A Nickel Phosphine Complex as a Fast and Efficient Hydrogen Production Catalyst
A Nickel Phosphine Complex as a Fast and Efficient Hydrogen Production Catalyst
复制标题
DOI：
10.1021/ja509779q
复制
发表时间：
2015-01-28
影响因子：
15
通讯作者：
Jones, Anne K.
中科院分区：
文献类型：
--
作者：
Gan, Lu;Groy, Thomas L.;Jones, Anne K.
在这里，我们报道了一种新型S2P2配位镍配合物[Ni(bdt)(dppf)]（bdt = 1,2-苯二硫醇，dppf = 1,1'-双（二苯基膦）二茂铁）将质子电催化还原为氢。该催化反应快速高效，周转频率为 1240 s(-1)，在低酸浓度下半活性的过电势仅为 265 mV。此外，可以使用弱酸进行催化，并且该络合物在酸性溶液中稳定至少4小时。在密度泛函理论水平 (DFT) 上进行的系统计算与两个质子化发生在镍中心的催化机制一致。
Here we report the electrocatalytic reduction of protons to hydrogen by a novel S2P2 coordinated nickel complex, [Ni(bdt)(dppf)] (bdt = 1,2-benzenedithiolate, dppf = 1,1'-bis(diphenylphosphino)ferrocene). The catalysis is fast and efficient with a turnover frequency of 1240 s(-1) and an overpotential of only 265 mV for half activity at low acid concentrations. Furthermore, catalysis is possible using a weak acid, and the complex is stable for at least 4 h in acidic solution. Calculations of the system carried out at the density functional level of theory (DFT) are consistent with a mechanism for catalysis in which both protonations take place at the nickel center.