Li Weimo, Liu Ran, Yu Guangtao, Chen Xiaojie, Yan Su, Ren Siyu, Chen Junjie, Chen Wei, Wang Ce, Lu Xiaofeng
Alan G. MacDiarmid Institute, College of Chemistry, Jilin University, Changchun, 130012, P. R. China.
Engineering Research Center of Industrial Biocatalysis, Fujian Provincial Key Laboratory of Advanced Materials Oriented Chemical Engineering, Fujian-Taiwan Science and Technology Cooperation Base of Biomedical Materials and Tissue Engineering, College of Chemistry and Materials Science, Fujian Normal University, Fuzhou, 350007, P. R. China.
Small. 2024 Apr;20(15):e2307164. doi: 10.1002/smll.202307164. Epub 2023 Nov 23.
Nowadays, highly active and stable alkaline bifunctional electrocatalysts toward water electrolysis that can work at high current density (≥1000 mA cm) are urgently needed. Herein, Mn-doped RuO (MnRuO) nanofibers (NFs) are constructed to achieve this object, presenting wonderful hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) performances with the overpotentials of only 269 and 461 mV at 1 A cm in 1 m KOH solution, and remarkably stability under industrial demand with 1 A cm, significantly better than the benchmark Pt/C and commercial RuO electrocatalysts, respectively. More importantly, the assembled MnRuO NFs||MnRuO NFs electrolyzer toward overall water splitting reaches the current density of 10 mA cm with a cell voltage of 1.52 V and also delivers an outstanding stability over 150 h of continuous operation, far surpassing commercial Pt/C||commercial RuO, RuO NFs||RuO NFs and most previously reported exceptional electrolyzers. Theoretical calculations indicate that Mn-doping into RuO can significantly optimize the electronic structure and weaken the strength of O─H bond to achieve the near-zero hydrogen adsorption free energy (ΔG) value for HER, and can also effectively weaken the adsorption strength of intermediate O at the relevant sites, achieving the higher OER catalytic activity, since the overlapping center of p-d orbitals is closer to the Fermi level.
如今，迫切需要能够在高电流密度（≥1000 mA cm）下工作的高活性和稳定的用于水电解的碱性双功能电催化剂。在此，构建了锰掺杂的RuO（MnRuO）纳米纤维（NFs）以实现这一目标，在1 m KOH溶液中，在1 A cm下，析氢反应（HER）和析氧反应（OER）性能出色，过电位仅为269和461 mV，并且在1 A cm的工业需求下具有显著的稳定性，分别明显优于基准Pt/C和商业RuO电催化剂。更重要的是，组装的MnRuO NFs||MnRuO NFs全水解电解槽在1.52 V的电池电压下达到了10 mA cm的电流密度，并且在连续运行超过150 h的过程中也表现出出色的稳定性，远远超过商业Pt/C||商业RuO、RuO NFs||RuO NFs以及大多数先前报道的优异电解槽。理论计算表明，在RuO中掺杂Mn可以显著优化电子结构并削弱O─H键的强度，以实现HER的近零氢吸附自由能（ΔG）值，并且还可以有效削弱相关位点上中间产物O的吸附强度，实现更高的OER催化活性，因为p-d轨道的重叠中心更接近费米能级。
