工程科学学报2025，Vol.47Issue(5)：1047-1054,8.DOI:10.13374/j.issn2095-9389.2024.07.11.001
负载型Ru/CN催化剂的制备及其催化氨硼烷水解制氢
Preparation of supported Ru/CN catalysts and their performance in hydrogen generation from the catalytic hydrolysis of ammonia borane
摘要
Abstract
Ammonia borane(AB)has a hydrogen mass fraction of 19.6%and is widely regarded as a safe and efficient medium for hydrogen storage and release.However,developing an effective catalyst to drive hydrogen evolution via AB hydrolysis remains a significant challenge.Carbon nitride(CN)materials exhibit a distinctive band structure,outstanding chemical stability,and a coordination framework composed of nitrogen and carbon atoms.The lone electron pairs on nitrogen atoms enhance their coordination with metal atoms more readily than those on carbon atoms.Consequently,most metal atoms preferentially coordinate with nitrogen,making CN a valuable support material for stabilizing noble-metal catalysts.Research indicates that noble metal catalysts,including ruthenium(Ru),silver,palladium,platinum,and rhodium,exhibit exceptionally high catalytic activity in hydrogen production via AB hydrolysis.Among these,Ru-based catalysts demonstrate superior performance in AB hydrolysis and are relatively more cost-effective than other noble metal-based catalysts.However,Ru nanoparticles are prone to agglomeration,highlighting the need for suitable support materials to mitigate this issue and enhance their stability.In this study,CN was synthesized via high-temperature calcination using melamine,cyanuric acid,and citric acid as raw materials.Subsequently,a Ru/CN-supported nanocatalyst was prepared via an impregnation-reduction method.Various characterization techniques were used to analyze the structural composition and microstructure of the catalysts.Additionally,the effects of different factors on the hydrogen production rate during the hydrolysis of ammonia borane(NH3BH3,AB)were systematically investigated.The results revealed that the Ru/CN catalyst exhibits an irregular morphology with a rough surface and depressions,which enhance its surface area and facilitate the formation of active metal sites.The lattice stripe spacing of 0.211 nm corresponds to the(002)crystal plane of Ru,confirming the successful loading of Ru nanoparticles onto the CN support.Furthermore,the Ru nanoparticles were highly dispersed on the support surface,providing abundant active sites for the hydrolytic dehydrogenation reaction of AB.The X-ray photoelectron spectroscopy full spectrum of the Ru/CN catalyst displayed distinct characteristic peaks for carbon(C),nitrogen(N),oxygen(O),and Ru,further verifying the successful incorporation of Ru onto the CN support.The detection of elemental Ru confirmed the successful reduction of Ru3+by sodium borohydride.The presence of Ru in a higher oxidation state is likely due to the partial oxidation of elemental Ru during characterization or performance testing.The Ru/CN catalyst,with a Ru loading of 0.05 mmol,achieved a TOF value of 446.4 min-1.The AB hydrolysis hydrogen production reaction catalyzed by Ru/CN can be approximated as a first-order reaction with respect to the catalyst amount.Increasing the reaction temperature enhances the effective collision frequency between reactant molecules,thereby facilitating hydrogen production.Calculations and analyses revealed that the concentration of AB positively influences the Ru/CN-catalyzed reaction,with an activation energy of 53.6 kJ·mol-1.After five cycles of use,the Ru/CN catalyst remains effective in catalyzing the complete hydrolysis of AB for hydrogen production.This study offers a promising pathway for designing efficient noble-metal catalysts for AB hydrolysis.关键词
氨硼烷/钌催化剂/氮化碳/水解制氢/储氢材料Key words
ammonia borane/Ru catalyst/carbon nitride/hydrolytic dehydrogenation/hydrogen storage material分类
矿业与冶金引用本文复制引用
刘纾羽,陈辛顺,任文婷,冯佳佳,郝思雨,王小燕,许立信,万超..负载型Ru/CN催化剂的制备及其催化氨硼烷水解制氢[J].工程科学学报,2025,47(5):1047-1054,8.基金项目
安徽省高校优秀青年项目(2024AH030008) （2024AH030008）
国家自然科学基金面上项目(22478001)和联合项目(U22A20408) （22478001）
安徽省自然科学基金优秀青年项目(2408085Y005) （2408085Y005）
国家自然科学基金青年项目(22108238) （22108238）
2023、2024年国家级大学生创新创业训练计划资助项目(S202310260212,S202410360211) （S202310260212,S202410360211）
