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Catalytic CO2 reduction by palladium-decorated silicon–hydride nanosheets

Abstract

Heterogeneous conversion of CO2 to fuels by Si surface hydrides has recently attracted broad research interest. Being earth-abundant, low-cost and non-toxic, elemental Si is a very attractive candidate for this process, which targets CO2 conversion to synthetic fuels on a gigatonne-per-year scale. It is well known, however, that silicon hydrides react stoichiometrically with CO2, and all attempts have failed to achieve catalytic conversion. The problem originates from the formation of inactive silanols and siloxanes with permanent loss of Si hydrides. Here, we deposit Pd on the surface of Si nanosheets, aiming to address the core of the problem. An operando infrared study shows Si hydrides successfully regenerating on such surfaces exposed to CO2 and H2. We demonstrate that silicon–hydride nanosheets decorated with Pd nanoparticles can enable the reverse water–gas shift reaction in a catalytic cycle.

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Fig. 1: Preparation and surface chemistry of Pd@SiNS.
Fig. 2: Materials characterization.
Fig. 3: CO2 reduction performance.
Fig. 4: Isotope labelled in situ DRIFTS experiments and interpretation (catalytic mechanism).
Fig. 5: DFT simulation results.

Data availability

The data that support the findings of this study are available from the corresponding author upon reasonable request.

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Acknowledgements

G.A.O. acknowledges financial support from the Ontario Ministry of Research and Innovation (MRI), the Ministry of Economic Development, Employment and Infrastructure (MEDI), the Ministry of the Environment and Climate Change’s (MOECC) Best in Science (BIS) Award, Ontario Center of Excellence Solutions 2030 Challenge Fund, Ministry of Research Innovation and Science (MRIS) Low Carbon Innovation Fund, Imperial Oil, the University of Toronto’s Connaught Innovation Fund (CIF), Connaught Global Challenge (CGC) Fund and the Natural Sciences and Engineering Research Council of Canada (NSERC). C.Q. and W.S. acknowledge the Connaught Fund and Department of Chemistry at the University of Toronto for funding. M.M. and C.V.S. acknowledge financial support in part by the Natural Sciences and Engineering Council of Canada (NSERC), University of Toronto, Connaught Global Challenge Award and Hart Professorship. The computations were carried out using University of Toronto computers and Compute Canada facilities, particularly SciNet and Calcul-Quebec. The authors acknowledge continued support from these supercomputing facilities. The authors thank X.Yan for helpful discussions on materials characterizations.

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Contributions

C.Qian, W.S. and G.A.O. conceived and designed the experiments. C.Qian, W.S., D.L.H.H. and S.G.H.K. prepared the materials and carried out the batch and flow experiments. C.Qian, W.S., C.Qiu and L.Wan. prepared the materials and carried out the batch with high-intensity light experiments. M.M. conducted DFT simulations under the supervision of C.V.S., and together they did the analysis and discussed the simulation data with C.Qian, W.S., M.G. and G.A.O. With the support of T.E.W., C.Qian, W.S. and D.L.H.H. performed the in situ DRIFTS study. A.A.T. conducted the Aspen simulation and estimated the equilibrium composition. Y.F.L. and I.G. performed SEM and TEM characterizations. M.X. and L.Wang performed XPS characterizations. Y.D. carried out the nitrogen sorption study. C.Qian, 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 Chandra Veer Singh or Geoffrey A. Ozin.

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Supplementary Figures 1–12; Supplementary Note 1

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Qian, C., Sun, W., Hung, D.L.H. et al. Catalytic CO2 reduction by palladium-decorated silicon–hydride nanosheets. Nat Catal 2, 46–54 (2019). https://doi.org/10.1038/s41929-018-0199-x

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