Unraveling the structure-activity-selectivity relationships in furfuryl alcohol photoreforming to H2 and hydrofuroin over ZnxIn2S3+x photocatalysts
Denny Gunawan, Jodie A. Yuwono, Priyank V. Kumar, Akasha Kaleem, Michael P. Nielsen, Murad J. Y. Tayebjee, Louis Oppong‐Antwi, Haotian Wen, Inga Kuschnerus, Shery L. Y. Chang, Yu Wang, Rosalie K. Hocking, Ting‐Shan Chan, Cui Ying Toe, Jason Scott, Rose Amal
Abstract
ZnxIn2S3+x has emerged as a promising candidate for alcohol photoreforming based on C-H activation and C-C coupling. However, the underlying structure-activity-selectivity relationships remain unclear. Here we report on ZnxIn2S3+x with varying Zn:In:S ratios for visible-light-driven furfuryl alcohol reforming into H2 and hydrofuroin, a jet fuel precursor, via C-H activation and C-C coupling. S-• radicals are directly identified as the catalytically active sites responsible for C-H activation in furfuryl alcohol, promoting selectivity toward H2 and hydrofuroin. The optimum ZnxIn2S3+x activity derives from a trade-off between enhanced carrier dynamics and diminished visible light absorption as the x value in ZnxIn2S3+x increases. Further, a higher Zn-S:In-S layer ratio prolongs the S-• lifetime in the Zn-S layer, promoting C-H activation and delivering a higher C-C coupling product selectivity. The findings represent a step toward further establishing sulfide-based photocatalysts for sustainable H2 production via organic photoreforming.