Molecularly engineered photocatalyst sheet for scalable solar formate production from carbon dioxide and water

Abstract

Harvesting solar energy to convert CO2 into chemical fuels is a promising technology to curtail the growing atmospheric CO2 levels and alleviate the global dependence on fossil fuels; however, the assembly of efficient and robust systems for the selective photoconversion of CO2 without sacrificial reagents and external bias remains a challenge. Here we present a photocatalyst sheet that converts CO2 and H2O into formate and O2 as a potentially scalable technology for CO2 utilization. This technology integrates lanthanum- and rhodium-doped SrTiO3 (SrTiO3:La,Rh) and molybdenum-doped BiVO4 (BiVO4:Mo) light absorbers modified by phosphonated Co(ii) bis(terpyridine) and RuO2 catalysts onto a gold layer. The monolithic device provides a solar-to-formate conversion efficiency of 0.08 ± 0.01% with a selectivity for formate of 97 ± 3%. As the device operates wirelessly and uses water as an electron donor, it offers a versatile strategy toward scalable and sustainable CO2 reduction using molecular-based hybrid photocatalysts.

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Fig. 1: CotpyP-loaded SrTiO3:La,Rh|Au|RuO2-BiVO4:Mo photocatalyst sheet.
Fig. 2: Photosynthetic activity of the CotpyP-loaded SrTiO3:La,Rh|Au|RuO2-BiVO4:Mo sheet for CO2RR coupled to water oxidation under AM 1.5 G irradiation.
Fig. 3: CotpyP-loaded SrTiO3:La,Rh|Au|RuO2-BiVO4:Mo photocatalyst sheet with an active irradiated area of ~20 cm2 for photosynthetic CO2RR coupled with water oxidation.
Fig. 4: Selectivity and stability of the CotpyP-loaded SrTiO3:La,Rh|Au|RuO2-BiVO4:Mo sheet for CO2RR coupled with water oxidation.
Fig. 5: O2-tolerance of CotpyP catalyst.

Data availability

The data supporting the findings of the study are available in the paper and its supplementary materials. Source data for the main figures (Figs. 25) are provided with the paper. Other source data supporting the findings of this study are available from the Cambridge data repository (https://doi.org/10.17863/CAM.54840).

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Acknowledgements

We thank C. Sahm and A. Eisenschmidt at the University of Cambridge for assisting with the isotopic labelling experiment, S. Roy and M. Rahaman at the University of Cambridge for helpful discussions, S. Young at the University of Cambridge for performing ICP–OES analysis, and M. Isaacs at HarwellXPS for carrying out XPS. This work was supported by EU Marie Sklodowska-Curie individual Fellowships (GAN 793996 to Q.W. and GAN 744317 to S.K.), European Commission Future and Emerging Technologies (FET) Open programme project SoFiA (GAN 828838 to S.R.-J. and E.R.), Christian Doppler Research Association (Austrian Federal Ministry for Digital and Economic Affairs and the National Foundation for Research, Technology and Development) and the OMV Group (to J.W. and E.R.). V.A. is grateful for the financial support from the Cambridge Trusts (Vice-Chancellor’s Award) and the Winton Programme for the Physics of Sustainability. J.J.L. is supported by the Woolf Fisher Trust in New Zealand. The XPS data collection was performed at the EPSRC National Facility for XPS (HarwellXPS)—operated by Cardiff University and University College London—under contract no. PR16195.

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Q.W. and E.R. conceived the idea. E.R. supervised the project. J.W., J.J.L. and S.R.-J. synthesised and characterized CotpyP. Q.W. prepared the photocatalyst sheet and photoelectrodes and conducted physical characterizations and photo(electro)chemical experiments. S.K. carried out NMR spectroscopy, V.A. assisted with O2 quantification and scalability tests. All authors analysed the data, discussed the results and assisted with manuscript preparation.

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Correspondence to Erwin Reisner.

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Supplementary Figs. 1–11, Tables 1–4 and refs. 1–10.

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Wang, Q., Warnan, J., Rodríguez-Jiménez, S. et al. Molecularly engineered photocatalyst sheet for scalable solar formate production from carbon dioxide and water. Nat Energy 5, 703–710 (2020). https://doi.org/10.1038/s41560-020-0678-6

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