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 

机构地区：[1]Department of Chemistry and the Center for the Science of Materials Berlin,Humboldt-Universität zu Berlin,Berlin,Germany [2]Max-Planck-Institut für Chemische Energiekonversion,Mülheim an der Ruhr,Germany [3]Institut für Physik and Center for the Science of Materials Berlin,Humboldt-Universität zu Berlin,Berlin,Germany [4]Helmholtz-Zentrum Berlin für Materialien und Energie GmbH,Berlin,Germany [5]State Key Laboratory of Structural Chemistry,Fujian Institute of Research on the Structure of Matter,Chinese Academy of Sciences,Fuzhou,China

出　　处：《Carbon Energy》2024年第9期80-92,共13页碳能源（英文）

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 task.Herein,Ru atoms in the Ru_(2)P structure were replaced with M=Co,Ni,or Mo to produce M_(2-x)Ru_(x)P nanocrystals.The 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 structures.The 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 centers.As a result,the intrinsic activity of CoRuP and NiRuP increases considerably compared to Ru_(2)P in both acidic and alkaline media.The effect is not observed for MoRuP,in which Mo prefers to occupy the pyramidal sites.In particular,CoRuP shows state-of-the-art activity,outperforming Ru_(2)P with Pt-like activity in 0.5 M H_(2)SO_(4)(η_(10)=12.3 mV;η100=52 mV;turnover frequency(TOF)=4.7 s^(-1)).It remains extraordinarily active in alkaline conditions(η10=12.9 mV;η_(100)=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/C.Further 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.

关 键 词：electrocatalysis ruthenium phosphide transition metal phosphonates 

分 类 号：O64[理学—物理化学]