Vanadiumvcatalyzed oxidation with o2 in acidic aqueous media now is the most common method to realize. Cyclic voltammogram of formic acid electrooxidation in 0. Formic acid is a product of the alphaoxidation of fatty. Electrocatalytic activities towards the electrochemical.
Hence, dfafcs can offer both a high power and an easy fuel handling at ambient conditions 2, 3, 4. Pdf formic acid oxidation at platinumbismuth catalysts. By electronic structure analyses, we show that a hydrophobic zone formed nearby the preadsorbed fomate on pt. The role of formic acidformate equilibria in the oxidation of formic. Formic acid oxidation at palladium nanoparticles supported. To meet the requirements of potential applications, it is of great importance to explore new catalysts for formic acid oxidation that have both ultrahigh mass activity and co resistance.
It is an unstable colorless liquid which can be produced by mixing formic acid with hydrogen peroxide. Sizecontrollable synthesis and highperformance formic. Both pt catalysts and au electrodes have been used extensively to study hcooh oxidation. The role of electrodeposited pd catalyst loading on the. The oleylaminecoated pd nanoparticles are readily cleaned with a 99% acetic acid wash, and the pd particles supported on ketjen carbon are catalytically active for formic acid oxidation in hclo4 solution. The results are compared to those at a polycrystalline platinum electrode surface. Information obtained from kinetic measurements is the result of a complex combination of different reaction pathways. The oxidation rate at each potential was determined as a function of elec trode preparation, ph, and formic acid concentration. The conversion of abundant renewable cellulose into versatile formic acid fa is a potential process for efficient energy storage and application. Metal alloys and binary metal catalysts co oxidation. Electrooxidation of formic acid, methanol, and ethanol on. The binary particles exhibited much less selfpoisoning and a lower activation energy relative to pt nanocubes, consistent with the single crystal study. Formic acid oxidation on platinum is a structuresensitive reaction that takes place via a mechanism with two paths. The boron content can be tailored easily by tuning the reaction time, and an optimal boron content is beneficial to promote the formic acid oxidation reaction.
Tunable periodically ordered mesoporosity in palladium. Pdf insight into the effect of sn on co and formic acid. Developing superior electrocatalysts for formic acid oxidation fao is the most crucial step in commercializing direct formic acid fuel cells. It is an important intermediate in chemical synthesis and occurs naturally, most notably in some ants. Surface structure and methanol electrocatalysis ex situ stm images taken during methanol oxidation via uhv transfer. Binary ptpd nanoparticles were synthesized by localized overgrowth of pd on cubic pt seeds for the investigation of electrocatalytic formic acid oxidation. Pt electrocatalysts have been widely studied for electrocatalysis oxidation of small organic molecules including methanol, ethanol, and formic acid. Formic acid oxidation feliu major reference works wiley. Formic acid, systematically named methanoic acid, is the simplest carboxylic acid, and has the chemical formula hcooh. Extraordinary electrocatalytic performance for formic acid. Herein, we electrodeposited palladium membranes with periodically ordered mesoporosity obtained by asymmetrically replicating the bicontinuous cubic phase structure of a lyotropic liquid. Conversion of cellulose into formic acid by ironiii.
One of the paths leads to the formation of co poison intermediate, which. Formic acid was first isolated from certain ants and was named after the latin formica, meaning ant. The oxidation of formic acid was examined by cyclic voltammetry and chronoamperometry in order to determine the rate of catalytic activity reaction turnover as. The excellent electrocatalytic activity of pdpani nanofiber film has been confirmed from the electro oxidation reaction of formic acid in acidic media and alcohols ethanol and methanol in alkaline medium, making it a potential candidate for direct fuel cells dfcs in both acidic and alkaline media. Oxidation of lower molecular weight carboxylic acids such as formic, acetic, glyoxalic, and oxalic acids is often the ratecontrolling step during wet oxidation wo of an aqueous waste stream exhibiting very high chemical oxygen demand cod.
Currently, fa can be produced either from fossil fuel or biomass, the latter being much more sustainable than the former. Pdf kinetic study of formic acid oxidation on carbon. Without the preadsorbed formate, formic acid is only able to adsorb with its carboxyl o linking to pt, which is however difficult to decompose further. By electronic structure analyses, we show that a hydrophobic zone formed nearby the preadsorbed fomate on pt 111 is the origin for the promoting role of formate. Preformed palladium nanoparticles pdnp have been dropcoated onto polyaniline panimodified carbon fibre paper to prepare extended reaction zone anodes for formic acid oxidation that take advantage of the promoting effect of polyaniline. Formic acid, the simplest of the carboxylic acids, used in processing textiles and leather. The size of pd nps can be tuned in a range of 1060 nm simply by adjusting the concentration of pd precursor. Performic acid pfa is an organic compound with the formula ch 2 o 3. In particular, the best catalyst, atomically ordered pt 45 sn 25 bi 30 nanoplates, exhibits an ultrahigh mass activity of 4394 ma mg. Pdcuau nas exhibit superior mass and specific activities to commercial pd black and pdcuau nas in alkaline solution. Pdf formic acid oxidation on metal electrodes researchgate. Pdf electrochemical instability of pt nanoparticles. Formic acid oxidation on bi pt111 electrode in perchloric acid media.
Kinetics of wet oxidation of formic acid and acetic acid. For this purpose, different levels of pd nanoparticle loading 0. Highly efficient catalysts are needed for formic acid oxidation. A systematic study was conducted on small pd nanocrystals 56 nm to understand the effects of catalyst structure and electrolyte on the oxygen reduction reaction orr and formic acid oxidation fao. Improving the electrochemical oxidation of formic acid by.
The formic acid oxidation reaction faor is a model electrocatalytic reaction involving multiple protoncoupled electron transfer steps. Formic acid fa is an important material in the chemical industry. Despite of repeated research extending over more than. A comparative study of the electrooxidation of hcooh and hcho on pd was carried out by online mass spectroscopy ms and cv rotating disc electrode.
The oxidation of formic acid is important as a prototype reaction for the oxidation of small organics and as such has relevance for understanding lowtemperature fuel cells. A new class of ptsnbi intermetallic nanoplates is synthesized to boost formic acid oxidation, which greatly outperforms binary ptsn and ptbi intermetallic, benefiting from the synergism of chosen three metals. As the formic acid solution on the surface of copper film has a certain role in corrosion, using formic acid solution treatment, better surface reduction and rougher surface for cu film were obtained. The orr activities of pd catalysts strongly depended on their structure and the electrolyte used. The order with respect to formic acid is less than one in the absence of perchloric acid whereas in the presence of perchloric. The marked reduction in formic acid production from betamethyl fatty acids in peroxisomedeficient skin fibroblasts suggests that peroxisomes are involved in the generation of c1 units. Trimetallic synergy in intermetallic ptsnbi nanoplates. Formic acid oxidation on pd thin film coated au nanocrystals.
Carbon supported pdm m fe, co electrocatalysts for. It is made by the action of sulfuric acid upon sodium formate, which is produced from. A catalytic study of formic acid oxidation on preferentially oriented. Catalytic oxidation of biomass to formic acid using o2 as. The electrocatalytic oxidation of formic acid at a ptbi ordered intermetallic electrode surface has been investigated using cyclic voltammetry, rotating disk electrode rde voltammetry and differential electrochemical mass spectrometry dems. Pdf kinetics and mechanism of the oxidation of formic. The surface active site model for formic acid electrooxidation at.
Oleylaminemediated synthesis of pd nanoparticles for. Formic acid oxidation at pth2o interface from periodic. In this work, we use the first method since not only uses co as a raw material but it is also the most extended technology for formic acid synthesis worldwide hietala et al. Electrochemical instability of pt nanoparticles probed by formic acid oxidation. A kinetic study article in journal of electroanalytical chemistry 5545551. Insight of sn influence on formic acid oxidation at pt based catalysts. Pdf insight of sn influence on formic acid oxidation at.
However, co poisoning and particle agglomeration can reduce the catalytic activity. Ceria nanocrystals supporting pd for formic acid electrocatalytic. Owing to its oxidizing and disinfecting action, it is used in the chemical, medical and food industries. Cuesta and others published formic acid oxidation on metal electrodes find, read and cite all the research you. Full text get a printable copy pdf file of the complete article 863k, or click on a page image below to browse page by page.
The oxidation of formic acid is of permanent interest as a model reaction for the mechanistic understanding of the electrooxidation of small. Insight into the effect of sn on co and formic acid oxidation at ptsn catalysts. The anodic maximum of formic acid oxidation below 0. Kinetic study of formic acid oxidation on carbonsupported platinum electrocatalyst. Density functional theory calculations reveal that the. Kinetic isotope effects in complex reaction networks. The methods of catalytic oxidation of biomass in aqueous solutions under oxygen o2 using catalysts is promising, since the conditions are mild, the purity of produced fa is high, and the catalysts can be. Adsorption and oxidation of formic acid on smooth platinum. This work reports the synthesis of a novel carbonsupported pddecorated ptcu nanocatalyst for formic acid oxidation.
Cuesta and others published formic acid oxidation on metal electrodes find, read and cite all the research you need on researchgate. The formic acid oxidation is enhanced at any of the ptsnc surfaces with sn in the surface layer. Abstract formic acid oxidation on platinum is a structure. A study of pt dissolution during formic acid oxidation acs. The catalyst shows no obvious activity degradation after 1500 cyclic voltammetry cycles under ambient conditions. Electrocatalytic activities towards the electrochemical oxidation of. The oxidation of formic acid on different pdcoated au nanocrystals started at around. The fuel molecule, formic acid, has a simple structure hcooh and itself is the intermediate of the oxidation of alcohol molecules. Article formic acid oxidation on pd thin film coated au nanocrystals yongan tang 1,y and shouzhong zou 2,y 1 dod technologies inc. The influence of the pani preparation conditions on the activity of the pdnp was investigated. Without using surfactants or polymers, ptcu alloy was firstly prepared through simply coreduction of pt and cu ions using ethylene glycol and sodium citrate as the reducing and stabilizing reagents.
Surfaces free fulltext formic acid oxidation on pd. Pdbi alloy nanoparticleenhanced catalytic activity toward. View enhanced pdf access article on wiley online library html view download pdf for offline viewing. Modeling electrocatalytic oxidation of formic acid at platinum.
As a consequence, the current is not entering plateau as on the ptc catalysts. This work addresses the effects of pd nanoparticle loading and dispersion on the mechanisms of formic acid fa electro oxidation. Pdf modeling electrocatalytic oxidation of formic acid. Pdf kinetic study of the formic acid oxidation on steady state. The word formic comes from the latin word for ant, formica, referring to its early isolation by the distillation of ant bodies. Direct formic acid fuel cells dfafcs are considered as promising power sources for portable applications with the merits of high opencircuit voltage, small fuel crossover, and low toxicity. The catalytic activity and stability of the asobtained pd nps toward formic acid oxidation. The formic acid oxidation reaction has been studied in concentrated perchloric acid solutions up to 9. Pd and pdm m fe or co nanostructured electrocatalysts were synthesized by the impregnation method and supported on carbon black vulcan xc72r for the formic acid oxidation reaction, faor, in acid. Pdf the formic acid oxidation fao reaction is studied on platinum in acid solutions using a specially designed flow cell and different experimental. Direct formic acid fuel cells dfafcs have received great attention since they combine the fast fuel oxidation rate of h2 pemfcs and the ability of dmfcs to directly utilize the liquid fuel. Formic acid fac can be synthesized through methyl formate hydrolysis, oxidation of hydrocarbons or hydrolysis of formamide.
Insight into the effect of sn on co and formic acid. Electrocatalytic oxidation of formic acid at an ordered. Singleatom rhndoped carbon electrocatalyst for formic. Formic acid oxidation occurs at the anode on a catalyst layer. The activity enhancement is explained by a reduced co poisoning of the surface pt sites.
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