Substantial progress has recently been made in the general understanding of the interfacial CO2 reduction reaction (CO2RR) in electro- and photocatalysis, but the influence of the local chemical environment and its effects on the catalytic interface at the molecular level remains largely elusive. Here, we introduce a classification scheme to group different aspects influencing the interfacial CO2RR thermodynamics and kinetics. This categorization allows a systematic survey of the literature focusing on the local chemical environment encompassing surface effects (adsorbates, support), solution interactions (electrolyte constituents) and three-dimensional chemical surroundings (polymers, metal organic frameworks (MOFs), covalent organic frameworks (COFs)). The review concludes with an outlook discussing possible future concepts for next-generation electrocatalytic and photocatalytic CO2RR.
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Artz, J. et al. Sustainable conversion of carbon dioxide: an integrated review of catalysis and life cycle assessment. Chem. Rev. 118, 434–504 (2018).
Wang, W.-H., Himeda, Y., Muckerman, J. T., Manbeck, G. F. & Fujita, E. CO2 hydrogenation to formate and methanol as an alternative to photo- and electrochemical CO2 reduction. Chem. Rev. 115, 12936–12973 (2015).
Liu, Q., Wu, L., Jackstell, R. & Beller, M. Using carbon dioxide as a building block in organic synthesis. Nat. Commun. 6, 5933 (2015).
Kuhl, K. P. et al. Electrocatalytic conversion of carbon dioxide to methane and methanol on transition metal surfaces. J. Am. Chem. Soc. 136, 14107–14113 (2014). This paper highlights that multiple transition metals beyond Cu facilitate the conversion of CO2 to reduced species beyond CO.
Mezzavilla, S., Horch, S., Stephens, I. E. L., Seger, B. & Chorkendorff, I. Structure sensitivity in the electrocatalytic reduction of CO2 with gold catalysts. Angew. Chem. Int. Ed. 58, 3774–3778 (2019).
Mariano, R. G., McKelvey, K., White, H. S. & Kanan, M. W. Selective increase in CO2 electroreduction activity at grain-boundary surface terminations. Science 358, 1187–1192 (2017).
Hall, A. S., Yoon, Y., Wuttig, A. & Surendranath, Y. Mesostructure-induced selectivity in CO2 reduction catalysis. J. Am. Chem. Soc. 137, 14834–14837 (2015).
Hansen, H. A., Varley, J. B., Peterson, A. A. & Nørskov, J. K. Understanding trends in the electrocatalytic activity of metals and enzymes for CO2 reduction to CO. J. Phys. Chem. Lett. 4, 388–392 (2013). The reactivity trends of a series of metals was rationalized via linear scaling relationships of the COOH and CO binding energy and compared to carbon monoxide dehydrogenase, which overcomes these limitations via NCI effects.
Akhade, S. A., Luo, W., Nie, X., Asthagiri, A. & Janik, M. J. Theoretical insight on reactivity trends in CO2 electroreduction across transition metals. Catal. Sci. Technol. 6, 1042–1053 (2016).
Bagger, A., Arnarson, L., Hansen, M. H., Spohr, E. & Rossmeisl, J. Electrochemical CO reduction: a property of the electrochemical interface. J. Am. Chem. Soc. 141, 1506–1514 (2019).
Calle-Vallejo, F. & Koper, M. T. M. Accounting for bifurcating pathways in the screening for CO2 reduction catalysts. ACS Catal. 7, 7346–7351 (2017).
Nie, X., Esopi, M. R., Janik, M. J. & Asthagiri, A. Selectivity of CO2 reduction on copper electrodes: the role of the kinetics of elementary steps. Angew. Chem. Int. Ed. 52, 2459–2462 (2013).
Dalle, K. E. et al. Electro- and solar-driven fuel synthesis with first row transition metal complexes. Chem. Rev. 119, 2752–2875 (2019).
Rao, H., Schmidt, L. C., Bonin, J. & Robert, M. Visible-light-driven methane formation from CO2 with a molecular iron catalyst. Nature 548, 74–77 (2017).
Wu, Y., Jiang, Z., Lu, X., Liang, Y. & Wang, H. Domino electroreduction of CO2 to methanol on a molecular catalyst. Nature 575, 639–642 (2019).
Shen, J. et al. Electrocatalytic reduction of carbon dioxide to carbon monoxide and methane at an immobilized cobalt protoporphyrin. Nat. Commun. 6, 8177 (2015).
Berggren, G. et al. Biomimetic assembly and activation of [FeFe]-hydrogenases. Nature 499, 66–69 (2013).
Bassegoda, A., Madden, C., Wakerley, D. W., Reisner, E. & Hirst, J. Reversible interconversion of CO2 and formate by a molybdenum-containing formate dehydrogenase. J. Am. Chem. Soc. 136, 15473–15476 (2014).
Shin, W., Lee, S. H., Shin, J. W., Lee, S. P. & Kim, Y. Highly selective electrocatalytic conversion of CO2 to CO at −0.57 V (NHE) by carbon monoxide dehydrogenase from Moorella thermoacetica. J. Am. Chem. Soc. 125, 14688–14689 (2003).
Evans, R. M. et al. Mechanism of hydrogen activation by [NiFe] hydrogenases. Nat. Chem. Biol. 12, 46–50 (2016).
Seh, Z. W. et al. Combining theory and experiment in electrocatalysis: insights into materials design. Science 355, eaad4998 (2017).
Birdja, Y. Y. et al. Advances and challenges in understanding the electrocatalytic conversion of carbon dioxide to fuels. Nat. Energy 4, 732–745 (2019). Review giving an overview on the electrocatalytic conversion of CO2.
Nitopi, S. et al. Progress and perspectives of electrochemical CO2 reduction on copper in aqueous electrolyte. Chem. Rev. 119, 7610–7672 (2019). In-depth review of electrocatalytic CO2 reduction on copper.
Marszewski, M., Cao, S., Yu, J. & Jaroniec, M. Semiconductor-based photocatalytic CO2 conversion. Mater. Horiz. 2, 261–278 (2015).
Chen, Y. & Mu, T. Conversion of CO2 to value-added products mediated by ionic liquids. Green Chem. 21, 2544–2574 (2019).
Handoko, A. D., Wei, F., Jenndy, Yeo, B. S. & Seh, Z. W. Understanding heterogeneous electrocatalytic carbon dioxide reduction through operando techniques. Nat. Catal. 1, 922–934 (2018).
Sun, L., Reddu, V., Fisher, A. C. & Wang, X. Electrocatalytic reduction of carbon dioxide: opportunities with heterogeneous molecular catalysts. Energy Environ. Sci. 13, 374–403 (2020).
Nam, D.-H. et al. Molecular enhancement of heterogeneous CO2 reduction. Nat. Mater. 19, 266–276 (2020).
Nørskov, J. K. et al. Trends in the exchange current for hydrogen evolution. J. Electrochem. Soc. 152, J23–J26 (2005).
Rodriguez, P., Kwon, Y. & Koper, M. T. M. The promoting effect of adsorbed carbon monoxide on the oxidation of alcohols on a gold catalyst. Nat. Chem. 4, 177–182 (2012).
Tong, Y. J. Unconventional promoters of catalytic activity in electrocatalysis. Chem. Soc. Rev. 41, 8195–8209 (2012).
Cave, E. R. et al. Trends in the catalytic activity of hydrogen evolution during CO2 electroreduction on transition metals. ACS Catal. 8, 3035–3040 (2018).
Jovanov, Z. P. et al. Opportunities and challenges in the electrocatalysis of CO2 and CO reduction using bifunctional surfaces: a theoretical and experimental study of Au–Cd alloys. J. Catal. 343, 215–231 (2016).
Le Duff, C. S., Lawrence, M. J. & Rodriguez, P. Role of the adsorbed oxygen species in the selective electrochemical reduction of CO2 to alcohols and carbonyls on copper electrodes. Angew. Chem. Int. Ed. 56, 12919–12924 (2017).
Bohra, D. et al. Lateral adsorbate interactions inhibit HCOO− while promoting CO selectivity for CO2 electrocatalysis on silver. Angew. Chem. Int. Ed. 58, 1345–1349 (2019).
Wuttig, A., Ryu, J. & Surendranath, Y. Electrolyte competition controls surface binding of CO intermediates to CO2 reduction catalysts. Preprint at https://doi.org/10.26434/chemrxiv.7929038.v2 (2019).
Gunathunge, C. M., Ovalle, V. J., Li, Y., Janik, M. J. & Waegele, M. M. Existence of an electrochemically inert CO population on Cu electrodes in alkaline pH. ACS Catal. 8, 7507–7516 (2018).
Wuttig, A., Yaguchi, M., Motobayashi, K., Osawa, M. & Surendranath, Y. Inhibited proton transfer enhances Au-catalyzed CO2-to-fuels selectivity. Proc. Natl Acad. Sci. USA 113, E4585–E4593 (2016).
Thevenon, A., Rosas-Hernández, A., Peters, J. C. & Agapie, T. In-situ nanostructuring and stabilization of polycrystalline copper by an organic salt additive promotes electrocatalytic CO2 reduction to ethylene. Angew. Chem. Int. Ed. 58, 16952–16958 (2019).
Ovalle, V. J. & Waegele, M. M. Understanding the impact of N-arylpyridinium ions on the selectivity of CO2 reduction at the Cu/electrolyte interface. J. Phys. Chem. C. 123, 24453–24460 (2019).
Fang, Y. & Flake, J. C. Electrochemical reduction of CO2 at functionalized Au electrodes. J. Am. Chem. Soc. 139, 3399–3405 (2017).
Kim, C. et al. Achieving selective and efficient electrocatalytic activity for CO2 reduction using immobilized silver nanoparticles. J. Am. Chem. Soc. 137, 13844–13850 (2015).
Li, F. & Tang, Q. Understanding the role of functional groups of thiolate ligands in electrochemical CO2 reduction over Au(111) from first-principles. J. Mater. Chem. A 7, 19872–19880 (2019).
Kim, C. et al. Insight into electrochemical CO2 reduction on surface-molecule-mediated Ag nanoparticles. ACS Catal. 7, 779–785 (2017).
Xie, M. S. et al. Amino acid modified copper electrodes for the enhanced selective electroreduction of carbon dioxide towards hydrocarbons. Energy Environ. Sci. 9, 1687–1695 (2016).
Wakerley, D. et al. Bio-inspired hydrophobicity promotes CO2 reduction on a Cu surface. Nat. Mater. 18, 1222–1227 (2019).
Han, Z., Kortlever, R., Chen, H.-Y., Peters, J. C. & Agapie, T. CO2 reduction selective for C≥2 products on polycrystalline copper with N-substituted pyridinium additives. ACS Cent. Sci. 3, 853–859 (2017).
Li, F. et al. Molecular tuning of CO2-to-ethylene conversion. Nature 577, 509–513 (2020).
Cao, Z. et al. Chelating N-heterocyclic carbene ligands enable tuning of electrocatalytic CO2 reduction to formate and carbon monoxide: surface organometallic chemistry. Angew. Chem. Int. Ed. 57, 4981–4985 (2018).
Cao, Z. et al. A molecular surface functionalization approach to tuning nanoparticle electrocatalysts for carbon dioxide reduction. J. Am. Chem. Soc. 138, 8120–8125 (2016). Early report using NHC ligands to improve the performance in electrocatalytic CO2 conversion.
Cao, Z. et al. Tuning gold nanoparticles with chelating ligands for highly efficient electrocatalytic CO2 reduction. Angew. Chem. Int. Ed. 57, 12675–12679 (2018).
Pankhurst, J. R., Guntern, Y. T., Mensi, M. & Buonsanti, R. Molecular tunability of surface-functionalized metal nanocrystals for selective electrochemical CO2 reduction. Chem. Sci. 10, 10356–10365 (2019).
Wagner, A. et al. Host–guest chemistry meets electrocatalysis: cucurbituril on a Au surface as a hybrid system in CO2 reduction. ACS Catal. 10, 751–761 (2020).
Liu, B.-J., Torimoto, T. & Yoneyama, H. Photocatalytic reduction of CO2 using surface-modified CdS photocatalysts in organic solvents. J. Photochem. Photobiol. A Chem. 113, 93–97 (1998).
Liao, Y. et al. Efficient CO2 capture and photoreduction by amine-functionalized TiO2. Chem. Eur. J. 20, 10220–10222 (2014).
Huang, Q., Yu, J., Cao, S., Cui, C. & Cheng, B. Efficient photocatalytic reduction of CO2 by amine-functionalized g-C3N4. Appl. Surf. Sci. 358, 350–355 (2015).
Cho, K. M. et al. Amine-functionalized graphene/CdS composite for photocatalytic reduction of CO2. ACS Catal. 7, 7064–7069 (2017).
Kuehnel, M. F. et al. ZnSe quantum dots modified with a Ni(cyclam) catalyst for efficient visible-light driven CO2 reduction in water. Chem. Sci. 9, 2501–2509 (2018). Study using capping ligand design to tune the product selectivity (H2 versus CO) through blocking of catalytic sites in QD-promoted photoreduction of CO2.
Corma, A. & Garcia, H. Supported gold nanoparticles as catalysts for organic reactions. Chem. Soc. Rev. 37, 2096–2126 (2008).
Kim, J.-H., Woo, H., Choi, J., Jung, H.-W. & Kim, Y.-T. CO2 electroreduction on Au/TiC: enhanced activity due to metal–support interaction. ACS Catal. 7, 2101–2106 (2017).
Gao, D. et al. Enhancing CO2 electroreduction with the metal–oxide interface. J. Am. Chem. Soc. 139, 5652–5655 (2017).
Schreier, M. et al. Solar conversion of CO2 to CO using earth-abundant electrocatalysts prepared by atomic layer modification of CuO. Nat. Energy 2, 17087 (2017).
Chu, S. et al. Photoelectrochemical CO2 reduction into syngas with the metal/oxide interface. J. Am. Chem. Soc. 140, 7869–7877 (2018).
Rogers, C. et al. Synergistic enhancement of electrocatalytic CO2 reduction with gold nanoparticles embedded in functional graphene nanoribbon composite electrodes. J. Am. Chem. Soc. 139, 4052–4061 (2017).
Varela, A. S. et al. Metal-doped nitrogenated carbon as an efficient catalyst for direct CO2 electroreduction to CO and hydrocarbons. Angew. Chem. Int. Ed. 54, 10758–10762 (2015).
Ju, W. et al. Understanding activity and selectivity of metal-nitrogen-doped carbon catalysts for electrochemical reduction of CO2. Nat. Commun. 8, 944 (2017).
Zhang, H. et al. A graphene-supported single-atom FeN5 catalytic site for efficient electrochemical CO2 reduction. Angew. Chem. Int. Ed. 58, 14871–14876 (2019).
Lin, L. et al. Synergistic catalysis over iron–nitrogen sites anchored with cobalt phthalocyanine for efficient CO2 electroreduction. Adv. Mater. 31, 1903470 (2019).
Corbin, N., Zeng, J., Williams, K. & Manthiram, K. Heterogeneous molecular catalysts for electrocatalytic CO2 reduction. Nano Res. 12, 2093–2125 (2019).
Birdja, Y. Y. et al. Effects of substrate and polymer encapsulation on CO2 electroreduction by immobilized indium(iii) protoporphyrin. ACS Catal. 8, 4420–4428 (2018).
Wang, J. et al. Linkage effect in the heterogenization of cobalt complexes by doped graphene for electrocatalytic CO2 reduction. Angew. Chem. Int. Ed. 58, 13532–13539 (2019).
Reuillard, B. et al. Tuning product selectivity for aqueous CO2 reduction with a Mn(bipyridine)-pyrene catalyst immobilized on a carbon nanotube electrode. J. Am. Chem. Soc. 139, 14425–14435 (2017).
Oh, S., Gallagher, J. R., Miller, J. T. & Surendranath, Y. Graphite-conjugated rhenium catalysts for carbon dioxide reduction. J. Am. Chem. Soc. 138, 1820–1823 (2016). A powerful surface functionalization strategy was utilized to bridge between heterogeneous and molecular catalysis and significantly alter the catalytic mechanism and performance.
Leung, J. J. et al. Solar-driven reduction of aqueous CO2 with a cobalt bis(terpyridine)-based photocathode. Nat. Catal. 2, 354–365 (2019).
Xie, S. et al. Photocatalytic reduction of CO2 with H2O: significant enhancement of the activity of Pt–TiO2 in CH4 formation by addition of MgO. Chem. Commun. 49, 2451 (2013).
Pang, R., Teramura, K., Asakura, H., Hosokawa, S. & Tanaka, T. Effect of thickness of chromium hydroxide layer on Ag cocatalyst surface for highly selective photocatalytic conversion of CO2 by H2O. ACS Sustain. Chem. Eng. 7, 2083–2090 (2019).
Zhang, B. A., Ozel, T., Elias, J. S., Costentin, C. & Nocera, D. G. Interplay of homogeneous reactions, mass transport, and kinetics in determining selectivity of the reduction of CO2 on gold electrodes. ACS Cent. Sci. 5, 1097–1105 (2019).
Resasco, J. et al. Promoter effects of alkali metal cations on the electrochemical reduction of carbon dioxide. J. Am. Chem. Soc. 139, 11277–11287 (2017). A detailed study on the effects of alkali metal cations showed varied implications on different reaction products and highlighted the role of dipole moments on surface-bound reaction intermediates.
Moura de Salles Pupo, M. & Kortlever, R. Electrolyte effects on the electrochemical reduction of CO2. ChemPhysChem 20, 2926–2935 (2019).
Singh, M. R., Kwon, Y., Lum, Y., Ager, J. W. III. & Bell, A. T. Hydrolysis of electrolyte cations enhances the electrochemical reduction of CO2 over Ag and Cu. J. Am. Chem. Soc. 138, 13006–13012 (2016).
Zhang, F. & Co, A. C. Direct evidence of local pH change and the role of alkali cation during CO2 electroreduction in aqueous media. Angew. Chem. Int. Ed. 59, 1674–1681 (2020).
Ayemoba, O. & Cuesta, A. Spectroscopic evidence of size-dependent buffering of interfacial pH by cation hydrolysis during CO2 electroreduction. ACS Appl. Mater. Interfaces 9, 27377–27382 (2017).
Wang, L. et al. Electrochemical carbon monoxide reduction on polycrystalline copper: effects of potential, pressure, and pH on selectivity toward multicarbon and oxygenated products. ACS Catal. 8, 7445–7454 (2018).
Pérez-Gallent, E., Marcandalli, G., Figueiredo, M. C., Calle-Vallejo, F. & Koper, M. T. M. Structure- and potential-dependent cation effects on CO reduction at copper single-crystal electrodes. J. Am. Chem. Soc. 139, 16412–16419 (2017).
Gunathunge, C. M., Ovalle, V. J. & Waegele, M. M. Probing promoting effects of alkali cations on the reduction of CO at the aqueous electrolyte/copper interface. Phys. Chem. Chem. Phys. 19, 30166–30172 (2017).
Chen, L. D., Urushihara, M., Chan, K. & Nørskov, J. K. Electric field effects in electrochemical CO2 reduction. ACS Catal. 6, 7133–7139 (2016).
Clark, M. L. et al. CO2 reduction catalysts on gold electrode surfaces influenced by large electric fields. J. Am. Chem. Soc. 140, 17643–17655 (2018).
Ringe, S. et al. Understanding cation effects in electrochemical CO2 reduction. Energy Environ. Sci. 12, 3001–3014 (2019).
Bohra, D., Chaudhry, J. H., Burdyny, T., Pidko, E. A. & Smith, W. A. Modeling the electrical double layer to understand the reaction environment in a CO2 electrocatalytic system. Energy Environ. Sci. 12, 3380–3389 (2019).
Akhade, S. A., McCrum, I. T. & Janik, M. J. The Impact of specifically adsorbed ions on the copper-catalyzed electroreduction of CO2. J. Electrochem. Soc. 163, F477–F484 (2016).
Liu, M. et al. Enhanced electrocatalytic CO2 reduction via field-induced reagent concentration. Nature 537, 382–386 (2016).
Jiang, H., Hou, Z. & Luo, Y. Unraveling the mechanism for the sharp-tip enhanced electrocatalytic carbon dioxide reduction: the kinetics decide. Angew. Chem. Int. Ed. 56, 15617–15621 (2017).
Burdyny, T. et al. Nanomorphology-enhanced gas-evolution intensifies CO2 reduction electrochemistry. ACS Sustain. Chem. Eng. 5, 4031–4040 (2017).
Li, J., Li, X., Gunathunge, C. M. & Waegele, M. M. Hydrogen bonding steers the product selectivity of electrocatalytic CO reduction. Proc. Natl Acad. Sci. USA 116, 9220–9229 (2019). This study highlights the interactions of interfacial H2O with surface-bound intermediates and the effect of quaternary alkyl ammonium cations.
Buckley, A. K. et al. Electrocatalysis at organic–metal interfaces: identification of structure–reactivity relationships for CO2 reduction at modified Cu surfaces. J. Am. Chem. Soc. 141, 7355–7364 (2019).
Barton Cole, E. et al. 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 (2010).
Dridi, H. et al. Catalysis and inhibition in the electrochemical reduction of CO2 on platinum in the presence of protonated pyridine. New insights into mechanisms and products. J. Am. Chem. Soc. 139, 13922–13928 (2017).
Olu, P.-Y., Li, Q. & Krischer, K. The true fate of pyridinium in the reportedly pyridinium-catalyzed carbon dioxide electroreduction on platinum. Angew. Chem. Int. Ed. 57, 14769–14772 (2018).
Hori, Y., Murata, A. & Takahashi, R. Formation of hydrocarbons in the electrochemical reduction of carbon dioxide at a copper electrode in aqueous solution. J. Chem. Soc., Faraday Trans. 1 85, 2309 (1989).
Resasco, J., Lum, Y., Clark, E., Zeledon, J. Z. & Bell, A. T. Effects of anion identity and concentration on electrochemical reduction of CO2. ChemElectroChem 5, 1064–1072 (2018).
Hashiba, H. et al. Effects of electrolyte buffer capacity on surface reactant species and the reaction rate of CO2 in electrochemical CO2 reduction. J. Phys. Chem. C. 122, 3719–3726 (2018).
Seifitokaldani, A. et al. Hydronium-induced switching between CO2 electroreduction pathways. J. Am. Chem. Soc. 140, 3833–3837 (2018).
Varela, A. S., Ju, W., Reier, T. & Strasser, P. Tuning the catalytic activity and selectivity of Cu for CO2 electroreduction in the presence of halides. ACS Catal. 6, 2136–2144 (2016).
Rosen, B. A. et al. Ionic liquid-mediated selective conversion of CO2 to CO at low overpotentials. Science 334, 643–644 (2011). The first example of an ionic liquid additive in the electrolyte that significantly enhances CO2 electroreduction on Ag through interactions of the ionic liquid with a catalytic intermediate.
Rosen, B. A. et al. In situ spectroscopic examination of a low overpotential pathway for carbon dioxide conversion to carbon monoxide. J. Phys. Chem. C. 116, 15307–15312 (2012).
Wang, Y. et al. Activation of CO2 by ionic liquid EMIM–BF4 in the electrochemical system: a theoretical study. Phys. Chem. Chem. Phys. 17, 23521–23531 (2015).
Zhao, S.-F., Horne, M., Bond, A. M. & Zhang, J. Is the imidazolium cation a unique promoter for electrocatalytic reduction of carbon dioxide? J. Phys. Chem. C. 120, 23989–24001 (2016).
Sun, L., Ramesha, G. K., Kamat, P. V. & Brennecke, J. F. Switching the reaction course of electrochemical CO2 reduction with ionic liquids. Langmuir 30, 6302–6308 (2014).
Lau, G. P. S. et al. New insights into the role of imidazolium-based promoters for the electroreduction of CO2 on a silver electrode. J. Am. Chem. Soc. 138, 7820–7823 (2016).
Asadi, M. et al. Nanostructured transition metal dichalcogenide electrocatalysts for CO2 reduction in ionic liquid. Science 353, 467–470 (2016).
Lim, H.-K. et al. Insight into the microenvironments of the metal–ionic liquid interface during electrochemical CO2 reduction. ACS Catal. 8, 2420–2427 (2018).
García Rey, N. & Dlott, D. D. Effects of water on low-overpotential CO2 reduction in ionic liquid studied by sum-frequency generation spectroscopy. Phys. Chem. Chem. Phys. 19, 10491–10501 (2017).
Hollingsworth, N. et al. Reduction of carbon dioxide to formate at low overpotential using a superbase ionic liquid. Angew. Chem. Int. Ed. 54, 14164–14168 (2015).
Atifi, A., Boyce, D. W., DiMeglio, J. L. & Rosenthal, J. Directing the outcome of CO2 reduction at bismuth cathodes using varied ionic liquid promoters. ACS Catal. 8, 2857–2863 (2018).
Vasilyev, D., Shirzadi, E., Rudnev, A. V., Broekmann, P. & Dyson, P. J. Pyrazolium ionic liquid co-catalysts for the electroreduction of CO2. ACS Appl. Energy Mater. 1, 5124–5128 (2018).
Chen, Y. et al. Visible-light-driven conversion of CO2 from air to CO using an ionic liquid and a conjugated polymer. Green Chem. 19, 5777–5781 (2017).
Feaster, J. T. et al. Understanding the influence of [EMIM]Cl on the suppression of the hydrogen evolution reaction on transition metal electrodes. Langmuir 33, 9464–9471 (2017).
Banerjee, S., Han, X. & Thoi, V. S. Modulating the electrode–electrolyte interface with cationic surfactants in carbon dioxide reduction. ACS Catal. 9, 5631–5637 (2019).
Quan, F., Xiong, M., Jia, F. & Zhang, L. Efficient electroreduction of CO2 on bulk silver electrode in aqueous solution via the inhibition of hydrogen evolution. Appl. Surf. Sci. 399, 48–54 (2017).
Kramer, W. W. & McCrory, C. C. L. Polymer coordination promotes selective CO2 reduction by cobalt phthalocyanine. Chem. Sci. 7, 2506–2515 (2016).
Kajiwara, T. et al. Photochemical reduction of low concentrations of CO2 in a porous coordination polymer with a ruthenium(ii)–CO complex. Angew. Chem. Int. Ed. 55, 2697–2700 (2016).
Varela, A. S., Kroschel, M., Reier, T. & Strasser, P. Controlling the selectivity of CO2 electroreduction on copper: the effect of the electrolyte concentration and the importance of the local pH. Catal. Today 260, 8–13 (2016).
Burdyny, T. & Smith, W. A. CO2 reduction on gas-diffusion electrodes and why catalytic performance must be assessed at commercially-relevant conditions. Energy Environ. Sci. 12, 1442–1453 (2019).
Larrazábal, G. O. et al. Analysis of mass flows and membrane cross-over in CO2 reduction at high current densities in an MEA-Type electrolyzer. ACS Appl. Mater. Interfaces 11, 41281–41288 (2019).
Nam, D.-H. et al. Metal–organic frameworks mediate Cu coordination for selective CO2 electroreduction. J. Am. Chem. Soc. 140, 11378–11386 (2018).
Wang, X. et al. Regulation of coordination number over single Co sites: triggering the efficient electroreduction of CO2. Angew. Chem. Int. Ed. 57, 1944–1948 (2018).
Guntern, Y. T. et al. Nanocrystal/Metal–organic framework hybrids as electrocatalytic platforms for CO2 conversion. Angew. Chem. Int. Ed. 58, 12632–12639 (2019).
Kornienko, N. et al. Metal–organic frameworks for electrocatalytic reduction of carbon dioxide. J. Am. Chem. Soc. 137, 14129–14135 (2015). This study presents one of the first examples of the incorporation of a molecular CO2RR catalyst into a metal–organic framework.
Hod, I. et al. Fe-porphyrin-based metal–organic framework films as high-surface concentration, heterogeneous catalysts for electrochemical reduction of CO2. ACS Catal. 5, 6302–6309 (2015).
Lin, S. et al. Covalent organic frameworks comprising cobalt porphyrins for catalytic CO2 reduction in water. Science 349, 1208–1213 (2015).
Fei, H., Sampson, M. D., Lee, Y., Kubiak, C. P. & Cohen, S. M. Photocatalytic CO2 reduction to formate using a Mn(i) molecular catalyst in a robust metal–organic framework. Inorg. Chem. 54, 6821–6828 (2015).
Wang, S., Yao, W., Lin, J., Ding, Z. & Wang, X. Cobalt imidazolate metal-organic frameworks photosplit CO2 under mild reaction conditions. Angew. Chem. Int. Ed. 53, 1034–1038 (2014).
Ryu, U. J. et al. Synergistic interaction of Re complex and amine functionalized multiple ligands in metal–organic frameworks for conversion of carbon dioxide. Sci. Rep. 7, 612 (2017).
Wang, Y. et al. Hydroxide ligands cooperate with catalytic centers in metal–organic frameworks for efficient photocatalytic CO2 reduction. J. Am. Chem. Soc. 140, 38–41 (2018).
Ahn, S. et al. Poly-amide modified copper foam electrodes for enhanced electrochemical reduction of carbon dioxide. ACS Catal. 8, 4132–4142 (2018).
Wei, X. et al. Highly selective reduction of CO2 to C2+ hydrocarbons at copper/polyaniline interfaces. ACS Catal. 10, 4103–4111 (2020).
Zhang, L. et al. A polymer solution to prevent nanoclustering and improve the selectivity of metal nanoparticles for electrocatalytic CO2 reduction. Angew. Chem. Int. Ed. 58, 15834–15840 (2019).
Liu, Y. & McCrory, C. C. L. Modulating the mechanism of electrocatalytic CO2 reduction by cobalt phthalocyanine through polymer coordination and encapsulation. Nat. Commun. 10, 1683 (2019). A detailed analysis of a functional polymer-encapsulation of a CO2RR catalyst and its effects on the chemical environment of the catalyst.
McNicholas, B. J. et al. Electrocatalysis of CO2 reduction in brush polymer ion gels. J. Am. Chem. Soc. 138, 11160–11163 (2016).
Leung, J. J., Vigil, J. A., Warnan, J., Edwardes Moore, E. & Reisner, E. Rational design of polymers for selective CO2 reduction catalysis. Angew. Chem. Int. Ed. 58, 7697–7701 (2019).
Liu, G., Xie, S., Zhang, Q., Tian, Z. & Wang, Y. Carbon dioxide-enhanced photosynthesis of methane and hydrogen from carbon dioxide and water over Pt-promoted polyaniline–TiO2 nanocomposites. Chem. Commun. 51, 13654–13657 (2015).
Li, A. et al. Three-phase photocatalysis for the enhanced selectivity and activity of CO2 reduction on a hydrophobic surface. Angew. Chem. Int. Ed. 58, 14549–14555 (2019). This work describes the introduction of a hydrophobic polymer on Pt-decorated carbon nitride photocatalyst, thus concentrating CO2 molecules in the vicinity of the catalytic site.
Govindarajan, N., Koper, M. T. M., Meijer, E. J. & Calle-Vallejo, F. Outlining the scaling-based and scaling-free optimization of electrocatalysts. ACS Catal. 9, 4218–4225 (2019).
Jeoung, J.-H. J.-H. & Dobbek, H. Carbon dioxide activation at the Ni, Fe-cluster of anaerobic carbon monoxide dehydrogenase. Science 318, 1461–1464 (2007).
Parkin, A., Seravalli, J., Vincent, K. A., Ragsdale, S. W. & Armstrong, F. A. Rapid and efficient electrocatalytic CO2/CO interconversions by Carboxydothermus hydrogenoformans CO dehydrogenase I on an electrode. J. Am. Chem. Soc. 129, 10328–10329 (2007).
Nakajima, T. et al. Photocatalytic reduction of low concentration of CO2. J. Am. Chem. Soc. 138, 13818–13821 (2016).
Kumagai, H. et al. Electrocatalytic reduction of low concentration CO2. Chem. Sci. 10, 1597–1606 (2019).
McDonald, T. M. et al. Cooperative insertion of CO2 in diamine-appended metal–organic frameworks. Nature 519, 303–308 (2015).
García de Arquer, F. P. et al. CO2 electrolysis to multicarbon products at activities greater than 1 A cm−2. Science 367, 661–666 (2020). This work highlights the possibilities of electrocatalytic CO2 conversion by reaching commercially relevant current densities through chemical modification of the gas diffusion electrode ionomer.
Ren, S. et al. Molecular electrocatalysts can mediate fast, selective CO2 reduction in a flow cell. Science 365, 367–369 (2019).
We gratefully acknowledge financial support by the Christian Doppler Research Association, the Austrian Federal Ministry for Digital and Economic Affairs, the National Foundation for Research, Technology and Development and the OMV Group. We would like to thank Dr. Souvik Roy and Dr. Tengfei Li for feedback and careful proofreading of the manuscript.
The authors declare no competing interests.
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Wagner, A., Sahm, C.D. & Reisner, E. Towards molecular understanding of local chemical environment effects in electro- and photocatalytic CO2 reduction. Nat Catal 3, 775–786 (2020). https://doi.org/10.1038/s41929-020-00512-x
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