A Heterogeneous Photocatalytic Hydrogen Evolution Dyad: [(tpy -CHO)₂Ni]Cl₂ Covalently Anchored to CdS-Amine Inorganic-Organic Hybrid Nanosheets

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• 作者：Dr. Weiwei Zhao ; Yi Huang ; Yang Liu ; Liming Cao ; Fang Zhang ; Dr. Yamei Guo and Prof. Bin Zhang
• 刊名：Chemistry - A European Journal
• 出版年：2016
• 出版时间：October 10, 2016
• 年：2016
• 卷：22
• 期：42
• 页码：15049-15057
• 全文大小：1417K
• ISSN：1521-3765

文摘

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.