A post-synthetic modification strategy has been used to prepare three solid base catalysts, including Er（btc）（ED）075（H2O）0.25 （2, btc = 1,3,5-benzenetricarboxylates, ED = 1,2-ethanediamine）, Er（btc）（PP）0.5...A post-synthetic modification strategy has been used to prepare three solid base catalysts, including Er（btc）（ED）075（H2O）0.25 （2, btc = 1,3,5-benzenetricarboxylates, ED = 1,2-ethanediamine）, Er（btc）（PP）0.55（H20）0.45 （3, PP = piperazine）, and Er（btc）（DABCO）0.15（H2O）0.85 （4, DABCO = 1,4- diazabicyclo[2.2.2]octane）, by grafting three different diamines onto the coordinatively unsaturated Er（III） ions into the channels of the desolvated lanthanide metal-organic framework （Er（otc））. The resulting metal-organic frameworks were characterized by elemental analysis, thermogravimetric analysis, powder X-ray diffraction, and N2 adsorption. Based on its higher loading ratio of the diamine, as well as its greater stability and porosity, catalyst 2 exhibited higher catalytic activity and reusability than catalysts 3 and 4- for the Knoevenagel condensation reaction. The catalytic mechanism of 2 has also been investigated using size-selective catalysis tests.展开更多
It is a very fine substitutable energy technology to synthesize ethanol from biomass-derived syngas. This paper summarized the development of preparing ethanol from syngas, and especially elaborated on the research st...It is a very fine substitutable energy technology to synthesize ethanol from biomass-derived syngas. This paper summarized the development of preparing ethanol from syngas, and especially elaborated on the research status of catalysts for the process. Based on the relative researches on the reaction mechanism, structure and performance of the catalysts, the optimum design of catalysts with high activity was presented in this review, which set the theoretical and application foundation for the industrial production of ethanol from syngas.展开更多
Organic electrosynthesis has been widely used as an environmentally conscious alternative to conventional methods for redox reactions because it utilizes electric current as a traceless redox agent instead of chemical...Organic electrosynthesis has been widely used as an environmentally conscious alternative to conventional methods for redox reactions because it utilizes electric current as a traceless redox agent instead of chemical redox agents. Indirect electrolysis employing a redox catalyst has received tremendous attention, since it provides various advantages compared to direct electrolysis. With indirect electrolysis, overpotential of electron transfer can be avoided, which is inherently milder, thus wide functional group tolerance can be achieved. Additionally, chemoselectivity, regioselectivity, and stereoselectivity can be tuned by the redox catalysts used in indirect electrolysis. Furthermore, electrode passivation can be avoided by preventing the formation of polymer films on the electrode surface. Common redox catalysts include N-oxyl radicals, hypervalent iodine species, halides, amines, benzoquinones(such as DDQ and tetrachlorobenzoquinone), and transition metals. In recent years, great progress has been made in the field of indirect organic electrosynthesis using transition metals as redox catalysts for reaction classes including C–H functionalization, radical cyclization, and cross-coupling of aryl halides-each owing to the diverse reactivity and accessible oxidation states of transition metals. Although various reviews of organic electrosynthesis are available, there is a lack of articles that focus on recent research progress in the area of indirect electrolysis using transition metals, which is the impetus for this review.展开更多
基金supported by the National Natural Science Foundation of China(21372087)~~
文摘A post-synthetic modification strategy has been used to prepare three solid base catalysts, including Er（btc）（ED）075（H2O）0.25 （2, btc = 1,3,5-benzenetricarboxylates, ED = 1,2-ethanediamine）, Er（btc）（PP）0.55（H20）0.45 （3, PP = piperazine）, and Er（btc）（DABCO）0.15（H2O）0.85 （4, DABCO = 1,4- diazabicyclo[2.2.2]octane）, by grafting three different diamines onto the coordinatively unsaturated Er（III） ions into the channels of the desolvated lanthanide metal-organic framework （Er（otc））. The resulting metal-organic frameworks were characterized by elemental analysis, thermogravimetric analysis, powder X-ray diffraction, and N2 adsorption. Based on its higher loading ratio of the diamine, as well as its greater stability and porosity, catalyst 2 exhibited higher catalytic activity and reusability than catalysts 3 and 4- for the Knoevenagel condensation reaction. The catalytic mechanism of 2 has also been investigated using size-selective catalysis tests.
基金Project (No. 06GG2209052) supported by the Natural Science Foundation of Shandong Province, China
文摘It is a very fine substitutable energy technology to synthesize ethanol from biomass-derived syngas. This paper summarized the development of preparing ethanol from syngas, and especially elaborated on the research status of catalysts for the process. Based on the relative researches on the reaction mechanism, structure and performance of the catalysts, the optimum design of catalysts with high activity was presented in this review, which set the theoretical and application foundation for the industrial production of ethanol from syngas.
基金supported by the National Natural Science Foundation of China (21821002, 21772222, and 91956112)Chinese Academy of Sciences (XDB20000000)Science and Technology Commission of Shanghai Municipality (18JC1415600 and 20JC1417100)。
文摘Organic electrosynthesis has been widely used as an environmentally conscious alternative to conventional methods for redox reactions because it utilizes electric current as a traceless redox agent instead of chemical redox agents. Indirect electrolysis employing a redox catalyst has received tremendous attention, since it provides various advantages compared to direct electrolysis. With indirect electrolysis, overpotential of electron transfer can be avoided, which is inherently milder, thus wide functional group tolerance can be achieved. Additionally, chemoselectivity, regioselectivity, and stereoselectivity can be tuned by the redox catalysts used in indirect electrolysis. Furthermore, electrode passivation can be avoided by preventing the formation of polymer films on the electrode surface. Common redox catalysts include N-oxyl radicals, hypervalent iodine species, halides, amines, benzoquinones(such as DDQ and tetrachlorobenzoquinone), and transition metals. In recent years, great progress has been made in the field of indirect organic electrosynthesis using transition metals as redox catalysts for reaction classes including C–H functionalization, radical cyclization, and cross-coupling of aryl halides-each owing to the diverse reactivity and accessible oxidation states of transition metals. Although various reviews of organic electrosynthesis are available, there is a lack of articles that focus on recent research progress in the area of indirect electrolysis using transition metals, which is the impetus for this review.
