Perovskite photoelectrocatalysis for solar driven chemical synthesis Virgil Andrei* Yusuf Hamied Department of Chemistry, University of Cambridge, United Kingdom *va291@cam.ac.uk, Photoelectrochemistry (PEC) presents a direct pathway to solar fuel synthesis by integrating light absorption and catalysis into compact electrodes. [1-3] Among established light absorbers, metal halide perovskites have emerged as promising alternatives for solar fuel synthesis, enabling unassisted water splitting [4,5] and CO 2 reduction to syngas. [6-9] Yet, PEC hydrocarbon production remains elusive due to high catalytic overpotentials and insufficient semiconductor photovoltage. Here we demonstrate ethane and ethylene synthesis by interfacing lead halide perovskite photoabsorbers with suitable copper nanoflower electrocatalysts. [10] The resulting perovskite photocathodes attain a 9.8% Faradaic yield towards C 2 hydrocarbon production at 0 V against the reversible hydrogen electrode. The catalyst and perovskite geometric surface areas strongly influence C 2 photocathode selectivity, which indicates a role of local current density in product distribution. The thermodynamic limitations of water oxidation are overcome by coupling the photocathodes to Si nanowire photoanodes for glycerol oxidation into value-added chemicals like glycerate, lactate, acetate and formate. These unassisted perovskite–silicon PEC devices attain partial C 2 hydrocarbon photocurrent densities of 155 µAcm −2 , 200-fold higher than conventional perovskite–BiVO 4 artificial leaves for water and CO 2 splitting. These insights establish perovskite semiconductors as a versatile platform towards PEC multicarbon synthesis. [10]
References 1. Sokol, K. P.; Andrei, V. Nat. Rev. Mater. 2022, 7, 251–253. 2. Andrei, V.; Roh, I.; Yang, P. Sci. Adv. 2023, 9, eade9044. 3. Andrei, V.; Jagt, R. A. et al. Nat. Mater. 2022, 21, 864–868. 4. Andrei, V. et al. Adv. Energy Mater. 2018, 8, 1801403.
5. Pornrungroj, C.; Andrei, V et al. Adv. Funct. Mater. 2021, 31, 2008182. 6. Andrei, V.; Reuillard, B.; Reisner, E. Nat. Mater. 2020, 19, 189–194. 7. Andrei, V.; Ucoski, G. M. et al. Nature 2022, 608, 518–522. 8. Pornrungroj, C.; Andrei, V.; Reisner, E. J. Am. Chem. Soc. 2023, 145, 13709–13714. 9. Andrei, V.; Chiang, Y.-H.; Rahaman, M.; Anaya, M. et al. Energy Environ. Sci. 2025. DOI: 10.1039/D4EE05780E. 10. Andrei, V.; Roh, I. et al. Nat. Catal. 2025, 8, 137–146.
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