LAUSR

Abstract Artificial photosynthesis for simultaneously producing H2 and valuable chemicals is extremely desirable to act as a promising alternative for overall water splitting. Herein, a Z-scheme Co9S8/CdS heterostructure was constructed by self-recognition of uniformly distributed metal cations during the sulfidation of a multivariate metal-organic framework. The intimate contact of in situ formed CdS and Co9S8 into direct Z-scheme heterostructure can facilitate interfacial charge separation and extend the oxidation and reduction potentials to 2.09 V and −0.74 V (vs. RHE), respectively. An excellent H2 evolution activity of 61,924 μmol g−1 with high selectivity for benzyl-alcohol (BA) oxidation in pure water is achieved, ca. 21 and 16 times higher than that of isolated CdS and physical mixture of Co9S8/CdS. This work supplies a new strategy for constructing Z-scheme heterostructure from a solid solution to dramatically boost coproduction of H2 fuel and valuable chemicals without any sacrificial agents.