(Invited) Photocatalyst Sheets for Scalable Solar Fuels Production from Water and CO2

Abstract

The development of sunlight-driven water splitting or CO2 reduction systems with high efficiency, scalability, and cost-competitiveness is a central issue for mass production of fuels and energy-rich chemicals.1 Z-scheme photocatalytic systems, employing the two-step photoexcitation of photocatalyst I (PC I) and photocatalyst II (PC II), have garnered significant attention. These systems can utilize narrow bandgap semiconductors capable of either water/CO2 reduction or oxidation potential, enabling the conversion of solar energy. The challenge in developing a Z-scheme system lies in ensuring efficient electron transfer between PC I and PC II.2 To address these challenges, we have developed all-solid-state devices—photocatalyst sheets—for photocatalytic water splitting.3,4 These sheets establish a direct connection between PC I and PC II particles via a conductive layer or conductive nanoparticles, effectively facilitating electron transfer between them. Consequently, these photocatalyst sheets achieve a high solar-to-H2 conversion efficiency exceeding 1%. They outperform analogous powder suspension and photoelectrochemical systems in their optimal reaction solutions due to the effective electron transfer enabled by the conductive layer or nanoparticles bridging PC I and PC II. Compared to traditional photoelectrochemical systems, the photocatalyst sheet design significantly reduces the effects of H+/OH− concentration overpotentials and the IR drop due to the proximity of PC I and PC II in the sheet. Hence, the design of these photocatalyst sheets proves highly suitable for efficient large-scale applications.Additionally, efforts to demonstrate fuel production from CO2 powered by sunlight are currently hampered by the requirements of sacrificial electron donors or external bias, and lack of efficiency, selectivity and scalability. To overcome those barriers, we integrate a selective molecular catalyst on semiconductor light absorbers to form a wireless and monolithic photocatalyst sheet.5 For instance, by incorporating a phosphonated cobalt(II) bis(terpyridine) catalyst (CotpyP) onto a modified SrTiO3:La,Rh|Au|BiVO4:Mo sheet, we have achieved a solar-to-formate conversion efficiency of 0.08%. This configuration harnesses the high selectivity of molecular catalysts for CO2 reduction and the strong water oxidation power of semiconductors, yielding a formate selectivity of 97±3% through the coupled process of CO2 reduction and water oxidation. We have also developed a bio-abiotic hybrid system by combining a photocatalyst sheet, capable of scalable photocatalytic water splitting, with nonphotosynthetic bacteria acting as biocatalysts.6 When pairing CO2-fixing acetogenic bacteria, Sporomusa ovata, with a SrTiO3:La,Rh|ITO|BiVO4:Mo sheet, a solar-to-acetate conversion efficiency of ~0.7% was achieved (as shown in the figure). This coupling exhibited an impressive selectivity for acetate production in CO2 reduction reactions, reaching ~100%.Our study offers novel and versatile strategies toward sustainable solar fuel production.References Q. Wang, C. Pornrungroj, S. Linley, E. Reisner. Nat. Energy 7 , 13–24 (2022)Y. Sasaki, H. Nemoto, K. Saito, A. Kudo. J. Phys. Chem. C 113, 17536–17542 (2009)Q. Wang, T. Hisatomi, Q. Jia, H. Tokudome, M. Zhong, C. Wang, Z. Pan, T. Takata, M. Nakabayashi, N. Shibata, Y. Li, I. D. Sharp, A. Kudo, T. Yamada, K. Domen. Nat. Mater. 15,611–615 (2016)Q. Wang, T. Hisatomi, Y. Suzuki, Z. Pan, J. Seo, M. Katayama, T. Minegishi, H. Nishiyama, T. Takata, K. Seki, A. Kudo, T. Yamada, K. Domen. J. Am. Chem. Soc. 139, 1675–1683 (2017)Q. Wang, J. Warnan, S. Rodríguez-Jiménez, J. J. Leung, S. Kalathil, V. Andrei, K. Domen, E, Reisner. Nat. Energy 5, 703–710 (2020)Q. Wang, S. Kalathil, C. Pornrungroj, D. C. Sahm, E. Reisner. Nat. Catal. 5, 633–641 (2022) Figure 1