Versatile photocatalytic systems for H2 generation in water based on an efficient DuBois-type nickel catalyst.
Versatile photocatalytic systems for H2 generation in water based on an efficient DuBois-type nickel catalyst.
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DOI：
10.1021/ja410592d
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发表时间：
2014-01-08
影响因子：
15
通讯作者：
Reisner E
中科院分区：
文献类型：
--
作者：
Gross MA;Reynal A;Durrant JR;Reisner E
通过有效的光化学途径产生可再生H2需要光诱导电子转移（ET）从光收集器到水中的有效电催化剂。本文报道了一种具有DuBois型[Ni（P2 R ′ N2 R ″）2]2+核（P2 R ′ N2 R ″ =双（1，5-R′-二磷杂-3，7-R″-二氮杂环辛烷））的分子式析氢催化剂（NiP），其外配位层含有膦酸基团.后一种功能允许在水中的良好溶解性和在金属氧化物半导体上的固定化。电化学研究证实，NiP在电解质水溶液中是高活性的电催化剂（在pH 4.5下的过电位约为200 mV，法拉第产率为85 ± 4%）。光催化实验和ET动力学的调查进行了结合与膦酸化钌（II）三（联吡啶）染料（RuP）在均相和非均相环境。时间分辨的发光和瞬态吸收光谱研究证实，直接ET从RuP到NiP发生在所有系统中有效地在纳米到微秒的时间尺度上，通过三个不同的路线：还原猝灭的RuP在溶液中或表面上的ZrO 2（“颗粒上”系统）或氧化猝灭的RuP时，该化合物被固定在TiO 2（“通过颗粒”系统）。我们的研究表明，NiP可以用于纯水溶液和半导体表面上具有高度的通用性。对于均相体系，使用分子Ni催化剂在水中进行光催化H2生成的高TOF为460 ± 60 h-1，TON为723 ± 171，并且光子-H2量子产率约为10%。
The generation of renewable H2 through an efficient photochemical route requires photoinduced electron transfer (ET) from a light harvester to an efficient electrocatalyst in water. Here, we report on a molecular H2 evolution catalyst (NiP) with a DuBois-type [Ni(P2R′N2R″)2]2+ core (P2R′N2R″ = bis(1,5-R′-diphospha-3,7-R″-diazacyclooctane), which contains an outer coordination sphere with phosphonic acid groups. The latter functionality allows for good solubility in water and immobilization on metal oxide semiconductors. Electrochemical studies confirm that NiP is a highly active electrocatalyst in aqueous electrolyte solution (overpotential of approximately 200 mV at pH 4.5 with a Faradaic yield of 85 ± 4%). Photocatalytic experiments and investigations on the ET kinetics were carried out in combination with a phosphonated Ru(II) tris(bipyridine) dye (RuP) in homogeneous and heterogeneous environments. Time-resolved luminescence and transient absorption spectroscopy studies confirmed that directed ET from RuP to NiP occurs efficiently in all systems on the nano- to microsecond time scale, through three distinct routes: reductive quenching of RuP in solution or on the surface of ZrO2 (“on particle” system) or oxidative quenching of RuP when the compounds were immobilized on TiO2 (“through particle” system). Our studies show that NiP can be used in a purely aqueous solution and on a semiconductor surface with a high degree of versatility. A high TOF of 460 ± 60 h–1 with a TON of 723 ± 171 for photocatalytic H2 generation with a molecular Ni catalyst in water and a photon-to-H2 quantum yield of approximately 10% were achieved for the homogeneous system.
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影响因子：
15
作者：
Gardner, James M.;Beyler, Maryline;Hammarstrom, Leif
通讯作者：
Hammarstrom, Leif
影响因子：
16.6
作者：
Fihri, Aziz;Artero, Vincent;Fontecave, Marc
通讯作者：
Fontecave, Marc
影响因子：
8.4
作者：
Brennaman, M. Kyle;Patrocinio, Antonio Otavio T.;Meyer, Thomas J.
通讯作者：
Meyer, Thomas J.
影响因子：
7.4
作者：
Espinosa, S;Bosch, E;Rosés, M
通讯作者：
Rosés, M
DOI：
10.1073/pnas.19.9.875
发表时间：
1933-01-01
影响因子：
11.1
作者：
Borsook, H;Keighley, G
通讯作者：
Keighley, G