A nickel complex of 2,2-dicyanoethylene-1,1-dithiolate, a catalyst for electrochemical and photochemical driven hydrogen evolution

作者：Liu, Wei-Xia; Wang, Chun-Li; Lei, Jia-Mei; Zhan, Shu-Zhong^*; Wu, Song-Ping^*

来源：Inorganic and Nano-Metal Chemistry, 2022, 52(4): 533-541.

DOI：10.1080/24701556.2021.1897615

• Nickel complex
• electrocatalyst
• photocatalyst
• hydrogen evolution

The reaction of NiCl2, K-2(i-mnt) (i-mnt(2-)= 2,2-dicyanoethylene-1,1-dithiolate) and 1-benzyl-4-amino-pyridinium bromide [BzPyNH(2)]Br affords a nickel complex, [BzPyNH(2)](2)[Ni(i-mnt)(2)], a molecular catalyst for electrochemical and photochemical driven hydrogen evolution. As an electrocatalyst, [BzPyNH(2)](2)[Ni(i-mnt)(2)] can electrocatalyze hydrogen generation from a neutral buffer with a turnover frequency (TOF) of 556 (+/- 3) mol of hydrogen per mole of catalyst per hour (mol H-2/mol catalyst/h) at an overpotential (OP) of 837.6 mV. As a photocatalyst, combining with CdS nanorods (CdS NRs) as a photosensitizer, and ascorbic acid (H(2)A) as a sacrificial electron donor, [BzPyNH(2)](2)[Ni(i-mnt)(2)] photocatalyzes hydrogen evolution in heterogeneous environments with a turnover number (TON) of 18420 (+/- 5) mol H-2 per mol of catalyst during 60 h irradiation. The highest apparent quantum yield (AQY) is similar to 10% at 469 nm. Several chemical and physical methods are employed to understand catalytic procedures for H-2 production.