Jiang Binbin, Xiao Han, Li Jiayi, Tang Huiling, Chen Hao, Deng Shengjue, Tan Yiwei, Yu Can, Wang Junwei, Huang Aijian, Cheng Tao, Yang Hao, Yin Kui, Wu Konglin
Anhui Provincial Key Laboratory of Advanced Catalysis and Energy Materials, School of Chemistry and Chemical Engineering, Anqing Normal University, Anqing, 246001, P. R. China.
Institute of Clean Energy and Advanced Nanocatalysis (iClean), School of Chemistry and Chemical Engineering, Anhui University of Technology, Maanshan, 243002, P. R. China.
Small. 2025 Jan;21(1):e2406900. doi: 10.1002/smll.202406900. Epub 2024 Nov 5.
Seawater electrolysis is an ideal approach to generating green hydrogen. Nevertheless, the sluggish kinetics of water dissociation and the detrimental chlorine chemistry environment are serious obstructions for industrial applications. Herein, constructing unique (Co) Lewis acid and (Ru-P) base pair sites in Ru-CoP decorated on nitrogen and phosphorus co-doped carbon (Ru-CoP/NPC) significantly optimizes the energy barrier of water dissociation and enhances the anti-corrosive ability for alkaline seawater splitting. As expected, the optimal Ru-CoP/NPC-2 exhibits exceptional hydrogen evolution reaction (HER) performances with overpotentials as low as 22.0 and 26.0 mV to derive 10 mA cm and operate steadily (@ 50 mA cm) over 30 h in alkaline and alkaline seawater electrolytes. The experimental and theoretical results elucidate that Co acting as Lewis acid sites prompts the water adsorption and breakage of the H─O bond, whereas Ru-P as Lewis base sites facilitates the hydrogen desorption in alkaline media. Furthermore, modulated chemical microenvironments can be beneficial to hinder chloride corrosion on the active sites of catalysts. This work sheds light on the rational construction of a highly efficient electrocatalyst for alkaline HER in seawater.
海水电解是生产绿色氢气的理想途径。然而，水离解动力学缓慢以及有害的氯化学环境是工业应用的严重障碍。在此，在氮磷共掺杂碳负载的Ru-CoP（Ru-CoP/NPC）中构建独特的（Co）路易斯酸和（Ru-P）碱基对位点，显著优化了水离解的能垒，并增强了碱性海水分解的抗腐蚀能力。正如预期的那样，最优的Ru-CoP/NPC-2在碱性和碱性海水电解质中展现出优异的析氢反应（HER）性能，在10 mA cm下过电位低至22.0和26.0 mV，并在50 mA cm下稳定运行超过30小时。实验和理论结果表明，作为路易斯酸位点的Co促使水吸附和H─O键断裂，而作为路易斯碱位点的Ru-P则促进碱性介质中的氢脱附。此外，调制的化学微环境有利于阻碍催化剂活性位点上的氯化物腐蚀。这项工作为合理构建用于海水中碱性HER的高效电催化剂提供了思路。
