Liu Yu, Xu Shengjie, Zheng Xinyu, Lu Yikai, Li Di, Jiang Deli
School of Chemistry and Chemical Engineering, Jiangsu University, Zhenjiang 212013, China.
Institute for Energy Research, Jiangsu University, Zhenjiang 212013, China.
J Colloid Interface Sci. 2022 Nov;625:457-465. doi: 10.1016/j.jcis.2022.06.059. Epub 2022 Jun 16.
Electrochemical water splitting is regarded as a prospective means for H production. The lack of efficient active sites and the sluggish kinetics in alkaline media remain the major obstacles for hydrogen evolution reaction (HER). Herein, a rational construction of Ru-doped cobalt phosphide leaf-like nanoarrays supported on carbon cloth (Ru-CoP NAs) was designed via a MOF-derived route and subsequent phosphating treatment for accelerating HER in the alkaline. The unique hierarchical structure is conductive to exposing more active sites and accelerating the diffusion of electrolyte and the release of H bubble. The optimized Ru-CoP-2.5 NAs exhibits a small overpotential of 52 mV to drive 10 mA cm for HER and a low Tafel slope of 39.7 mV dec in 1 M KOH, which outperforms most of other reported CoP-based electrocatalysts. Furthermore, density functional theory (DFT) calculations unveil that Ru dopants can modulate the electron environment around pure CoP and optimize the adsorption energy of H*, accelerating the reaction kinetics. This work provides an insight to promote the electrocatalytic activity of metal phosphide for hydrogen production.
电化学水分解被认为是一种有前景的制氢方法。缺乏高效活性位点以及在碱性介质中缓慢的动力学仍然是析氢反应（HER）的主要障碍。在此，通过一种金属有机框架（MOF）衍生路线和随后的磷化处理，设计了一种合理构建的负载在碳布上的钌掺杂磷化钴叶状纳米阵列（Ru-CoP NAs），以加速碱性条件下的析氢反应。独特的分级结构有助于暴露更多活性位点，并加速电解质的扩散和氢气泡的释放。优化后的Ru-CoP-2.5 NAs在1 M KOH中驱动10 mA cm的析氢反应时表现出52 mV的小过电位和39.7 mV dec的低塔菲尔斜率，优于大多数其他报道的基于CoP的电催化剂。此外，密度泛函理论（DFT）计算表明，Ru掺杂剂可以调节纯CoP周围的电子环境并优化H*的吸附能，从而加速反应动力学。这项工作为促进金属磷化物用于制氢的电催化活性提供了见解。
