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) 2 Ni]Cl 2 (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 H 2 for 6 h, which is 1.27 times that generated from the mechanically mixed system of CdS–DETA NSs and [(tpy‐CH=NR) 2 Ni]Cl 2 ( 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 .