Electrocatalytic carbon dioxide reduction: from fundamental principles to catalyst design

Materials Today Advances - Tập 7 - Trang 100074 - 2020
Xiaolong Zhang1, Si-Xuan Guo1,2, Karl A. Gandionco1,2, Alan M. Bond1,2, Jie Zhang1,2
1School of Chemistry, Monash University, Clayton, VIC 3800, Australia
2ARC Centre of Excellence for Electromaterials Science, Monash University, Clayton, VIC 3800, Australia

Tài liệu tham khảo

Hansen, 2013, Assessing “dangerous climate change”: required reduction of carbon emissions to protect young people, future generations and nature, PloS One, 8, 10.1371/journal.pone.0081648 Hewitt, 1994 Wang, 2017, A multi-region structural decomposition analysis of global CO2 emission intensity, Ecol. Econ., 142, 163, 10.1016/j.ecolecon.2017.06.023 Kondratenko, 2013, Status and perspectives of CO2 conversion into fuels and chemicals by catalytic, photocatalytic and electrocatalytic processes, Energy Environ. Sci., 6, 3112, 10.1039/c3ee41272e Notz, 2016, Observed Arctic sea-ice loss directly follows anthropogenic CO2 emission, Science, 354, 747, 10.1126/science.aag2345 Aresta, 2010 Vasileff, 2017, Carbon solving carbon's problems: recent progress of nanostructured carbon-based catalysts for the electrochemical reduction of CO2, Adv. Energy Mater., 7, 1700759, 10.1002/aenm.201700759 Seh, 2017, Combining theory and experiment in electrocatalysis: insights into materials design, Science, 355, 146, 10.1126/science.aad4998 Albo, 2015, Towards the electrochemical conversion of carbon dioxide into methanol, Green Chem., 17, 2304, 10.1039/C4GC02453B Appel, 2013, Frontiers, opportunities, and challenges in biochemical and chemical catalysis of CO2 fixation, Chem. Rev., 113, 6621, 10.1021/cr300463y Olah, 2011, Anthropogenic chemical carbon cycle for a sustainable future, J. Am. Chem. Soc., 133, 12881, 10.1021/ja202642y Poliakoff, 2015, The twelve principles of CO2 CHEMISTRY, Faraday Discuss, 183, 9, 10.1039/C5FD90078F Jouny, 2018, General techno-economic analysis of CO2 electrolysis systems, Ind. Eng. Chem. Res., 57, 2165, 10.1021/acs.iecr.7b03514 Balbuena, 2010 Bard, 2001 Wang, 2006, Fundamental concepts, Anal. Electrochem., 1 Bard, 2010, Inner-sphere heterogeneous electrode reactions. Electrocatalysis and photocatalysis: the challenge, J. Am. Chem. Soc., 132, 7559, 10.1021/ja101578m Dunwell, 2018, Understanding the influence of the electrochemical double-layer on heterogeneous electrochemical reactions, Curr. Opin. Chem. Eng., 20, 151, 10.1016/j.coche.2018.05.003 1997, 8 - carbon, 268 Darwent, 1970 Atkins, 2018 Zhang, 2020, Mechanistic understanding of the electrocatalytic CO2 reduction reaction – new developments based on advanced instrumental techniques, Nano Today, 100835, 10.1016/j.nantod.2019.100835 Bard, 2017 Hori, 2008 Jean, 1993 Barron, 2012, 322 Solymosi, 1991, The bonding, structure and reactions of CO2 adsorbed on clean and promoted metal surfaces, J. Mol. Catal., 65, 337, 10.1016/0304-5102(91)85070-I Kolasinksi, 2012 Feng, 2017, Recent advances in transition-metal-mediated electrocatalytic CO2 reduction: from homogeneous to heterogeneous systems, Catalysts, 7, 373, 10.3390/catal7120373 Guo, 2013, Graphene-supported {Ru4O4(OH)2(H2O)4}-(γ-SiW10O36)210- for highly efficient electrocatalytic water oxidation, Energy Environ. Sci., 6, 2654, 10.1039/c3ee41892h Sun, 2018, Impact of surface area in evaluation of catalyst activity, Joule, 2, 1024, 10.1016/j.joule.2018.05.003 Kuhl, 2012, New insights into the electrochemical reduction of carbon dioxide on metallic copper surfaces, Energy Environ. Sci., 5, 7050, 10.1039/c2ee21234j Sabatier, 1920 Greeley, 2016, Theoretical heterogeneous catalysis: scaling relationships and computational catalyst design, Ann. Rev. Chem. Biomol. Eng., 7, 605, 10.1146/annurev-chembioeng-080615-034413 Vasileff, 2018, Surface and interface engineering in copper-based bimetallic materials for selective CO2 electroreduction, Inside Chem., 4, 1809 Li, 2016, Recent advances in breaking scaling relations for effective electrochemical conversion of CO2, Adv. Energy Mater., 6, 1600463, 10.1002/aenm.201600463 Peterson, 2012, Activity descriptors for CO2 electroreduction to methane on transition-metal catalysts, J. Phys. Chem. Lett., 3, 251, 10.1021/jz201461p Chen, 2017, Electrochemical reduction of carbon dioxide in a monoethanolamine capture medium, Chemsuschem, 10, 4109, 10.1002/cssc.201701075 Kortlever, 2013, Electrochemical carbon dioxide and bicarbonate reduction on copper in weakly alkaline media, J. Solid State Electrochem., 17, 1843, 10.1007/s10008-013-2100-9 Teeter, 1954, Reduction of carbon dioxide on mercury cathodes, J. Chem. Phys., 22, 759, 10.1063/1.1740178 Hursán, 2018, Electrochemical reduction of carbon dioxide on nitrogen-doped carbons: insights from isotopic labeling studies, ACS Energy Lett., 3, 722, 10.1021/acsenergylett.8b00212 Dunwell, 2017, The central role of bicarbonate in the electrochemical reduction of carbon dioxide on gold, J. Am. Chem. Soc., 139, 3774, 10.1021/jacs.6b13287 Zhu, 2017, Direct observation on reaction intermediates and the role of bicarbonate anions in CO2 electrochemical reduction reaction on Cu surfaces, J. Am. Chem. Soc., 139, 15664, 10.1021/jacs.7b10462 Resasco, 2017, Promoter effects of alkali metal cations on the electrochemical reduction of carbon dioxide, J. Am. Chem. Soc., 139, 11277, 10.1021/jacs.7b06765 Welch, 1969, Tracer studies with radioactive oxygen-15. Exchange between carbon dioxide and water, J. Phys. Chem., 73, 3351, 10.1021/j100844a033 Feaster, 2017, Understanding selectivity for the electrochemical reduction of carbon dioxide to formic acid and carbon monoxide on metal electrodes, ACS Catal., 7, 4822, 10.1021/acscatal.7b00687 Chen, 2012, Aqueous CO2 reduction at very low overpotential on oxide-derived Au nanoparticles, J. Am. Chem. Soc., 134, 19969, 10.1021/ja309317u Zhang, 2014, Nanostructured tin catalysts for selective electrochemical reduction of carbon dioxide to formate, J. Am. Chem. Soc., 136, 1734, 10.1021/ja4113885 Cheng, 2017, Full atomistic reaction mechanism with kinetics for CO reduction on Cu(100) from ab initio molecular dynamics free-energy calculations at 298 K, Proc. Natl. Acad. Sci. USA, 201612106 Wang, 2018, Defect and interface engineering for aqueous electrocatalytic CO2 reduction, Joule, 2, 2551, 10.1016/j.joule.2018.09.021 Raciti, 2018, Recent advances in CO2 reduction electrocatalysis on copper, ACS Energy Lett., 3, 1545, 10.1021/acsenergylett.8b00553 Lee, 2018, New challenges of electrokinetic studies in investigating the reaction mechanism of electrochemical CO2 reduction, J. Mater. Chem., 6, 14043, 10.1039/C8TA03480J He, 2018, Electrocatalytic alloys for CO2 reduction, ChemSusChem, 11, 48, 10.1002/cssc.201701825 Takeda, 2016, Electrons, photons, protons and earth-abundant metal complexes for molecular catalysis of CO2 reduction, ACS Catal., 7, 70, 10.1021/acscatal.6b02181 Lu, 2016, Electrochemical CO2 reduction: electrocatalyst, reaction mechanism, and process engineering, Nano Energy, 29, 439, 10.1016/j.nanoen.2016.04.009 Qiao, 2014, A review of catalysts for the electroreduction of carbon dioxide to produce low-carbon fuels, Chem. Soc. Rev., 43, 631, 10.1039/C3CS60323G Kuhl, 2014, Electrocatalytic conversion of carbon dioxide to methane and methanol on transition metal surfaces, J. Am. Chem. Soc., 136, 14107, 10.1021/ja505791r Xu, 2019, Theoretical insights into heterogeneous (Photo)electrochemical CO2 reduction, Chem. Rev., 119, 6631, 10.1021/acs.chemrev.8b00481 Agarwal, 2011, The electrochemical reduction of carbon dioxide to formate/formic acid: engineering and economic feasibility, ChemSusChem, 4, 1301, 10.1002/cssc.201100220 Cook, 1989, Evidence for formaldehyde, formic acid, and acetaldehyde as possible intermediates during electrochemical carbon dioxide reduction at copper, J. Electrochem. Soc., 136, 1982, 10.1149/1.2097110 Hori, 1989, Formation of hydrocarbons in the electrochemical reduction of carbon dioxide at a copper electrode in aqueous solution, J. Chem. Soc., 85, 2309 Zhang, 2017, Enhancing CO2 electrolysis to formate on facilely synthesized Bi catalysts at low overpotential, Appl. Catal., B, 218, 46, 10.1016/j.apcatb.2017.06.032 Kim, 2017, Shape-controlled bismuth nanoflakes as highly selective catalysts for electrochemical carbon dioxide reduction to formate, Nano Energy, 39, 44, 10.1016/j.nanoen.2017.05.065 Chen, 2018, Nitrogen-doped graphene quantum dots enhance the activity of Bi2 O3 nanosheets for electrochemical reduction of CO2 in a wide negative potential region, Angew. Chem. Int. Ed., 57, 12790, 10.1002/anie.201807643 Oh, 2018, Atomic and molecular adsorption on the Bi(111) surface: insights into catalytic CO2 reduction, J. Phys. Chem. C, 122, 23084, 10.1021/acs.jpcc.8b07865 He, 2018, The p-orbital delocalization of main-group metals to boost CO2 electroreduction, Angew. Chem., 130, 16346, 10.1002/ange.201810538 Pander, 2016, Probing the mechanism of aqueous CO2 reduction on post-transition-metal electrodes using ATR-IR spectroelectrochemistry, ACS Catal., 6, 7824, 10.1021/acscatal.6b01879 Koh, 2017, Facile CO2 electro-reduction to formate via oxygen bidentate intermediate stabilized by high-index planes of Bi dendrite catalyst, ACS Catal., 7, 5071, 10.1021/acscatal.7b00707 Bi, 2018, Atomically thin two-dimensional solids: an emerging platform for CO2 electroreduction, ACS Energy Lett., 3, 624, 10.1021/acsenergylett.7b01343 Li, 2018, Recent advances in the nanoengineering of electrocatalysts for CO2 reduction, Nanoscale, 10, 6235, 10.1039/C7NR09620H Gao, 2017, Nanostructured heterogeneous catalysts for electrochemical reduction of CO2, Curr. Opin. Green Sustain. Chem., 3, 39, 10.1016/j.cogsc.2016.10.004 Kumar, 2017, Reduced SnO2 porous nanowires with a high density of grain boundaries as catalysts for efficient electrochemical CO2-into-HCOOH conversion, Angew. Chem., 129, 3699, 10.1002/ange.201612194 Luc, 2017, Ag–Sn bimetallic catalyst with a core–shell structure for CO2 reduction, J. Am. Chem. Soc., 139, 1885, 10.1021/jacs.6b10435 Zheng, 2018, Theory-guided Sn/Cu alloying for efficient CO2 electroreduction at low overpotentials, Nat. Catal., 2, 55, 10.1038/s41929-018-0200-8 Morimoto, 2017, Electrodeposited Cu-Sn alloy for electrochemical CO2 reduction to CO/HCOO−, Electrocatalysis, 9, 323, 10.1007/s12678-017-0434-2 Bai, 2017, Exclusive formation of formic acid from CO2 electroreduction by a tunable Pd-Sn alloy, Angew. Chem., 129, 12387, 10.1002/ange.201707098 Wen, 2018, Orbital interactions in Bi-Sn bimetallic electrocatalysts for highly selective electrochemical CO2 reduction toward formate production, Adv. Energy Mater., 8, 1802427, 10.1002/aenm.201802427 Zhang, 2018, Stannate derived bimetallic nanoparticles for electrocatalytic CO2 reduction, J. Mater. Chem., 6, 7851, 10.1039/C8TA02429D Wang, 2000, Bismuth-coated carbon electrodes for anodic stripping voltammetry, Anal. Chem., 72, 3218, 10.1021/ac000108x Zhong, 2016, Bismuth nanodendrites as a high performance electrocatalyst for selective conversion of CO2 to formate, J. Mater. Chem., 4, 13746, 10.1039/C6TA06202D Zhang, 2018, Liquid-phase exfoliated ultrathin Bi nanosheets: uncovering the origins of enhanced electrocatalytic CO2 reduction on two-dimensional metal nanostructure, Nano Energy, 53, 808, 10.1016/j.nanoen.2018.09.053 Yang, 2018, Selective CO2 reduction on 2D mesoporous Bi nanosheets, Adv. Energy Mater., 1801536, 10.1002/aenm.201801536 Su, 2018, Ultrathin bismuth nanosheets as a highly efficient CO2 reduction electrocatalyst, ChemSusChem, 11, 848, 10.1002/cssc.201702229 Han, 2018, Ultrathin bismuth nanosheets from in situ topotactic transformation for selective electrocatalytic CO2 reduction to formate, Nat. Commun., 9, 1320, 10.1038/s41467-018-03712-z Zhang, 2018, Polyethylene glycol induced reconstructing Bi nanoparticle size for stabilized CO2 electroreduction to formate, J. Catal., 365, 63, 10.1016/j.jcat.2018.06.019 Lee, 2018, Selective electrochemical production of formate from carbon dioxide with bismuth-based catalysts in an aqueous electrolyte, ACS Catal., 8, 931, 10.1021/acscatal.7b03242 Zhang, 2018, Controllable synthesis of few-layer bismuth subcarbonate by electrochemical exfoliation for enhanced CO2 reduction performance, Angew. Chem. Int. Ed., 57, 13283, 10.1002/anie.201807466 Gao, 2015, Size-dependent electrocatalytic reduction of CO2 over Pd nanoparticles, J. Am. Chem. Soc., 137, 4288, 10.1021/jacs.5b00046 Podlovchenko, 1994, Electroreduction of carbon dioxide on palladium electrodes at potentials higher than the reversible hydrogen potential, J. Electroanal. Chem., 373, 185, 10.1016/0022-0728(94)03324-2 Stalder, 1984, Electrochemical reduction of aqueous bicarbonate to formate with high current efficiency near the thermodynamic potential at chemically derivatized electrodes, J. Am. Chem. Soc., 106, 3673, 10.1021/ja00324a046 Min, 2015, Pd-catalyzed electrohydrogenation of carbon dioxide to formate: high mass activity at low overpotential and identification of the deactivation pathway, J. Am. Chem. Soc., 137, 4701, 10.1021/ja511890h Phillips, 2018, Sulfide-derived copper for electrochemical conversion of CO2 to formic acid, J. Phys. Chem. Lett., 9, 4407, 10.1021/acs.jpclett.8b01601 Gao, 2016, Partially oxidized atomic cobalt layers for carbon dioxide electroreduction to liquid fuel, Nature, 529, 68, 10.1038/nature16455 Li, 2017, Unlocking the electrocatalytic activity of antimony for CO2 reduction by two-dimensional engineering of the bulk material, Angew. Chem., 129, 14910, 10.1002/ange.201710038 Han, 2019, Self-templated synthesis of hierarchical mesoporous SnO2 nanosheets for selective CO2 reduction, J. Mater. Chem., 7, 1267, 10.1039/C8TA10959A Deng, 2019, Crucial role of surface hydroxyls on the activity and stability in electrochemical CO2 reduction, J. Am. Chem. Soc., 141, 2911, 10.1021/jacs.8b13786 Zhang, 2018, Nickel doping in atomically thin tin disulfide nanosheets enables highly efficient CO2 reduction, Angew. Chem. Int. Ed., 57, 10954, 10.1002/anie.201806043 Liang, 2018, High efficiency electrochemical reduction of CO2 beyond the two-electron transfer pathway on grain boundary rich ultra-small SnO2 nanoparticles, J. Mater. Chem., 6, 10313, 10.1039/C8TA01367E Zhu, 2017, Single-atom electrocatalysts, Angew. Chem. Int. Ed., 56, 13944, 10.1002/anie.201703864 Lei, 2016, Metallic tin quantum sheets confined in graphene toward high-efficiency carbon dioxide electroreduction, Nat. Commun., 7, 12697, 10.1038/ncomms12697 Zhang, 2019, Formation of lattice-dislocated bismuth nanowires on copper foam for enhanced electrocatalytic CO2 reduction at low overpotential, Energy Environ. Sci., 12, 1334, 10.1039/C9EE00018F Zu, 2018, Copper-modulated bismuth nanocrystals alter the formate formation pathway to achieve highly selective CO2 electroreduction, J. Mater. Chem., 6, 16804, 10.1039/C8TA05355C Zhang, 2018, Electrochemical reduction of CO2 on defect-rich Bi derived from Bi2S3 with enhanced formate selectivity, J. Mater. Chem., 6, 4714, 10.1039/C8TA00023A Guo, 2019, Phosphomolybdic acid-assisted growth of ultrathin bismuth nanosheets for enhanced electrocatalytic reduction of CO2 to formate, ChemSusChem, 12, 1091, 10.1002/cssc.201802409 Jiang, 2018, Boosting formate production in electrocatalytic CO2 reduction over wide potential window on Pd surfaces, J. Am. Chem. Soc., 140, 2880, 10.1021/jacs.7b12506 Zhou, 2017, Electrocatalytic CO2 reduction to formate at low overpotentials on electrodeposited Pd films: stabilized performance by suppression of CO formation, ChemSusChem, 10, 1509, 10.1002/cssc.201601870 Klinkova, 2016, Rational design of efficient palladium catalysts for electroreduction of carbon dioxide to formate, ACS Catal., 6, 8115, 10.1021/acscatal.6b01719 Pander, 2019, The importance of morphology on the activity of lead cathodes for the reduction of carbon dioxide to formate, J. Mater. Chem., 7, 4093, 10.1039/C8TA10752A Lee, 2015, Controlling H+ vs CO2 reduction selectivity on Pb electrodes, ACS Catal., 5, 465, 10.1021/cs5017672 Ma, 2019, Promoting electrocatalytic CO2 reduction to formate via sulfur-boosting water activation on indium surfaces, Nat. Commun., 10, 892, 10.1038/s41467-019-08805-x Gu, 2019, Atomically dispersed Fe3+ sites catalyze efficient CO2 electroreduction to CO, Science, 364, 1091, 10.1126/science.aaw7515 Wang, 2018, Regulation of coordination number over single Co sites: triggering the efficient electroreduction of CO2, Angew. Chem. Int. Ed., 57, 1944, 10.1002/anie.201712451 Yan, 2018, Coordinatively unsaturated nickel–nitrogen sites towards selective and high-rate CO2 electroreduction, Energy Environ. Sci., 11, 1204, 10.1039/C8EE00133B Wu, 2015, Achieving highly efficient, selective, and stable CO2 reduction on nitrogen-doped carbon nanotubes, ACS Nano, 9, 5364, 10.1021/acsnano.5b01079 Sharma, 2015, Nitrogen-doped carbon nanotube Arrays for high-efficiency electrochemical reduction of CO2: on the understanding of defects, defect density, and selectivity, Angew. Chem. Int. Ed., 54, 13701, 10.1002/anie.201506062 Fu, 2018, Low overpotential for electrochemically reducing CO2 to CO on nitrogen-doped graphene quantum dots-wrapped single-crystalline gold nanoparticles, ACS Energy Lett, 3, 946, 10.1021/acsenergylett.8b00261 Li, 2014, Electroreduction of carbon monoxide to liquid fuel on oxide-derived nanocrystalline copper, Nature, 508, 504, 10.1038/nature13249 Verdaguer-Casadevall, 2015, Probing the active surface sites for CO reduction on oxide-derived copper electrocatalysts, J. Am. Chem. Soc., 137, 9808, 10.1021/jacs.5b06227 Feng, 2016, A direct grain-boundary-activity correlation for CO electroreduction on Cu nanoparticles, ACS Cent. Sci., 2, 169, 10.1021/acscentsci.6b00022 Feng, 2015, Grain-boundary-dependent CO2 electroreduction activity, J. Am. Chem. Soc., 137, 4606, 10.1021/ja5130513 Mariano, 2017, Selective increase in CO2 electroreduction activity at grain-boundary surface terminations, Science, 358, 1187, 10.1126/science.aao3691 Zhang, 2018, Iodide-derived nanostructured silver promotes selective and efficient carbon dioxide conversion into carbon monoxide, Chem. Commun. (Cambridge, U. K.), 54, 2666, 10.1039/C8CC00984H Luan, 2018, High-performance carbon dioxide electrocatalytic reduction by easily fabricated large-scale silver nanowire arrays, ACS Appl. Mater. Interfaces, 10, 17950, 10.1021/acsami.8b03461 Mistry, 2017, Enhanced carbon dioxide electroreduction to carbon monoxide over defect-rich plasma-activated silver catalysts, Angew. Chem. Int. Ed., 56, 11394, 10.1002/anie.201704613 Liu, 2017, Shape-dependent electrocatalytic reduction of CO2 to CO on triangular silver nanoplates, J. Am. Chem. Soc., 139, 2160, 10.1021/jacs.6b12103 Yu, 2016, Superfine Ag nanoparticle decorated Zn nanoplates for the active and selective electrocatalytic reduction of CO2 to CO, Chem. Commun. (Cambridge, U. K.), 52, 14105, 10.1039/C6CC06466C Ma, 2018, In situ fabrication and reactivation of highly selective and stable Ag catalysts for electrochemical CO2 conversion, ACS Energy Lett., 3, 1301, 10.1021/acsenergylett.8b00472 Zhang, 2018, Electrochemical CO2 reduction with atomic iron-dispersed on nitrogen-doped graphene, Adv. Energy Mater., 8, 1703487, 10.1002/aenm.201703487 Zhao, 2019, Solid-diffusion synthesis of single-atom catalysts directly from bulk metal for efficient CO2 reduction, Joule, 3, 584, 10.1016/j.joule.2018.11.008 Cheng, 2018, Atomically dispersed transition metals on carbon nanotubes with ultrahigh loading for selective electrochemical carbon dioxide reduction, Adv. Mater., 30 Zhao, 2017, Ionic exchange of metal–organic frameworks to access single nickel sites for efficient electroreduction of CO2, J. Am. Chem. Soc., 139, 8078, 10.1021/jacs.7b02736 Urbain, 2018, Tailoring copper foam with silver dendrite catalysts for highly selective carbon dioxide conversion into carbon monoxide, ACS Appl. Mater. Inter., 10, 43650, 10.1021/acsami.8b15379 Dinh, 2018, High rate, selective, and stable electroreduction of CO2 to CO in basic and neutral media, ACS Energy Lett., 2835, 10.1021/acsenergylett.8b01734 Yoon, 2016, Tuning of silver catalyst mesostructure promotes selective carbon dioxide conversion into fuels, Angew. Chem. Int. Ed., 55, 15282, 10.1002/anie.201607942 Ma, 2016, Carbon nanotube containing Ag catalyst layers for efficient and selective reduction of carbon dioxide, J. Mater. Chem., 4, 8573, 10.1039/C6TA00427J Ma, 2016, Selective and efficient reduction of carbon dioxide to carbon monoxide on oxide-derived nanostructured silver electrocatalysts, Angew. Chem. Int. Ed., 55, 9748, 10.1002/anie.201604654 Zhu, 2018, formation of enriched vacancies for enhanced CO2 electrocatalytic reduction over AuCu alloys, ACS Energy Lett., 3, 2144, 10.1021/acsenergylett.8b01286 Zhu, 2018, Tuning structural and compositional effects in Pd–Au nanowires for highly selective and active CO2 electrochemical reduction reaction, Adv. Energy Mater., 1802238, 10.1002/aenm.201802238 Zhao, 2018, Engineering surface amine modifiers of ultrasmall gold nanoparticles supported on reduced graphene oxide for improved electrochemical CO2 reduction, Adv. Energy Mater., 8, 1801400, 10.1002/aenm.201801400 Cho, 2018, The role of adsorbed CN and Cl on an Au electrode for electrochemical CO2 reduction, ACS Catal., 8, 1178, 10.1021/acscatal.7b03449 Cao, 2018, Tuning gold nanoparticles with chelating ligands for highly efficient electrocatalytic CO2 reduction, Angew. Chem. Int. Ed., 57, 12675, 10.1002/anie.201805696 Sun, 2017, Ultrahigh mass activity for carbon dioxide reduction enabled by gold–iron core–shell nanoparticles, J. Am. Chem. Soc., 139, 15608, 10.1021/jacs.7b09251 Rogers, 2017, Synergistic enhancement of electrocatalytic CO2 reduction with gold nanoparticles embedded in functional graphene nanoribbon composite electrodes, J. Am. Chem. Soc., 139, 4052, 10.1021/jacs.6b12217 Kim, 2017, Electrochemical activation of CO2 through atomic ordering transformations of AuCu nanoparticles, J. Am. Chem. Soc., 139, 8329, 10.1021/jacs.7b03516 Liu, 2016, Enhanced electrocatalytic CO2 reduction via field-induced reagent concentration, Nature, 537, 382, 10.1038/nature19060 Won, 2016, Highly efficient, selective, and stable CO2 electroreduction on a hexagonal Zn catalyst, Angew. Chem. Int. Ed., 55, 9297, 10.1002/anie.201602888 Rosen, 2015, Electrodeposited Zn dendrites with enhanced CO selectivity for electrocatalytic CO2 reduction, ACS Catal., 5, 4586, 10.1021/acscatal.5b00922 He, 2018, Achieving the widest range of syngas proportions at high current density over cadmium sulfoselenide nanorods in CO2 electroreduction, Adv. Mater., 30, 1705872, 10.1002/adma.201705872 Zhao, 2018, Tunable and efficient tin modified nitrogen-doped carbon nanofibers for electrochemical reduction of aqueous carbon dioxide, Adv. Energy Mater., 8, 1702524, 10.1002/aenm.201702524 Gu, 2018, Densely packed, ultra small SnO nanoparticles for enhanced activity and selectivity in electrochemical CO2 reduction, Angew. Chem., 130, 2993, 10.1002/ange.201713003 Li, 2017, Tuning Sn-catalysis for electrochemical reduction of CO2 to CO via the core/shell Cu/SnO2 structure, J. Am. Chem. Soc., 139, 4290, 10.1021/jacs.7b00261 Sarfraz, 2016, Cu–Sn bimetallic catalyst for selective aqueous electroreduction of CO2 to CO, ACS Catal., 6, 2842, 10.1021/acscatal.6b00269 Rasul, 2015, A highly selective copper-indium bimetallic electrocatalyst for the electrochemical reduction of aqueous CO2 to CO, Angew. Chem. Int. Ed., 54, 2146, 10.1002/anie.201410233 Wu, 2016, Incorporation of nitrogen defects for efficient reduction of CO2 via two-electron pathway on three-dimensional graphene foam, Nano Lett., 16, 466, 10.1021/acs.nanolett.5b04123 Schouten, 2014, The influence of pH on the reduction of CO and CO2 to hydrocarbons on copper electrodes, J. Electroanal. Chem., 716, 53, 10.1016/j.jelechem.2013.08.033 Kortlever, 2015, Catalysts and reaction pathways for the electrochemical reduction of carbon dioxide, J. Phys. Chem. Lett., 6, 4073, 10.1021/acs.jpclett.5b01559 Peterson, 2010, How copper catalyzes the electroreduction of carbon dioxide into hydrocarbon fuels, Energy Environ. Sci., 3, 1311, 10.1039/c0ee00071j Nie, 2013, Selectivity of CO2 reduction on copper electrodes: the role of the kinetics of elementary steps, Angew. Chem. Int. Ed., 52, 2459, 10.1002/anie.201208320 DeWulf, 1989, Electrochemical and surface studies of carbon dioxide reduction to methane and ethylene at copper electrodes in aqueous solutions, J. Electrochem. Soc., 136, 1686, 10.1149/1.2096993 Xie, 2014, Efficient electrochemical CO2 reduction on a unique chrysanthemum-like Cu nanoflower electrode and direct observation of carbon deposite, Electrochim. Acta, 139, 137, 10.1016/j.electacta.2014.06.034 Lee, 2001, Electrocatalytic activity of Cu electrode in electroreduction of CO2, Electrochim. Acta, 46, 3015, 10.1016/S0013-4686(01)00527-8 Cheng, 2015, Free-energy barriers and reaction mechanisms for the electrochemical reduction of CO on the Cu(100) surface, including multiple layers of explicit solvent at pH 0, J. Phys. Chem. Lett., 6, 4767, 10.1021/acs.jpclett.5b02247 Ulissi, 2017, Machine-learning methods enable exhaustive searches for active bimetallic facets and reveal active site motifs for CO2 reduction, ACS Catal., 7, 6600, 10.1021/acscatal.7b01648 Nie, 2014, Reaction mechanisms of CO2 electrochemical reduction on Cu(111) determined with density functional theory, J. Catal., 312, 108, 10.1016/j.jcat.2014.01.013 Roberts, 2015, High selectivity for ethylene from carbon dioxide reduction over copper nanocube electrocatalysts, Angew. Chem., 127, 5268, 10.1002/ange.201412214 Ren, 2015, Selective electrochemical reduction of carbon dioxide to ethylene and ethanol on copper(I) oxide catalysts, ACS Catal., 5, 2814, 10.1021/cs502128q Lee, 2015, Electrocatalytic production of C3-C4 compounds by conversion of CO2 on a chloride-induced Bi-phasic Cu2O-Cu catalyst, Angew. Chem. Int. Ed., 54, 14701, 10.1002/anie.201505730 Varela, 2016, Tuning the catalytic activity and selectivity of Cu for CO2 electroreduction in the presence of halides, ACS Catal., 6, 2136, 10.1021/acscatal.5b02550 Wang, 2018, Single-atomic Cu with multiple oxygen vacancies on ceria for electrocatalytic CO2 reduction to CH4, ACS Catal., 8, 7113, 10.1021/acscatal.8b01014 Dutta, 2018, Beyond copper in CO2 electrolysis: effective hydrocarbon production on silver-nanofoam catalysts, ACS Catal., 8, 8357, 10.1021/acscatal.8b01738 Zhang, 2018, Electrochemical reduction of carbon dioxide to methanol on hierarchical Pd/SnO2 nanosheets with abundant Pd-O-Sn interfaces, Angew. Chem. Int. Ed., 57, 9475, 10.1002/anie.201804142 Yang, 2019, Selective electroreduction of carbon dioxide to methanol on copper selenide nanocatalysts, Nat. Commun., 10, 677, 10.1038/s41467-019-08653-9 Sun, 2016, Molybdenum–bismuth bimetallic chalcogenide nanosheets for highly efficient electrocatalytic reduction of carbon dioxide to methanol, Angew. Chem. Int. Ed., 55, 6771, 10.1002/anie.201603034 Wu, 2019, Facet-dependent active sites of a single Cu2O particle photocatalyst for CO2 reduction to methanol, Nat. Energy, 4, 957, 10.1038/s41560-019-0490-3 Montoya, 2015, Theoretical insights into a CO dimerization mechanism in CO2 electroreduction, J. Phys. Chem. Lett., 6, 2032, 10.1021/acs.jpclett.5b00722 Li, 2014, Bond-making and breaking between carbon, nitrogen, and oxygen in electrocatalysis, J. Am. Chem. Soc., 136, 15694, 10.1021/ja508649p Bertheussen, 2016, Acetaldehyde as an intermediate in the electroreduction of carbon monoxide to ethanol on oxide-derived copper, Angew. Chem. Int. Ed., 55, 1450, 10.1002/anie.201508851 Liu, 2017, Understanding trends in electrochemical carbon dioxide reduction rates, Nat. Commun., 8, 15438, 10.1038/ncomms15438 Liu, 2019, pH effects on the electrochemical reduction of CO2 towards C2 products on stepped copper, Nat. Commun., 10, 32, 10.1038/s41467-018-07970-9 Calle-Vallejo, 2013, Theoretical considerations on the electroreduction of CO to C2 species on Cu(100) electrodes, Angew. Chem. Int. Ed., 52, 7282, 10.1002/anie.201301470 Pérez-Gallent, 2017, Spectroscopic observation of a hydrogenated CO dimer intermediate during CO reduction on Cu(100) electrodes, Angew. Chem. Int. Ed., 56, 3621, 10.1002/anie.201700580 Cheng, 2017, Full atomistic reaction mechanism with kinetics for CO reduction on Cu(100) from ab initio molecular dynamics free-energy calculations at 298 K, Proc. Natl. Acad. Sci. USA, 114, 1795, 10.1073/pnas.1612106114 Zhuang, 2018, Steering post-C–C coupling selectivity enables high efficiency electroreduction of carbon dioxide to multi-carbon alcohols, Nat. Catal., 1, 421, 10.1038/s41929-018-0084-7 Jung, 2019, Electrochemical fragmentation of Cu2O nanoparticles enhancing selective C-C coupling from CO2 reduction reaction, J. Am. Chem. Soc., 141, 4624, 10.1021/jacs.8b11237 Huang, 2019, Structural sensitivities in bimetallic catalysts for electrochemical CO2 reduction revealed by Ag-Cu nanodimers, J. Am. Chem. Soc., 141, 2490, 10.1021/jacs.8b12381 Morales-Guio, 2018, Improved CO2 reduction activity towards C2+ alcohols on a tandem gold on copper electrocatalyst, Nat. Catal., 1, 764, 10.1038/s41929-018-0139-9 Lv, 2018, A highly porous copper electrocatalyst for carbon dioxide reduction, Adv. Mater., 30, 1803111, 10.1002/adma.201803111 Lee, 2018, Mixed copper states in anodized Cu electrocatalyst for stable and selective ethylene production from CO2 reduction, J. Am. Chem. Soc., 140, 8681, 10.1021/jacs.8b02173 De Luna, 2018, Catalyst electro-redeposition controls morphology and oxidation state for selective carbon dioxide reduction, Nat. Catal., 1, 103, 10.1038/s41929-017-0018-9 Hoang, 2017, Nanoporous copper films by additive-controlled electrodeposition: CO2 reduction catalysis, ACS Catal., 7, 3313, 10.1021/acscatal.6b03613 Song, 2017, Metal-free nitrogen-doped mesoporous carbon for electroreduction of CO2 to ethanol, Angew. Chem. Int. Ed., 56, 10840, 10.1002/anie.201706777 Liu, 2017, Selective electrochemical reduction of carbon dioxide to ethanol on a boron- and nitrogen-Co-doped nanodiamond, Angew. Chem. Int. Ed., 56, 15607, 10.1002/anie.201706311 Scott, 2019, Absence of oxidized phases in Cu under CO reduction conditions, ACS Energy Lett., 4, 803, 10.1021/acsenergylett.9b00172 Song, 2016, High-selectivity electrochemical conversion of CO2 to ethanol using a copper nanoparticle/N-doped graphene electrode, ChemistrySelect, 1, 6055, 10.1002/slct.201601169 Hoang, 2017, Nanoporous copper films by additive-controlled electrodeposition: CO2 reduction catalysis, ACS Catal., 7, 3313, 10.1021/acscatal.6b03613 Ren, 2016, Tuning the selectivity of carbon dioxide electroreduction toward ethanol on oxide-derived CuxZn catalysts, ACS Catal., 6, 8239, 10.1021/acscatal.6b02162 Clark, 2017, Electrochemical CO2 reduction over compressively strained CuAg surface alloys with enhanced multi-carbon oxygenate selectivity, J. Am. Chem. Soc., 139, 15848, 10.1021/jacs.7b08607 McCrory, 2013, Benchmarking heterogeneous electrocatalysts for the oxygen evolution reaction, J. Am. Chem. Soc., 135, 16977, 10.1021/ja407115p Dunwell, 2018, Understanding surface-mediated electrochemical reactions: CO2 reduction and beyond, ACS Catal., 8, 8121, 10.1021/acscatal.8b02181 Fletcher, 2009, Tafel slopes from first principles, J. Solid State Electrochem., 13, 537, 10.1007/s10008-008-0670-8 Li, 2018, Tafel analysis in practice, J. Electroanal. Chem., 826, 117, 10.1016/j.jelechem.2018.08.018 Batchelor-McAuley, 2012, Voltammetry of multi-electron electrode processes of organic species, J. Electroanal. Chem., 669, 73, 10.1016/j.jelechem.2012.01.016 Zhang, 2012, Carbon capture with ionic liquids: overview and progress, Energy Environ. Sci., 5, 6668, 10.1039/c2ee21152a Zhao, 2012, The research progress of CO2 capture with ionic liquids, Chin. J. Chem. Eng., 20, 120, 10.1016/S1004-9541(12)60371-1 Chen, 2017, Electrochemical reduction of carbon dioxide in a monoethanolamine capture medium, ChemSusChem, 10, 4109, 10.1002/cssc.201701075 Feng, 2018, Insights into carbon dioxide electroreduction in ionic liquids: carbon dioxide activation and selectivity tailored by ionic microhabitat, ChemSusChem, 11, 3191, 10.1002/cssc.201801373 Rosen, 2011, Ionic liquid–mediated selective conversion of CO2 to CO at low overpotentials, Science, 334, 643, 10.1126/science.1209786 Weekes, 2018, Electrolytic CO2 reduction in a flow cell, Acc. Chem. Res., 51, 910, 10.1021/acs.accounts.8b00010 Verma, 2016, A gross-margin model for defining technoeconomic benchmarks in the electroreduction of CO2, ChemSusChem, 9, 1972, 10.1002/cssc.201600394 Burdyny, 2019, CO2 reduction on gas-diffusion electrodes and why catalytic performance must be assessed at commercially-relevant conditions, Energy Environ. Sci., 12, 1442, 10.1039/C8EE03134G Thevenon, 2019, In-situ nanostructuring and stabilization of polycrystalline copper by an organic salt additive promotes electrocatalytic CO2 reduction to ethylene, Angew. Chem., 131, 17108, 10.1002/ange.201907935