A Heterogeneous Photocatalytic Hydrogen Evolution Dyad: [(tpy

The development of an artificial heterogeneous dyad by covalently anchoring a hydrogen‐evolving molecule catalyst to a semiconductor photosensitizer through a bridging ligand is highly challenging. Herein, we adopt the inorganic–organic hybrid CdS–DETA NSs (DETA=diethylenetriamine, NSs=nanosheets) as initial matrix to successfully construct an imine bond (‐CH=N‐) linked heterogeneous dyad CdS?N=CH?Ni] through the condensation reaction between the amino groups of CdS–DETA and the aldehyde group of the water reduction molecular catalyst, (tpy‐CHO)₂Ni]Cl₂ (tpy=terpyridine). The CdS?N=CH?Ni] enables a turnover number (TON) of about 43 815 versus Ni catalysts and an initial turnover frequency (TOF) of approximately 0.47 s^?1 in 26 h under visible‐light irradiation (λ>420 nm). The apparent quantum yield (AQY) reaches (9.9±0.8) % at 420 nm. Under optical conditions, the CdS?N=CH?Ni] can achieve a considerable amount of hydrogen production, 507.1±27 μmol H₂ for 6 h, which is 1.27 times that generated from the mechanically mixed system of CdS–DETA NSs and (tpy‐CH=NR)₂Ni]Cl₂ ( III ) under otherwise identical conditions. Furthermore, its TON value based on Ni species is also higher than that of the mixed system of CdS–DETA and III .