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Unlocking the potential of the formate pathway in the photo-assisted Sabatier reaction


Although solar irradiation has demonstrated beneficial synergy for catalytic CO2 hydrogenation, it has long been debated as to whether the observed photo-assisted catalytic enhancement has a photo-activation component or is driven solely by the heating effect. Here, we confirm that surface adsorbates play a critical role in photo-assisted CO2 activation. We isolate the rate-determining intermediate species in the photo-assisted Sabatier reaction by in situ isotopic spectroscopy. Specifically, we reveal that photo-activation of the formate adsorbate (HCO2*) offers an eightfold photo-enhancement on NiOx/La2O3@TiO2. Concurrently, the active La2O3@TiO2 support facilitates the adsorption of CO2, which may contribute to the sustained HCO2* formation and conversion. The findings are crucial as they provide surface intermediary insights in the design of catalysts for photo-assisted CO2 conversion. Ultimately, the understanding may unlock the solar-driven hydrogenation catalytic pathway for other reactions involving HCO2* such as the synthesis of methanol.

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Fig. 1: Isotopic tracking of surface-adsorbed intermediates based on 12C/13C isotopes.
Fig. 2: Transient SSITKA-DRIFTS spectra of the photo-assisted Sabatier reaction.
Fig. 3: Temperature dependence of the photo-assisted Sabatier reaction.
Fig. 4: Elemental mapping of the synthesized catalysts.
Fig. 5: Ni K-edge XAS of supported NiOx catalysts.
Fig. 6: Effect of light on the chemical states of supported NiOx catalysts.
Fig. 7: Proposed mechanism for the photo-assisted Sabatier reaction.

Data availability

The SSITKA-DRIFTS data that support the findings of this study are available in figshare with the identifier 10.6084/m9.figshare.1300394061. Additional data that support the plots within this paper and the other findings of this study are available from the corresponding authors upon reasonable request.


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This work was supported by the Australian Research Council (ARC) under the Laureate Fellowship Scheme FL140100081 and ARC Discovery Project DP170102410. R.A.T. gratefully acknowledges the ARC under the DECRA Fellowship Scheme (DE160100131). We acknowledge the use of the facilities within the UNSW Mark Wainwright Analytical Centre and the UoW Electron Microscopy Centre. In addition, this work used the 10-ID-B and 11-ID-B beamlines of the Advanced Photon Source, a US Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under contract no. DE-AC02-06CH11357. 10-ID-B is managed by the Materials Research Collaborative Access Team (MRCAT), which is supported by the Department of Energy and the MRCAT member institutions. We also thank J. Wright for assistance with XAS experiments at 10-ID-B.

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T.H.T., B.X., J.S., Y.H.N. and R.A. conceived and designed the experiments. T.H.T., B.X. and S.F.B.A. synthesized and characterized the catalysts with inputs from J.S., Y.H.N. and R.A. T.H.T., B.X. and S.F.B.A. performed the isotopic spectroscopies. Further deconvolution of spectral data was conducted and interpreted by T.H.T., B.X. and H.Y.M.T. with inputs from J.S. and R.A. K.-F.A.-Z. aided in the set-up and provided support with the isotopic spectroscopies. T.H.T., J.S., Y.H.N., R.A.T., K.-F.A.-Z. and R.A. contributed to the design and assembly of the online detection and isotropic spectroscopy systems. N.B. performed the XAS measurements. N.B. and T.H.T. interpreted the XAS results. T.H.T., B.X., J.S. and R.A. wrote the Article. All authors discussed the results and commented on the manuscript.

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Correspondence to Rose Amal or Jason Scott.

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Supplementary Figs. 1–29, Tables 1–3 and notes 1–4.

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Tan, T.H., Xie, B., Ng, Y.H. et al. Unlocking the potential of the formate pathway in the photo-assisted Sabatier reaction. Nat Catal 3, 1034–1043 (2020).

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