Targeted construction of high-performance single-atom platinum-based electrocatalysts for hydrogen evolution reaction  

靶向构筑高性能单原子铂基氢析出反应电催化剂

作　　者：Jing Liu Xiandi Ma Jeonghan Roh Dongwon Shin Ara Cho Jeong Woo Han Jianping Long Zhen Zhou Menggai Jiao Kug-Seung Lee EunAe Cho 刘京;马贤迪;卢政汉;申东元;赵阿雅;韩晸宇;龙剑平;周震;焦梦改;李国承;赵恩爱(成都理工大学材料与化学化工学院,四川成都610059;韩国科学技术院材料科学与工程系,韩国大田;郑州大学化工学院,新能源科学与工程交又研究中心,河南郑州450001;浦项科技大学化学工程系,韩国浦项;南开大学材料科学与工程学院,新能源材料化学研究所,新能源转化与存储交又科学中心,先进能源材料化学教育部重点实验室,天津300350;龙门实验室,河南洛阳471023;浦项科技大学浦项加速器实验室,韩国浦项)

机构地区：[1]College of Materials and Chemistry&Chemical Engineering,Chengdu University of Technology,Chengdu 610059,Sichuan,China [2]Department of Materials Science and Engineering,Korea Advanced Institute of Science and Technology,291 Daehak-Ro,Yuseong-Gu,Daejeon 34141,Korea [3]Interdisciplinary Research Center for Sustainable Energy Science and Engineering(IRC4SE2),School of Chemical Engineering,Zhengzhou University,Zhengzhou 450001,Henan,China [4]Department of Chemical Engineering,Pohang University of Science and Technology,Pohang,Gyeongbuk 37673,Korea [5]School of Materials Science and Engineering,Institute of New Energy Material Chemistry,Renewable Energy Conversion and Storage Center,Key Laboratory of Advanced Energy Materials Chemistry(Ministry of Education),Nankai University,Tianjin 300350,China [6]Longmen Laboratory,Luoyang 471023,Henan,China [7]Beamline Division,Pohang Accelerator Laboratory,Pohang University of Science and Technology,Pohang,Gyeongbuk 37673,Korea

出　　处：《Chinese Journal of Catalysis》2025年第2期259-270,共12页催化学报(英文)

基　　金：韩国政府国家研究基金会(NRF-2019M3D1A1079306,NRF-2021R1A2C1011415);四川省自然科学基金(2023NSFSC1079);河南省高等学校重点研究项目(24A530009);龙门实验室前沿探索项目(LMQYTSKT021).

摘　　要：Exploring platinum single-atom electrocatalysts(SACs)is of great significance for effectively catalyzing the hydrogen evolution reaction in order to maximize the utilization of metal atoms.Herein,ruthenium clusters with several atoms(Rux)supported on nitrogen-doped,cost-efficient Black Pearls 2000(Ru_(x)NBP),were synthesized as initial materials via a simple hydrothermal method.Then,[PtCl_(4)]^(2–)ion was reductively deposited on RuxNBP to obtain a Pt SAC(Pt1/RuxNBP).Electrochemical measurements demonstrate the excellent HER performance of Pt_(1)/Ru_(x)NBP with a 5.7-fold increase in mass activity compared to the commercial Pt/C at 20 mV.Moreover,the cell voltage of the proton exchange membrane electrolyzer with Pt_(1)/Ru_(x)NBP is 20 mV lower compared to that with commercial Pt/C at 1.0 A cm^(−2).Physical characterization and density functional theory calculations revealed that the preserved Pt–Cl bond of[PtCl_(4)]^(2–)and the RuxNBP support co-regulate the 5d state of isolated Pt atoms and enhance the catalytic HER capacity of Pt1/RuxNBP.因具有高能量密度和零排放等优点,氢能被认为是传统化石能源的最佳替代品.质子交换膜水电解(PEMWE)是实现可持续环保制氢的一种有效策略.其中,析氢反应(HER)是电解水制氢的关键半反应.贵金属铂(Pt)因具有适当的氢结合能,被认为是酸性条件下电催化HER的首选材料.而开发高性能的单原子Pt基HER电催化剂(PtSAC)可以大幅度提高Pt的利用率,进而降低催化剂的成本。已有研究证实,通过调控配位环境可以使PtSAC在三电极系统中表现出与商业Pt/C相当的电催化HER活性.然而,有关将PtSAC用作阴极材料构筑酸性电解槽并获得高性能水电解的报道较少.因此,探索一种简便易行的合成策略,靶向构建在PEMWE实际应用中具有优异HER性能的PtSAC是本文的主要研究思路.本文首先以氮掺杂的活性炭黑珍珠2000为载体(NBP),通过低温水热还原反应,制备含几个金属原子的钉原子簇前驱体材料(Ru_(x)NBP)。随后以K_(2)PtCl_(4)为Pt源,通过碳缺陷辅助还原的静电置换反应制备了Ru_(x)NBP负载的PtSAC(Pt/Ru_(x)NBP).X射线衍射、高角环形暗场扫描透射电镜、X射线光电子能谱及X射线吸收谱结果表明,Pt/Ru,NBP催化剂中的金属原子均匀分散.其中,Pt主要以孤立的单原子形成分散存在,且与吡啶氮基碳缺陷及两个CI原子配位,而Ru主要以含两个原子的Ru_(2)单元分散存在.作为控制实验,分别以NBP和BP为载体,以K,PtC1_(4)为Pt源,通过碳缺陷辅助还原的静电置换反应制备了与Pt/Ru_(x)NBP目标Pt含量相同的PtSAC(Pt/NBP和Pt/BP);分别以NBP和Ru,NBP为载体,以Pt(acac),为Pt源通过热水反应制备了与Pt/Ru_(x)NBP目标Pt含量相同的PtSAC(Pt/NBP和Pt/Ru_(x)NBP).电化学测试上述PtSAC在酸性条件下电催化HER活性的结果表明,催化剂Pt/BP和Pt/NBP对电催化HER几乎没有活性;而Pt/Ru_(x)NBP则展现出较好的电催化HER活性,其在10mAcm^(2)时的过电位(nio)仅为11mV,远小于催化剂Ru,N

关 键 词：PLATINUM Single-atomeletrocatalyst Ruthenium cluster Hydrogen evolution reaction Density functional theory 

分 类 号：O643.36[理学—物理化学]