The activity of Lewis (Nb2O5) and Br nsted (Amberlyst 70) acid catalysts for the cyclodehydration of xylose to furfural was studied. The nature of the acidity resulted in significant changes in the reaction mechanism....The activity of Lewis (Nb2O5) and Br nsted (Amberlyst 70) acid catalysts for the cyclodehydration of xylose to furfural was studied. The nature of the acidity resulted in significant changes in the reaction mechanism. Lewis acid sites promote the formation of xylulose, while Br nsted acid sites are required to further dehydrate the sugar to furfural. Amberlyst 70 in water/toluene at 175 ℃ showed lower activity but gave a higher furfural yield. Using N2 as the stripping agent considerably improved the furfural yield and product purity in the stripped stream. Catalyst stability was also studied.展开更多
ZSM-5分子筛是合成三聚甲醛的有效催化剂。本工作通过XRF、XRD、SEM、NH3-TPD、Py-FTIR和27Al MAS NMR等手段对一系列不同SiO2/Al2O3物质的量比的ZSM-5分子筛催化剂进行了表征,研究了ZSM-5分子筛中BrΦnsted酸中心和Lewis酸中心对其甲...ZSM-5分子筛是合成三聚甲醛的有效催化剂。本工作通过XRF、XRD、SEM、NH3-TPD、Py-FTIR和27Al MAS NMR等手段对一系列不同SiO2/Al2O3物质的量比的ZSM-5分子筛催化剂进行了表征,研究了ZSM-5分子筛中BrΦnsted酸中心和Lewis酸中心对其甲醛合成三聚甲醛催化性能的影响。结果表明,SiO2/Al2O3物质的量比为250的ZSM-5分子筛具有合适的BrΦnsted酸中心用于催化甲醛缩聚为三聚甲醛的反应,同时其Lewis酸中心量极少,可有效抑制Cannizzaro或Tishchenko等副反应,提高三聚甲醛的选择性,因而具有最佳的合成三聚甲醛催化性能。寿命实验评价结果显示,SiO2/Al2O3物质的量比为250的ZSM-5分子筛具有良好的催化稳定性,单程寿命长达114 h,并且可通过550℃焙烧再生恢复其催化活性。展开更多
This review divides the acidic deep eutectic solvents(ADES) into Br?nsted and Lewis DES according to their diversity of acidic character.The hydrogen bond donors and halide salts for formulating an ADES are classified...This review divides the acidic deep eutectic solvents(ADES) into Br?nsted and Lewis DES according to their diversity of acidic character.The hydrogen bond donors and halide salts for formulating an ADES are classified, the synthesis methods are described, and the physicochemical properties including freezing point, acidity, density, viscosity and conductivity are presented. Furthermore, the applications of Br?nsted acidic deep eutectic solvents(BADES) and Lewis acidic deep eutectic solvents(LADES) are overviewed, respectively, covering the fields in dissolution, extraction, organic reaction and metal electrodeposition. It is expected that the ADES has great potential to replace the pollutional mineral acid, expensive and unstable solid acid, and costly ionic liquid in many acid-employed chemical processes, thus meeting the demands of green chemistry.展开更多
Series of Cu-USY zeolite catalyst with different Cu loading content were synthesized through simple impregnation method.The obtained catalysts were subjected to selective catalytic reduction of NOxwith NH_(3)(NH_(3)-S...Series of Cu-USY zeolite catalyst with different Cu loading content were synthesized through simple impregnation method.The obtained catalysts were subjected to selective catalytic reduction of NOxwith NH_(3)(NH_(3)-SCR) performance evaluation,structural/chemical characterizations such as X-ray diffraction (XRD),N2adsorption/desorption,H_(2)temperature-programmed reduction (H_(2)-TPR),NH_(3)temperature-programmed desorption (NH_(3)-TPD) as well as detailed in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) experiments including CO adsorption,NH_(3)adsorption and NO+O_(2)in situ reactions.Results show that Cu-USY with proper Cu loading (in this work 5Cu-USY with5 wt.%Cu) could be promising candidates with highly efficient NH_(3)-SCR catalytic performance,relatively low byproduct formation and excellent hydrothermal stability,although its SO_(2)poisoning tolerability needs alleviation.Further characterizations reveal that such catalytic advantages can be attributed to both active cu species and surface acid centers evolution modulated by Cu loading.On one hand,Cu species in the super cages of zeolites increases with higher Cu content and being more conducive for NH_(3)-SCR reactivity.On the other hand,higher Cu loading leads to depletion of Br?nsted acid centers and simultaneous formation of abundant Lewis acid centers,which facilitates NH_(4)NO_(3)reduction via NH_(3)adsorbed on Lewis acid centers,thus improving SCR reactivity.However,Cu over-introduction leads to formation of surface highly dispersed CuOx,causing unfavorable NH_(3)oxidation and inferior N2selectivity.展开更多
Recently,homogeneous gold catalysis has attracted tremendous attention and has also been widely used in multistep synthesis.The current reaction methodology starts from the gold activation of unsaturated carbon bond a...Recently,homogeneous gold catalysis has attracted tremendous attention and has also been widely used in multistep synthesis.The current reaction methodology starts from the gold activation of unsaturated carbon bond and subsequent nucleophilic attack.The combination of a gold catalyst with another acid catalyst,including Brønsted acid and Lewis acid,is possible to bring two distinctive catalytic systems together and deliver unprecedented new reactions.More essentially,it avoids the purification of unstable intermediates and improves the step and atom economy.Here,the recent progress in the Au/Acid combined catalysis is reviewed,including the scope of reactions,mechanism and synthetic applications.展开更多
基金supported by funds from the Spanish Ministerio de Economíay Competitividad(CTQ‐2012‐38204‐C03‐03 and ENE2009‐12743‐C04‐03)from the Gobierno Vasco(Programa de Formación de Personal Investigador del Departamento de Educación,Universidades e Investigación)the Junta de Andalucía(P09‐FQM‐5070) for financial support
文摘The activity of Lewis (Nb2O5) and Br nsted (Amberlyst 70) acid catalysts for the cyclodehydration of xylose to furfural was studied. The nature of the acidity resulted in significant changes in the reaction mechanism. Lewis acid sites promote the formation of xylulose, while Br nsted acid sites are required to further dehydrate the sugar to furfural. Amberlyst 70 in water/toluene at 175 ℃ showed lower activity but gave a higher furfural yield. Using N2 as the stripping agent considerably improved the furfural yield and product purity in the stripped stream. Catalyst stability was also studied.
基金supported by the National Natural Science Foundation of China (21273107, 21103087)the Fundamental Research Funds for the Central Universities (1107020524)the Specialized Research Fund for the Doctoral Program of Higher Education (20100091120035)~~
基金supported by the National Key R&D Program of China(2018YFB0604902).
文摘ZSM-5分子筛是合成三聚甲醛的有效催化剂。本工作通过XRF、XRD、SEM、NH3-TPD、Py-FTIR和27Al MAS NMR等手段对一系列不同SiO2/Al2O3物质的量比的ZSM-5分子筛催化剂进行了表征,研究了ZSM-5分子筛中BrΦnsted酸中心和Lewis酸中心对其甲醛合成三聚甲醛催化性能的影响。结果表明,SiO2/Al2O3物质的量比为250的ZSM-5分子筛具有合适的BrΦnsted酸中心用于催化甲醛缩聚为三聚甲醛的反应,同时其Lewis酸中心量极少,可有效抑制Cannizzaro或Tishchenko等副反应,提高三聚甲醛的选择性,因而具有最佳的合成三聚甲醛催化性能。寿命实验评价结果显示,SiO2/Al2O3物质的量比为250的ZSM-5分子筛具有良好的催化稳定性,单程寿命长达114 h,并且可通过550℃焙烧再生恢复其催化活性。
基金The financial support from National Natural Science Foundation of China(21776074,21576081,and 2181101120)is greatly acknowledged
文摘This review divides the acidic deep eutectic solvents(ADES) into Br?nsted and Lewis DES according to their diversity of acidic character.The hydrogen bond donors and halide salts for formulating an ADES are classified, the synthesis methods are described, and the physicochemical properties including freezing point, acidity, density, viscosity and conductivity are presented. Furthermore, the applications of Br?nsted acidic deep eutectic solvents(BADES) and Lewis acidic deep eutectic solvents(LADES) are overviewed, respectively, covering the fields in dissolution, extraction, organic reaction and metal electrodeposition. It is expected that the ADES has great potential to replace the pollutional mineral acid, expensive and unstable solid acid, and costly ionic liquid in many acid-employed chemical processes, thus meeting the demands of green chemistry.
基金supported by the Key Program of Science Technology Department of Zhejiang Province (No.2018C03037)the Natural Science Foundation of the Jiangsu Higher Education Institutions of China (No.20KJB610005)+2 种基金the Natural Science Foundation of Jiangsu Province (Nos.BK20201037,BK20190705)Key Research and Development Program of Anhui Province (No.202104g01020006)the Scientific Research Fund of Nanjing Institute of Technology (Nos.YKJ2019111 and YKJ2019110)。
文摘Series of Cu-USY zeolite catalyst with different Cu loading content were synthesized through simple impregnation method.The obtained catalysts were subjected to selective catalytic reduction of NOxwith NH_(3)(NH_(3)-SCR) performance evaluation,structural/chemical characterizations such as X-ray diffraction (XRD),N2adsorption/desorption,H_(2)temperature-programmed reduction (H_(2)-TPR),NH_(3)temperature-programmed desorption (NH_(3)-TPD) as well as detailed in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) experiments including CO adsorption,NH_(3)adsorption and NO+O_(2)in situ reactions.Results show that Cu-USY with proper Cu loading (in this work 5Cu-USY with5 wt.%Cu) could be promising candidates with highly efficient NH_(3)-SCR catalytic performance,relatively low byproduct formation and excellent hydrothermal stability,although its SO_(2)poisoning tolerability needs alleviation.Further characterizations reveal that such catalytic advantages can be attributed to both active cu species and surface acid centers evolution modulated by Cu loading.On one hand,Cu species in the super cages of zeolites increases with higher Cu content and being more conducive for NH_(3)-SCR reactivity.On the other hand,higher Cu loading leads to depletion of Br?nsted acid centers and simultaneous formation of abundant Lewis acid centers,which facilitates NH_(4)NO_(3)reduction via NH_(3)adsorbed on Lewis acid centers,thus improving SCR reactivity.However,Cu over-introduction leads to formation of surface highly dispersed CuOx,causing unfavorable NH_(3)oxidation and inferior N2selectivity.
基金Natural Science Foundation of China(No.21102085)the Fundamental Research Funds of Shandong University(No.2014JC008)the Subject Construction Funds of Shandong University(No.104.205.2.5).
文摘Recently,homogeneous gold catalysis has attracted tremendous attention and has also been widely used in multistep synthesis.The current reaction methodology starts from the gold activation of unsaturated carbon bond and subsequent nucleophilic attack.The combination of a gold catalyst with another acid catalyst,including Brønsted acid and Lewis acid,is possible to bring two distinctive catalytic systems together and deliver unprecedented new reactions.More essentially,it avoids the purification of unstable intermediates and improves the step and atom economy.Here,the recent progress in the Au/Acid combined catalysis is reviewed,including the scope of reactions,mechanism and synthetic applications.
