在B3LYP/6-311+G(d,p)水平上研究了2-(1H-咪唑)苯硫酚(1d)、2-(噁唑)苯硫酚(2d)、2-(噻唑)苯硫酚(3d)及其衍生物的基态质子转移过程,探讨取代基电子效应对质子转移的影响.结果表明:吸电子引入后分子平面电子密度减小,N2-H1间距减小,分...在B3LYP/6-311+G(d,p)水平上研究了2-(1H-咪唑)苯硫酚(1d)、2-(噁唑)苯硫酚(2d)、2-(噻唑)苯硫酚(3d)及其衍生物的基态质子转移过程,探讨取代基电子效应对质子转移的影响.结果表明:吸电子引入后分子平面电子密度减小,N2-H1间距减小,分子内氢键增强,醇式到酮式质子转移能垒减小;供电子基引入后分子平面电子密度增大,N2-H1间距增大,分子内氢键减弱,质子转移能垒增大.Localized orbital locator(LOL)分析表明:取代基的引入对N1原子成键性质产生影响明显.三者质子转移能垒大小为1d<3d<2d,取代基引后能垒相对大小不变.展开更多
Developing highly active, low-cost and organic surfactants-free Pd-based catalysts for ethanol oxidation reaction（EOR） is now critically important for direct ethanol fuel cells. Herein, surface-clean low-doped PdB/C...Developing highly active, low-cost and organic surfactants-free Pd-based catalysts for ethanol oxidation reaction（EOR） is now critically important for direct ethanol fuel cells. Herein, surface-clean low-doped PdB/C catalysts（typically ca. 1.5 at% of B） are successfully prepared in an aqueous condition without adding any organic surfactants. TEM characterization shows that as-prepared low-doped Pd B nanoparticles are evenly distributed on carbon support. Cyclic voltommagrams of as-prepared low-doped PdB/C in 0.5 M NaOH ＋ 1 M C2H5OH indicate that its onset oxidation potential of ethanol is ca. 80-120 mV more negative than that on commercial Pd/C. Meanwhile, the EOR mass activity of our home-made catalysts is up to 4018 m A·mg-1 Pd. Moreover, the durability on low-doped PdB/C catalysts is at most 2 times higher than that on commercial Pd/C. Geometric and electronic effects are adopted to understand the above mentioned enhancement of activity and durability. This work may provide a facile, low-cost and green strategy on preparing electrocatalysts toward EOR in alkaline media.展开更多
A phenol-containing dibenzhydryl-based α-diimine ligand bearing hydroxy group on para-position of aniline moiety was designed, synthesized, and investigated in Ni-and Pd-catalyzed ethylene polymerization. The Ni comp...A phenol-containing dibenzhydryl-based α-diimine ligand bearing hydroxy group on para-position of aniline moiety was designed, synthesized, and investigated in Ni-and Pd-catalyzed ethylene polymerization. The Ni complex bearing hydroxy groups resulted in not only high polyethylene molecular weight(Mn up to 1.5 × 10^~6), but also significantly increased melting temperature(Tm up to 123℃) and greatly decreased branching density(33/1000 C) versus the Ni catalyst bearing OMe group on para-position of aniline moiety. This is consistent with the hypothesis that the deprotonation of the phenol moiety generated a phenoxide bearing strong electrondonating O-substituent by methylaluminoxane(MAO) cocatalyst. The Pd complexes bearing hydroxy groups exhibited similar catalytic properties to those of the Pd catalyst bearing OMe groups did.展开更多
文摘在B3LYP/6-311+G(d,p)水平上研究了2-(1H-咪唑)苯硫酚(1d)、2-(噁唑)苯硫酚(2d)、2-(噻唑)苯硫酚(3d)及其衍生物的基态质子转移过程,探讨取代基电子效应对质子转移的影响.结果表明:吸电子引入后分子平面电子密度减小,N2-H1间距减小,分子内氢键增强,醇式到酮式质子转移能垒减小;供电子基引入后分子平面电子密度增大,N2-H1间距增大,分子内氢键减弱,质子转移能垒增大.Localized orbital locator(LOL)分析表明:取代基的引入对N1原子成键性质产生影响明显.三者质子转移能垒大小为1d<3d<2d,取代基引后能垒相对大小不变.
基金supported by NSFC (No.21603177)the Natural Science Foundation of Sichuan Province (No.2016JY0212)+1 种基金the Fundamental Research Funds for the Central Universities (No.2017NGJPY05)the Innovation Funds for SMU students (No. 201710656023)
文摘Developing highly active, low-cost and organic surfactants-free Pd-based catalysts for ethanol oxidation reaction（EOR） is now critically important for direct ethanol fuel cells. Herein, surface-clean low-doped PdB/C catalysts（typically ca. 1.5 at% of B） are successfully prepared in an aqueous condition without adding any organic surfactants. TEM characterization shows that as-prepared low-doped Pd B nanoparticles are evenly distributed on carbon support. Cyclic voltommagrams of as-prepared low-doped PdB/C in 0.5 M NaOH ＋ 1 M C2H5OH indicate that its onset oxidation potential of ethanol is ca. 80-120 mV more negative than that on commercial Pd/C. Meanwhile, the EOR mass activity of our home-made catalysts is up to 4018 m A·mg-1 Pd. Moreover, the durability on low-doped PdB/C catalysts is at most 2 times higher than that on commercial Pd/C. Geometric and electronic effects are adopted to understand the above mentioned enhancement of activity and durability. This work may provide a facile, low-cost and green strategy on preparing electrocatalysts toward EOR in alkaline media.
基金financially supported by the National Natural Science Foundation of China (No. 21690071)
文摘A phenol-containing dibenzhydryl-based α-diimine ligand bearing hydroxy group on para-position of aniline moiety was designed, synthesized, and investigated in Ni-and Pd-catalyzed ethylene polymerization. The Ni complex bearing hydroxy groups resulted in not only high polyethylene molecular weight(Mn up to 1.5 × 10^~6), but also significantly increased melting temperature(Tm up to 123℃) and greatly decreased branching density(33/1000 C) versus the Ni catalyst bearing OMe group on para-position of aniline moiety. This is consistent with the hypothesis that the deprotonation of the phenol moiety generated a phenoxide bearing strong electrondonating O-substituent by methylaluminoxane(MAO) cocatalyst. The Pd complexes bearing hydroxy groups exhibited similar catalytic properties to those of the Pd catalyst bearing OMe groups did.
