Cambridge University Press



SUPPLEMENTARY INFORMATIONElectrochemical reduction of CO2 to formic acid on Bi2O2CO3 / carbon fiber electrodesLara G. Puppin,1 Mohd. Khalid,1 Gelson T. T. da Silva,2 Caue Ribeiro,2,3 Hamilton Varela,1 Osmando F. Lopes1,4*1 Institute of Chemistry of Sao Carlos, University of Sao Paulo, POB 780, BR-13560970, Sao Carlos, SP, Brazil2 Embrapa Instrumentation, Rua XV de Novembro, 1452, CEP: 13560-970, S?o Carlos, SP, Brazil.3 Forschungszentrum Jülich GmbH, Institute of Energy and Climate Research (IEK-3): Electrochemical Process Engineering, 52425 Jülich, Germany.4 Laboratory of Photochemistry and Materials Science, Institute of Chemistry, Federal University of Uberlandia, BR-38400902, Uberlandia, MG, BrazilFIG. S1. SEM representative images of the electrodes with different amounts of Bi2O2CO3 deposited on carbon fiber, Bi2O2CO3 - 18 mg a) and b), Bi2O2CO3 - 90 mg c) and d). FIG. S2. Adsorption–desorption isotherms of N2 at 77 K for Bi2O2CO3 sample.FIG. S3. a) Cyclic voltammetry and b) electrolysis under galvanostatic conditions (applied current –50 mA) in KHCO3 (0.5 M) electrolyte solution for 18 mg-Bi2O2CO3 electrocatalysts with different Nafion concentrations.FIG. S4 – Formation Kinetic of CO from CO2 photoreduction by Bi2O2CO3 sample exposed to UV irradiation in 0.5 M of KHCO3 solution.FIG. S5. Chronoamperometry curve of Bi2O2CO3 electrode in KHCO3 (0.5 M) saturated with CO2, applied potential of -1.3 V during 24 hours.TABLE SI – Comparison of catalytic performances of electrocatalysts for reduction of CO2 to formate.CatalystFE (%)Current density (mA cm-2)Ref.Sn plate843.7ADDIN CSL_CITATION {"citationItems":[{"id":"ITEM-1","itemData":{"DOI":"10.1016/j.apsusc.2015.08.006","ISSN":"01694332","abstract":"The importance of oxide layer on Sn electrode to the efficiency of CO 2 reduction has been evaluated by comparing the activities of Sn electrodes treated via etching and annealing. In KHCO 3 aqueous solution saturated with CO 2 , Sn electrode with a native oxide layer exhibits high catalytic activity for CO 2 reduction, in contrast, Sn electrode which is etched in HCl solution to remove the oxide layer or treated by annealing exhibits lower activity for CO 2 reduction. If the etched Sn electrode is exposed in the air over 24 h, its catalytic performance for CO 2 reduction will restore, meanwhile, the electrolysis current density for this electrode is around 1.5-fold than that for a untreated Sn electrode because the etching treatment makes the electrode rough and behave a larger superficial area.","author":[{"dropping-particle":"","family":"Zhang","given":"Rui","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Lv","given":"Weixin","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Lei","given":"Lixu","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"Applied Surface Science","id":"ITEM-1","issued":{"date-parts":[["2015"]]},"page":"24-29","publisher":"Elsevier B.V.","title":"Role of the oxide layer on Sn electrode in electrochemical reduction of CO 2 to formate","type":"article-journal","volume":"356"},"uris":[""]}],"mendeley":{"formattedCitation":"³⁹","plainTextFormattedCitation":"39","previouslyFormattedCitation":"³⁸"},"properties":{"noteIndex":0},"schema":""}39Polycrystalline Pb53< 10ADDIN CSL_CITATION {"citationItems":[{"id":"ITEM-1","itemData":{"DOI":"10.1007/s12678-010-0017-y","ISSN":"18682529","abstract":"Formic acid is electrochemically generated from carbon dioxide (CO 2 ) on nanolayered lead (Pb) electrode. Stepwise potential deposition method is applied to prepare nanostructured Pb, composed of particles and platelets with hexagonal and cubic crystallinities. Their electrocatalytic activities in an electroreduction of CO 2 are compared. We observed higher faradaic efficiencies of 94. 1% on a cubic Pb surface than that of polycrystalline Pb smooth films (52. 3%) at 278 K. Analyzing the mass changes of the electrodes by electrochemical quartz crystal microbalance, the mechanistic origin of CO 2 reduction is studied, and the indirect reduction of CO 2 via H ad atoms might be more reasonable than the direct electron transfer of CO 2 molecules. ? 2010 Springer.","author":[{"dropping-particle":"","family":"Kwon","given":"Youngkook","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Lee","given":"Jaeyoung","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"Electrocatalysis","id":"ITEM-1","issue":"2-3","issued":{"date-parts":[["2010"]]},"page":"108-115","title":"Formic Acid from Carbon Dioxide on Nanolayered Electrocatalyst","type":"article-journal","volume":"1"},"uris":[""]}],"mendeley":{"formattedCitation":"⁴⁰","plainTextFormattedCitation":"40","previouslyFormattedCitation":"³⁹"},"properties":{"noteIndex":0},"schema":""}40S-doped In9325-100ADDIN CSL_CITATION {"citationItems":[{"id":"ITEM-1","itemData":{"DOI":"10.1038/s41467-019-08805-x","ISSN":"2041-1723","author":[{"dropping-particle":"","family":"Ma","given":"Wenchao","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Xie","given":"Shunji","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Zhang","given":"Xia-guang","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Sun","given":"Fanfei","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Kang","given":"Jincan","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Jiang","given":"Zheng","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Wu","given":"De-yin","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Wang","given":"Ye","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Zhang","given":"Qinghong","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"Nature Communications","id":"ITEM-1","issued":{"date-parts":[["2019"]]},"page":"892","title":"Promoting electrocatalytic CO2 reduction to formate via sulfur-boosting water activation on Indium Surfaces","type":"article-journal","volume":"10"},"uris":[""]}],"mendeley":{"formattedCitation":"⁴¹","plainTextFormattedCitation":"41","previouslyFormattedCitation":"⁴⁰"},"properties":{"noteIndex":0},"schema":""}41Bi plate151.9ADDIN CSL_CITATION {"citationItems":[{"id":"ITEM-1","itemData":{"DOI":"10.1016/j.apsusc.2016.10.017","ISSN":"01694332","abstract":"Electrochemical reduction of carbon dioxide (CO 2 ) to formate is energetically inefficient because high overpotential is required for reduction of CO 2 to formate on most traditional catalysts. In this paper, a novel nano-sized Bi-based electrocatalyst deposited on a Cu foil has been synthesized, which can be used as a cathode for electrochemical reduction of CO 2 to formate with a low overpotential (0.69?V) and a high selectivity (91.3%). The electrocatalyst can show excellent catalytic performance toward reduction of CO 2 which can probably be attributed to the nano-sized structure and the surface oxide layer. The energy efficiency for reduction of CO 2 to formate can reach to 50% when an Ir x Sn y Ru z O 2 /Ti electrode is used as anode, it is one of the highest values found in the literatures and very practicable for sustainable fuel synthesis.","author":[{"dropping-particle":"","family":"Lv","given":"Weixin","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Zhou","given":"Jing","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Bei","given":"Jingjing","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Zhang","given":"Rui","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Wang","given":"Lei","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Xu","given":"Qi","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Wang","given":"Wei","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"Applied Surface Science","id":"ITEM-1","issued":{"date-parts":[["2017"]]},"page":"191-196","title":"Electrodeposition of nano-sized bismuth on copper foil as electrocatalyst for reduction of CO 2 to formate","type":"article-journal","volume":"393"},"uris":[""]}],"mendeley":{"formattedCitation":"⁴²","plainTextFormattedCitation":"42","previouslyFormattedCitation":"⁴¹"},"properties":{"noteIndex":0},"schema":""}42Cu/CuO46< 10ADDIN CSL_CITATION {"citationItems":[{"id":"ITEM-1","itemData":{"DOI":"10.1002/slct.201802102","ISBN":"0003-0147","ISSN":"23656549","PMID":"18811407","author":[{"dropping-particle":"","family":"Lopes","given":"Osmando F.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Varela","given":"Hamilton","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"ChemistrySelect","id":"ITEM-1","issue":"31","issued":{"date-parts":[["2018"]]},"page":"9046-9055","title":"Effect of Annealing Treatment on Electrocatalytic Properties of Copper Electrodes toward Enhanced CO2Reduction","type":"article-journal","volume":"3"},"uris":[""]}],"mendeley":{"formattedCitation":"⁴³","plainTextFormattedCitation":"43","previouslyFormattedCitation":"⁴²"},"properties":{"noteIndex":0},"schema":""}43Bi2O3 nanoparticle9122ADDIN CSL_CITATION {"citationItems":[{"id":"ITEM-1","itemData":{"DOI":"10.1002/celc.201801036","ISSN":"21960216","abstract":"In this paper, Bi2O3 electrocatalysts for the electroreduction of CO2 to\nformate were synthesized with different morphologies, including\nnanoparticles and thin nanorods. Comparatively, Bi2O3 nanoparticles have\nhigher catalytic activity than Bi2O3 thin nanorods. The Faradaic\nefficiency of formate formation at a moderate potential of -1.2 vs. RHE\nin aqueous solution could reach 91 %. In addition, a maximum current\ndensity for formate production of up to 22 mA cm(-2) was achieved, which\nis almost 3 times higher than that of Bi2O3 thin nanorods. In\nparticular, the catalytic activity of the Bi2O3 nanoparticle catalyst\nwas almost stable over a 23-hour period of electrolysis, exhibiting its\napplication prospect in the electroreduction of CO2 to formate.","author":[{"dropping-particle":"","family":"Miao","given":"Can Can","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Yuan","given":"Gao Qing","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"ChemElectroChem","id":"ITEM-1","issue":"23","issued":{"date-parts":[["2018"]]},"page":"3741-3747","title":"Morphology-Controlled Bi2O3 Nanoparticles as Catalysts for Selective Electrochemical Reduction of CO2 to Formate","type":"article-journal","volume":"5"},"uris":[""]}],"mendeley":{"formattedCitation":"⁴⁴","plainTextFormattedCitation":"44","previouslyFormattedCitation":"⁴³"},"properties":{"noteIndex":0},"schema":""}44Bi2O2CO3801.0ADDIN CSL_CITATION {"citationItems":[{"id":"ITEM-1","itemData":{"DOI":"10.1021/acsomega.7b00437","ISSN":"2470-1343","abstract":"Electrochemical reduction of carbon dioxide (CO2) to formate is energetically inefficient because a high overpotential (>1.0 V) is required for most traditional catalysts. In this work, Bi2O2CO3 (BOC) nanosheets were synthesized as electrocatalysts of CO2 reduction for the first time. Additionally, BOC decorated on the glassy carbon electrode was reduced in situ to metal Bi (RB) for comparing the catalytic performance toward CO2 reduction to that of BOC. The maximum faradaic efficiency of BOC was 83% at an overpotential of 0.59 V, which is a little lower than that of RB (90% obtained at the overpotential of 0.99 V). However, the overpotential for the reduction of CO2 to formate on BOC is obviously decreased compared to that on RB. After 27 h of electrolysis, approximately 80% formate selectivity was obtained using the BOC catalyst. According to the experimental results and the related literature, a new mechanism for the CO2 reduction reaction on BOC was proposed, which may play a guiding role in future ca...","author":[{"dropping-particle":"","family":"Lv","given":"Weixin","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Bei","given":"Jingjing","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Zhang","given":"Rui","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Wang","given":"Wenjuan","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Kong","given":"Fenying","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Wang","given":"Lei","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Wang","given":"Wei","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"ACS Omega","id":"ITEM-1","issue":"6","issued":{"date-parts":[["2017","6","30"]]},"page":"2561-2567","publisher":"American Chemical Society","title":"Bi ₂ O ₂ CO ₃ Nanosheets as Electrocatalysts for Selective Reduction of CO ₂ to Formate at Low Overpotential","type":"article-journal","volume":"2"},"uris":[""]}],"mendeley":{"formattedCitation":"²²","plainTextFormattedCitation":"22","previouslyFormattedCitation":"²²"},"properties":{"noteIndex":0},"schema":""}22Bi2O2CO3 microsheets6850This workFIG. S6. Liquid chromatography results of the (a) standard organics compound and (b) products of the CO2 electroreduction catalyzed by electrodes with different amount of Bi2O2CO3 (18, 45, 90 mg).FIG. S7. Liquid phase chromatogram resulting from electroreduction of CO2 using electrode with 18mg of Bi2O2CO3 and different amounts of Nafion.FIG. S8. Chromatogram of the liquid phase in the region of formic acid resulting from the electrode stability test containing 18 mg Bi2O2CO3 for the CO2 electroreduction reactions.FIG. S9. Chromatogram of the liquid phase of the CO2 electroreduction reaction using an electrode containing 18mg of Bi2O2CO3 and different electrolyte (KHCO3) concentrations.FIG. S10. Liquid phase chromatogram of the CO2 electroreduction reaction using the 18mg Bi2O2CO3 electrode and different electrolytes (NaHCO3 and KHCO3) in the same concentration (0.5 mol/L). ................
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