scholarly journals How palladium inhibits CO poisoning during electrocatalytic formic acid oxidation and carbon dioxide reduction

2022 ◽  
Vol 13 (1) ◽  
Author(s):  
Xiaoting Chen ◽  
Laura P. Granda-Marulanda ◽  
Ian T. McCrum ◽  
Marc T. M. Koper
Keyword(s):  
Carbon Dioxide ◽  
Formic Acid ◽  
Modified Electrode ◽  
Density Functional ◽  
Formic Acid Oxidation ◽  
Carbon Dioxide Reduction ◽  
Acid Oxidation ◽  
Co Poisoning ◽  
Platinum Single Crystal ◽  
Single Crystal Electrode

AbstractDevelopment of reversible and stable catalysts for the electrochemical reduction of CO2 is of great interest. Here, we elucidate the atomistic details of how a palladium electrocatalyst inhibits CO poisoning during both formic acid oxidation to carbon dioxide and carbon dioxide reduction to formic acid. We compare results obtained with a platinum single-crystal electrode modified with and without a single monolayer of palladium. We combine (high-scan-rate) cyclic voltammetry with density functional theory to explain the absence of CO poisoning on the palladium-modified electrode. We show how the high formate coverage on the palladium-modified electrode protects the surface from poisoning during formic acid oxidation, and how the adsorption of CO precursor dictates the delayed poisoning during CO2 reduction. The nature of the hydrogen adsorbed on the palladium-modified electrode is considerably different from platinum, supporting a model to explain the reversibility of this reaction. Our results help in designing catalysts for which CO poisoning needs to be avoided.

Formic acid oxidation on platinum: a simple mechanistic study

2015 ◽  
Vol 17 (32) ◽  
pp. 20805-20813 ◽  
Author(s):  
Kathleen A. Schwarz ◽  
Ravishankar Sundararaman ◽  
Thomas P. Moffat ◽  
Thomas C. Allison
Keyword(s):  
Carbon Dioxide ◽  
Formic Acid ◽  
Formic Acid Oxidation ◽  
Mechanistic Study ◽  
Acid Oxidation

Formic acid oxidation on Pt(111) under electrocatalytic conditions occurs when a formate anion approaches the Pt(111) surface in the CH-down orientation, and barrierlessly releases carbon dioxide as the H binds to the surface.

scholarly journals In Situ Exfoliation and Pt Deposition of Antimonene for Formic Acid Oxidation via a Predominant Dehydrogenation Pathway

Research ◽  
2020 ◽  
Vol 2020 ◽  
pp. 1-11 ◽  
Author(s):  
Yiqiong Zhang ◽  
Man Qiao ◽  
Yucheng Huang ◽  
Yuqin Zou ◽  
Zhijuan Liu ◽  
...  
Keyword(s):  
Formic Acid ◽  
Density Functional ◽  
Specific Activity ◽  
Pt Nanoparticles ◽  
Formic Acid Oxidation ◽  
Pt Catalyst ◽  
Acid Oxidation ◽  
Electronic Interaction ◽  
Pt Electrocatalysts

Direct formic acid fuel cell (DFAFC) has been considered as a promising energy conversion device for stationary and mobile applications. Advanced platinum (Pt) electrocatalysts for formic acid oxidation reaction (FAOR) are critical for DFAFC. However, the oxidation of formic acid on Pt catalysts often occurs via a dual pathway mechanism, which hinders the catalytic activity owing to the CO poisoning. Herein, we directly exfoliate bulk antimony to 2D antimonene (Sb) and in situ load Pt nanoparticles onto antimonene sheets with the assistance of ethylenediamine. According to the Bader charge analysis, the charge transfer from antimonene to Pt occurs, confirming the electronic interaction between Pt and Sb. Interestingly, antimonene, as a cocatalyst, alters the oxidation pathway for FAOR over Pt catalyst and makes FAOR follow the more efficient dehydrogenation pathway. The density functional theory (DFT) calculation demonstrates that antimonene can activate Pt to be a lower oxidative state and facilitate the oxidation of HCOOH into CO2 via a direct pathway, resulting in a weakened intermediate binding strength and better CO tolerance for FAOR. The specific activity of FAOR on Pt/Sb is 4.5 times, and the mass activity is 2.6 times higher than the conventional Pt/C.

THE CONVERSION OF CARBON TETRACHLORIDE AND CHLOROFORM TO CARBON DIOXIDE BY RAT LIVER HOMOGENATES

1964 ◽  
Vol 42 (11) ◽  
pp. 1577-1585 ◽  
Author(s):  
David Rubinstein ◽  
Lewis Kanics
Keyword(s):  
Carbon Dioxide ◽  
Carbon Tetrachloride ◽  
Formic Acid ◽  
Pyridine Nucleotide ◽  
Formic Acid Oxidation ◽  
Acid Oxidation ◽  
Optimum Ph ◽  
Liver Homogenates ◽  
Soluble Fractions ◽  
Reduced State

Conditions for the conversion of C14HCl3and C14Cl4to C14O2by liver homogenates were determined. The addition of a pyridine nucleotide in either the oxidized or reduced state was required for a significant C14O2production. This effect was abolished when the homogenate was denatured. Glutathione further increased the activity. The optimum pH for the oxidation of CHCl3to CO2lay between 8.0 and 8.5. The dehalogenation of CCl4was relatively insensitive to changes in the pH of the incubation medium. At least two enzymes are probably required for the formation of CO2from the chloromethanes, since both the microsomal and soluble fractions of the homogenate are required for activity. Production of CO2was inhibited by tetrahydrofolate and p-chloromercuribenzoate. Inhibition by the latter could be overcome by glutathione.The coenzyme requirements suggest that CHCl3may be reduced to CH2Cl2, then successively oxidized to formaldehyde and formic acid. However, the formation of significant quantities of these substances from CHCl2could not be demonstrated. Inhibition of formic acid oxidation did not affect the production of C14O2from C14HCl3. Radioactivity from C14HCl3was found in the protein of the homogenate.

A High-Performance Bimetallic Pd-Cu Nanoparticles Membrane on Glassy Carbon Electrode for Formic Acid Oxidation

2013 ◽  
Vol 704 ◽  
pp. 264-269 ◽  
Author(s):  
Wei Wei ◽  
Yi Liu ◽  
Qi Jin Wan ◽  
Nian Jun Yang
Keyword(s):  
Formic Acid ◽  
Modified Electrode ◽  
High Performance ◽  
Formic Acid Oxidation ◽  
Acid Oxidation ◽  
Carbon Electrode ◽  
Mixed Solution ◽  
Glass Carbon Electrode ◽  
Cu Content ◽  
Glass Carbon

The Palladium-copper nanoparticles (PdCu NPs) have been prepared by potentiostatic electrodeposition from a mixture electrolyte of H2PdCl4 and CuSO4,then placed the electrode in sulfuric acid using cyclic voltammetry sweep a few laps to fabricate the PdCu NPs/glass carbon electrode (Pd-Cu/GCE). The modified electrode electrochemical properties of a preliminary study found that this modified electrode has good stability and electrochemical activity, experiments show that formic aicd has good voltammetric response of the electrode. The electrical activity of the formic acid in the Pd/GCE is lower than that in the Pd-Cu/GCE, this is due to the synergistic effect of the bimetal. When the Cu content is increased gradually in H2PdCl4 and CuSO4 a mixed solution, the formic acid oxidation peak currentlower, because Cu has no electrocatalytic activity for formic acid oxidation.

scholarly journals Formic Acid Oxidation of Electrodeposited Platinum Nanostructures on Graphene Oxide Modified Electrode in Acid Medium

2019 ◽  
Vol 8 (4S2) ◽  
pp. 517-523
Keyword(s):  
Graphene Oxide ◽  
Formic Acid ◽  
Modified Electrode ◽  
Modified Electrodes ◽  
Formic Acid Oxidation ◽  
Catalytic Performance ◽  
Acid Oxidation ◽  
X Ray Diffraction ◽  
Catalytic Current ◽  
Mass Activity

In this report, we investigated an electrochemical oxidation of formic acid using electrodeposited platinum (Pt) nanostructures on graphene oxide (GO) coated glassy carbon (GC) electrode. The modified electrode is well characterized with the aid of cyclic voltammetry (CV), scanning electron microscopy (SEM), X-ray diffraction (XRD) and Raman analyses. A crystalline flower-like Pt nanostructures were found on GO modified electrode. The GO-Pt modified electrode displayed improved catalytic current signal in formic acid oxidation than the bare GC and Pt nanastrutures modified electrodes. The loading of GO amount dependent catalytic performance was studied to optimize the GO amount for the efficient electrocatalytic activity. The mass activity of the GO-Pt modified electrode is 2.2 times higher than the Pt modified electrode in formic acid electrooxidation. The GO-Pt nanostructures show good stability in amperometric i-t curve and consequently, show the higher turnover number than the only Pt modified electrode.

NANOELECTROCATALYSTS BASED PALLADIUM FOR FUEL CELLS WITH DIRECT OXIDATION OF FORMIC ACID

2019 ◽  
Vol 6 (3) ◽  
pp. 104-107
Author(s):  
Marina Vladimirovna Lebedeva ◽  
Alexey Petrovich Antropov ◽  
Alexander Victorovich Ragutkin ◽  
Nicolay Andreevich Yashtulov
Keyword(s):  
Formic Acid ◽  
Palladium Nanoparticles ◽  
Oxidation Reaction ◽  
Electrode Materials ◽  
Formic Acid Oxidation ◽  
Energy Sources ◽  
Acid Oxidation ◽  
Direct Oxidation ◽  
Atomic Force ◽  
Formic Acid Oxidation Reaction

In paper electrode materials with palladium nanoparticles on polymer matrix substrates for energy sources have been formed. Nanocomposites were investigated by atomic force and scanning electron microscopy. The catalytic activity of formed electrodes in the formic acid oxidation reaction was evaluated by voltammetry method.

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