE (2008) Electrocatalysis in oscillatory kinetics of anodic oxidation of formic acid At Pt nanogravimetry and voltammetry studies on the role of reactive surface oxide. J Electroanal Chem 616 45-56... 

Chapter 1 discusses the current status of electrocatalysts development for methanol and ethanol oxidation. Chapter 2 presents a systematic study of electrocatalysis of methanol oxidation on pure and Pt or Pd overlayer-modified tungsten carbide, which has similar catalytic behavior to Pt. Chapters 3 and 4 outline the understanding of formic acid oxidation mechanisms on Pt and non-Pt catalysts and recent development of advanced electrocatalysts for this reaction. The faster kinetics of the alcohol oxidation reaction in alkaline compared to acidic medium opens up the possibility of using less expensive metal catalysts. Chapters 5 and 6 discuss the applications of Pt and non-Pt-based catalysts for direct alcohol alkaline fuel cells. 

Figure 4.27. The effect of Ru/Pt layer electrodeposited over Pt on the HCOOH cyclic voltammogram. Solid line Ru/Pt deposited onto Pt dashed line polycrystalline Pt. Electrolyte 1 M HCOOH - 0.1 M HCIO4 and 1 M HCOOH-0.1 M H2SO4 (inset figure). 298 K. Scan rate 20 mV s Electrode potential expressed vs. RHE [150], (Reprinted from Journal of Power Sources, 163(2), Lemos SG, Oliveira RTS, Santos MC, Nascente PAP, Bulhoes LOS, Pereira EC, Electrocatalysis of methanol, ethanol and formic acid using a Ru/Pt metallic bilayer, 695-701, 2007, with permission from Elsevier.)...

Lamy C, Leger J-M, Clavilier J, Parsons R. Structural effects in electrocatalysis. A comparative study of the oxidation of carbon monoxide, formic acid and methanol on single crystal platinum electrodes. J Electroanal Chem 1983 150 71-7. 

Lemos GS, Oliveira RTS, Santos MC, Nascente PAP, Bulhoes LOS, Perreira EC. Electrocatalysis of methanol, ethanol and formic acid using a Ru/Pt metallic bilayer. J Power Sources 2007 163 695-701. 

Among such aqueous fuels, formic acid and methanol with energy densities of 2.08 and 4.69 kWh 1 attracted more attention for the use in membraneless LFFCs due to the ease of access and well-studied electrocatalysis. A formic acid/ O2 fuel cell has a high theoretical electromotive force of 1.45 V, while the corresponding value of methanol is 1.2 V. 

Ad-atom electrocatalysis in the case of formic acid oxidation can be divided into two terms (1) inhibition of surface poisoning by CO formation (indirect pathway), and (2) true enhancement of the rate of oxidation (direct pathway). For most adatoms, these eftects are mixed. An example for the mixed case is the Sb ad-atom adsorption on Pt(lOO) [96]. The reaction takes place on single Pt sites and randomly... 

R.R. Adzid, M.O. Spasojevic and A.R. Despic, Electrocatalysis by foreign metal monolayers oxidation of formic acid on palladium, J. Electroanal. Chem., 92 (1978) 31-43. 

Jarvi TD, Stuve EM. 1998. Fundamental aspects of vacuum and electrocatalytic reactions of methanol and formic acid on platinum surfaces. In Lipkowski J, Ross PN, eds. Electrocatalysis. New York Wiley-VCH. pp. 75-153. 

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