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Cl~–…苯氰…H_2O中阴离子氢键协同效应与芳香性理论研究 被引量:1
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作者 宋慧 李斌 +2 位作者 赵光明 武红娟 龙泽清 《原子与分子物理学报》 CAS CSCD 北大核心 2015年第1期15-25,共11页
本文采用DFT-B3LYP和MP2(full)方法对三聚体Cl–…苯氰…H2O中O/C–H…Cl–阴离子氢键与传统氢键O–H…N和C–H…O之间的协同效应、热力学性质以及芳香性进行了研究.结果表明阴离子氢键O/C–H…Cl–对O–H…N或C–H…O相互作用的影响更... 本文采用DFT-B3LYP和MP2(full)方法对三聚体Cl–…苯氰…H2O中O/C–H…Cl–阴离子氢键与传统氢键O–H…N和C–H…O之间的协同效应、热力学性质以及芳香性进行了研究.结果表明阴离子氢键O/C–H…Cl–对O–H…N或C–H…O相互作用的影响更显著.在线性结构中发生正协同效应,熵变是促进热力学协同效应的主要因素,而在环状结构中发生反协同效应,焓变成为主要因素.在三聚体形成过程中,苯氰环的芳香性是减弱的,而苯氰中π→π*共轭效应是增强的.结果表明,协同效应能Ecoop.分别与Rc(NICS(1)ternary/NICS(1)binary),ΔΔδ(Δδternary-Δδbinary),Rc'((NICS(1)ternary-NICS(1)binary)/NICS(1)binary)和RBDE(C–CN)(BDE(C–CN)ternary/BDE(C–CN)binary)均具有良好的线性关系.同时,AIM的分析也佐证了协同效应的存在. 展开更多
关键词 协同效应 阴离子氢键 热力学协同效应 芳香性 MP2
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Solar-heating boosted catalytic reduction of CO_(2) under full-solar spectrum 被引量:2
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作者 Hongjia Wang Yanjie Wang +3 位作者 Lingju Guo Xuehua Zhang Caue Ribeiro Tao He 《Chinese Journal of Catalysis》 SCIE EI CAS CSCD 北大核心 2020年第1期131-139,共9页
Catalytic converting CO2 into fuels with the help of solar energy is regarded as‘dream reaction’,as both energy crisis and environmental issue can be mitigated simultaneously.However,it is still suffering from low e... Catalytic converting CO2 into fuels with the help of solar energy is regarded as‘dream reaction’,as both energy crisis and environmental issue can be mitigated simultaneously.However,it is still suffering from low efficiency due to narrow solar-spectrum utilization and sluggish heterogeneous reaction kinetics.In this work,we demonstrate that catalytic reduction of CO2 can be achieved over Au nanoparticles(NPs)deposited rutile under full solar-spectrum irradiation,boosted by solar-heating effect.We found that UV and visible light can initiate the reaction,and the heat from IR light and local surface-plasmon resonance relaxation of Au NPs can boost the reaction kinetically.The apparent activation energy is determined experimentally and is used to explain the superior catalytic activity of Au/rutile to rutile in a kinetic way.We also find the photo-thermal synergy in the Au/rutile system.We envision that this work may facilitate understanding the kinetics of CO2 reduction and developing feasible catalytic systems with full solar spectrum utilization for practical artificial photosynthesis. 展开更多
关键词 CO_(2) reduction Apparent activation energy Reaction kinetics Solar heating Photo-thermal synergy
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