泡沫铜支撑Ru掺杂Cu3P自支撑催化剂及其析氢性能
A Self-Supported Ru-Cu3P Catalyst toward Alkaline Hydrogen Evolution
#These authors contribute equally to the paper.
Received date: 2022-06-23
Revised date: 2022-07-26
Online published: 2022-08-23
过渡金属磷化物(TMP)是一种用于碱性条件下析氢反应(HER)的有效催化剂, 然而其活性严重受限于水解离步。本文通过在泡沫铜(CF)上生长Cu(OH)2纳米阵列, RuCl3溶液浸泡和磷酸化, 制备了一种具有较大比表面积和适当Ru掺杂的Ru-Cu3P自支撑催化剂(Ru-Cu3P/CF)。作为一种优良的HER催化剂,在电流密度为10 mA·cm-2时, 其过电位为95.6 mV, 比Cu3P/CF降低149.4 mV。其决速步由Volmer向Heyrovsky机制过渡。HER性能的提高可以归因于Ru掺杂磷化铜促进水解离过程,以及Cu(OH)2纳米阵列衍生Cu3P纳米结构具有更高的电化学活性面积, 从而保证了更多的活性位点。本论文突出了具有空的d轨道的金属掺杂促进水解离的重要性,为高性能电解水析氢催化剂的设计提供了新思路。
万紫轩 , 王超辉 , 康雄武 . 泡沫铜支撑Ru掺杂Cu3P自支撑催化剂及其析氢性能[J]. 电化学, 2022 , 28(10) : 2214005 . DOI: 10.13208/j.electrochem.2214005
Transition metal phosphide (TMP) is a kind of effective catalysts toward hydrogen evolution reaction (HER) in alkaline electrolytes. However, the performance of TMP catalysts is strongly limited by water splitting. In this work, we developed a method to prepare a copper foam (CF) supported Ru-doped Cu3P catalyst (Ru-Cu3P/CF) by a consecutive growth of Cu(OH)2 nanoarrays, soaking in RuCl3 solution and phosphorization. A large surface area was obtained by the self-supported catalysts with the appropriative Ru doping. As an excellent HER catalyst, it exhibited a low overpotential of 95.6 mV at a current density of 10 mA·cm-2, which is 149.4 mV lower than that of Cu3P/CF without Ru-doping. The Tafel slope was reduced from 136.6 to 73.6 mA·dec-1 and the rate determining step was changed from Volmer step to Heyrovsky step. The improvement of HER performance might be attributed to the facilitated water splitting step by Ru-doping, which provides more active sites for water splitting. The nanoparticles morphology of Ru-Cu3P derived from the Cu(OH)2 arrays ensured large electrochemical surface areas of the supported electrodes, which could promote the mass and electron transfers, and promote gas production and bubble release. This work highlights the importance of the tuning of the water splitting step and surface engineering by the transition metal with emptier d orbitals, which may pave the road for design of high-performance HER electrocatalyst.
Key words： electrocatalysis; water splitting; hydrogen evolution; copper phosphide; Ru-doping
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