陶瓷学报2025，Vol.46Issue(2)：248-258,11.DOI:10.13957/j.cnki.tcxb.2025.02.003
质子交换膜燃料电池钌基硫属化物催化剂的研究进展
Research Progress in Ruthenium-based Chalcogenide Catalysts for Proton Exchange Membrane Fuel Cell Applications
摘要
Abstract
[Significance]Proton exchange membrane fuel cells(PEMFCs)have various advantages,such as high efficiency,fast start-up,and zero emissions,making them promising candidates to replace traditional power sources in the field of transportation.As the core component of PEMFCs,electrocatalysts primarily facilitate the hydrogen oxidation reaction(HOR)at the anode and the oxygen reduction reaction(ORR)at the cathode,which critically govern the performance,durability,and cost of PEMFCs.Notably,the sluggish kinetics of the ORR heavily depend on precious platinum(Pt)as cathode catalysts,hindering the large-scale application of PEMFC.Therefore,it is urgent to develop non-platinum catalysts with low cost,high activity,and high stability to promote the commercial application of PEMFCs.Ruthenium(Ru),the most cost-effective metal in the platinum group,with a price approximately one-third that of Pt,has relatively abundant reserves.When combined with chalcogenides(Ch=S,Se,Te),Ru forms ruthenium-based chalcogenides,which exhibit good ORR activity and methanol resistance,making them potential candidates for practical applications in PEMFCs or direct methanol fuel cells.In recent years,researchers have conducted extensive studies on Ru-based chalcogenide catalysts,including preparation methods,compositions,structures,electrocatalytic performances,enhancement mechanisms,and fuel cell performances,with significant progress achieved.This paper summarizes the preparation methods of ruthenium-based chalcogenides and comprehensively reviews their current research status as oxygen reduction reaction(ORR)catalysts,while addressing existing challenges and future development trends. [Progress]Based on composition and structure,ruthenium-based chalcogenides can be categorized into three types:(1)Nonstoichiometric RuxChy(y/x<1.0),in which a small fraction of chalcogen elements modify the surface of Ru without forming stable compounds;(2)Stoichiometric RuCh2(e.g.,RuS2,RuSe2,RuTe2)with stable crystallographic structures;(3)Ternary Ru-based chalcogenides,in which a third element is introduced to modify RuxChy(y/x<1.0)or RuCh2 catalysts.It is generally believed that metallic Ru serves as the active site in the RuxChy(y/x<1.0)catalyst,where a small content of chalcogen elements distributed on the surface to suppresses Ru oxidation,thereby weakening the oxygen adsorption and enhancing ORR activity.The type of chalcogen element has an important effect on the size of the Ru core clusters and the interaction strength between Ru and surface chalcogens,ultimately modulating the ORR activity.Among RuxChy(y/x<1.0)catalysts,RuxSey(y/x<1.0)exhibits the highest ORR activity.However,the main component of RuxSey catalyst is Ru,and Se and Ru have not formed stable chemical bonds.The surface Se used to suppress Ru oxidation can be easily oxidized,causing the exposed Ru surface to be oxidized and deactivated,weakening the electrochemical stability.In contrast,RuCh2 compounds(e.g.,RuS2,RuSe2,RuTe2)have stable Ru-Ch chemical bonds and lower Ru loading,demonstrating promising fuel cell performance.RuTe2 and RuSe2 exhibit ORR activity comparable to RuxSe(y/x<1.0)while demonstrating significantly enhanced stability.Notably,the orthorhombic-structured RuTe2/C catalyst achieved a breakthrough maximum power density of 672 mW·cm-2 in H2/O2 fuel cells.The cell performance remains unchanged after a 55-hour constant-current test,highlighting its promising performance and durability.To further reduce the Ru content and enhance the catalytic performance,researchers have attempted to modify Ru-based chalcogenides by introducing elements such as Cr,Mo,W,Fe,Co,and Ni,aiming to tailor their surface structures and electronic environments.However,ternary Ru-based chalcogenide catalysts have not demonstrated significant improvements in fuel cell performance.Currently,the maximum power density of ternary catalysts(e.g.,RuxMoySez/C)in fuel cells remains limited to 247 mW·cm-2. [Conclusions and Prospects]With the development of PEMFC towards commercialization,it is necessary and urgent to explore high-performance non-platinum catalysts.Ru-based chalcogenides,as promising candidate catalysts,have garnered significant attention.The preparation methods of Ru-based chalcogenide catalysts and their recent advances in structure/performance regulation and fuel cell applications are systematically summarized,aiming to provide insights for future research on Ru-based chalcogenide catalysts.In recent years,the synthesis of ruthenium-based chalcogenides has become more efficient and simplified,with steady improvements in catalytic activity and fuel cell performance.However,their development and practical application in PEMFCs still face critical challenges: (1)The primary component of RuxChy(y/x<1.0)remains precious metal Ru,and its poor electrochemical stability results in unsatisfactory durability in practical fuel cell applications.Reducing Ru loading while simultaneously enhancing stability remains a critical unresolved challenge for RuxChy(y/x<1.0)catalysts. (2)RuCh2 catalysts demonstrate promising fuel cell performance yet still lag far behind commercial Pt/C catalysts,with their oxygen reduction activity requiring further enhancement.Current limitations include relatively large particle sizes(>5.0 nm)and ill-defined active sites,both of which hinder further improvement in ORR activity.Developing novel synthesis methods to reduce particle size and elucidating their oxygen reduction catalytic mechanisms represent critical future directions for RuCh2 catalysts. (3)Research on ternary Ru-based chalcogenide catalysts has predominantly focused on modifying Ru-Se systems,while studies targeting Ru-Te systems remain scarce.Exploring the incorporation of elements such as Co,Ni,Fe,N,and P into RuTe2 catalysts is considered a promising strategy to enhance their ORR activity and fuel cell performance in future studies.关键词
钌基硫属化物/质子交换膜燃料电池/氧还原反应/电催化剂Key words
Ru-based chalcogenide/proton exchange membrane fuel cell/oxygen reduction reaction/electrocatalyst分类
化学化工引用本文复制引用
龚青,陈泊宏,程刚,邹俊华..质子交换膜燃料电池钌基硫属化物催化剂的研究进展[J].陶瓷学报,2025,46(2):248-258,11.基金项目
江西省自然科学基金(20232BAB213011) （20232BAB213011）
江西省科学院基础研究项目(2022YJC2011,2023YSBG22016,N202460004280002). （2022YJC2011,2023YSBG22016,N202460004280002）
