Nickel Complexes for Robust Light-Driven and Electrocatalytic Hydrogen Production from Water
Nickel Complexes for Robust Light-Driven and Electrocatalytic Hydrogen Production from Water
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DOI：
10.1021/acscatal.5b00045
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发表时间：
2015-03-01
期刊：
影响因子：
12.9
通讯作者：
Eisenberg, Richard
中科院分区：
文献类型：
--
作者：
Das, Amit;Han, Zhiji;Eisenberg, Richard
研究了一系列具有正方形平面配位的镍双（螯合）配合物的光驱动和电催化制氢性能。以荧光素（F1）为光敏剂（PS），三乙醇胺（TEOA）为牺牲电子给体，在pH = 9.8的碱性水溶液中，合成了三种配合物Ni（abt）_2（abt = 2-氨基苯硫酚盐）、Ni（mp）_2（mp = 2-巯基酚盐）和Ni（mpo）_2（mpo = 2-巯基吡啶-N-氧化物）.这些分子系统实现了类似于6000（相对于催化剂）的周转数（TON），并在H-2生成条件下稳定超过100小时。当水溶性CdSe量子点与三脚架S-供体封端剂被用作PS和抗坏血酸（AA）被用作牺牲电子供体在pH 4.5，获得一个积极的和强大的系统的光驱动产生H-2从水溶液质子。对于三种活性催化剂，实现了超过280 000吨。这些配合物也检查电化学在有机溶剂中与弱有机酸作为质子源，并在水和水/有机介质中的质子还原。活性最高的光化学催化剂在中性pH水中也显示出优异的电催化活性，在厌氧条件下实现法拉第产率接近100%，在有氧条件下接近80%。
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.