Facet Engineering of CdS/Bi ₂ S ₃ Heterojunction Photocatalysts for High‐Rate, Ultraselective CH ₄ Production from Acetic Acid

Abstract Photocatalytic upcycling of organic molecules to methane is challenging due to the requisite multi‐electron transfers and competing formation of CO and H 2 . Here, we demonstrate the tunable production of CO or CH 4 by the photocatalytic reforming of acetic acid over Z‐scheme Bi 2 S 3 /CdS semiconductors. Electron transport and the adsorption of reactively‐formed * CO over (101) facets of the CdS component favours a mixture of CH 4 (1741 µmol·g cat −1 ·h −1 ) and CO (1659 µmol·g cat −1 ·h −1 ), whereas the (100) facet promotes 99% selectivity to CH 4 (3024 µmol·g cat −1 ·h −1 ) outperforming state‐of‐the‐art photocatalysts for CO 2 reduction. In situ spectroscopy and quantum chemical calculations reveal electron delocalisation across (101) Cd‐sites weakens * CO adsorption, while a decrease in the energy of the d‐band centre and charge localisation at (100) Cd‐sites strengthens * CO adsorption and lowers the energy barrier to its hydrogenation. Photoexcited holes at Bi‐sites in Bi 2 S 3 promote C‐C cleavage of acetic acid to * CH 3 and * CO 2 − intermediates, with the latter undergoing reduction to * CO over CdS. Shallow trap states in (100) facets promote migration of photoexcited electrons to surface intermediates with concomitant proton‐coupled electron transfer exclusively forming CH 4 . Deep trap states in (101) facets favour * CO desorption. Facet engineering of Z‐scheme heterojunction photocatalysts offers facile control of product selectivity.