To date, effective control over the electrochemical reduction of CO2 to multicarbon products (C ≥ 2) has been very challenging. Here, we report a design principle for the creation of a selective yet robust catalytic interface for heterogeneous electrocatalysts in the reduction of CO2 to C2 oxygenates, demonstrated by rational tuning of an assembly of nitrogen-doped nanodiamonds and copper nanoparticles. The catalyst exhibits a Faradaic efficiency of ~63% towards C2 oxygenates at applied potentials of only −0.5 V versus reversible hydrogen electrode. Moreover, this catalyst shows an unprecedented persistent catalytic performance up to 120 h, with steady current and only 19% activity decay. Density functional theory calculations show that CO binding is strengthened at the copper/nanodiamond interface, suppressing CO desorption and promoting C2 production by lowering the apparent barrier for CO dimerization. The inherent compositional and electronic tunability of the catalyst assembly offers an unrivalled degree of control over the catalytic interface, and thereby the reaction energetics and kinetics.
Subscribe to Journal
Get full journal access for 1 year
only $4.92 per issue
All prices are NET prices.
VAT will be added later in the checkout.
Tax calculation will be finalised during checkout.
Rent or Buy article
Get time limited or full article access on ReadCube.
All prices are NET prices.
The data that support the plots within this paper and other findings of this study are available from the corresponding author on reasonable request.
Lewis, N. S. & Nocera, D. G. Powering the planet: chemical challenges in solar energy utilization. Proc. Natl Acad. Sci. USA 103, 15729–15735 (2006).
Chu, S., Cui, Y. & Liu, N. The path towards sustainable energy. Nat. Mater. 16, 16–22 (2017).
Voiry, D., Shin, H. S., Loh, K. P. & Chhowalla, M. Low-dimensional catalysts for hydrogen evolution and CO2 reduction. Nat. Rev. Chem. 1, 0105 (2018).
Liu, C., Colón, B. C., Ziesack, M., Silver, P. A. & Nocera, D. G. Water splitting–biosynthetic system with CO2 reduction efficiencies exceeding photosynthesis. Science 352, 1210–1213 (2016).
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).
Hori, Y. in Modern Aspects of Electrochemistry Vol. 42 (eds Vayenas, C. et al.) 89–189 (Springer, 2008).
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).
Zhu, W. et al. Monodisperse Au nanoparticles for selective electrocatalytic reduction of CO2 to CO. J. Am. Chem. Soc. 135, 16833–16836 (2013).
Gao, D. et al. Size-dependent electrocatalytic reduction of CO2 over Pd nanoparticles. J. Am. Chem. Soc. 137, 4288–4291 (2015).
Gao, S. et al. Partially oxidized atomic cobalt layers for carbon dioxide electroreduction to liquid fuel. Nature 529, 68–71 (2016).
Wang, H. et al. Self-selective catalyst synthesis for CO2 reduction. Joule 3, 1927–1936 (2019).
Zhang, S., Kang, P. & Meyer, T. J. Nanostructured tin catalysts for selective electrochemical reduction of carbon dioxide to formate. J. Am. Chem. Soc. 136, 1734–1737 (2014).
Gao, D. et al. Enhancing CO2 electroreduction with the metal–oxide interface. J. Am. Chem. Soc. 139, 5652–5655 (2017).
Angamuthu, R., Byers, P., Lutz, M., Spek, A. L. & Bouwman, E. Electrocatalytic CO2 conversion to oxalate by a copper complex. Science 327, 313–315 (2010).
Costentin, C., Drouet, S., Robert, M. & Savéant, J.-M. A local proton source enhances CO2 electroreduction to CO by a molecular Fe catalyst. Science 338, 90–94 (2012).
Lin, S. et al. Covalent organic frameworks comprising cobalt porphyrins for catalytic CO2 reduction in water. Science 349, 1208–1213 (2015).
Diercks, C. S. et al. Reticular electronic tuning of porphyrin active sites in covalent organic frameworks for electrocatalytic carbon dioxide reduction. J. Am. Chem. Soc. 140, 1116–1122 (2017).
Kornienko, N. et al. Metal–organic frameworks for electrocatalytic reduction of carbon dioxide. J. Am. Chem. Soc. 137, 14129–14135 (2015).
Wang, C., Xie, Z., deKrafft, K. E. & Lin, W. Doping metal–organic frameworks for water oxidation, carbon dioxide reduction, and organic photocatalysis. J. Am. Chem. Soc. 133, 13445–13454 (2011).
Verma, S., Kim, B., Jhong, H. R., Ma, S. & Kenis, P. J. A gross‐margin model for defining technoeconomic benchmarks in the electroreduction of CO2. ChemSusChem 9, 1972–1979 (2016).
Luc, W. & Jiao, F. Nanoporous metals as electrocatalysts: state-of-the-art, opportunities, and challenges. ACS Catal. 7, 5856–5861 (2017).
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).
Zhang, X. et al. Highly selective and active CO2 reduction electrocatalysts based on cobalt phthalocyanine/carbon nanotube hybrid structures. Nat. Commun. 8, 14675 (2017).
Li, J. et al. Efficient electrocatalytic CO2 reduction on a three-phase interface. Nat. Catal. 1, 592–600 (2018).
Dinh, C. T. et al. CO2 electroreduction to ethylene via hydroxide-mediated copper catalysis at an abrupt interface. Science 360, 783–787 (2018).
De Luna, P. et al. Catalyst electro-redeposition controls morphology and oxidation state for selective carbon dioxide reduction. Nat. Catal. 1, 103–110 (2018).
Jiang, K. et al. Metal ion cycling of Cu foil for selective C–C coupling in electrochemical CO2 reduction. Nat. Catal. 1, 111–119 (2018).
Kim, D., Kley, C. S., Li, Y. & Yang, P. Copper nanoparticle ensembles for selective electroreduction of CO2 to C2–C3 products. Proc. Natl Acad. Sci. USA 114, 10560–10565 (2017).
Mistry, H. et al. Highly selective plasma-activated copper catalysts for carbon dioxide reduction to ethylene. Nat. Commun. 7, 12123 (2016).
Kuhl, K. P., Cave, E. R., Abram, D. N. & Jaramillo, T. F. New insights into the electrochemical reduction of carbon dioxide on metallic copper surfaces. Energy Environ. Sci. 5, 7050–7059 (2012).
Tzeng, Y.-K. et al. Time-resolved luminescence nanothermometry with nitrogen-vacancy centers in nanodiamonds. Nano Lett. 15, 3945–3952 (2015).
Mochalin, V. N., Shenderova, O., Ho, D. & Gogotsi, Y. The properties and applications of nanodiamonds. Nat. Nanotechnol. 7, 11–23 (2012).
Liu, Y., Chen, S., Quan, X. & Yu, H. Efficient electrochemical reduction of carbon dioxide to acetate on nitrogen-doped nanodiamond. J. Am. Chem. Soc. 137, 11631–11636 (2015).
Guo, D. et al. Active sites of nitrogen-doped carbon materials for oxygen reduction reaction clarified using model catalysts. Science 351, 361–365 (2016).
Wang, H., Chen, Y., Hou, X., Ma, C. & Tan, T. Nitrogen-doped graphenes as efficient electrocatalysts for the selective reduction of carbon dioxide to formate in aqueous solution. Green Chem. 18, 3250–3256 (2016).
Zou, Y. S. et al. Structural characterization of nitrogen doped diamond-like carbon films deposited by arc ion plating. Appl. Surf. Sci. 241, 295–302 (2005).
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. Engl. 54, 10758–10762 (2015).
Song, Y. et al. High‐selectivity electrochemical conversion of CO2 to ethanol using a copper nanoparticle/N‐doped graphene electrode. ChemistrySelect 1, 6055–6061 (2016).
Peterson, A. A., Abild-Pedersen, F., Studt, F., Rossmeisl, J. & Nørskov, J. K. How copper catalyzes the electroreduction of carbon dioxide into hydrocarbon fuels. Energy Environ. Sci. 3, 1311–1315 (2010).
Birdja, Y. Y. & Koper, M. T. The importance of cannizzaro-type reactions during electrocatalytic reduction of carbon dioxide. J. Am. Chem. Soc. 139, 2030–2034 (2017).
Li, C. W., Ciston, J. & Kanan, M. W. Electroreduction of carbon monoxide to liquid fuel on oxide-derived nanocrystalline copper. Nature 508, 504–507 (2014).
Bhattacharyya, S. et al. Synthesis and characterization of highly-conducting nitrogen-doped ultrananocrystalline diamond films. Appl. Phys. Lett. 79, 1441–1443 (2001).
Henkelman, G., Arnaldsson, A. & Jónsson, H. A fast and robust algorithm for Bader decomposition of charge density. Comput. Mater. Sci. 36, 354–360 (2006).
Liu, C. et al. Stability and effects of subsurface oxygen in oxide-derived Cu catalyst for CO2 reduction. J. Phys. Chem. C 121, 25010–25017 (2017).
Liu, X. et al. Understanding trends in electrochemical carbon dioxide reduction rates. Nat. Commun. 8, 15438 (2017).
Liu, X. et al. pH effects on the electrochemical reduction of CO(2) towards C2 products on stepped copper. Nat. Commun. 10, 32 (2019).
Jens, K., Studt, F., Abild-Pedersen, F. & Bligaard, T. (eds) Fundamental Concepts in Heterogeneous Catalysis (John Wiley & Sons, 2014).
Cavalca, F. et al. Nature and distribution of stable subsurface oxygen in copper electrodes during electrochemical CO2 reduction. J. Phys. Chem. C 121, 25003–25009 (2017).
Garza, A., Bell, A. T. & Head-Gordon, M. Is subsurface oxygen necessary for the electrochemical reduction of CO2 on copper? J. Phys. Chem. Lett. 9, 601–606 (2018).
Yang, H. J. et al. Promoting ethylene selectivity from CO2 electroreduction on CuO supported onto CO2 capture materials. ChemSusChem 11, 881–887 (2018).
Waszczuk, P., Zelenay, P. & Sobkowski, J. Surface interaction of benzoic-acid with a copper electrode. Electrochim. Acta 40, 1717–1721 (1995).
Giannozzi, P. et al. QUANTUM ESPRESSO: a modular and open-source software project for quantum simulations of materials. J. Phys. Condens. Matter 21, 395502 (2009).
Kresse, G. & Furthmüller, J. Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set. Comput. Mater. Sci. 6, 15–50 (1996).
Kresse, G. & Hafner, J. Norm-conserving and ultrasoft pseudopotentials for first-row and transition elements. J. Phys. Condens. Matter 6, 8245 (1994).
Vanderbilt, D. Soft self-consistent pseudopotentials in a generalized eigenvalue formalism. Phys. Rev. B 41, 7892–7895 (1990).
Bahn, S. R. & Jacobsen, K. W. An object-oriented scripting interface to a legacy electronic structure code. Comput. Sci. Eng. 4, 56–66 (2002).
Wellendorff, J. et al. Density functionals for surface science: exchange-correlation model development with Bayesian error estimation. Phys. Rev. B 85, 235149 (2012).
Monkhorst, H. J. & Pack, J. D. Special points for Brillouin-zone integrations. Phys. Rev. B 13, 5188–5192 (1976).
Bengtsson, L. Dipole correction for surface supercell calculations. Phys. Rev. B 59, 12301–12304 (1999).
Tang, W., Sanville, E. & Henkelman, G. A grid-based bader analysis algorithm without lattice bias. J. Phys. Condens. Matter 21, 084204 (2009).
Henkelman, G., Uberuaga, B. P. & Jónsson, H. A climbing image nudged elastic band method for finding saddle points and minimum energy paths. J. Chem. Phys. 113, 9901–9904 (2000).
Henkelman, G. & Jónsson, H. Improved tangent estimate in the nudged elastic band method for finding minimum energy paths and saddle points. J. Chem. Phys. 113, 9978–9985 (2000).
Nørskov, J. K. et al. Origin of the overpotential for oxygen reduction at a fuel-cell cathode. J. Phys. Chem. B 108, 17886–17892 (2004).
This work was initiated by the support of the Department of Energy, Office of Basic Energy Sciences, Materials Sciences and Engineering Division, under contract no. DE-AC02-76SF00515. Theoretical calculations were supported through the Office of Science of the US Department of Energy under award no. DE-SC0004993 and Office of Science of the US Department of Energy under contract no. DE-AC02-05CH11231. H.W. acknowledges funding support from the National Postdoctoral Program for Innovative Talents (grant no. BX201600011). Y.T. acknowledges support by grant no. 4309 from the Moore Foundation. T. T. acknowledges the support from National Nature Science Foundation of China (grant no. 21436002 and U1663227). We acknowledge Stanford Nano Shares Facilities for sample preparation and characterization. We acknowledge C. Zhu from Lawrence Berkeley National Laboratory for his help in GIWAXS characterization. Use of the Stanford Synchrotron Radiation Light Source, SLAC National Accelerator Laboratory, is supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences under contract no. DE-AC02-76SF00515.
The authors declare no competing interests.
Peer review information Nature Nanotechnology thanks Antonio Martin and other, anonymous, reviewer(s) for their contribution to the peer review of this work.
Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
About this article
Cite this article
Wang, H., Tzeng, YK., Ji, Y. et al. Synergistic enhancement of electrocatalytic CO2 reduction to C2 oxygenates at nitrogen-doped nanodiamonds/Cu interface. Nat. Nanotechnol. 15, 131–137 (2020). https://doi.org/10.1038/s41565-019-0603-y
Materials Chemistry Frontiers (2021)
Energy & Fuels (2021)
Enhanced Electrochemical Methanation of Carbon Dioxide at the Single-Layer Hexagonal Boron Nitride/Cu Interfacial Perimeter
Nano Letters (2021)
When amine-based conducting polymers meet Au nanoparticles: suppressing H2 evolution and promoting the selective electroreduction of CO2 to CO at low overpotentials
Sustainable Energy & Fuels (2021)
Rational design of copper-based electrocatalysts and electrochemical systems for CO2 reduction: From active sites engineering to mass transfer dynamics
Materials Today Physics (2021)