石墨炔负载的双金属单团簇催化剂用于碱性析氢反应  

Bimetallic single‐cluster catalysts anchored on graphdiyne for alkaline hydrogen evolution reaction

作　　者：陈斌[1] 蒋亚飞 肖海 李隽[1,2] Bin Chen;Ya‐Fei Jiang;Hai Xiao;Jun Li(Department of Chemistry and Engineering Research Center of Advanced Rare‐Earth Materials of Ministry of Education,Tsinghua University,Beijing 100084,China;Department of Chemistry and Guangdong Provincial Key Laboratory of Catalytic Chemistry,Southern University of Science and Technology,Shenzhen 518055,Guangdong,China)

机构地区：[1]清华大学化学系,稀土新材料教育部工程研究中心,北京100084 [2]南方科技大学化学系,广东省催化化学重点实验室,广东深圳518055

出　　处：《Chinese Journal of Catalysis》2023年第7期306-313,共8页催化学报（英文）

基　　金：国家自然科学基金(92261111,22122304);国家重点研发计划(2022YFA1503000,2022YFA1503900);广东省催化化学重点实验室(2020B121201002);清华大学自主科研计划(20221080065).

摘　　要：氢气(H_(2))可以存储可再生能源并应用于燃料电池,其中电化学析氢反应(HER)是可持续制备高纯氢气的方法之一.铂(Pt)是HER最有效的电催化剂之一,但其在碱性介质中存在较高的水解离能垒,限制了Pt电催化剂整体的HER活性,而提高水解离动力学可能会增强H吸附,不利于制H_(2),这使得进一步优化Pt基碱性HER电催化剂面临类似Sabatier原则的限制.本文预测,石墨炔(GDY)负载的具有金字塔结构的双金属M1A3(M为后过渡金属,A为前过渡金属)四原子单团簇催化剂(SCCs)是高性能的碱性HER电催化剂.通过第一性原理计算发现,Pt_(1)Ti_(3)/GDYSCC在工作条件下热力学和动力学稳定,能够通过Volmer-Heyrovsky机制提供碱性HER的高催化活性.一方面,Ti金属位点可以协同促进水的解离,降低水解离能垒,并促进水解离形成的H中间体(*H)向邻近的Pt金属位点转移,从而加快了碱性HER过程的Volmer决速步;另一方面,相邻带负电荷的Pt金属位点的d带中心下移,从而有利于H的脱附,提供了更优化的H吸附自由能(ΔG*H).因此,Pt_(1)Ti_(3)/GDY SCC有希望突破Pt基电催化剂类似Sabatier原则的限制.通过筛选M1替代Pt1,获得最佳的ΔG*H和水解离,进一步预测Ir1Ti3/GDY SCC在低*OH覆盖率下是一个更有前景的碱性HER电催化剂.综上,本文提出了一种新型的M1A3/GDYSCCs,它具有作为碱性HER高性能电催化剂的巨大潜力,同时为碱性HER电催化剂的理性设计提供了新见解.Pt‐based electrocatalysts suffer from high water dissociation barriers that limit their overall hydrogen evolution reaction(HER)activities in alkaline media.Here we predict the bimetallic four‐atom single‐cluster catalysts(SCCs)M_(1)A_(3)(M as later transition metal and A as early transition metal)with pyramidal structure supported on graphdiyne(GDY)for alkaline HER.Theoretical calculations show that the stable Pt_(1)Ti_(3)/GDY SCC delivers high alkaline HER activity via the Volmer‐Heyrovsky mechanism.The excellent catalytic performance of Pt_(1)Ti_(3)/GDY SCC is attributed to both the low‐valent Pt site that renders an optimal hydrogen adsorption free energy(ΔG^(*)H),and the synergic effect of adjacent Ti sites that leads to a low water dissociation barrier.By screening alternative M1 in M1Ti3/GDY for optimalΔG*H and facile water dissociation,we further identify the Ir_(1)Ti_(3)/GDY SCC to be a potentially high‐performing alkaline HER electrocatalyst at low*OH coverage.Our work provides new insights and guidelines for the rational design of alkaline HER electrocatalysts.

关 键 词：碱性析氢反应 水解离动力学 单团簇催化 Pt1Ti3/Graphdiyne 

分 类 号：O64[理学—物理化学]