Beijing National Laboratory for Molecular Sciences CAS Key Laboratory of Organic Solids, Institute of Chemistry, Chinese Academy of Sciences , Beijing 100190, China.
University of Chinese Academy of Sciences , Beijing 100049, China.
ACS Appl Mater Interfaces. 2017 Nov 22;9(46):40752-40759. doi: 10.1021/acsami.7b14523. Epub 2017 Nov 8.
A graphene-like coordination polymer based on copper(II) benzenehexathiol (Cu-BHT, 1) with high electric conductivity (10 S·cm) was prepared recently. The high conductivity makes this material a good candidate for electrocatalysis, and here its catalytic activity toward hydrogen evolution reaction (HER) was evaluated. Cu-BHT shows good activity and stability for HER in acidic solutions under high current densities. By changing the preparation conditions, the morphology of Cu-BHT materials was controlled at the mesoscale, which allows the preparation of a thin film (TF-1), nanocrystal (NC-1), and amorphous nanoparticle (NP-1) of Cu-BHT. The overpotential of Cu-BHT toward HER shows an improved activity from 760 mV (NC-1) to 450 mV (NP-1) at a current density of 10 mA·cm. A Tafel slope of ∼95 mV·dec and an exchange current density of 10 mA·cm were achieved under optimized conditions. Density functional theory calculations suggest that the "Cu-edge site" on the (100) surface plays an important role in improving the HER catalytic performance of Cu-BHT nanoparticles.
最近，一种基于铜（II）苯六硫醇（Cu-BHT，1）的类石墨烯配位聚合物被制备出来，其电导率高达 10 S·cm。高导电性使该材料成为电催化的良好候选物，在此评估了其对析氢反应（HER）的催化活性。Cu-BHT 在高电流密度下的酸性溶液中对 HER 表现出良好的活性和稳定性。通过改变制备条件，在介观尺度上控制了 Cu-BHT 材料的形态，从而可以制备 Cu-BHT 的薄膜（TF-1）、纳米晶体（NC-1）和非晶纳米颗粒（NP-1）。在电流密度为 10 mA·cm 时，Cu-BHT 对 HER 的过电位从 760 mV（NC-1）改善至 450 mV（NP-1），表现出更高的活性。在优化条件下，获得了约 95 mV·dec 的塔菲尔斜率和 10 mA·cm 的交换电流密度。密度泛函理论计算表明，（100）表面上的“Cu 边缘位”在提高 Cu-BHT 纳米颗粒的 HER 催化性能方面发挥了重要作用。
