Nickel Complexes for Robust Light-Driven and Electrocatalytic Hydrogen Production from Water

作者：Das Amit; Han Zhiji; Brennessel William W; Holland Patrick L; Eisenberg Richard^*

来源：ACS Catalysis, 2015, 5(3): 1397-1406.

DOI：10.1021/acscatal.5b00045

• photochemistry
• hydrogen evolution
• molecular HER catalysis
• Ni catalysts with redox active ligands
• CdSe quantum dots
• HER mechanism
• fluorescein
• heterocoupling

A series of nickel bis(chelate) complexes having square planar coordination are studied for light-driven and electrocatalytic hydrogen production from water. The complexes Ni(abt)2 (abt = 2-aminobenzenethiolate), Ni(mp)(2) (mp = 2-mercaptophenolate) and Ni(mpo)(2) (mpo = 2-mercaptopyridyl-N-oxide) are found to be active catalysts under light-driven conditions, using fluorescein (Fl) as the photosensitizer (PS) and triethanolamine (TEOA) as the sacrificial electron donor in water under basic pH (pH = 9.8). These molecular systems achieve a turnover number (TON) of similar to 6000 (relative to catalyst) and are stable for more than 100 h under H-2-generating conditions. When water-soluble CdSe quantum dots with tripodal S-donor capping agents are employed as PS and ascorbic acid (AA) is used as the sacrificial electron donor at pH 4.5, an active and robust system is obtained for the light-driven generation of H-2 from aqueous protons. A TON of over 280 000 is achieved for the three active catalysts. These complexes are also examined electrochemically in organic solvents with weak organic acids as the proton source and in aqueous and aqueous/organic media for proton reduction. The most active photochemical catalysts also show excellent electrocatalytic activity in neutral pH water, achieving Faradaic yields close to 100% under anaerobic conditions and similar to 80% under aerobic conditions.

• 出版日期2015-3