寻找稳定高效的储氢材料是实现氢经济的关键.过渡金属修饰石墨烯储氢材料在理论上被广泛研究,但存在H2解离和金属团聚的问题.本文基于密度泛函理论对Sc,Ti,V修饰单缺陷石墨烯的结构及储氢性能进行计算.结果表明:单缺陷使Sc,Ti,V与石墨...寻找稳定高效的储氢材料是实现氢经济的关键.过渡金属修饰石墨烯储氢材料在理论上被广泛研究,但存在H2解离和金属团聚的问题.本文基于密度泛函理论对Sc,Ti,V修饰单缺陷石墨烯的结构及储氢性能进行计算.结果表明:单缺陷使Sc,Ti,V与石墨烯的结合能提高4—5倍;Sc,Ti,V离子特性增强,可以通过静电相互作用吸附7,3和4个分子形式的氢;平均氢分子吸附能分别为–0.13,–0.20和–0.18 e V,处于室温和中等压力下储氢的最佳能量范围.而Sc,Ti,V修饰的完整石墨烯上第1个氢解离吸附,氢分子吸附能分别为–1.34,–1.34和–1.16 e V.特别重要的是,Sc,V修饰的缺陷石墨烯吸附和脱附氢分子过程中重构能仅为0.00 e V和0.03 e V,对实现快速吸放氢气非常有利.本研究将有利于深入认识3d过渡金属修饰碳材料的储氢机理.展开更多
A systematic theoretical investigation has been studied on Fujiwara-Moritani reaction between 3-methoxyacetanilide with n-butyl acrylate by means of density functional theory(DFT) calculations when two types of Pd(Ⅱ)...A systematic theoretical investigation has been studied on Fujiwara-Moritani reaction between 3-methoxyacetanilide with n-butyl acrylate by means of density functional theory(DFT) calculations when two types of Pd(Ⅱ) catalysts are employed. In [Pd(MeCN)_4](BF_4)_2 catalytic cycle, a 1,4-benzoquinone(BQ)-induced C-H activation of trans-(MeCN)_2Pd(BQ)~(2+) with 3-methoxyacetanilide occurs as the first step to give DC-4_(MeCN), facilitating the insertion of n-butyl acrylate and β-hydride elimination, followed by recycling of catalyst through hydrogen abstraction of monocationic BQ fragment. In Pd(OAc)_(2) catalytic cycle, it is proposed that the most favored reaction pathway should proceed in dicationic mechanism involving a BQ-assisted hydrogen transfer for C-H activation by Pd active catalyst(HOAc)_(2)Pd(BQ)^(2+) to generate DC-4_(HOAc), promoting acrylate insertion and β-hydride elimination, followed by the regeneration of catalyst to give the final product. The calculations indicate that the rate-determining step in [Pd(MeCN)_(4)](BF_4)_(2) catalytic system is the acrylate insertion, while it is the regeneration of catalyst in the Pd(OAc)_(2) catalytic system. In particular, the roles of BQ and ligand effects have also been investigated.展开更多
文摘寻找稳定高效的储氢材料是实现氢经济的关键.过渡金属修饰石墨烯储氢材料在理论上被广泛研究,但存在H2解离和金属团聚的问题.本文基于密度泛函理论对Sc,Ti,V修饰单缺陷石墨烯的结构及储氢性能进行计算.结果表明:单缺陷使Sc,Ti,V与石墨烯的结合能提高4—5倍;Sc,Ti,V离子特性增强,可以通过静电相互作用吸附7,3和4个分子形式的氢;平均氢分子吸附能分别为–0.13,–0.20和–0.18 e V,处于室温和中等压力下储氢的最佳能量范围.而Sc,Ti,V修饰的完整石墨烯上第1个氢解离吸附,氢分子吸附能分别为–1.34,–1.34和–1.16 e V.特别重要的是,Sc,V修饰的缺陷石墨烯吸附和脱附氢分子过程中重构能仅为0.00 e V和0.03 e V,对实现快速吸放氢气非常有利.本研究将有利于深入认识3d过渡金属修饰碳材料的储氢机理.
基金supported by the Natural Science Foundations of China(21501115)。
文摘A systematic theoretical investigation has been studied on Fujiwara-Moritani reaction between 3-methoxyacetanilide with n-butyl acrylate by means of density functional theory(DFT) calculations when two types of Pd(Ⅱ) catalysts are employed. In [Pd(MeCN)_4](BF_4)_2 catalytic cycle, a 1,4-benzoquinone(BQ)-induced C-H activation of trans-(MeCN)_2Pd(BQ)~(2+) with 3-methoxyacetanilide occurs as the first step to give DC-4_(MeCN), facilitating the insertion of n-butyl acrylate and β-hydride elimination, followed by recycling of catalyst through hydrogen abstraction of monocationic BQ fragment. In Pd(OAc)_(2) catalytic cycle, it is proposed that the most favored reaction pathway should proceed in dicationic mechanism involving a BQ-assisted hydrogen transfer for C-H activation by Pd active catalyst(HOAc)_(2)Pd(BQ)^(2+) to generate DC-4_(HOAc), promoting acrylate insertion and β-hydride elimination, followed by the regeneration of catalyst to give the final product. The calculations indicate that the rate-determining step in [Pd(MeCN)_(4)](BF_4)_(2) catalytic system is the acrylate insertion, while it is the regeneration of catalyst in the Pd(OAc)_(2) catalytic system. In particular, the roles of BQ and ligand effects have also been investigated.
