Activating Ru in the pyramidal sites of Ru_(2)P-type structures with earth-abundant transition metals for achieving extremely high HER activity while minimizing noble metal content

作     者：Sayed M.El-Refaei Patrícia A.Russo Thorsten Schultz Zhe-Ning Chen Patrick Amsalem Norbert Koch Nicola Pinna 

作者机构：Department of Chemistry and the Center for the Science of Materials BerlinHumboldt-Universität zu BerlinBerlinGermany Max-Planck-Institut für Chemische EnergiekonversionMülheim an der RuhrGermany Institut für Physik and Center for the Science of Materials BerlinHumboldt-Universität zu BerlinBerlinGermany Helmholtz-Zentrum Berlin für Materialien und Energie GmbHBerlinGermany State Key Laboratory of Structural ChemistryFujian Institute of Research on the Structure of MatterChinese Academy of SciencesFuzhouChina 

出 版 物：《Carbon Energy》 (碳能源（英文）)

年 卷 期：2024年第6卷第9期

页      面：80-92页

核心收录：

学科分类：081704[工学-应用化学] 07[理学] 070304[理学-物理化学(含∶化学物理)] 08[工学] 0817[工学-化学工程与技术] 0703[理学-化学] 

基　　金：The authors thank C. Erdmann for the transmission electron microscopy measurements 

主　　题：electrocatalysis ruthenium phosphide transition metal phosphonates 

摘      要：Rational design of efficient pH-universal hydrogen evolution reaction catalysts to enable large-scale hydrogen production via electrochemical water splitting is of great significance,yet a challenging ***,Ru atoms in the Ru_(2)P structure were replaced with M=Co,Ni,or Mo to produce M_(2-x)Ru_(x)P *** metals show strong site preference,with Co and Ni occupying the tetrahedral sites and Ru the square pyramidal sites of the CoRuP and NiRuP Ru_(2)P-type *** presence of Co or Ni in the tetrahedral sites leads to charge redistribution for Ru and,according to density functional theory calculations,a significant increase in the Ru d-band *** a result,the intrinsic activity of CoRuP and NiRuP increases considerably compared to Ru_(2)P in both acidic and alkaline *** effect is not observed for MoRuP,in which Mo prefers to occupy the pyramidal *** particular,CoRuP shows state-of-the-art activity,outperforming Ru_(2)P with Pt-like activity in 0.5 M H_(2)SO_(4)(η10=12.3 mV;η100=52 mV;turnover frequency(TOF)=4.7 s^(-1)).It remains extraordinarily active in alkaline conditions(η10=12.9 mV;η100=43.5 mV)with a TOF of 4.5 s^(-1),which is 4x higher than that of Ru_(2)P and 10x that of Pt/*** increase in the Co content does not lead to drastic loss of activity,especially in alkaline medium,where,for example,the TOF of Co_(1.9)Ru_(0.1)P remains comparable to that of Ru_(2)P and higher than that of Pt/C,highlighting the viability of the adopted approach to prepare cost-efficient catalysts.