Acid-catalyzed dehydration of alcohols has been widely employed for the synthesis of alkenes. However, activated alcohols when employed as substrates in dehydration reactions are often pla-gued by the lack of alkene s...Acid-catalyzed dehydration of alcohols has been widely employed for the synthesis of alkenes. However, activated alcohols when employed as substrates in dehydration reactions are often pla-gued by the lack of alkene selectivity. In this work, the reaction system can be significantly improved through enhancing the performance of Lewis acid catalysts in the dehydration of activated alcohols by combining with a Lewis base. Observations of the reaction mechanism revealed that the Lewis base component might have changed the reaction rate order. Although both the principal and side reaction rates decreased, the effect was markedly more observed on the latter reaction. Therefore, the selectivity of the dehydration reaction was improved. On the basis of this observation, a new route to synthesize 2-cinnamyl-1,3-dicarbonyl compounds was developed by using 2-aryl-3,4- di-hydropyran as a starting substrate in the presence of a Lewis acid/Lewis base combined catalyst system.展开更多
The novel solid acid with both sulfonic and carbonyl acid groups has been synthesized from 3-((2-sulfoethoxy) carbonyl)acrylic acid and tetraethyl orthosilicate(TEOS). The catalytic activities were investigated throug...The novel solid acid with both sulfonic and carbonyl acid groups has been synthesized from 3-((2-sulfoethoxy) carbonyl)acrylic acid and tetraethyl orthosilicate(TEOS). The catalytic activities were investigated through the acetalization. The results showed that the novel solid acid was very efficient for the reactions with the high yields. The high acidity, high stability and reusability were the key feature of the novel solid acid. Moreover, the sulfonic and carbonyl acid groups could cooperate during the catalytic process, which improved its catalytic activities. The catalyst shows recyclability, and hold great potential for replacement of homogeneous catalysts.展开更多
The nanosized binary mixed oxides of Zn/Sn had been prepared by the fractional homogeneous precipitation route using urea as the latent precipitant under boiling reflux condition The samples prepared with the differen...The nanosized binary mixed oxides of Zn/Sn had been prepared by the fractional homogeneous precipitation route using urea as the latent precipitant under boiling reflux condition The samples prepared with the different initial concentrations of urea or calcined at different temperatures had been investigated by X-ray diffration (XRD) or transmission electron microscopy (TEM). The calcination temperature had obvious effect on the phase composition and the crystal size of the samples attained, and the precipitant concentration also had obvious effect on the oxide particles size and the production rate of ZnO.展开更多
In the present study, the modified (non-Keggin-type) aqueous solutions of Mo-V-phosphoric heteropoly acids HaPzMoyVx,Oh (HPA-x') were applied as homogeneous catalysts for the two-stage oxidation of TMP (2,3,6-tr...In the present study, the modified (non-Keggin-type) aqueous solutions of Mo-V-phosphoric heteropoly acids HaPzMoyVx,Oh (HPA-x') were applied as homogeneous catalysts for the two-stage oxidation of TMP (2,3,6-trimethylphenol) by oxygen into TMQ (2,3,5-trimethyl-l,4-benzoquinone), the latter being the key intermediate in the synthesis of vitamin E. The TMQ yield was analyzed regarding solvent type, reaction temperature, molar HPA-x ':TMP ratio, and the concentration of vanadium (V) in the HPA-x' solution. The TMQ yield was found to depend strongly on the catalyst redox potential and the rate of electron transfer. The results obtained enabled to establish the optimal reaction conditions as well as to suggest the reaction mechanism. In the target reaction, which proceeds in the two-phase system, the TMQ yield is higher than 99%. After phase separation, the catalyst is rapidly regenerated by oxygen and reused.展开更多
A combined process of catalytic ozonation in the presence of a novel heterogeneous catalyst and biological activated carbon was investigated for the removal of priority control organic pollutants, the reduction of gen...A combined process of catalytic ozonation in the presence of a novel heterogeneous catalyst and biological activated carbon was investigated for the removal of priority control organic pollutants, the reduction of genotoxicity, and the improvement of biodegradable dissolved organic carbon (BDOC). Results confirm that the catalytic ozonation has higher effectiveness for the removal of refractory harmful organic pollutants, the reduction of genotoxicity and the increase of bio-degradability of organics than ozonation alone, which results in lower pollution load for subsequent biological activated carbon process, and then leads to less organic pollutants penetrating biological activated carbon. The novel catalytic ozonation with this combined process exhibits excellent performance to guarantee the safety of drinking water.展开更多
Chemical conversion of carbon dioxide(CO2)to value-added useful chemicals like cyclic carbonates represents one potential solution to climate warming.Here,a kind of porous organic polymer(HAT-TP)with large surface are...Chemical conversion of carbon dioxide(CO2)to value-added useful chemicals like cyclic carbonates represents one potential solution to climate warming.Here,a kind of porous organic polymer(HAT-TP)with large surface area and excellent carbon dioxide uptake capacity is prepared via a condensation reaction to introduce hexaazatriphenylene(HAT)units into triptycene(TP)-based microporous polymer.HAT-TP can coordinate with zinc ions,and the resulting polymer(Zn/HAT-TP)can be utilized as an efficient recyclable catalyst for chemical conversion of CO2 into cyclic carbonates with epoxides.展开更多
基金supported by the National Natural Science Foundation of China (21173089 and 21373093)the Fundamental Research Funds for the Central Universities of China (2014ZZGH019)the Cooperative Innovation Center of Hubei Province
文摘Acid-catalyzed dehydration of alcohols has been widely employed for the synthesis of alkenes. However, activated alcohols when employed as substrates in dehydration reactions are often pla-gued by the lack of alkene selectivity. In this work, the reaction system can be significantly improved through enhancing the performance of Lewis acid catalysts in the dehydration of activated alcohols by combining with a Lewis base. Observations of the reaction mechanism revealed that the Lewis base component might have changed the reaction rate order. Although both the principal and side reaction rates decreased, the effect was markedly more observed on the latter reaction. Therefore, the selectivity of the dehydration reaction was improved. On the basis of this observation, a new route to synthesize 2-cinnamyl-1,3-dicarbonyl compounds was developed by using 2-aryl-3,4- di-hydropyran as a starting substrate in the presence of a Lewis acid/Lewis base combined catalyst system.
基金Supported by the Chinese National General Administration of Quality Supervision,Inspection and Quarantine(2012IK048,2011IK041)the National Natural Science Foundation of China(21103111)
文摘The novel solid acid with both sulfonic and carbonyl acid groups has been synthesized from 3-((2-sulfoethoxy) carbonyl)acrylic acid and tetraethyl orthosilicate(TEOS). The catalytic activities were investigated through the acetalization. The results showed that the novel solid acid was very efficient for the reactions with the high yields. The high acidity, high stability and reusability were the key feature of the novel solid acid. Moreover, the sulfonic and carbonyl acid groups could cooperate during the catalytic process, which improved its catalytic activities. The catalyst shows recyclability, and hold great potential for replacement of homogeneous catalysts.
基金Acknowledgments: This work was supported by the National Natural Science Foundation of China (No. 20673042), the Natural Science Foundation of Anhui Provincial Education Committee (No. K12007B014), the Natural Science Foundation of Anhui Province (No. 070415211), China Postdoctoral Science Foundation (No. 2004036511), the Laboratory Open Foundation of Green Materials Chemistry (No. KLSF(I)09), and the Laboratory Open Foundation of Guangdong Public Laboratory of Environmental Science and Technology. The authors thank Mr. LUO S. M., Mr. CHEN D. Z., and Mr. TAO Q. for their assistance.
文摘The nanosized binary mixed oxides of Zn/Sn had been prepared by the fractional homogeneous precipitation route using urea as the latent precipitant under boiling reflux condition The samples prepared with the different initial concentrations of urea or calcined at different temperatures had been investigated by X-ray diffration (XRD) or transmission electron microscopy (TEM). The calcination temperature had obvious effect on the phase composition and the crystal size of the samples attained, and the precipitant concentration also had obvious effect on the oxide particles size and the production rate of ZnO.
文摘In the present study, the modified (non-Keggin-type) aqueous solutions of Mo-V-phosphoric heteropoly acids HaPzMoyVx,Oh (HPA-x') were applied as homogeneous catalysts for the two-stage oxidation of TMP (2,3,6-trimethylphenol) by oxygen into TMQ (2,3,5-trimethyl-l,4-benzoquinone), the latter being the key intermediate in the synthesis of vitamin E. The TMQ yield was analyzed regarding solvent type, reaction temperature, molar HPA-x ':TMP ratio, and the concentration of vanadium (V) in the HPA-x' solution. The TMQ yield was found to depend strongly on the catalyst redox potential and the rate of electron transfer. The results obtained enabled to establish the optimal reaction conditions as well as to suggest the reaction mechanism. In the target reaction, which proceeds in the two-phase system, the TMQ yield is higher than 99%. After phase separation, the catalyst is rapidly regenerated by oxygen and reused.
基金Sponsored by the National High Technology Research and Development Program (863) of China(Grant No. 2006AA06Z306)the National Natural Science Foundation of China(Grant No.50578051)
文摘A combined process of catalytic ozonation in the presence of a novel heterogeneous catalyst and biological activated carbon was investigated for the removal of priority control organic pollutants, the reduction of genotoxicity, and the improvement of biodegradable dissolved organic carbon (BDOC). Results confirm that the catalytic ozonation has higher effectiveness for the removal of refractory harmful organic pollutants, the reduction of genotoxicity and the increase of bio-degradability of organics than ozonation alone, which results in lower pollution load for subsequent biological activated carbon process, and then leads to less organic pollutants penetrating biological activated carbon. The novel catalytic ozonation with this combined process exhibits excellent performance to guarantee the safety of drinking water.
基金supported by the National Natural Science Foundation of China (21875079 and 21672078)
文摘Chemical conversion of carbon dioxide(CO2)to value-added useful chemicals like cyclic carbonates represents one potential solution to climate warming.Here,a kind of porous organic polymer(HAT-TP)with large surface area and excellent carbon dioxide uptake capacity is prepared via a condensation reaction to introduce hexaazatriphenylene(HAT)units into triptycene(TP)-based microporous polymer.HAT-TP can coordinate with zinc ions,and the resulting polymer(Zn/HAT-TP)can be utilized as an efficient recyclable catalyst for chemical conversion of CO2 into cyclic carbonates with epoxides.