The modification of oxide-derived Cu electrode with Ni, Zn, and Au was examined to improve the catalytic activity of COz electroreduction. The experimental results showed that Ni modification increased the Faraday eff...The modification of oxide-derived Cu electrode with Ni, Zn, and Au was examined to improve the catalytic activity of COz electroreduction. The experimental results showed that Ni modification increased the Faraday efficiency of the formation of formic acid and n-propanol. The Faraday effi- ciency relating to the formation of the liquid products was as high as 34.3% at -1.5 V versus the saturated calomel electrode reference potential. In contrast, modification with Zn reduced the for- mic acid formation efficiency but enhanced the alcohol formation efficiency. Finally, modification with Au suppressed the selectivity toward the formation of both formic acid and alcohols.展开更多
The possibilities of changes of ORP （oxidation-reduction water potential） with the help of chemical and physical-chemical methods were explored. Distillation and membrane technology were used as physical-chemical me...The possibilities of changes of ORP （oxidation-reduction water potential） with the help of chemical and physical-chemical methods were explored. Distillation and membrane technology were used as physical-chemical methods. In the case of application of chemical methods well-soluble substances were added into water. It was ascertained that the application of membrane technology makes it possible to obtain antioxidant water with negative ORR. Different energy change in a time unit can be applied in a whole number of technological processes and reveals new possibilities for many branches of industry.展开更多
Trifluoromethylation reactions are important transformations in the research and development of drugs, agrochemicals and functional materials. An oxidation/reduction process of trifluoromethyl-containing compounds is ...Trifluoromethylation reactions are important transformations in the research and development of drugs, agrochemicals and functional materials. An oxidation/reduction process of trifluoromethyl-containing compounds is thought to be involved in many recently tested catalytic trifluoromethylation reactions. To provide helpful physical chemical data for mechanistic studies on trifluoromethylation reactions, the redox potentials of a variety of trifluoromethyl-containing compounds and trifluoro- methylated radicals were studied by quantum-chemical methods. First, eoB97X-D was found to be a reliable method in predicting the ionization potentials, electron affinities, bond dissociation enthalpies and redox potentials of trifluoromethylcontaining compounds. One-electron absolute redox potentials of 79 trifluoromethyl substrates and 107 trifluoromethylated radicals in acetonitrile were then calculated with this method. The theoretical results were found to be helpful for interpreting experimental observations such as the relative reaction efficiency of different trifluoromethylation reagents. Finally, the bond dissociation free energies （BDFE） of various compounds were found to have a good linear relationship with the related bond dissociation enthalpies （BDE）. Based on this observation, a convenient method was proposed to predict one-electron redox potentials of neutral molecules.展开更多
基金supported by the National Natural Science Foundation of China(21573183,21222310,21361140374,21321062)the Funda-mental Research Funds for the Central Universities(20720160045)~~
文摘The modification of oxide-derived Cu electrode with Ni, Zn, and Au was examined to improve the catalytic activity of COz electroreduction. The experimental results showed that Ni modification increased the Faraday efficiency of the formation of formic acid and n-propanol. The Faraday effi- ciency relating to the formation of the liquid products was as high as 34.3% at -1.5 V versus the saturated calomel electrode reference potential. In contrast, modification with Zn reduced the for- mic acid formation efficiency but enhanced the alcohol formation efficiency. Finally, modification with Au suppressed the selectivity toward the formation of both formic acid and alcohols.
文摘The possibilities of changes of ORP （oxidation-reduction water potential） with the help of chemical and physical-chemical methods were explored. Distillation and membrane technology were used as physical-chemical methods. In the case of application of chemical methods well-soluble substances were added into water. It was ascertained that the application of membrane technology makes it possible to obtain antioxidant water with negative ORR. Different energy change in a time unit can be applied in a whole number of technological processes and reveals new possibilities for many branches of industry.
基金supported by the National Natural Science Foundation of China(21325208,21172209,21361140372,21202006)Specialized Research Fund for the Doctoral Program(20123402110051)+5 种基金Fundamental Research Funds for the Central Universities(WK2060190025)Chinese Academy of Sciences(KJCX2-EW-J02)Fok Ying Tung Education FoundationAnhui Provincial Natural Science Foundation(1308085QB38)China Grid project funded by Ministry of Education of Chinathe supercomputer center of Shanghai and University of Science and Technology of China
文摘Trifluoromethylation reactions are important transformations in the research and development of drugs, agrochemicals and functional materials. An oxidation/reduction process of trifluoromethyl-containing compounds is thought to be involved in many recently tested catalytic trifluoromethylation reactions. To provide helpful physical chemical data for mechanistic studies on trifluoromethylation reactions, the redox potentials of a variety of trifluoromethyl-containing compounds and trifluoro- methylated radicals were studied by quantum-chemical methods. First, eoB97X-D was found to be a reliable method in predicting the ionization potentials, electron affinities, bond dissociation enthalpies and redox potentials of trifluoromethylcontaining compounds. One-electron absolute redox potentials of 79 trifluoromethyl substrates and 107 trifluoromethylated radicals in acetonitrile were then calculated with this method. The theoretical results were found to be helpful for interpreting experimental observations such as the relative reaction efficiency of different trifluoromethylation reagents. Finally, the bond dissociation free energies （BDFE） of various compounds were found to have a good linear relationship with the related bond dissociation enthalpies （BDE）. Based on this observation, a convenient method was proposed to predict one-electron redox potentials of neutral molecules.
