Influence of Water Molecules on CO2 Reduction at the Pt Electrocatalyst in the Membrane Electrode Assembly System.

CO2 electroreduction using a Pt catalyst in an aqueous solution system is known to produce only H2. Recently, a remarkable result has been reported that CH4 can be obtained by reducing CO2 using a membrane electrode assembly (MEA) containing a Pt catalyst. A big difference that exists between the two systems is the number of water molecules. Therefore, this study investigated the influence of water molecules on the CO2-reduction process at the Pt electrocatalyst in the MEA system. As a result, cyclic voltammetry indicated that adsorbed CO (COads) was formed by CO2 reduction in the MEA system more preferably than the aqueous solution system. In detail, the ratio of COads at the atop sites (linear CO, COL) on Pt, which participates in the CH4 generation reaction, to the total COads formed by the CO2 reduction became higher as the lower relative humidity (RH) at 50 °C in the MEA system. Cyclic voltammetry combined with in-line mass spectrometry revealed that the amount of COL and CH4 generated by the CO2 reduction reached their maximums at 63.1% RH. CH4 production by the extremely low-overpotential CO2 reduction was significantly achieved under all the RH conditions. Consequently, the Faradaic efficiency of the CH4 production at 63.1% RH was improved by 1.35 times compared to that at 100% RH. These results would be mainly obtained based on the H2O-involved chemical equilibrium of the reactions for the COads and CH4 formation. Overall, the present study experimentally clarified that the formation of COads (particularly COL) and the following CH4 from the CO2 reduction at the Pt electrocatalyst in the MEA system was facilitated by appropriately controlling the water-molecule content.

[1]  Wei Tang,et al.  Layer-Stacked Zn with Abundant Corners for Selective CO2 Electroreduction to CO , 2023, ACS Applied Energy Materials.

[2]  Hongliang Dong,et al.  Electronic Perturbation of Copper Single-Atom CO2 Reduction Catalysts in a Molecular Way. , 2022, Angewandte Chemie.

[3]  Shofu Matsuda,et al.  Highly‐Efficient CO2 Electromethanation with Extremely Low Overpotentials on Pt/C Catalysts: Strategic Design of Multi‐Potential‐Step Method , 2022, ChemElectroChem.

[4]  Shofu Matsuda,et al.  Energy conversion efficiency comparison of different aqueous and semi-aqueous CO2 electroreduction systems. , 2022, Analytical methods : advancing methods and applications.

[5]  Shofu Matsuda,et al.  Electroreduction of CO2 to CH4 without overpotential using Pt‐black catalysts: Enhancement of faradaic efficiency , 2022, International Journal of Energy Research.

[6]  Jie Zhang,et al.  Architectural Design for Enhanced C2 Product Selectivity in Electrochemical CO2 Reduction Using Cu-Based Catalysts: A Review. , 2021, ACS nano.

[7]  Hong Zhu,et al.  Heterostructure of ZnO Nanosheets/Zn with a Highly Enhanced Edge Surface for Efficient CO2 Electrochemical Reduction to CO. , 2021, ACS applied materials & interfaces.

[8]  Yan Liu,et al.  Core–shell-structured CNT@hydrous RuO2 as a H2/CO2 fuel cell cathode catalyst to promote CO2 methanation and generate electricity , 2021 .

[9]  Shofu Matsuda,et al.  H2-CO2 polymer electrolyte fuel cell that generates power while evolving CH4 at the Pt0.8Ru0.2/C cathode , 2020, Scientific Reports.

[10]  C. Berlinguette,et al.  Quantification of water transport in a CO2 electrolyzer , 2020, Energy & Environmental Science.

[11]  Minghui Zhu,et al.  Recent Advances in Electrochemical CO2 Reduction on Indium‐Based Catalysts , 2020 .

[12]  S. Kawi,et al.  A review of recent catalyst advances in CO2 methanation processes , 2020 .

[13]  Shofu Matsuda,et al.  Minimization of Pt-electrocatalyst deactivation in CO2 reduction using a polymer electrolyte cell , 2020 .

[14]  Shofu Matsuda,et al.  Highly selective methane generation by carbon dioxide electroreduction on carbon-supported platinum catalyst in polymer electrolyte fuel cell , 2020 .

[15]  Yuhan Sun,et al.  Promotion of CO2 electrochemical reduction via Cu nanodendrites. , 2020, ACS applied materials & interfaces.

[16]  Shofu Matsuda,et al.  Electrochemical Reduction of CO2 to Methane on Platinum Catalysts without Overpotentials: Strategies for Improving Conversion Efficiency , 2020 .

[17]  Charlotte K. Williams,et al.  The technological and economic prospects for CO2 utilization and removal , 2019, Nature.

[18]  Shofu Matsuda,et al.  Theoretical study of CO2 adsorption on Pt , 2019, New Journal of Chemistry.

[19]  Martin Thema,et al.  Power-to-Gas: Electrolysis and methanation status review , 2019, Renewable and Sustainable Energy Reviews.

[20]  Alexis T. Bell,et al.  Towards membrane-electrode assembly systems for CO2 reduction: a modeling study , 2019, Energy & Environmental Science.

[21]  T. Andreu,et al.  On the role of ceria in Ni-Al2O3 catalyst for CO2 plasma methanation , 2019, Applied Catalysis A: General.

[22]  N. Marzari,et al.  An In Situ Surface-Enhanced Infrared Absorption Spectroscopy Study of Electrochemical CO2 Reduction: Selectivity Dependence on Surface C-Bound and O-Bound Reaction Intermediates , 2018, The Journal of Physical Chemistry C.

[23]  A. Rowan,et al.  Highly Selective Reduction of Carbon Dioxide to Methane on Novel Mesoporous Rh Catalysts. , 2018, ACS applied materials & interfaces.

[24]  C. Majumder,et al.  CO2 capture and electro-conversion into valuable organic products: A batch and continuous study , 2018, Journal of CO2 Utilization.

[25]  Shofu Matsuda,et al.  CO 2 electroreduction characteristics of Pt-Ru/C powder and Pt-Ru sputtered electrodes under acidic condition , 2018 .

[26]  Wilson A. Smith,et al.  Electrochemical Reduction of CO2 on Compositionally Variant Au-Pt Bimetallic Thin Films , 2017 .

[27]  J. Rossmeisl,et al.  Electrochemical CO2 Reduction: A Classification Problem. , 2017, Chemphyschem : a European journal of chemical physics and physical chemistry.

[28]  Y. Nakano,et al.  A broad parameter range for selective methane production with bicarbonate solution in electrochemical CO2 reduction , 2017 .

[29]  Gastón O Larrazábal,et al.  Building Blocks for High Performance in Electrocatalytic CO2 Reduction: Materials, Optimization Strategies, and Device Engineering. , 2017, The journal of physical chemistry letters.

[30]  M. Koper,et al.  Competition between Hydrogen Evolution and Carbon Dioxide Reduction on Copper Electrodes in Mildly Acidic Media , 2017, Langmuir : the ACS journal of surfaces and colloids.

[31]  Joshua M. Spurgeon,et al.  Reduced SnO2 Porous Nanowires with a High Density of Grain Boundaries as Catalysts for Efficient Electrochemical CO2 -into-HCOOH Conversion. , 2017, Angewandte Chemie.

[32]  Angel Irabien,et al.  Electrochemical membrane reactors for the utilisation of carbon dioxide , 2016 .

[33]  Miaofang Chi,et al.  High-Selectivity Electrochemical Conversion of CO2 to Ethanol using a Copper Nanoparticle/N-Doped Graphene Electrode , 2016 .

[34]  A. Bell,et al.  Hydrolysis of Electrolyte Cations Enhances the Electrochemical Reduction of CO2 over Ag and Cu. , 2016, Journal of the American Chemical Society.

[35]  Yun Zhang,et al.  Enhanced CH4 yield by photocatalytic CO2 reduction using TiO2 nanotube arrays grafted with Au, Ru, and ZnPd nanoparticles , 2016, Nano Research.

[36]  Christopher J. Chang,et al.  A Molecular Surface Functionalization Approach to Tuning Nanoparticle Electrocatalysts for Carbon Dioxide Reduction. , 2016, Journal of the American Chemical Society.

[37]  Ibram Ganesh,et al.  Electrochemical conversion of carbon dioxide into renewable fuel chemicals – The role of nanomaterials and the commercialization , 2016 .

[38]  S. Qiao,et al.  Recent Advances in Inorganic Heterogeneous Electrocatalysts for Reduction of Carbon Dioxide , 2016, Advanced materials.

[39]  Yu Zhang,et al.  Effect of Chloride Anions on the Synthesis and Enhanced Catalytic Activity of Silver Nanocoral Electrodes for CO2 Electroreduction , 2015 .

[40]  Y. Nakano,et al.  Effect of CO2 Bubbling into Aqueous Solutions Used for Electrochemical Reduction of CO2 for Energy Conversion and Storage , 2015 .

[41]  Matthew W. Kanan,et al.  Controlling H+ vs CO2 Reduction Selectivity on Pb Electrodes , 2015 .

[42]  George A. Olah,et al.  Electrochemical CO2 Reduction: Recent Advances and Current Trends , 2014 .

[43]  Feng Jiao,et al.  A selective and efficient electrocatalyst for carbon dioxide reduction , 2014, Nature Communications.

[44]  P. Strasser,et al.  Controlling Catalytic Selectivities during CO2 Electroreduction on Thin Cu Metal Overlayers , 2013 .

[45]  K. Ogura,et al.  Electrochemical reduction of carbon dioxide to ethylene: Mechanistic approach , 2013 .

[46]  S. Shironita,et al.  Feasibility investigation of methanol generation by CO2 reduction using Pt/C-based membrane electrode assembly for a reversible fuel cell , 2013 .

[47]  Y. Ishikawa,et al.  Interactions between interfacial water and CO adsorbed on Pt and Pt–Ru alloy surfaces under electrochemical conditions: Density-functional theory study , 2010 .

[48]  Sung-Yong Cho,et al.  Electrochemical analysis of polymer electrolyte membrane fuel cell operated with dry-air feed , 2009 .

[49]  K. Hara,et al.  Electrochemical reduction of high pressure CO2 at Pb, Hg and In electrodes in an aqueous KHCO3 solution , 1995 .

[50]  S. Taguchi,et al.  Reduced CO2 on polycrystalline Pd and Pt electrodes in neutral solution: electrochemical and in situ Fourier transform IR studies , 1994 .

[51]  S. Mezyk,et al.  Reduction potential of the carboxyl radical anion in aqueous solutions , 1989 .

[52]  A. Bewick,et al.  On the nature of reduced CO2: An IR spectroscopic investigation , 1982 .

[53]  Shofu Matsuda,et al.  CO2 Reduction Performance of Pt-Ru/C Electrocatalyst and Its Power Generation in Polymer Electrolyte Fuel Cell , 2019, Journal of The Electrochemical Society.

[54]  André Faaij,et al.  A review at the role of storage in energy systems with a focus on Power to Gas and long-term storage , 2018 .

[55]  Ahmet Kusoglu,et al.  Water Uptake of Fuel-Cell Catalyst Layers , 2012 .

[56]  H. Schwarz,et al.  Reduction potentials of CO2- and the alcohol radicals , 1989 .

[57]  F. Hoffmann,et al.  Infrared reflection-absorption spectroscopy of adsorbed molecules , 1983 .