Abstract
As a greenhouse gas, carbon dioxide in the atmosphere is one of the key contributors to climate change. Many strategies have been proposed to address this issue, such as CO2 capture and sequestration (CCS) and CO2 utilization (CCU). Electroreduction of CO2 into useful fuels is proving to be a promising technology as it not only consumes CO2 but can also store the redundant electrical energy generated from renewable energy sources (e.g., solar, wind, geothermal, wave, etc.) as chemical energy in the produced chemicals. Among all of products from CO2 electroconversion, formic acid is one of the highest value-added chemicals, which is economically feasible for large-scale applications. This paper summarizes the work on inorganic cathode catalysts for the electrochemical reduction of CO2 to formic acid or formate. The reported metal and oxide cathode catalysts are discussed in detail according to their performance including current density, Faradaic efficiency, and working potentials. In addition, the effects of electrolyte, temperature, and pressure are also analyzed. The electroreduction of CO2 to formic acid or formate is still at an early stage with several key challenges that need to be addressed before commercialization. The major challenges and the future directions for developing new electrocatalysts for the reduction of CO2 to formic acid are discussed in this review.
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Lim RJ, Xie M, Sk MA et al (2014) A review on the electrochemical reduction of CO2 in fuel cells, metal electrodes and molecular catalysts. Catal Today 233:169–180
Global Greenhouse Gas Reference Network. http://www.esrl.noaa.gov/gmd/ccgg/trends/. Accessed 10 Mar 2017
Le Quéré C, Andres RJ, Boden T et al (2012) The global carbon budget 1959–2011. Earth Syst Sci Data Discuss 5:1107–1157
Le Quéré C, Moriarty R, Andrew RM et al (2015) Global carbon budget 2014. Earth Syst Sci Data 7:47–85
Le Quéré C, Moriarty R, Andrew RM et al (2015) Global carbon budget 2015. Earth Syst Sci Data 7:349–396
Ampelli C, Perathoner S, Centi G (2015) CO2 utilization: an enabling element to move to a resource-and energy-efficient chemical and fuel production. Philos Trans R Soc Lond A Math Phys Eng Sci 373:20140177
Solomon S, Plattner G-K, Knutti R, Friedlingstein P (2009) Irreversible climate change due to carbon dioxide emissions. Proc Natl Acad Sci USA 106:1704–1709
Agarwal AS, Zhai Y, Hill D, Sridhar N (2011) The electrochemical reduction of carbon dioxide to formate/formic acid: engineering and economic feasibility. ChemSusChem 4:1301–1310
Aresta M (2010) Carbon dioxide as chemical feedstock. Wiley, Hoboken
Berndt ME, Allen DE, Seyfried WE (1996) Reduction of CO2 during serpentinization of olivine at 300 C and 500 bar. Geology 24:351–354
Centi G, Perathoner S (2009) Opportunities and prospects in the chemical recycling of carbon dioxide to fuels. Catal Today 148:191–205
Wang W, Wang SP, Ma XB, Gong JL (2011) Recent advances in catalytic hydrogenation of carbon dioxide. Chem Soc Rev 40:3703–3727
Varghese OK, Paulose M, LaTempa TJ, Grimes CA (2009) High-rate solar photocatalytic conversion of CO2 and water vapor to hydrocarbon fuels. Nano Lett 9:731–737
Roy SC, Varghese OK, Paulose M, Grimes CA (2010) Toward solar fuels: photocatalytic conversion of carbon dioxide to hydrocarbons. ACS Nano 4:1259–1278
Sydney EB, Sturm W, de Carvalho JC et al (2010) Potential carbon dioxide fixation by industrially important microalgae. Bioresour Technol 101:5892–5896
Wang B, Li YQ, Wu N, Lan CQ (2008) CO2 bio-mitigation using microalgae. Appl Microbiol Biotechnol 79:707–718
Collombdunandsauthier MN, Deronzier A, Ziessel R (1994) Electrocatalytic reduction of carbon-dioxide with mono(bipyridine)carbonylruthenium complexes in solution or as polymeric thin-films. Inorg Chem 33:2961–2967
Kuhl KP, Cave ER, Abram DN, Jaramillo TF (2012) New insights into the electrochemical reduction of carbon dioxide on metallic copper surfaces. Energy Environ Sci 5:7050–7059
Peterson AA, Abild-Pedersen F, Studt F, Rossmeisl J, Norskov JK (2010) How copper catalyzes the electroreduction of carbon dioxide into hydrocarbon fuels. Energy Environ Sci 3:1311–1315
Finn C, Schnittger S, Yellowlees LJ, Love JB (2012) Molecular approaches to the electrochemical reduction of carbon dioxide. Chem Commun (Camb) 48:1392–1399
Qiao J, Liu Y, Hong F, Zhang J (2014) A review of catalysts for the electroreduction of carbon dioxide to produce low-carbon fuels. Chem Soc Rev 43:631–675
Finn C, Schnittger S, Yellowlees LJ, Love JB (2012) Molecular approaches to the electrochemical reduction of carbon dioxide. Chem Commun 48:1392–1399
Rice C, Ha S, Masel R, Waszczuk P, Wieckowski A, Barnard T (2002) Direct formic acid fuel cells. J Power Sources 111:83–89
Zhu Y, Ha SY, Masel RI (2004) High power density direct formic acid fuel cells. J Power Sources 130:8–14
Yu X, Pickup PG (2008) Recent advances in direct formic acid fuel cells (DFAFC). J Power Sources 182:124–132
Zelitch I, Ochoa S (1953) Oxidation and reduction of glycolic and glyoxylic acids in plants I. Glycolic acid oxidase. J Biol Chem 201:707–718
Grasemann M, Laurenczy G (2012) Formic acid as a hydrogen source–recent developments and future trends. Energy Environ Sci 5:8171–8181
Genovese C, Ampelli C, Perathoner S, Centi G (2013) Electrocatalytic conversion of CO 2 on carbon nanotube-based electrodes for producing solar fuels. J Catal 308:237–249
Shown I, Hsu H-C, Chang Y-C et al (2014) Highly efficient visible light photocatalytic reduction of CO2 to hydrocarbon fuels by Cu-nanoparticle decorated graphene oxide. Nano Lett 14:6097–6103
De Falco M, Capocelli M, Centi G (2016) Dimethyl ether production from CO2 rich feedstocks in a one-step process: thermodynamic evaluation and reactor simulation. Chem Eng J 294:400–409
Subramanian K, Asokan K, Jeevarathinam D, Chandrasekaran M (2007) Electrochemical membrane reactor for the reduction of carbondioxide to formate. J Appl Electrochem 37:255–260
Song CS (2006) Global challenges and strategies for control, conversion and utilization of CO2 for sustainable development involving energy, catalysis, adsorption and chemical processing. Catal Today 115:2–32
Rosen BA, Salehi-Khojin A, Thorson MR et al (2011) Ionic liquid–mediated selective conversion of CO2 to CO at low overpotentials. Science 334:643–644
Li CW, Kanan MW (2012) CO2 reduction at low overpotential on Cu electrodes resulting from the reduction of thick Cu2O films. J Am Chem Soc 134:7231–7234
Lu Q, Rosen J, Zhou Y et al (2014) A selective and efficient electrocatalyst for carbon dioxide reduction. Nat Commun 5:3242
Zhu W, Zhang Y-J, Zhang H et al (2014) Active and selective conversion of CO2 to CO on ultrathin Au nanowires. J Am Chem Soc 136:16132–16135
Chen Y, Kanan MW (2012) Tin oxide dependence of the CO2 reduction efficiency on tin electrodes and enhanced activity for tin/tin oxide thin-film catalysts. J Am Chem Soc 134:1986–1989
Innocent B, Liaigre D, Pasquier D, Ropital F, Léger J-M, Kokoh K (2009) Electro-reduction of carbon dioxide to formate on lead electrode in aqueous medium. J Appl Electrochem 39:227–232
Barton Cole E, Lakkaraju PS, Rampulla DM, Morris AJ, Abelev E, Bocarsly AB (2010) Using a one-electron shuttle for the multielectron reduction of CO2 to methanol: kinetic, mechanistic, and structural insights. J Am Chem Soc 132:11539–11551
Le M, Ren M, Zhang Z, Sprunger PT, Kurtz RL, Flake JC (2011) Electrochemical reduction of CO2 to CH3OH at copper oxide surfaces. J Electrochem Soc 158:E45–E49
Yan Y, Zeitler EL, Gu J, Hu Y, Bocarsly AB (2013) Electrochemistry of aqueous pyridinium: exploration of a key aspect of electrocatalytic reduction of CO2 to methanol. J Am Chem Soc 135:14020–14023
Back S, Kim H, Jung Y (2015) Selective heterogeneous CO2 electroreduction to methanol. ACS Catal 5:965–971
Reske R, Duca M, Oezaslan M, Schouten KJP, Koper MT, Strasser P (2013) Controlling catalytic selectivities during CO2 electroreduction on thin Cu metal overlayers. J Phys Chem Lett 4:2410–2413
Roberts FS, Kuhl KP, Nilsson A (2015) High selectivity for ethylene from carbon dioxide reduction over copper nanocube electrocatalysts. Angew Chem 127:5268–5271
Peterson AA, Nørskov JK (2012) Activity descriptors for CO2 electroreduction to methane on transition-metal catalysts. J Phys Chem Lett 3:251–258
Manthiram K, Beberwyck BJ, Alivisatos AP (2014) Enhanced electrochemical methanation of carbon dioxide with a dispersible nanoscale copper catalyst. J Am Chem Soc 136:13319–13325
Jhong H-R, Ma S, Kenis PJ (2013) Electrochemical conversion of CO2 to useful chemicals: current status, remaining challenges, and future opportunities. Curr Opin Chem Eng 2:191–199
Zhu DD, Liu JL, Qiao SZ (2016) Recent advances in inorganic heterogeneous electrocatalysts for reduction of carbon dioxide. Adv Mater 28:3423–3452
Chaplin R, Wragg A (2003) Effects of process conditions and electrode material on reaction pathways for carbon dioxide electroreduction with particular reference to formate formation. J Appl Electrochem 33:1107–1123
Lu X, Leung DYC, Wang H, Leung MKH, Xuan J (2014) Electrochemical reduction of carbon dioxide to formic acid. ChemElectroChem 1:836–849
Taheri A, Berben LA (2016) Making C–H bonds with CO2: production of formate by molecular electrocatalysts. Chem Commun 52:1768–1777
Oloman C, Li H (2008) Electrochemical processing of carbon dioxide. ChemSusChem 1:385–391
Kaneco S, Iwao R, Iiba K, Ohta K, Mizuno T (1998) Electrochemical conversion of carbon dioxide to formic acid on Pb in KOH/methanol electrolyte at ambient temperature and pressure. Energy 23:1107–1112
Lide DR (2004) CRC handbook of chemistry and physics. CRC Press, Boca Raton
Köleli F, Balun D (2004) Reduction of CO2 under high pressure and high temperature on Pb-granule electrodes in a fixed-bed reactor in aqueous medium. Appl Catal A 274:237–242
Jing W, Hua W, Zhenzhen H, Jinyu H (2015) Electrodeposited porous Pb electrode with improved electrocatalytic performance for the electroreduction of CO2 to formic acid. Front Chem Sci Eng 9:57–63
Kwon Y, Lee J (2010) Formic acid from carbon dioxide on nanolayered electrocatalyst. Electrocatalysis 1:108–115
Alvarez-Guerra M, Quintanilla S, Irabien A (2012) Conversion of carbon dioxide into formate using a continuous electrochemical reduction process in a lead cathode. Chem Eng J 207:278–284
Lee CH, Kanan MW (2014) Controlling H+ vs CO2 reduction selectivity on Pb electrodes. ACS Catal 5:465–469
Back S, Kim J-H, Kim Y-T, Jung Y (2016) On the mechanism of high product selectivity for HCOOH using Pb in CO2 electroreduction. Phys Chem Chem Phys 18:9652–9657
Lv W, Zhang R, Gao P, Lei L (2014) Studies on the faradaic efficiency for electrochemical reduction of carbon dioxide to formate on tin electrode. J Power Sources 253:276–281
Zhang R, Lv W, Li G, Mezaal MA, Li X, Lei L (2014) Retarding of electrochemical oxidation of formate on the platinum anode by a coat of Nafion membrane. J Power Sources 272:303–310
Wu J, Harris B, Sharma PP, Zhou X-D (2013) Morphological stability of Sn electrode for electrochemical conversion of CO2. ECS Trans 58:71–80
Wang Q, Dong H, Yu H (2014) Development of rolling tin gas diffusion electrode for carbon dioxide electrochemical reduction to produce formate in aqueous electrolyte. J Power Sources 271:278–284
Prakash GS, Viva FA, Olah GA (2013) Electrochemical reduction of CO2 over Sn-Nafion® coated electrode for a fuel-cell-like device. J Power Sources 223:68–73
Wang Q, Dong H, Yu H (2014) Fabrication of a novel tin gas diffusion electrode for electrochemical reduction of carbon dioxide to formic acid. RSC Adv 4:59970–59976
Lei F, Liu W, Sun Y et al (2016) Metallic tin quantum sheets confined in graphene toward high-efficiency carbon dioxide electroreduction. Nat Commun 7:12697
Zhang S, Kang P, Meyer TJ (2014) Nanostructured tin catalysts for selective electrochemical reduction of carbon dioxide to formate. J Am Chem Soc 136:1734–1737
Zhao C, Wang J (2016) Electrochemical reduction of CO2 to formate in aqueous solution using electro-deposited Sn catalysts. Chem Eng J 293:161–170
Du D, Lan R, Humphreys J et al (2016) Achieving both high selectivity and current density for CO2 reduction to formate on nanoporous tin foam electrocatalysts. ChemistrySelect 1:1711–1715
Wang Y, Zhou J, Lv W, Fang H, Wang W (2016) Electrochemical reduction of CO2 to formate catalyzed by electroplated tin coating on copper foam. Appl Surf Sci 362:394–398
Choi SY, Jeong SK, Kim HJ, Baek IH, Park KT (2016) Electrochemical reduction of carbon dioxide to formate on tin-lead alloys. ACS Sustain Chem Eng 4:1311–1318
Wu J, Risalvato FG, Ma S, Zhou X-D (2014) Electrochemical reduction of carbon dioxide III. The role of oxide layer thickness on the performance of Sn electrode in a full electrochemical cell. J Mater Chem A 2:1647–1651
Zhao C, Wang J, Goodenough JB (2016) Comparison of electrocatalytic reduction of CO2 to HCOOH with different tin oxides on carbon nanotubes. Electrochem Commun 65:9–13
Li F, Chen L, Knowles GP, MacFarlane DR, Zhang J (2017) Hierarchical mesoporous SnO2 Nanosheets on carbon cloth: a robust and flexible electrocatalyst for CO2 reduction with high efficiency and selectivity. Angew Chem 129:520–524
Kumar B, Atla V, Brian JP et al (2017) Reduced SnO2 porous nanowires with a high density of grain boundaries as catalysts for efficient electrochemical CO2-into-HCOOH conversion. Angew Chem Int Ed 56:3645–3649
Kapusta S, Hackerman N (1983) The electroreduction of carbon dioxide and formic acid on tin and indium electrodes. J Electrochem Soc 130:607–613
Hori Y, Kikuchi K, Suzuki S (1985) Production of CO and CH4 in electrochemical reduction of CO2 at metal electrodes in aqueous hydrogencarbonate solution. Chem Lett 14:1695–1698
Ikeda S, Takagi T, Ito K (1987) Selective formation of formic acid, oxalic acid, and carbon monoxide by electrochemical reduction of carbon dioxide. Bull Chem Soc Jpn 60:2517–2522
Martindale BC, Compton RG (2012) Formic acid electro-synthesis from carbon dioxide in a room temperature ionic liquid. Chem Commun 48:6487–6489
Rosen BA, Zhu W, Kaul G, Salehi-Khojin A, Masel RI (2013) Water enhancement of CO2 conversion on silver in 1-ethyl-3-methylimidazolium tetrafluoroborate. J Electrochem Soc 160:H138–H141
Watkins JD, Bocarsly AB (2014) Direct reduction of carbon dioxide to formate in high-gas-capacity ionic liquids at post-transition-metal electrodes. ChemSusChem 7:284–290
Cherevko S, Zeradjanin AR, Keeley GP, Mayrhofer KJ (2014) A comparative study on gold and platinum dissolution in acidic and alkaline media. J Electrochem Soc 161:H822–H830
Rand D, Woods R (1972) A study of the dissolution of platinum, palladium, rhodium and gold electrodes in 1 M sulphuric acid by cyclic voltammetry. J Electroanal Chem Interfacial Electrochem 35:209–218
Yadav VSK, Purkait MK (2015) Electrochemical reduction of CO2 to HCOOH using zinc and cobalt oxide as electrocatalysts. New J Chem 39:7348–7354
Yadav VSK, Purkait MK (2016) Solar cell driven electrochemical process for the reduction of CO2 to HCOOH on Zn and Sn electrocatalysts. Sol Energy 124:177–183
Hori Y, Takahashi I, Koga O, Hoshi N (2002) Selective formation of C2 compounds from electrochemical reduction of CO2 at a series of copper single crystal electrodes. J Phys Chem B 106:15–17
Kaneco S, Hiei N-H, Xing Y et al (2003) High-efficiency electrochemical CO2-to-methane reduction method using aqueous KHCO3 media at less than 273 K. J Solid State Electrochem 7:152–156
Yim K-J, Song D-K, Kim C-S et al (2015) Selective, high efficiency reduction of CO2 in a non-diaphragm-based electrochemical system at low applied voltage. RSC Adv 5:9278–9282
Kaneco S, Iiba K, Hiei N-H, Ohta K, Mizuno T, Suzuki T (1999) Electrochemical reduction of carbon dioxide to ethylene with high Faradaic efficiency at a Cu electrode in CsOH/methanol. Electrochim Acta 44:4701–4706
Takahashi I, Koga O, Hoshi N, Hori Y (2002) Electrochemical reduction of CO2 at copper single crystal Cu(S)-[n(111) × (111)] and Cu(S)-[n(110) × (100)] electrodes. J Electroanal Chem 533:135–143
Kaneco S, Katsumata H, Suzuki T, Ohta K (2006) Electrochemical reduction of CO2 to methane at the Cu electrode in methanol with sodium supporting salts and its comparison with other alkaline salts. Energy Fuels 20:409–414
Sen S, Liu D, Palmore GTR (2014) Electrochemical reduction of CO2 at copper nanofoams. ACS Catal 4:3091–3095
Guo S, Zhao S, Gao J et al (2017) Cu-CDots nanocorals as electrocatalyst for highly efficient CO2 reduction to formate. Nanoscale 9:298–304
Zhao Y, Nakamura R, Kamiya K, Nakanishi S, Hashimoto K (2013) Nitrogen-doped carbon nanomaterials as non-metal electrocatalysts for water oxidation. Nat Commun 4:1–7
Gong K, Du F, Xia Z, Durstock M, Dai L (2009) Nitrogen-doped carbon nanotube arrays with high electrocatalytic activity for oxygen reduction. Science 323:760–764
Liu R, Wu D, Feng X, Müllen K (2010) Nitrogen-doped ordered mesoporous graphitic arrays with high electrocatalytic activity for oxygen reduction. Angew Chem 122:2619–2623
Wu J, Yadav RM, Liu M et al (2015) Achieving highly efficient, selective, and stable CO2 reduction on nitrogen-doped carbon nanotubes. ACS Nano 9:5364–5371
Sharma PP, Wu J, Yadav RM et al (2015) Nitrogen-Doped Carbon Nanotube Arrays for High-Efficiency Electrochemical Reduction of CO2: on the Understanding of Defects, Defect Density, and Selectivity. Angew Chem 127:13905–13909
Kumar B, Asadi M, Pisasale D et al (2013) Renewable and metal-free carbon nanofibre catalysts for carbon dioxide reduction. Nat Commun 4:2819–2826
Zhang S, Kang P, Ubnoske S et al (2014) Polyethylenimine-enhanced electrocatalytic reduction of CO2 to formate at nitrogen-doped carbon nanomaterials. J Am Chem Soc 136:7845–7848
Wang H, Chen Y, Hou X, Ma C, Tan T (2016) Nitrogen-doped graphenes as efficient electrocatalysts for the selective reduction of carbon dioxide to formate in aqueous solution. Green Chem 18:3250–3256
Sreekanth N, Nazrulla MA, Vineesh TV, Sailaja K, Phani KL (2015) Metal-free boron-doped graphene for selective electroreduction of carbon dioxide to formic acid/formate. Chem Commun 51:16061–16064
Gao S, Jiao X, Sun Z et al (2016) Ultrathin Co3O4 Layers Realizing Optimized CO2 Electroreduction to Formate. Angew Chem Int Ed 55:698–702
Gao S, Lin Y, Jiao X et al (2016) Partially oxidized atomic cobalt layers for carbon dioxide electroreduction to liquid fuel. Nature 529:68–71
Gao S, Sun Z, Liu W et al (2017) Atomic layer confined vacancies for atomic-level insights into carbon dioxide electroreduction. Nat Commun 8:14503–14511
Kortlever R, Balemans C, Kwon Y, Koper MT (2015) Electrochemical CO2 reduction to formic acid on a Pd-based formic acid oxidation catalyst. Catal Today 244:58–62
Rahaman M, Dutta A, Broekmann P (2017) Size-dependent activity of palladium nanoparticles: efficient conversion of CO2 into formate at low overpotentials. ChemSusChem. doi:10.1002/cssc.201601778
Isaacs M, Armijo F, Ramírez G et al (2005) Electrochemical reduction of CO2 mediated by poly-M-aminophthalocyanines (M = Co, Ni, Fe): poly-Co-tetraaminophthalocyanine, a selective catalyst. J Mol Catal A Chem 229:249–257
Isaacs M, Canales J, Aguirre M et al (2002) Electrocatalytic reduction of CO2 by aza-macrocyclic complexes of Ni (II), Co (II), and Cu (II). Theoretical contribution to probable mechanisms. Inorg Chim Acta 339:224–232
Pérez-Rodríguez S, Barreras F, Pastor E, Lázaro M (2016) Electrochemical reactors for CO2 reduction: from acid media to gas phase. Int J Hydrog Energy 41:19756–19765
Pérez-Rodríguez S, García G, Calvillo L, Celorrio V, Pastor E, Lázaro M (2011) Carbon-supported Fe catalysts for CO2 electroreduction to high-added value products: a DEMS study: effect of the functionalization of the support. Int J Electrochem. doi:10.4061/2011/249804
Ampelli C, Genovese C, Marepally B, Papanikolaou G, Perathoner S, Centi G (2015) Electrocatalytic conversion of CO2 to produce solar fuels in electrolyte or electrolyte-less configurations of PEC cells. Faraday Discuss 183:125–145
Reda T, Plugge CM, Abram NJ, Hirst J (2008) Reversible interconversion of carbon dioxide and formate by an electroactive enzyme. Proc Natl Acad Sci USA 105:10654–10658
Wu J, Risalvato FG, Ke F-S, Pellechia P, Zhou X-D (2012) Electrochemical reduction of carbon dioxide I. Effects of the electrolyte on the selectivity and activity with Sn electrode. J Electrochem Soc 159:F353–F359
Won DH, Choi CH, Chung J, Chung MW, Kim EH, Woo SI (2015) Rational design of a hierarchical tin dendrite electrode for efficient electrochemical reduction of CO2. ChemSusChem 8:3092–3098
Tezuka M, Yajima T, Tsuchiya A, Matsumoto Y, Uchida Y, Hidai M (1982) Electroreduction of carbon dioxide catalyzed by iron-sulfur cluster compounds [Fe4S4(SR)4]2. J Am Chem Soc 104:6834–6836
Ishida H, Tanaka H, Tanaka K, Tanaka T (1987) Selective formation of HCOO− in the electrochemical CO2 reduction catalyzed by Ru(bpy)2(CO) 2+2 (bpy = 2,2′-bipyridine). J Chem Soc Chem Commun 2:131–132
Ali MM, Sato H, Mizukawa T, Tsuge K, Haga M, Tanaka K (1998) Selective formation of HCO2 − and C2O4 2− in electrochemical reduction of CO2 catalyzed by mono- and di-nuclear ruthenium complexes. Chemical Communications 2:249–250
Ahn ST, Bielinski EA, Lane EM et al (2015) Enhanced CO2 electroreduction efficiency through secondary coordination effects on a pincer iridium catalyst. Chem Commun 51:5947–5950
Kortlever R, Peters I, Koper S, Koper MT (2015) Electrochemical CO2 reduction to formic acid at low overpotential and with high faradaic efficiency on carbon supported bimetallic Pd-Pt nanoparticles. ACS Catal 5:3916–3923
Feroci M, Orsini M, Rossi L, Sotgiu G, Inesi A (2007) Electrochemically promoted C–N bond formation from amines and CO2 in ionic liquid BMIm–BF4: synthesis of carbamates. J Org Chem 72:200–203
Snuffin LL, Whaley LW, Yu L (2011) Catalytic electrochemical reduction of CO2 in ionic liquid EMIMBF3Cl. J Electrochem Soc 158:F155–F158
Grace AN, Choi SY, Vinoba M et al (2014) Electrochemical reduction of carbon dioxide at low overpotential on a polyaniline/Cu2O nanocomposite based electrode. Appl Energy 120:85–94
Eneau-Innocent B, Pasquier D, Ropital F, Léger J-M, Kokoh K (2010) Electroreduction of carbon dioxide at a lead electrode in propylene carbonate: a spectroscopic study. Appl Catal B 98:65–71
Jitaru M, Lowy D, Toma M, Toma B, Oniciu L (1997) Electrochemical reduction of carbon dioxide on flat metallic cathodes. J Appl Electrochem 27:875–889
Ogura K, Ferrell JR III, Cugini AV, Smotkin ES, Salazar-Villalpando MD (2010) CO2 attraction by specifically adsorbed anions and subsequent accelerated electrochemical reduction. Electrochim Acta 56:381–386
Bhugun I, Lexa D, Saveant JM (1996) Catalysis of the electrochemical reduction of carbon dioxide by iron(0) porphyrins. Synergistic effect of Lewis acid cations. J Phys Chem 100:19981–19985
Thorson MR, Siil KI, Kenis PJ (2013) Effect of cations on the electrochemical conversion of CO2 to CO. J Electrochem Soc 160:F69–F74
Ryu J, Andersen T, Eyring H (1972) Electrode reduction kinetics of carbon dioxide in aqueous solution. J Phys Chem 76:3278–3286
Mizuno T, Ohta K, Sasaki A, Akai T, Hirano M, Kawabe A (1995) Effect of temperature on electrochemical reduction of high-pressure CO2 with In, Sn, and Pb electrodes. Energy Sources 17:503–508
Ito K, Ikeda S, Okabe M (1980) Electrochemical reduction of carbon-dioxide dissolved under high-pressure 1. in an aqueous-solution of inorganic salt. Denki Kagaku 48:247–252
Ito K, Ikeda S, Iida T, Niwa H (1981) Electrochemical reduction of carbon-dioxide dissolved under high-pressure 2. in aqueous-solution of tetraalkylammonium salts. Denki Kagaku 49:106–112
Ito K, Ikeda S, Iida T, Nomura A (1982) Electrochemical reduction of carbon-dioxide dissolved under high-pressure 3. in non-aqueous electrolytes. Denki Kagaku 50:463–469
Asano K, Hibino T, Iwahara H (1995) A novel solid oxide fuel cell system using the partial oxidation of methane. J Electrochem Soc 142:3241–3245
Todoroki M, Hara K, Kudo A, Sakata T (1995) Electrochemical reduction of high pressure CO2 at Pb, Hg and In electrodes in an aqueous KHCO3 solution. J Electroanal Chem 394:199–203
Scialdone O, Galia A, Nero GL, Proietto F, Sabatino S, Schiavo B (2016) Electrochemical reduction of carbon dioxide to formic acid at a tin cathode in divided and undivided cells: effect of carbon dioxide pressure and other operating parameters. Electrochim Acta 199:332–341
Martín AJ, Larrazábal GO, Pérez-Ramírez J (2015) Towards sustainable fuels and chemicals through the electrochemical reduction of CO 2: lessons from water electrolysis. Green Chem 17:5114–5130
Hirunsit P (2013) Electroreduction of carbon dioxide to methane on copper, copper–silver, and copper–gold catalysts: a DFT study. J Phys Chem C 117:8262–8268
Kahl T, Schröder K, Lawrence F, Marshall W, Höke H, Jäckh R (2002) Ullmann’s Encyclopedia of industrial chemistry. Wiley, Weinheim
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One of the authors (Du) thanks the University of Warwick for a PhD studentship.
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Du, D., Lan, R., Humphreys, J. et al. Progress in inorganic cathode catalysts for electrochemical conversion of carbon dioxide into formate or formic acid. J Appl Electrochem 47, 661–678 (2017). https://doi.org/10.1007/s10800-017-1078-x
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DOI: https://doi.org/10.1007/s10800-017-1078-x