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Understanding Selectivity for the Electrochemical Reduction of Carbon Dioxide to Formic Acid and Carbon Monoxide on Metal Electrodes
Increases in energy demand and in chemical production, together with the rise in CO 2 levels in the atmosphere, motivate the development of renewable energy sources. Electrochemical CO 2 reduction to fuels and chemicals is an appealing alternative to traditional pathways to fuels and chemicals due to its intrinsic ability to couple to solar and wind energy sources. Formate (HCOO – ) is a key chemical for many industries; however, greater understanding is needed regarding the mechanism and key intermediates for HCOO – production. This work reports a joint experimental and theoretical investigation of the electrochemical reduction of CO 2 to HCOO – on polycrystalline Sn surfaces, which have been identified as promising catalysts for selectively producing HCOO – . Our results show that Sn electrodes produce HCOO – , carbon monoxide (CO), and hydrogen (H 2 ) across a range of potentials and that HCOO – production becomes favored at potentials more negative than –0.8 V vs RHE, reaching a maximum Faradaic efficiency of 70% at –0.9 V vs RHE. Scaling relations for Sn and other transition metals are examined using experimental current densities and density functional theory (DFT) binding energies. While *COOH was determined to be the key intermediate for CO production on metal surfaces, we suggest that it is unlikely to be the primary intermediate for HCOO – production. Instead, *OCHO is suggested to be the key intermediate for the CO 2 RR to HCOO – transformation, and Sn’s optimal *OCHO binding energy supports its high selectivity for HCOO – . Lastly, these results suggest that oxygen-bound intermediates are critical to understand the mechanism of CO 2 reduction to HCOO – on metal surfaces.
Theoretical Analysis of Transition-Metal Catalysts for Formic Acid Decomposition
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CO 2 Hydrogenation to Formate and Formic Acid by Bimetallic Palladium–Copper Hydride Clusters
Mass spectrometric analysis of the anionic products of interaction between bimetallic palladium-copper tetrahydride anions, PdCuH 4 – , and carbon dioxide, CO 2 , in a reaction cell shows an efficient generation of the PdCuCO 2 H 4 – intermediate and formate/formic acid complexes. Multiple structures of PdCuH 4 – and PdCuCO 2 H 4 – are identified by a synergy between anion photoelectron spectroscopy and quantum chemical calculations. The higher energy PdCuH 4 – isomer is shown to drive the catalytic hydrogenation of CO 2 , emphasizing the importance of accounting for higher energy isomers for cluster catalytic activity. In conclusion, this study represents the first example of CO 2 hydrogenation by bimetallic hydride clusters.
Dynamics of Interfacial Charge Transfer to Formic Acid, Formaldehyde, and Methanol on the Surface of TiO2 Nanoparticles and Its Role in Methane Production
Abstract not provided
One-Pot Synthesis of Intermetallic Electrocatalysts in Ordered, Large-Pore Mesoporous Carbon/Silica toward Formic Acid Oxidation
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Mesoporous Ti 0.5 Cr 0.5 N Supported PdAg Nanoalloy as Highly Active and Stable Catalysts for the Electro-oxidation of Formic Acid and Methanol
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A facile route to monodisperse MPd (M=Co or Cu) alloy nanoparticles and their catalysis for electrooxidation of formic acid
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Block copolymer templated synthesis of PtIr bimetallic nanocatalysts for the formic acid oxidation reaction
Arrays of PtIr alloy nanoparticle (NP) clusters are synthesized from a method using block copolymer templates, which allows for relatively narrow NP diameter distributions (~4–13 nm) and uniform intercluster spacing (~60 or ~100 nm).
Reaction-driven selective CO 2 hydrogenation to formic acid on Pd(111)
Selective CO 2 conversion to HCOOH over a Pd(111) surface – a result of surface modification under reactive conditions.
High-Pressure Far-Infrared Spectroscopic Studies of Hydrogen Bonding in Formic Acid
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Development of a scalable, robust electrocatalytic technology for conversion of CO 2 to formic acid via microstructured materials
This project was funded by the Bioenergy Engineering for Product Synthesis (BEEPS) program under the Funding Opportunity Announcement (FOA) DE-FOA-0001916 Topic Area 5 “Rewiring Carbon Utilization”. This FOA sought projects that would electrocatalytically reduce CO 2 to a carbon intermediate and then upconvert to a multi-carbon product or fuel via non-photosynthetic biological system engineering. The project sought to combine the expertise of OCO Chem, whose chief scientist had previously developed an efficient electrocatalytic reactor for conversion of CO 2 to formate with potential to scale, Montana State University investigators who had recently patented a method for laterally grading membranes with the potential of improving reactant distribution and more uniform efficiency across membrane-based reactors, and University of South Florida which had recently discovered a novel C-C bond forming reaction not known to naturally occur in biological systems and which uses C1 substrates and circumvents the central microbial metabolism.
Replication Data for: Tuning reactivity layer-by-layer: formic acid activation on Ag/Pd(111)
The data underlying this published work have been made publicly available in this repository as part of the IMASC Data Management Plan. This work was supported as part of the Integrated Mesoscale Architectures for Sustainable Catalysis (IMASC), an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences under Award # DE-SC0012573.
Quantum chemical studies of a model for peptide bond formation Formation of formamide and water from ammonia and formic acid
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Quantum chemical studies of a model for peptide bond formation. II - Role of amine catalyst in formation of formamide and water from ammonia and formic acid
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Highly Efficient D2 Generation by Dehydrogenation of Formic Acid in D2O Through H+/D+ Exchange on an Iridium Catalyst: Application to the Synthesis of Deuterated Compounds by Transfer Deuterogenation
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