Electrocatalytic reduction of CO2 to formate using particulate Sn electrodes: Effect of metal loading and particle size

The development of electrochemical processes for the conversion of CO2 into value-added products allows innovative carbon capture & utilization (CCU) instead of carbon capture & storage (CCS). In addition, coupling this conversion with renewable energy sources would make it possible to chemically store electricity from these intermittent renewable sources. The electroreduction of CO2 to formate in aqueous solution has been performed using Sn particles deposited over a carbon support. The effect of the particle size and Sn metal loading has been evaluated using cyclic voltammetry and chronoamperometry. The selected electrode has been tested on an experimental filter-press type cell system for continuous and single pass CO2 electroreduction to obtain formate as main product at ambient pressure and temperature. Experimental results show that using electrodes with 0.75mgSncm−2, 150nmSn particles, and working at a current density of 90mAcm−2, it is possible to achieve rates of formate production over 3.2mmolm−2s−1 and faradaic efficiencies around 70% for 90min of continuous operation. These experimental conditions allow formate concentrations of about 1.5gL−1 to be obtained on a continuous mode and with a single pass of catholyte through the cell.

[1]  Weixin Lv,et al.  Studies on the faradaic efficiency for electrochemical reduction of carbon dioxide to formate on tin electrode , 2014 .

[2]  P. Kenis,et al.  Investigation of a Cu(core)/CuO(shell) Catalyst for Electrochemical Reduction of CO2 in Aqueous Soultion , 2014, International Journal of Electrochemical Science.

[3]  Song Yi Choi,et al.  Electrochemical reduction of carbon dioxide at low overpotential on a polyaniline/Cu2O nanocomposite based electrode , 2014 .

[4]  Bart W. Terwel,et al.  Initial public reactions to carbon capture and storage (CCS): differentiating general and local views , 2012 .

[5]  Thomas F. Jaramillo,et al.  New insights into the electrochemical reduction of carbon dioxide on metallic copper surfaces , 2012 .

[6]  Á. Irabien,et al.  Conversion of carbon dioxide into formate using a continuous electrochemical reduction process in a lead cathode , 2012 .

[7]  G. Olah,et al.  Anthropogenic chemical carbon cycle for a sustainable future. , 2011, Journal of the American Chemical Society.

[8]  A. Agarwal,et al.  3‐D Tin‐Carbon Fiber Paper Electrodes for Electrochemically Converting CO2 to Formate/Formic Acid , 2013 .

[9]  R. Compton,et al.  Sustainable energy: a review of formic acid electrochemical fuel cells , 2011 .

[10]  D. Liaigre,et al.  Electro-reduction of carbon dioxide to formate on lead electrode in aqueous medium , 2009 .

[11]  Pierce W.F. Riemer,et al.  Greenhouse gas mitigation technologies, an overview of the CO2 capture, storage and future activities of the IEA Greenhouse Gas R&D programme , 1996 .

[12]  G. Centi,et al.  Catalysis for CO2 conversion: a key technology for rapid introduction of renewable energy in the value chain of chemical industries , 2013 .

[13]  Angel Irabien,et al.  Towards the electrochemical conversion of carbon dioxide into methanol , 2015 .

[14]  Xin Liu,et al.  Electrocatalytic reduction of CO2 to formic acid on palladium-graphene nanocomposites gas-diffusion electrode. , 2014, Journal of Nanoscience and Nanotechnology.

[15]  E. Hertwich,et al.  Global warming footprint of the electrochemical reduction of carbon dioxide to formate , 2015 .

[16]  K. Asokan,et al.  Electrochemical membrane reactor for the reduction of carbondioxide to formate , 2007 .

[17]  Jaeyoung Lee,et al.  Microstructural surface changes of electrodeposited Pb on gas diffusion electrode during electroreduction of gas‐phase CO2 , 2010 .

[18]  Jingjie Wu,et al.  Electrochemical reduction of carbon dioxide: IV dependence of the Faradaic efficiency and current density on the microstructure and thickness of tin electrode , 2014 .

[19]  Jingjie Wu,et al.  Electrochemical Reduction of Carbon Dioxide II. Design, Assembly, and Performance of Low Temperature Full Electrochemical Cells , 2013 .

[20]  Hongbing Yu,et al.  Fabrication of a novel tin gas diffusion electrode for electrochemical reduction of carbon dioxide to formic acid , 2014 .

[21]  Emma ter Mors,et al.  It's not only about safety: Beliefs and attitudes of 811 local residents regarding a CCS project in Barendrecht , 2012 .

[22]  Jae Kwang Lee,et al.  Sustainable production of formic acid by electrolytic reduction of gaseous carbon dioxide , 2015 .

[23]  Revocatus Lazaro Machunda,et al.  Electrocatalytic reduction of CO2 gas at Sn based gas diffusion electrode , 2011 .

[24]  Á. Irabien,et al.  Ionic liquids in the electrochemical valorisation of CO2 , 2015 .

[25]  A. Aldaz,et al.  Electrochemical approaches to alleviation of the problem of carbon dioxide accumulation , 2001 .

[26]  Hui Li,et al.  Development of a continuous reactor for the electro-reduction of carbon dioxide to formate – Part 2: Scale-up , 2007 .

[27]  Chengyu Ma,et al.  Highly-active copper oxide/copper electrocatalysts induced from hierarchical copper oxide nanospheres for carbon dioxide reduction reaction , 2015 .

[28]  Paul J. A. Kenis,et al.  Electrochemical Reduction of Carbon Dioxide on Cu/CuO Core/Shell Catalysts , 2014 .

[29]  Heng Dong,et al.  Enhanced performance of gas diffusion electrode for electrochemical reduction of carbon dioxide to formate by adding polytetrafluoroethylene into catalyst layer , 2015 .

[30]  P. Edwards,et al.  Turning carbon dioxide into fuel , 2010, Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences.

[31]  Mikkel Jørgensen,et al.  The teraton challenge. A review of fixation and transformation of carbon dioxide , 2010 .

[32]  Seunghwan Lee,et al.  Alkaline CO2 Electrolysis toward Selective and Continuous HCOO– Production over SnO2 Nanocatalysts , 2015 .

[33]  G. Laurenczy,et al.  Formic acid as a hydrogen source – recent developments and future trends , 2012 .

[34]  C. Oloman,et al.  Development of a continuous reactor for the electro-reduction of carbon dioxide to formate – Part 1: Process variables , 2006 .

[35]  G. Frankel,et al.  Degradation and deactivation of Sn catalyst used for CO2 reduction as function of overpotential , 2014 .

[36]  T. Meyer,et al.  Rapid selective electrocatalytic reduction of carbon dioxide to formate by an iridium pincer catalyst immobilized on carbon nanotube electrodes. , 2014, Angewandte Chemie.

[37]  T. Meyer,et al.  Nanostructured tin catalysts for selective electrochemical reduction of carbon dioxide to formate. , 2014, Journal of the American Chemical Society.

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

[39]  Angel Irabien,et al.  Continuous electrochemical reduction of carbon dioxide into formate using a tin cathode: Comparison with lead cathode , 2014 .

[40]  A. Wragg,et al.  Effects of process conditions and electrode material on reaction pathways for carbon dioxide electroreduction with particular reference to formate formation , 2003 .

[41]  N. Wagner,et al.  Electrochemical reduction of CO2 to formate at high current density using gas diffusion electrodes , 2014, Journal of Applied Electrochemistry.

[42]  Marc T. M. Koper,et al.  Electrochemical CO2 reduction to formic acid on a Pd-based formic acid oxidation catalyst , 2015 .

[43]  P. Upham,et al.  Public perceptions of CCS: Emergent themes in pan-European focus groups and implications for communications , 2011 .

[44]  Devin T. Whipple.  Microfluidic reactor for the electrochemical reduction of carbon dioxide , 2010 .

[45]  Thomas I. Valdez,et al.  Electrochemical Conversion of Carbon Dioxide to Formate in Alkaline Polymer Electrolyte Membrane Cells , 2011 .

[46]  K. Trenberth,et al.  Modern Global Climate Change , 2003, Science.

[47]  Hui Li,et al.  The Electro-Reduction of Carbon Dioxide in a Continuous Reactor , 2005 .

[48]  D. Lowy,et al.  Electrochemical reduction of carbon dioxide on flat metallic cathodes , 1997 .

[49]  Toshio Tsukamoto,et al.  Electrocatalytic process of CO selectivity in electrochemical reduction of CO2 at metal electrodes in aqueous media , 1994 .

[50]  G. Kelsall,et al.  Effect of solution pH on CO: formate formation rates during electrochemical reduction of aqueous CO2 at Sn cathodes , 2014 .

[51]  G. Olah,et al.  Electrochemical reduction of CO2 over Sn-Nafion® coated electrode for a fuel-cell-like device , 2013 .

[52]  J. Glass,et al.  Polyethylenimine-enhanced electrocatalytic reduction of CO₂ to formate at nitrogen-doped carbon nanomaterials. , 2014, Journal of the American Chemical Society.

[53]  G. Centi,et al.  Carbon dioxide recycling: emerging large-scale technologies with industrial potential. , 2011, ChemSusChem.

[54]  P. Kenis,et al.  Prospects of CO2 Utilization via Direct Heterogeneous Electrochemical Reduction , 2010 .

[55]  Sung Jong Yoo,et al.  Analysis on the effect of operating conditions on electrochemical conversion of carbon dioxide to formic acid , 2014 .

[56]  E. J. Anthony,et al.  Carbon capture and storage update , 2014 .

[57]  Weixin Lv,et al.  Electrochemical reduction of CO2 on SnO2/nitrogen-doped multiwalled carbon nanotubes composites in KHCO3 aqueous solution , 2015 .

[58]  Neil S. Spinner,et al.  Recent Progress in the Electrochemical Conversion and Utilization of CO2 , 2012 .

[59]  A. Majumdar,et al.  Opportunities and challenges for a sustainable energy future , 2012, Nature.

[60]  M. Kanan,et al.  Pd-catalyzed electrohydrogenation of carbon dioxide to formate: high mass activity at low overpotential and identification of the deactivation pathway. , 2015, Journal of the American Chemical Society.

[61]  Anil Verma,et al.  Effect of solid polymer electrolyte on electrochemical reduction of CO2 , 2012 .

[62]  Hongbing Yu,et al.  Development of rolling tin gas diffusion electrode for carbon dioxide electrochemical reduction to produce formate in aqueous electrolyte , 2014 .

[63]  Jingjie Wu,et al.  Electrochemical reduction of carbon dioxide III. The role of oxide layer thickness on the performance of Sn electrode in a full electrochemical cell , 2014 .

[64]  A. Azapagic,et al.  Carbon capture, storage and utilisation technologies: A critical analysis and comparison of their life cycle environmental impacts , 2015 .

[65]  Geoff Kelsall,et al.  Tinned graphite felt cathodes for scale-up of electrochemical reduction of aqueous CO2 , 2015 .

[66]  Timothy E. Fout,et al.  Advances in CO2 capture technology—The U.S. Department of Energy's Carbon Sequestration Program ☆ , 2008 .

[67]  Jiujun Zhang,et al.  A review of catalysts for the electroreduction of carbon dioxide to produce low-carbon fuels. , 2014, Chemical Society reviews.

[68]  Yumei Zhai,et al.  The electrochemical reduction of carbon dioxide to formate/formic acid: engineering and economic feasibility. , 2011, ChemSusChem.

[69]  Chengyu Ma,et al.  Aqueous CO2 reduction on morphology controlled CuxO nanocatalysts at low overpotential , 2014 .

[70]  S. Kapusta,et al.  Anodic passivation of tin in slightly alkaline solutions , 1980 .

[71]  Angel Irabien,et al.  Continuous electroreduction of CO2 to formate using Sn gas diffusion electrodes , 2014 .

[72]  A. Bocarsly,et al.  Direct reduction of carbon dioxide to formate in high-gas-capacity ionic liquids at post-transition-metal electrodes. , 2014, ChemSusChem.

[73]  Jinyu Han,et al.  Preparation of a Pb loaded gas diffusion electrode and its application to CO2 electroreduction , 2012, Frontiers of Chemical Science and Engineering.

[74]  Xingwen Yu,et al.  Recent advances in direct formic acid fuel cells (DFAFC) , 2008 .

[75]  Paul J. A. Kenis,et al.  Electrochemical conversion of CO2 to useful chemicals: current status, remaining challenges, and future opportunities , 2013 .

[76]  Hui Li,et al.  Electrochemical processing of carbon dioxide. , 2008, ChemSusChem.