美国俄亥俄州立大学Claudia Turro团队开发了一种红光光电催化析氢用Dirhodium(II,II)/ NiO光电阴极。 相关研究成果于2021年1月11日出版的《美国化学会志》。

研究人员合成了一种新的Rh2（II，II）二聚体，并将其固定在NiO光电阴极上。铱配合物既可以作为敏化剂向NiO中注入空穴，也可以作为制氢的催化剂。单分子设计通过单独的敏化剂和催化剂绕过了传统多组分方法的限制，从而简化了制氢途径，并减少了与额外的分子间电荷转移步骤相关的能量损失。Rh2(II,II)配合物在整个可见光范围内对紫外光有很强的吸收，并延伸到近红外的∼800 nm处，与染料敏化太阳能电池和光电合成电池中使用的传统染料相比，其可以吸收更大比例的太阳辐照度。

在对甲苯磺酸（0.1 M）存在下，用655 nm光（53 mW cm–2）辐照Rh2–NiO光电极，在0.2 V下与Ag/AgCl相比产生52μA cm–2的光电流，2.5 h后，在没有光电极降解的情况下，法拉第产氢效率高达85±5%。

该项工作提出了一种单分子光催化剂，作为NiO的光吸收体和催化中心，当锚定在p型半导体上时，能够从带有红光的酸性溶液中生成氢气，从而为太阳能燃料生产提供了一个有希望的新系统。

附：英文原文

Title: Dirhodium(II,II)/NiO Photocathode for Photoelectrocatalytic Hydrogen Evolution with Red Light

Author: Jie Huang, Jiaonan Sun, Yiying Wu, Claudia Turro

Issue&Volume: January 11, 2021

Abstract: A new Rh2(II,II) dimer has been synthesized and anchored onto a NiO photocathode. The dirhodium complex acts as both the sensitizer to inject holes into NiO and as catalyst for the production of hydrogen. The single-molecule design circumvents limitations of the conventional multicomponent approach with separate sensitizer and catalyst, thus simplifying the hydrogen production pathway and reducing energy losses associated with additional intermolecular charge transfer steps. The Rh2(II,II) complex absorbs strongly from the ultraviolet throughout the visible range and tails into the near-IR to ～800 nm, permitting absorption of a significantly greater portion of the solar irradiance as compared to traditional dyes used in dye-sensitized solar cells and photoelectrosynthesis cells. The irradiation of the Rh2–NiO photoelectrode with 655 nm light (53 mW cm–2) results in a photocurrent that reaches 52 μA cm–2 at 0.2 V vs Ag/AgCl in the presence of p-toluenesulfonic acid (0.1 M), with Faradaic efficiencies of H2 production up to 85 ± 5% after 2.5 h without photoelectrode degradation. This work presents the first single-molecule photocatalyst, acting as both the light absorber and catalytic center on NiO, able to generate hydrogen from acidic solutions with red light when anchored to a p-type semiconductor, providing a promising new system for solar fuel production.

DOI: 10.1021/jacs.0c12171

Source: https://pubs.acs.org/doi/10.1021/jacs.0c12171