The reaction kinetics of SO 2 oxidation on Cs Rb V series sulfuric acid catalyst promoted by alkali salts such as cesium and rubidium was studied. A three step reaction mechanism of SO 2 oxidation was proposed, in whi...The reaction kinetics of SO 2 oxidation on Cs Rb V series sulfuric acid catalyst promoted by alkali salts such as cesium and rubidium was studied. A three step reaction mechanism of SO 2 oxidation was proposed, in which it was assumed that oxidation of quadrivalent vanadium complex was a controlling step. Then, a mechanism model equation was concluded according to the three step reaction mechanism. The SO 2 oxidation rate was measured with a non gradient reactor under the conditions of temperature of 380～520?℃ and space velocity of 3?600～7?200?h -1 . Through calculating with Powell nonlinear regression method, the parameters of model equation were obtained: K 1=0.152?exp(-62?073/ (RT) ), K 2=8.18?exp(-2?384/ (RT) ), K 3=0.221?exp(-18?949/ (RT) ). It was found that the model equation could fit with all the experimental reaction rate data very well. [展开更多
In this study, the oxidation rates of sulfur dioxide （SO2） in sulphuric acid solution by ozone and oxygen were compared, and the oxidation mechanism of ozone on SO2 was investigated. The results showed that the oxid...In this study, the oxidation rates of sulfur dioxide （SO2） in sulphuric acid solution by ozone and oxygen were compared, and the oxidation mechanism of ozone on SO2 was investigated. The results showed that the oxidation-reduction potential of the acidic solution was enhanced, the transformation rate of sulfuric acid to sulphuric acid was increased and the absorption driving force was improved in the presence of ozone. By comparing the amount of sulfate ions measured in the experiments and the theoretical amount of sulfate ions calculated from the amount of ozone consumed in the reaction, it can be confirmed that oxygen free radicals from dissociation of ozone are reactive as an efficient oxidant and oxygen from ozone generator participates in the reaction with SO2. 0.602 mol of effective oxygen was introduced into the reaction by one mole of ozone in 10.15 rain at sulphuric acid concentration of 3% （by mass）, SO2 concentration of 1.33% （by volume） and oxygen flow rate of 1.5 L.min^-1 from ozone generator.展开更多
Cs Rb V series low temperature sulphuric acid catalyst was prepared for the first time by using carbonized mother liquor containing alkali metal salts. The results show that the conversion of SO 2 on catalyst prepared...Cs Rb V series low temperature sulphuric acid catalyst was prepared for the first time by using carbonized mother liquor containing alkali metal salts. The results show that the conversion of SO 2 on catalyst prepared directly with carbonized mother liquor could reach to 24.8% at 410?℃. If n (Na)/ n (V) was adjusted properly, the conversion of SO 2 could be increased to 35.6% at 410?℃. Refined carbonized mother liquor could make the catalytic activity even higher at low temperature, the conversion of SO 2 could be increased to 36.65% at 410?℃. The catalyst was examined with differential thermal analysis. It was found that both endothermic peaks and exothermic peaks of catalyst shifted forward obviously and the catalyst possessed higher activity at low temperature.展开更多
The aim of this work was to investigate the effects of calcination/acid-activation on the composition, structure, and photocatalytic （PC） reduction property of an anodic oxidation TiO2/Ti film catalyst. The surface ...The aim of this work was to investigate the effects of calcination/acid-activation on the composition, structure, and photocatalytic （PC） reduction property of an anodic oxidation TiO2/Ti film catalyst. The surface morphology and phase composition were examined by scanning electron microscopy and X-ray diffraction. The catalytic property of the film catalysts was evaluated through the removal rate of potassium chromate during the PC reduction process. The results showed that the film catalysts were composed of anatase and rutile TiO2 with a micro-porous surface structure. The calcination treatment increased the content of TiO2 in the film, changed the relative ratio of anatase and rutile TiO2, and decreased the size of the micro pores of the film catalysts. The removal rate of potassium chromate was related to the technique parameters of calcination/acid-activation treatment. When the anodic oxidation TiO2/Ti film catalyst was calcined at 873 K for 30 min and then acid-activated in the concentrated H2SO4 for 60 min, it presented the highest catalytic property, with the removal rate of potassium chromate of 96.3% during the PC reduction process under the experimental conditions.展开更多
The PdPtVO_(x)/CeO_(2)-ZrO_(2)(PdPtVO_(x)/CZO)catalysts were obtained by using different approaches,and their physical and chemical properties were determined by various techniques.Catalytic activities of these materi...The PdPtVO_(x)/CeO_(2)-ZrO_(2)(PdPtVO_(x)/CZO)catalysts were obtained by using different approaches,and their physical and chemical properties were determined by various techniques.Catalytic activities of these materials in the presence of H_(2)O or SO_(2)were evaluated for the oxidation of ethylbenzene(EB).The PdPtVO_(x)/CZO sample exhibited high catalytic activity,good hydrothermal stability,and reversible sulfur dioxide-poisoning performance,over which the specific reaction rate at 160℃,turnover frequency at 160℃(TOF_(Pd or Pt)),and apparent activation energy were 72.6 mmol/(g_(Pt)·sec)or 124.2 mmol/(g_(Pd)·sec),14.2 sec^(-1)(TOF_(Pt))or 13.1 sec^(-1)(TOF_(Pd)),and 58 k J/mol,respectively.The large EB adsorption capacity,good reducibility,and strong acidity contributed to the good catalytic performance of PdPtVO_(x)/CZO.Catalytic activity of PdPtVO_(x)/CZO decreased when 50 ppm SO_(2)or(1.0 vol.%H_(2)O+50 ppm SO_(2))was added to the feedstock,but was gradually restored to its initial level after the SO_(2)was cut off.The good reversible sulfur dioxide-resistant performance of PdPtVO_(x)/CZO was associated with the facts:(i)the introduction of SO_(2)leads to an increase in surface acidity;(ii)V can adsorb and activate SO_(2),thus accelerating formation of the SO_(x)^(2-)(x=3 or 4)species at the V and CZO sites,weakening the adsorption of sulfur species at the PdPt active sites,and hence protecting the PdPt active sites to be not poisoned by SO_(2).EB oxidation over PdPtVO_(x)/CZO might take place via the route of EB→styrene→phenyl methyl ketone→benzaldehyde→benzoic acid→maleic anhydride→CO_(2)and H_(2)O.展开更多
Electrochemical energy storage and conversion toward sustainable carbon neutrality cycle is of great interest in today's society.In this perspective,we highlight the interconversion between carbon dioxide and form...Electrochemical energy storage and conversion toward sustainable carbon neutrality cycle is of great interest in today's society.In this perspective,we highlight the interconversion between carbon dioxide and formic acid by means of electrocatalytic CO_(2)reduction reaction(CO_(2)RR)and formic acid oxidation reaction(FAOR)as an effective way to achieve that goal.In line with the distinctive catalytic nature of Pd to reversibly drive both FAOR and CO_(2)RR,we first illustrate the intimate mechanistic relation between these two reversed reactions over Pd surfaces.Next,recent advances in developing Pd-based bifunctional catalysts and relevant optimization strategies are briefly summarized,including geometric structure engineering with preferential facet exposure,construction of crystallographic ordering intermetallic,electronic structure manipulation through metal or metalloid doping to fine tune the binding strength for active and poisoning intermediates.At the end,our viewpoints on the design principles at both microscopic and macroscopic scales are offered toward an efficient CO_(2)and HCOOH interconversion loop.展开更多
Ti Ce complex oxide catalysts for catalytic wet air oxidation of acetic acid as model reactant were prepared by coprecipitation and impregnation methods. The catalysts are very stable during the reaction. The presence...Ti Ce complex oxide catalysts for catalytic wet air oxidation of acetic acid as model reactant were prepared by coprecipitation and impregnation methods. The catalysts are very stable during the reaction. The presence of Bi as base center has promotion effect on the catalyst activity. The optimal Bi content is about 4% (molar fraction). With the increase of calcination temperature, the BET surface area of the catalysts is decreased and so is the activity of the catalysts. The activity of the catalysts and the Bi effect are discussed based on the reference results.展开更多
文摘The reaction kinetics of SO 2 oxidation on Cs Rb V series sulfuric acid catalyst promoted by alkali salts such as cesium and rubidium was studied. A three step reaction mechanism of SO 2 oxidation was proposed, in which it was assumed that oxidation of quadrivalent vanadium complex was a controlling step. Then, a mechanism model equation was concluded according to the three step reaction mechanism. The SO 2 oxidation rate was measured with a non gradient reactor under the conditions of temperature of 380～520?℃ and space velocity of 3?600～7?200?h -1 . Through calculating with Powell nonlinear regression method, the parameters of model equation were obtained: K 1=0.152?exp(-62?073/ (RT) ), K 2=8.18?exp(-2?384/ (RT) ), K 3=0.221?exp(-18?949/ (RT) ). It was found that the model equation could fit with all the experimental reaction rate data very well. [
文摘In this study, the oxidation rates of sulfur dioxide （SO2） in sulphuric acid solution by ozone and oxygen were compared, and the oxidation mechanism of ozone on SO2 was investigated. The results showed that the oxidation-reduction potential of the acidic solution was enhanced, the transformation rate of sulfuric acid to sulphuric acid was increased and the absorption driving force was improved in the presence of ozone. By comparing the amount of sulfate ions measured in the experiments and the theoretical amount of sulfate ions calculated from the amount of ozone consumed in the reaction, it can be confirmed that oxygen free radicals from dissociation of ozone are reactive as an efficient oxidant and oxygen from ozone generator participates in the reaction with SO2. 0.602 mol of effective oxygen was introduced into the reaction by one mole of ozone in 10.15 rain at sulphuric acid concentration of 3% （by mass）, SO2 concentration of 1.33% （by volume） and oxygen flow rate of 1.5 L.min^-1 from ozone generator.
文摘Cs Rb V series low temperature sulphuric acid catalyst was prepared for the first time by using carbonized mother liquor containing alkali metal salts. The results show that the conversion of SO 2 on catalyst prepared directly with carbonized mother liquor could reach to 24.8% at 410?℃. If n (Na)/ n (V) was adjusted properly, the conversion of SO 2 could be increased to 35.6% at 410?℃. Refined carbonized mother liquor could make the catalytic activity even higher at low temperature, the conversion of SO 2 could be increased to 36.65% at 410?℃. The catalyst was examined with differential thermal analysis. It was found that both endothermic peaks and exothermic peaks of catalyst shifted forward obviously and the catalyst possessed higher activity at low temperature.
基金supported by the National High Technology Research and Development Program of China (No. 2007AA03Z337)the Harbin Special Creation Foundation for Science and Technology of Fellow in China (No. 2006RFQXG032)
文摘The aim of this work was to investigate the effects of calcination/acid-activation on the composition, structure, and photocatalytic （PC） reduction property of an anodic oxidation TiO2/Ti film catalyst. The surface morphology and phase composition were examined by scanning electron microscopy and X-ray diffraction. The catalytic property of the film catalysts was evaluated through the removal rate of potassium chromate during the PC reduction process. The results showed that the film catalysts were composed of anatase and rutile TiO2 with a micro-porous surface structure. The calcination treatment increased the content of TiO2 in the film, changed the relative ratio of anatase and rutile TiO2, and decreased the size of the micro pores of the film catalysts. The removal rate of potassium chromate was related to the technique parameters of calcination/acid-activation treatment. When the anodic oxidation TiO2/Ti film catalyst was calcined at 873 K for 30 min and then acid-activated in the concentrated H2SO4 for 60 min, it presented the highest catalytic property, with the removal rate of potassium chromate of 96.3% during the PC reduction process under the experimental conditions.
基金supported by the National Natural Science Foundation Committee of China-Liaoning Provincial People’s Government Joint Fund(No.U1908204)the National Natural Science Foundation of China(21976009)+2 种基金the National Key R&D Program of China(Nos.2022YFB3506200 and 2022YFB3504100)the Beijing Natural Science Foundation(J210006)the R&D Program of Beijing Municipal Education Commisson(No.KZ202210005011)。
文摘The PdPtVO_(x)/CeO_(2)-ZrO_(2)(PdPtVO_(x)/CZO)catalysts were obtained by using different approaches,and their physical and chemical properties were determined by various techniques.Catalytic activities of these materials in the presence of H_(2)O or SO_(2)were evaluated for the oxidation of ethylbenzene(EB).The PdPtVO_(x)/CZO sample exhibited high catalytic activity,good hydrothermal stability,and reversible sulfur dioxide-poisoning performance,over which the specific reaction rate at 160℃,turnover frequency at 160℃(TOF_(Pd or Pt)),and apparent activation energy were 72.6 mmol/(g_(Pt)·sec)or 124.2 mmol/(g_(Pd)·sec),14.2 sec^(-1)(TOF_(Pt))or 13.1 sec^(-1)(TOF_(Pd)),and 58 k J/mol,respectively.The large EB adsorption capacity,good reducibility,and strong acidity contributed to the good catalytic performance of PdPtVO_(x)/CZO.Catalytic activity of PdPtVO_(x)/CZO decreased when 50 ppm SO_(2)or(1.0 vol.%H_(2)O+50 ppm SO_(2))was added to the feedstock,but was gradually restored to its initial level after the SO_(2)was cut off.The good reversible sulfur dioxide-resistant performance of PdPtVO_(x)/CZO was associated with the facts:(i)the introduction of SO_(2)leads to an increase in surface acidity;(ii)V can adsorb and activate SO_(2),thus accelerating formation of the SO_(x)^(2-)(x=3 or 4)species at the V and CZO sites,weakening the adsorption of sulfur species at the PdPt active sites,and hence protecting the PdPt active sites to be not poisoned by SO_(2).EB oxidation over PdPtVO_(x)/CZO might take place via the route of EB→styrene→phenyl methyl ketone→benzaldehyde→benzoic acid→maleic anhydride→CO_(2)and H_(2)O.
基金supported by the National Natural Science Foundation of China(NSFC,21733004,22002088)the INTERNATIONAL COOPERATION Program of Shanghai Science and Technology Committee(STCSM,17520711200)+1 种基金the Shanghai Sailing Program(20YF1420500)the Oceanic Interdisciplinary Program of Shanghai Jiao Tong University(SL2020MS007).
文摘Electrochemical energy storage and conversion toward sustainable carbon neutrality cycle is of great interest in today's society.In this perspective,we highlight the interconversion between carbon dioxide and formic acid by means of electrocatalytic CO_(2)reduction reaction(CO_(2)RR)and formic acid oxidation reaction(FAOR)as an effective way to achieve that goal.In line with the distinctive catalytic nature of Pd to reversibly drive both FAOR and CO_(2)RR,we first illustrate the intimate mechanistic relation between these two reversed reactions over Pd surfaces.Next,recent advances in developing Pd-based bifunctional catalysts and relevant optimization strategies are briefly summarized,including geometric structure engineering with preferential facet exposure,construction of crystallographic ordering intermetallic,electronic structure manipulation through metal or metalloid doping to fine tune the binding strength for active and poisoning intermediates.At the end,our viewpoints on the design principles at both microscopic and macroscopic scales are offered toward an efficient CO_(2)and HCOOH interconversion loop.
文摘Ti Ce complex oxide catalysts for catalytic wet air oxidation of acetic acid as model reactant were prepared by coprecipitation and impregnation methods. The catalysts are very stable during the reaction. The presence of Bi as base center has promotion effect on the catalyst activity. The optimal Bi content is about 4% (molar fraction). With the increase of calcination temperature, the BET surface area of the catalysts is decreased and so is the activity of the catalysts. The activity of the catalysts and the Bi effect are discussed based on the reference results.
