Cu2O nanocubes with mixed oxidation-state facets for (photo)catalytic hydrogenation of carbon dioxide


Cuprous oxide (Cu2O), an earth-abundant, low-cost metal-oxide semiconductor, has received enormous attention for its CO2 reduction ability in aqueous media by photochemical, photoelectrochemical and electrochemical methods. An unresolved problem with all of these approaches, however, is the instability of the Cu2O caused by its tendency to undergo an irreversible redox disproportionation reaction. Here, we report a way to circumvent this troublesome behaviour of Cu2O by driving the CO2 reduction in the gas-phase via heterogeneous photocatalytic hydrogenation. To this end, Cu2O nanocubes with surfaces comprising mixed oxidation-state copper Cu(0,I,II) sites, oxygen vacancies [O] and hydroxyl OH groups were synthesized. These surfaces enable heterolysis of H2 and adsorption of CO2 under mild conditions; they facilitate the reverse water–gas shift reaction, while rendering the redox disproportionation reaction reversible. This synergism provides Cu2O nanocubes with high photocatalytic activity and stability.

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Fig. 1: Growth mechanism of CF-Cu2O.
Fig. 2: Structure of CF-Cu2O.
Fig. 3: Photocatalytic performance of CF-Cu2O.
Fig. 4: In situ DRIFTS results for CF-Cu2O at 25 °C.
Fig. 5: In situ DRIFTS results for CF-Cu2O under light irradiation.
Fig. 6: Proposed reaction pathways for the photocatalytic hydrogenation of CO2.

Data availability

The data that support the plots within this paper and other findings of this study are available from the corresponding author upon reasonable request.


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Q.Z. wishes to thank NSFC (grant no. 21677080) for the partial support of this study. G.A.O. acknowledges the financial support of the following agencies: Ontario Ministry of Research and Innovation; Ministry of Economic Development, Employment and Infrastructure; Ministry of the Environment and Climate Change; Best in Science; Ministry of Research Innovation and Science Low Carbon Innovation Fund; Ontario Centre of Excellence Solutions 2030 Challenge Fund; Alexander von Humboldt Foundation; Imperial Oil; University of Toronto Connaught Innovation Fund; Connaught Global Challenge Fund and the Natural Sciences and Engineering Research Council of Canada. L.Wan acknowledges the financial support of the China Scholarship Council. W.S. acknowledges the 100-talents program of Zhejiang University, and Young Scientists Fund of the National Natural Science Foundation of China (grant no. 51902287). A. Tountas’ help on ASPEN estimation is acknowledged by all authors.

Author information




L.Wan, W.S., Q.Z. and G.A.O. conceived and designed the experiments. L.Wan, W.S. and T.L. prepared the materials and performed the SEM, XRD and FTIR characterization with the support of X.W. L.Wan and W.S. carried out the batch with high intensity light experiments with the support of T.E.W. and J.J. W.S. and T.E.W. performed the long-term stability test in LED reactor. L.Wan, W.S., J.G., X.Y. and Y.F.L. performed the in situ DRIFTS study with the support of P.N.D. M.X. and L.Wang performed XPS characterizations. A.A.J. performed the TEM characterizations. U.U. performed the ICP–OES detection. L.Wan, W.S. and G.A.O. co-wrote the manuscript. All authors discussed the results and commented on the manuscript.

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Correspondence to Qixing Zhou or Wei Sun or Geoffrey A. Ozin.

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Supplementary Information

Supplementary Notes 1 and 2, Figs. 1–18, Tables 1–3 and references.

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Wan, L., Zhou, Q., Wang, X. et al. Cu2O nanocubes with mixed oxidation-state facets for (photo)catalytic hydrogenation of carbon dioxide. Nat Catal 2, 889–898 (2019).

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