单原子Ru_(1)-N_(x)/C(x=3,4)催化剂活化H_(2)、H_(2)O和CH_(3)OH的理论研究  

Theoretical study on the activation of H_(2),H_(2)O and CH_(3)OH over single-atom Ru_(1)-N_(x)/C(x=3,4)catalysts

作　　者：张寅胜 苟进韬 刘挺豪 杨华清[1] ZHANG Yin-sheng;GOU Jin-tao;LIU Ting-hao;YANG Hua-qing(College of Chemical Engineering,Sichuan University,Chengdu 610065,China)

机构地区：[1]四川大学化学工程学院,四川成都610065

出　　处：《化学研究与应用》2024年第10期173-178,共6页Chemical Research and Application

基　　金：国家自然科学基金项目(22073064)资助。

摘　　要：在GGA-PBE/DNP水平下,构建了两种氮掺杂石墨烯负载Ru单原子催化剂,记作Ru_(1)-N_(x)/C(x=3,4)。在热力学上,Ru_(1)-N_(4)/C比Ru_(1)-N_(3)/C更稳定。研究了Ru_(1)-N_(x)/C(x=3,4)对H_(2)、H_(2)O和CH_(3)OH的活化性能。H_(2)、H_(2)O和CH_(3)OH在Ru_(1)-N_(3)/C上的化学吸附比在Ru_(1)-N_(4)/C上的化学吸附更强。同时,在实验温度下,它们在Ru_(1)-N_(x)/C(x=3,4)上的解离均为吸能反应。在动力学上,Ru_(1)-N_(4)/C活化解离H_(2)、H_(2)O和CH_(3)OH的能力均强于Ru_(1)-N_(3)/C。在水溶液中,两种催化剂对H2的活化较H_(2)O更强。在甲醇溶液中,Ru_(1)-N_(3)/C对CH_(3)OH的活化强于对H_(2)的活化;Ru_(1)-N_(4)/C对H_(2)的活化强于对CH_(3)OH的活化。Two nitrogen doped graphene supported Ru single-atom catalysts are modelled at GGA-PBE/DNP level,denoted as Ru_(1)-N_(x)/C(x=3,4).Thermodynamically,Ru_(1)-N_(4)/C is more stable than Ru_(1)-N_(3)/C.Over Ru_(1)-N,/C(x=3,4),the activations of H_(2),H_(2)O,and CH_(3)OH are investigated.The chemical adsorption of H_(2),H_(2)O and CH_(3)OH on Ru-N,/C is stronger than that on Ru_(1)-N_(4)/C.Meanwhile,the dissociations of H_(2),H_(2)O and CH_(3)OH on Ru_(1)-N/C(x=3,4)are endoergic under experimental temperature.Ki-netically,the dissociations of H_(2),H_(2)O and CH_(3)OH on Ru_(1)-N_(4)/C are more favorable than those on Ru_(1)-N_(3)/C.In aqueous solution,the two catalysts exhibit higher activity for H_(2) activation than for H_(2)O activation.In methanol solution,Ru_(1)-N_(x)/C shows higher ac-tivity for CH_(2)OH activation than for H,activation,whereas Ru_(1)-N_(4)/C displays higher activity for H_(2) activation.

关 键 词：GGA-PBE Ru_(1)-N_(x)/C H_(2) H_(2)O CH_(3)OH 活化 

分 类 号：O647.32[理学—物理化学]