title: A Heterogeneous Photocatalytic Hydrogen Evolution Dyad: [(tpy.
abstract: 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-1in 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 H2for 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.
authors: Department of Chemistry, School of Science, Tianjin University, and Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin, 300072, P. R. China.|Department of Chemistry, School of Science, Tianjin University of Science & Technology, Tianjin, 300457, P. R. China.
authors: Weiwei
authors: W
authors: Zhao
authors: Department of Chemistry, School of Science, Tianjin University, and Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin, 300072, P. R. China.
authors: Yi
authors: Y
authors: Huang
authors: Analysis and Testing Center of Tianjin University, Tianjin University, Tianjin, 300072, P. R. China.
authors: Yang
authors: Y
authors: Liu
authors: Department of Chemistry, School of Science, Tianjin University, and Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin, 300072, P. R. China.
authors: Liming
authors: L
authors: Cao
authors: Department of Chemistry, School of Science, Tianjin University, and Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin, 300072, P. R. China.
authors: Fang
authors: F
authors: Zhang
authors: Department of Chemistry, School of Science, Tianjin University, and Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin, 300072, P. R. China.
authors: Yamei
authors: Y
authors: Guo
authors: Department of Chemistry, School of Science, Tianjin University, and Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin, 300072, P. R. China. bzhang@tju.edu.cn.
authors: Bin
authors: B
authors: Zhang
keywords: heterogeneous catalysts; hybrid materials; hydrogen production; photocatalysis; water splitting