In this paper,low-temperature dielectric-blocked discharge plasma(DBD)was employed for the first time to treat silica-doped H_(4)PMo_(11)VO_(40)(HPAV)catalysts(DBD(Ar/x)-MF-Catal)and apply them in the catalytic methac...In this paper,low-temperature dielectric-blocked discharge plasma(DBD)was employed for the first time to treat silica-doped H_(4)PMo_(11)VO_(40)(HPAV)catalysts(DBD(Ar/x)-MF-Catal)and apply them in the catalytic methacrolein(MAL)selective oxidation to produce methacrylic acid(MAA).This work investigates in detail the controllable regulation of the concentration of oxidation states on silica-doped HPAV catalysts by adjusting the DBD discharge with controlled changes in voltage,current,treatment time,and treatment medium.It reports the intrinsic correlation between oxidation states and MAL oxidation performance.The research results indicated that the catalytic performance was related to the presence of oxygen vacancies and oxygen species(VO^(2+)),and are the main reason for the selective oxidation of MAL to MAA.Besides,the generation of oxygen vacancies and VO^(2+)altered localized electrons,which resulted in the easier activation of O_(2).Theoretical calculations of DFT also proved the formation mechanism of oxygen vacancies and VO^(2+)and electron properties on high-performance polymers,which elucidated the intrinsic influence of catalyst components.The DBD(Ar/10)-MF-Catal catalysts with suitable VO^(2+)and oxygen vacancy concentrations exhibited the highest catalytic performance with 90%MAL conversion and 70%MAA selectivity and showed good stability(500 h).展开更多
The purpose of this study is to develop novel P-Mo-V heteropoly compound catalysts for the oxidation of methacrolein to methacrylic acid.The introduction of Cu,as a modifying element,was employed to enhance the cataly...The purpose of this study is to develop novel P-Mo-V heteropoly compound catalysts for the oxidation of methacrolein to methacrylic acid.The introduction of Cu,as a modifying element,was employed to enhance the catalytic performance.Experimental results show that the addition of Cu significantly improved the catalyst performance,increasing the conversion rate of methacrolein from 17.2%to 84.2%,while the yield of methacrylic acid was boosted from 5.5%to 51.7%.A series of characterization results showed that both P-Mo-V and Cu-P-Mo-V catalysts primarily exhibited the crystal phase of[PMo_(12)O_(40)]^(3−),with a small amount of[PMo_(11)VO_(40)]^(3−)phase.However,the Cu-P-Mo-V catalyst exhibited much better oxidation–reduction ability compared to the P-Mo-V catalyst.Isolated Cu atoms were found to exist in a highly decentralized tetrahedral coordination structure,bridged by oxygen atoms within the heteropoly compound framework.The addition of Cu resulted in notable alterations in the modulation of the surface electronic structure,enhancement of oxidation–reduction ability,and optimization of the reaction pathway,thereby improving the overall catalytic activity of the catalyst.This study not only provides new insights into the modification of P-Mo-V heteropoly compound catalysts but also lays a foundation for understanding their catalytic mechanisms in organic synthesis reactions,demonstrating the potential of modifying elements in improving catalyst performance.展开更多
Novel Mg O–SBA-15 supported catalysts were prepared for oxidative esterification of methacrolein(MAL) with methanol to methyl methacrylate(MMA). The Mg O–SBA-15 supports were synthesized with different magnesia load...Novel Mg O–SBA-15 supported catalysts were prepared for oxidative esterification of methacrolein(MAL) with methanol to methyl methacrylate(MMA). The Mg O–SBA-15 supports were synthesized with different magnesia loadings from different magnesium precursors and hydrochloric acid molar concentrations. The Mg O–SBA-15 supports and Pd–Pb/Mg O–SBA-15 catalysts were characterized by several analysis methods. The results revealed that the addition of Mg O improved the ordered structure of SBA-15 supports and provided surface alkalinity of SBA-15 supports. The average size of the Pd3 Pb particles on magnesia-modified Pd–Pb/Mg O–SBA-15 catalysts was smaller than that on the pure silica-based Pd–Pb/SBA-15 catalysts. The experiments on catalyst performance showed that the magnesia-modified Pd–Pb/Mg O–SBA-15 catalysts had higher activity than pure silica-based Pd–Pb/SBA-15 catalysts, showing the strong dependence of catalytic activity on the average size of active particles. The difference of activity between Pd–Pb/SBA-15 catalysts and Pd–Pb/Mg O–SBA-15 catalysts was due to the discrepant structural properties and surface alkalinity provided by Mg O, which led to the different Pd3 Pb particle sizes and then resulted in the different number of active sites. Besides magnesia loadings, other factors, such as hydrochloric acid molar concentration and magnesium precursors, had considerable influences on the catalytic activity.展开更多
Supported palladium catalysts, which were used in the oxidative esterification of methacrolein to methyl methacrylate, have been prepared with different carriers and Pd precursors. Experimental results revealed that P...Supported palladium catalysts, which were used in the oxidative esterification of methacrolein to methyl methacrylate, have been prepared with different carriers and Pd precursors. Experimental results revealed that Pd catalysts with r-Al2O3 support and Na2PdC14 precursor showed good performance. Pd catalyst modified with Pb and Mg indicated that Pd-Mg bimetallic catalyst exhibited considerably higher activity and Pd-Pb exhibited both higher activity and selectivity. 92.27% methacrolein conversion and 90.57% methyl methacrylate selectivity were obtained on Pd-Pb-Mg catalyst.展开更多
A series of supported intermetallic Pb-Pb catalysts were prepared with the impregnation method by changing the support(silica,molecular sieve or γ-alumina)and the pore size.The chemical states of the two metals were ...A series of supported intermetallic Pb-Pb catalysts were prepared with the impregnation method by changing the support(silica,molecular sieve or γ-alumina)and the pore size.The chemical states of the two metals were characterized by XPS analysis,the process for producing methyl methacrylate based on the direct oxidative esterification of methacrolein with methanol in the presence of oxygen was performed in a slurry reactor with the above-mentioned catalysts.The influence of the calcination temperature and the kinds of support as well as the pore size on catalytic activity had been extensively investigated.Under the conditions of temperature at 80℃,catalyst 3.8%(ω)and the reaction time 2 h,the conversion rate of methacrolein reached 85%,the selectivity and the yield of methyl methacrylate were 90% and 76.5%,respectively.展开更多
The effects of Bi on the catalytic performance of selective oxidation of isobutane to methacrolein over MoVO/AlPO4 catalyst were investigated by XRD, FT-Raman, XPS, UV-vis DRS techniques. The results show that the add...The effects of Bi on the catalytic performance of selective oxidation of isobutane to methacrolein over MoVO/AlPO4 catalyst were investigated by XRD, FT-Raman, XPS, UV-vis DRS techniques. The results show that the addition of Bi component into the MoVO/AlPO4 catalyst obviously improves the catalytic performance, and the selectivity to methacrolein can increase from 14.2% to 45.1% with the increase of Bi/V molar ratio from 0 to 1. Combining the characterization results with the reaction evaluation, it is concluded that the catalytic activities of the MoV0.3Bix/AlPO4 catalysts are related to the crystalline phase composition and the dispersion of molybdenum and vanadium oxides species in general, and also to the V5＋/V4＋ molar ratio on the surface in particular.展开更多
Methacrolein(MACR) and methyl vinyl ketone(MVK) are two major intermediate products from the photochemical oxidation of isoprene, the most important biogenic volatile organic compound. In addition, MACR and MVK have p...Methacrolein(MACR) and methyl vinyl ketone(MVK) are two major intermediate products from the photochemical oxidation of isoprene, the most important biogenic volatile organic compound. In addition, MACR and MVK have primary emissions. Investigating the sources and evolution of MACR and MVK could provide helpful information for the oxidative capacity of the atmosphere. In this study, hourly measurements of isoprene, MACR, and MVK were conducted at a receptor site in the Pearl River Delta region(PRD), i.e., the Heshan site(HS), from 22 October to 20 November, 2014. The average mixing ratios of isoprene,MACR and MVK were 151 ± 17, 91 ± 6 and 79 ± 6 pptv, respectively. The daily variations and the ratios of MVK/MACR during daytime and nighttime suggested that other sources besides isoprene photooxidation influenced the MACR and MVK abundances at the HS.Positive matrix factorization was utilized to resolve the sources of MACR and MVK. Five sources were identified and quantified, including biogenic emissions, biomass burning,secondary formation, diesel, and gasoline vehicular emissions. Among them, secondary formation made the greatest contribution to observed MACR and MVK with average contributions of ～ 45% and ～ 70%, respectively. Through the yields of secondary products from the oxidation of MACR and MVK by the OH radical and the concentrations of MACR and MVK, it was found that methylglyoxal and formaldehyde were the main oxidation products of MACR and MVK at the HS site. Overall, this study evaluated the roles of primary emissions on ambient levels of MACR and MVK and advanced the understanding of photochemical oxidation of MACR and MVK in the PRD.展开更多
Heteropolyacid nanoparticles(NPs)were supported on Cs-modified three-dimensionally ordered macroporous(3DOM)SiO2 and used as the catalyst for the oxidation of methacrolein(MAL)to methacrylic acid(MAA).Hydrothermal tre...Heteropolyacid nanoparticles(NPs)were supported on Cs-modified three-dimensionally ordered macroporous(3DOM)SiO2 and used as the catalyst for the oxidation of methacrolein(MAL)to methacrylic acid(MAA).Hydrothermal treatment and incipient wetness impregnation were employed respectively for the Cs-modification.It was found that hydrothermal Cs-modification of 3DOM SiO2 promoted the dispersion of the supported heteropolyacid,which showed an average particle size of 5.2 nm,much smaller than that(17.6 nm)on the Csmodified 3DOM SiO2 prepared by incipient wetness impregnation.The effects of hydrothermal treatment on the structure and catalytic performance of the catalyst were investigated.Results showed that the ion exchange between Cs+and the surface silanol groups on 3DOM SiO2 was promoted with the increase of the hydrothermal temperature.Meanwhile,Cs-modification helped the heteropolyacid to retain intact Keggin structure,inhibiting the formation of MoO3.Highly dispersed heteropolyacid NPs with enhanced structural stability exhibited excellent selectivity to MAA in the oxidation of MAL.展开更多
Iron and oxalic acids are widely distributed in the atmosphere and easily form ferric oxalate complex(Fe(III)-Ox).The tropospheric aqueous-phase could provide a medium to enable the photo-Fenton reaction with Fe(III)-...Iron and oxalic acids are widely distributed in the atmosphere and easily form ferric oxalate complex(Fe(III)-Ox).The tropospheric aqueous-phase could provide a medium to enable the photo-Fenton reaction with Fe(III)-Ox under solar irradiation.Although the photolysis mechanisms of Fe(III)-Ox have been investigated extensively,information about the oxidation of volatile organic compounds(VOC),specifically the potential for Secondary Organic Aerosol(SOA)formation in the Fe(III)-Ox system,is lacking.In this study,a ubiquitous VOC methacrolein(MACR)is chosen as a model VOC,and the oxidation of MACR with Fe(III)-Ox is investigated under typical atmospheric water conditions.The effects of oxalate concentration,Fe(III)concentration,MACR concentration,and pH on the oxidation of MACR are studied in detail.Results show that the oxidation rate of MACR greatly accelerates in the presence of oxalate when compared with only Fe(III).The oxidation rate of MACR also accelerates with increasing concentration of oxalate.The effect of Fe(III)is found to be more complicated.The oxidation rate of MACR first increases and then decreases with increasing Fe(III)concentration.The oxidation rate of MACR increases monotonically with decreasing pH in the common atmospheric water pH range or with decreasing MACR concentration.The production of ferrous and hydrogen peroxide,pH,and aqueous absorbance are monitored throughout the reaction process.The quenching experiments verify that·OH and O_(2)^(+)are both responsible for the oxidation of MACR.MACR is found to rapidly oxidize into small organic acids with higher boiling points and oligomers with higher molecular weight,which contributes to the yield of SOA.These results suggest that Fe(III)-Ox plays an important role in atmospheric oxidation.展开更多
The oxidative esterification of methacrolein(MAL)is an important way to prepare high-valued methyl methacrylate(MMA),but this process is ultra-complex due to the high reactivity of both C=O and C=C bonds in MAL molecu...The oxidative esterification of methacrolein(MAL)is an important way to prepare high-valued methyl methacrylate(MMA),but this process is ultra-complex due to the high reactivity of both C=O and C=C bonds in MAL molecule.In order to further improve MMA selectivity,the reaction network and relevant mechanisms have been proposed and profoundly investigated in this paper.Five kinds of fundamental reactions are involved in this process,including(a)the acetal reaction;(b)the aerobic oxidation of hemiacetal;(c)the alkoxylation of C=C double bond;(d)the Diels-Alder reaction;and(e)the hydrogenation reaction of unsaturated double bond.Among them,the Diels-Alder reaction of MAL is non-catalyzed,and the Brönsted acid sites or the Lewis acid sites favor promoting acetal reaction of MAL with methanol,while the alkoxylation of C=C bond with methanol is enhanced under alkaline condition.In particular,by employing the Pd-based catalysts,hydrogenation products are formed in alkaline methanol solution,hence with lower than those obtained by the Au-based catalysts.Notably,it is necessary to match the hemiacetal fromation and aerobic oxidation of hemiacetal,which is relevant with the amount and strength of acid and redox sites.Consequently,this work can provide a good guidance for the further design of both catalysts and processes in future.展开更多
Methacrolein（MACR） is an abundant multifunctional carbonyl compound with high reactivity in the atmosphere. In this study, we investigated the hydroxyl radical initiated oxidation of MACR at various NO/MACR ratios（...Methacrolein（MACR） is an abundant multifunctional carbonyl compound with high reactivity in the atmosphere. In this study, we investigated the hydroxyl radical initiated oxidation of MACR at various NO/MACR ratios（0 to 4.04） and relative humidities（＆lt; 3% to80%） using a flow tube. Meanwhile, a box model based on the Master Chemical Mechanism was performed to test our current understanding of the mechanism. In contrast to the reasonable predictions for hydroxyacetone production, the modeled yields of formaldehyde（HCHO） were twice higher than the experimental results. The discrepancy was ascribed to the existence of unconsidered non-HCHO forming channels in the chemistry of CH3-UC（=CH2）OO, which account for approx. 50%. In addition, the production of hydroxyacetone and HCHO were affected by water vapor as well as the initial NO/MACR ratio. The yields of HCHO were higher under humid conditions than that under dry condition. The yields of hydroxyacetone were higher under humid conditions at low-NOx level, while lower at high-NOxlevel. The reasonable explanation for the lower hydroxyacetone yield under humid conditions at high-NOx level is that water vapor promotes the production of Umethacrolein nitrate in the reaction of HOCH2 C（CH3）（OO）CHO with NO due to the peroxy radical-water complex formation, which was evidenced by calculational results. And the minimum equilibrium constant of this water complex formation was estimated to be 1.89 × 10 （-18） cm3/molecule. These results provide new insights into the MACR oxidation mechanism and the effects of water vapor.展开更多
Heteropoly compounds with the general formula Cs1Mo.5X＋H3-o.5xP1.2MOllVO4o （M = Fe, Co, Ni, Cu or Zn） and CslCuyH3_2yP1.2MO11VO40 （y = 0.1, 0.3 or 0.7） were synthesized and then used as catalysts for the selectiv...Heteropoly compounds with the general formula Cs1Mo.5X＋H3-o.5xP1.2MOllVO4o （M = Fe, Co, Ni, Cu or Zn） and CslCuyH3_2yP1.2MO11VO40 （y = 0.1, 0.3 or 0.7） were synthesized and then used as catalysts for the selective oxidation of methacrolein to methacrylic acid. The effects of the transition metals on the structure and activity of the catalysts were investigated. FTIR spectra showed that the transition metal-doped catalysts main- tained the Keggin structure of the undoped catalysts. X-ray diffraction results indicated that before calcination, the catalysts doped with Fe and Cu had cubic secondary structures, while the catalysts doped with Co, Ni or Zn had both triclinic and cubic phases and the Co-doped catalyst had the highest content of the triclinic form. Thermal treatment can decrease the content of the triclinic phase. NH3 temperature-programmed desorption and H2 tem- perature-programmed reduction results showed that the transition metals changed the acid and redox properties of the catalysts. The addition of Fe or Cu had positive effects on the activities of the catalyst which is due to the improvement of the electron transfer between the Fe or Cu and the Mo. The effects of the copper content on structure and catalytic activity were also investigated. The CSlCUo.3H2P1.2MO11VO40 catalyst had the best performance for the selective oxidation of methacrolein to methacrylic acid.展开更多
Ionic liquid（IL）,[bmim]PF6,was used in the reaction of one-step oxidative esterification from methacrolein to methyl methacrylate. It was found that ionic liquid not only increased the selectivity of methyl methacry...Ionic liquid（IL）,[bmim]PF6,was used in the reaction of one-step oxidative esterification from methacrolein to methyl methacrylate. It was found that ionic liquid not only increased the selectivity of methyl methacrylate but also inhibited its polymerization. The selectivity of methyl methacrylate was increased from 45% to 100% with ionic liquid. The experiment results showed that the content of ionic liquid had no effects on the selectivity of methyl methacrylate in a certain range of IL concentration,which indicated that ionic liquid could be used as a potential inhibitor of polymerization. [WT5HZ]展开更多
Mixed oxide catalyst Cs 0 1 Fe 2Co 6BiMnMo 12 O x was prepared by the interprecipitation method,then the catalyst was calcined at different temperature.Selective oxidation of isobutene was carried out in a fixed bed r...Mixed oxide catalyst Cs 0 1 Fe 2Co 6BiMnMo 12 O x was prepared by the interprecipitation method,then the catalyst was calcined at different temperature.Selective oxidation of isobutene was carried out in a fixed bed reactor.The results showed that the catalyst has high catalytic activity.Under the optimum reaction conditions (n( C = 4)∶n(O 2)=1∶2 1∶4,space velocity=180h 1 ,T=360℃),the yield of methacrolein and methacrylic reached 80%,8%,respectively.The total yields of liquid products(methacrolein,methacrylic acid and acetic acid)reached about 90%.展开更多
基金financially supported by the Taishan Scholars Program of Shandong Province(No.tsqn202103051)the Science and Technology Project of Xinjiang Bingtuan Supported by the Central Government(No.2022BC001)the Project of Scientific Research in Shihezi University(No.CXFZ202205)。
文摘In this paper,low-temperature dielectric-blocked discharge plasma(DBD)was employed for the first time to treat silica-doped H_(4)PMo_(11)VO_(40)(HPAV)catalysts(DBD(Ar/x)-MF-Catal)and apply them in the catalytic methacrolein(MAL)selective oxidation to produce methacrylic acid(MAA).This work investigates in detail the controllable regulation of the concentration of oxidation states on silica-doped HPAV catalysts by adjusting the DBD discharge with controlled changes in voltage,current,treatment time,and treatment medium.It reports the intrinsic correlation between oxidation states and MAL oxidation performance.The research results indicated that the catalytic performance was related to the presence of oxygen vacancies and oxygen species(VO^(2+)),and are the main reason for the selective oxidation of MAL to MAA.Besides,the generation of oxygen vacancies and VO^(2+)altered localized electrons,which resulted in the easier activation of O_(2).Theoretical calculations of DFT also proved the formation mechanism of oxygen vacancies and VO^(2+)and electron properties on high-performance polymers,which elucidated the intrinsic influence of catalyst components.The DBD(Ar/10)-MF-Catal catalysts with suitable VO^(2+)and oxygen vacancy concentrations exhibited the highest catalytic performance with 90%MAL conversion and 70%MAA selectivity and showed good stability(500 h).
基金funding support received from China Petrochemical Corporation(Sinopec Group).
文摘The purpose of this study is to develop novel P-Mo-V heteropoly compound catalysts for the oxidation of methacrolein to methacrylic acid.The introduction of Cu,as a modifying element,was employed to enhance the catalytic performance.Experimental results show that the addition of Cu significantly improved the catalyst performance,increasing the conversion rate of methacrolein from 17.2%to 84.2%,while the yield of methacrylic acid was boosted from 5.5%to 51.7%.A series of characterization results showed that both P-Mo-V and Cu-P-Mo-V catalysts primarily exhibited the crystal phase of[PMo_(12)O_(40)]^(3−),with a small amount of[PMo_(11)VO_(40)]^(3−)phase.However,the Cu-P-Mo-V catalyst exhibited much better oxidation–reduction ability compared to the P-Mo-V catalyst.Isolated Cu atoms were found to exist in a highly decentralized tetrahedral coordination structure,bridged by oxygen atoms within the heteropoly compound framework.The addition of Cu resulted in notable alterations in the modulation of the surface electronic structure,enhancement of oxidation–reduction ability,and optimization of the reaction pathway,thereby improving the overall catalytic activity of the catalyst.This study not only provides new insights into the modification of P-Mo-V heteropoly compound catalysts but also lays a foundation for understanding their catalytic mechanisms in organic synthesis reactions,demonstrating the potential of modifying elements in improving catalyst performance.
基金Supported by the Key Program of the National Natural Science Foundation of China(21036007)the National High-Tech Project of China(2012AA062903)
文摘Novel Mg O–SBA-15 supported catalysts were prepared for oxidative esterification of methacrolein(MAL) with methanol to methyl methacrylate(MMA). The Mg O–SBA-15 supports were synthesized with different magnesia loadings from different magnesium precursors and hydrochloric acid molar concentrations. The Mg O–SBA-15 supports and Pd–Pb/Mg O–SBA-15 catalysts were characterized by several analysis methods. The results revealed that the addition of Mg O improved the ordered structure of SBA-15 supports and provided surface alkalinity of SBA-15 supports. The average size of the Pd3 Pb particles on magnesia-modified Pd–Pb/Mg O–SBA-15 catalysts was smaller than that on the pure silica-based Pd–Pb/SBA-15 catalysts. The experiments on catalyst performance showed that the magnesia-modified Pd–Pb/Mg O–SBA-15 catalysts had higher activity than pure silica-based Pd–Pb/SBA-15 catalysts, showing the strong dependence of catalytic activity on the average size of active particles. The difference of activity between Pd–Pb/SBA-15 catalysts and Pd–Pb/Mg O–SBA-15 catalysts was due to the discrepant structural properties and surface alkalinity provided by Mg O, which led to the different Pd3 Pb particle sizes and then resulted in the different number of active sites. Besides magnesia loadings, other factors, such as hydrochloric acid molar concentration and magnesium precursors, had considerable influences on the catalytic activity.
基金Financial supported by the National Natural Science Foundation of China （No.20436050）Foundation of Graduate University of the Chinese Academy of Sciences.
文摘Supported palladium catalysts, which were used in the oxidative esterification of methacrolein to methyl methacrylate, have been prepared with different carriers and Pd precursors. Experimental results revealed that Pd catalysts with r-Al2O3 support and Na2PdC14 precursor showed good performance. Pd catalyst modified with Pb and Mg indicated that Pd-Mg bimetallic catalyst exhibited considerably higher activity and Pd-Pb exhibited both higher activity and selectivity. 92.27% methacrolein conversion and 90.57% methyl methacrylate selectivity were obtained on Pd-Pb-Mg catalyst.
基金Supported by the National Natural Science Foundation of China(No.20436050)and the National High Technology Development Program of China(No.2004AA649240).
文摘A series of supported intermetallic Pb-Pb catalysts were prepared with the impregnation method by changing the support(silica,molecular sieve or γ-alumina)and the pore size.The chemical states of the two metals were characterized by XPS analysis,the process for producing methyl methacrylate based on the direct oxidative esterification of methacrolein with methanol in the presence of oxygen was performed in a slurry reactor with the above-mentioned catalysts.The influence of the calcination temperature and the kinds of support as well as the pore size on catalytic activity had been extensively investigated.Under the conditions of temperature at 80℃,catalyst 3.8%(ω)and the reaction time 2 h,the conversion rate of methacrolein reached 85%,the selectivity and the yield of methyl methacrylate were 90% and 76.5%,respectively.
基金supported by the National Natural Science Foundation of China (20806059)
文摘The effects of Bi on the catalytic performance of selective oxidation of isobutane to methacrolein over MoVO/AlPO4 catalyst were investigated by XRD, FT-Raman, XPS, UV-vis DRS techniques. The results show that the addition of Bi component into the MoVO/AlPO4 catalyst obviously improves the catalytic performance, and the selectivity to methacrolein can increase from 14.2% to 45.1% with the increase of Bi/V molar ratio from 0 to 1. Combining the characterization results with the reaction evaluation, it is concluded that the catalytic activities of the MoV0.3Bix/AlPO4 catalysts are related to the crystalline phase composition and the dispersion of molybdenum and vanadium oxides species in general, and also to the V5＋/V4＋ molar ratio on the surface in particular.
基金supported by the National Key Research and Development Program of China(No.2016YFC0202206)the State Key Program of National Natural Science Foundation of China(No.91644215)+3 种基金the National Natural Science Foundation of China(Nos.41405112 and 41505103)the Pearl River Science&Technology Nova Program of Guangzhou(No.201806010146)the National Nature Science Fund for Distinguished Young Scholars(No.41425020)the Hong Kong Research Grands Council(No.25221215)
文摘Methacrolein(MACR) and methyl vinyl ketone(MVK) are two major intermediate products from the photochemical oxidation of isoprene, the most important biogenic volatile organic compound. In addition, MACR and MVK have primary emissions. Investigating the sources and evolution of MACR and MVK could provide helpful information for the oxidative capacity of the atmosphere. In this study, hourly measurements of isoprene, MACR, and MVK were conducted at a receptor site in the Pearl River Delta region(PRD), i.e., the Heshan site(HS), from 22 October to 20 November, 2014. The average mixing ratios of isoprene,MACR and MVK were 151 ± 17, 91 ± 6 and 79 ± 6 pptv, respectively. The daily variations and the ratios of MVK/MACR during daytime and nighttime suggested that other sources besides isoprene photooxidation influenced the MACR and MVK abundances at the HS.Positive matrix factorization was utilized to resolve the sources of MACR and MVK. Five sources were identified and quantified, including biogenic emissions, biomass burning,secondary formation, diesel, and gasoline vehicular emissions. Among them, secondary formation made the greatest contribution to observed MACR and MVK with average contributions of ～ 45% and ～ 70%, respectively. Through the yields of secondary products from the oxidation of MACR and MVK by the OH radical and the concentrations of MACR and MVK, it was found that methylglyoxal and formaldehyde were the main oxidation products of MACR and MVK at the HS site. Overall, this study evaluated the roles of primary emissions on ambient levels of MACR and MVK and advanced the understanding of photochemical oxidation of MACR and MVK in the PRD.
基金financially supported by the National Natural Science Foundation of China(21206179)the Natural Science Foundation of Shandong Province(ZR2018MB033)。
文摘Heteropolyacid nanoparticles(NPs)were supported on Cs-modified three-dimensionally ordered macroporous(3DOM)SiO2 and used as the catalyst for the oxidation of methacrolein(MAL)to methacrylic acid(MAA).Hydrothermal treatment and incipient wetness impregnation were employed respectively for the Cs-modification.It was found that hydrothermal Cs-modification of 3DOM SiO2 promoted the dispersion of the supported heteropolyacid,which showed an average particle size of 5.2 nm,much smaller than that(17.6 nm)on the Csmodified 3DOM SiO2 prepared by incipient wetness impregnation.The effects of hydrothermal treatment on the structure and catalytic performance of the catalyst were investigated.Results showed that the ion exchange between Cs+and the surface silanol groups on 3DOM SiO2 was promoted with the increase of the hydrothermal temperature.Meanwhile,Cs-modification helped the heteropolyacid to retain intact Keggin structure,inhibiting the formation of MoO3.Highly dispersed heteropolyacid NPs with enhanced structural stability exhibited excellent selectivity to MAA in the oxidation of MAL.
基金The authors gratefully acknowledge financial support from the Ministry of Science and Technology of the People’s Republic of China(Grant Nos.2017YFC0210005 and 2016YFE0112200).
文摘Iron and oxalic acids are widely distributed in the atmosphere and easily form ferric oxalate complex(Fe(III)-Ox).The tropospheric aqueous-phase could provide a medium to enable the photo-Fenton reaction with Fe(III)-Ox under solar irradiation.Although the photolysis mechanisms of Fe(III)-Ox have been investigated extensively,information about the oxidation of volatile organic compounds(VOC),specifically the potential for Secondary Organic Aerosol(SOA)formation in the Fe(III)-Ox system,is lacking.In this study,a ubiquitous VOC methacrolein(MACR)is chosen as a model VOC,and the oxidation of MACR with Fe(III)-Ox is investigated under typical atmospheric water conditions.The effects of oxalate concentration,Fe(III)concentration,MACR concentration,and pH on the oxidation of MACR are studied in detail.Results show that the oxidation rate of MACR greatly accelerates in the presence of oxalate when compared with only Fe(III).The oxidation rate of MACR also accelerates with increasing concentration of oxalate.The effect of Fe(III)is found to be more complicated.The oxidation rate of MACR first increases and then decreases with increasing Fe(III)concentration.The oxidation rate of MACR increases monotonically with decreasing pH in the common atmospheric water pH range or with decreasing MACR concentration.The production of ferrous and hydrogen peroxide,pH,and aqueous absorbance are monitored throughout the reaction process.The quenching experiments verify that·OH and O_(2)^(+)are both responsible for the oxidation of MACR.MACR is found to rapidly oxidize into small organic acids with higher boiling points and oligomers with higher molecular weight,which contributes to the yield of SOA.These results suggest that Fe(III)-Ox plays an important role in atmospheric oxidation.
基金The authors acknowledge supports from the National Key Basic Research Development Plan“973”Project(2006CB202508)the SINOPEC Project(411058,413025)the National Natural Science Foundation(21808244).
文摘The oxidative esterification of methacrolein(MAL)is an important way to prepare high-valued methyl methacrylate(MMA),but this process is ultra-complex due to the high reactivity of both C=O and C=C bonds in MAL molecule.In order to further improve MMA selectivity,the reaction network and relevant mechanisms have been proposed and profoundly investigated in this paper.Five kinds of fundamental reactions are involved in this process,including(a)the acetal reaction;(b)the aerobic oxidation of hemiacetal;(c)the alkoxylation of C=C double bond;(d)the Diels-Alder reaction;and(e)the hydrogenation reaction of unsaturated double bond.Among them,the Diels-Alder reaction of MAL is non-catalyzed,and the Brönsted acid sites or the Lewis acid sites favor promoting acetal reaction of MAL with methanol,while the alkoxylation of C=C bond with methanol is enhanced under alkaline condition.In particular,by employing the Pd-based catalysts,hydrogenation products are formed in alkaline methanol solution,hence with lower than those obtained by the Au-based catalysts.Notably,it is necessary to match the hemiacetal fromation and aerobic oxidation of hemiacetal,which is relevant with the amount and strength of acid and redox sites.Consequently,this work can provide a good guidance for the further design of both catalysts and processes in future.
基金supported by the National Natural Science Foundation of China (Nos. 21477002, 41421064)the National Key Research and Development Program of China (No. 2016YFC0202704)
文摘Methacrolein（MACR） is an abundant multifunctional carbonyl compound with high reactivity in the atmosphere. In this study, we investigated the hydroxyl radical initiated oxidation of MACR at various NO/MACR ratios（0 to 4.04） and relative humidities（＆lt; 3% to80%） using a flow tube. Meanwhile, a box model based on the Master Chemical Mechanism was performed to test our current understanding of the mechanism. In contrast to the reasonable predictions for hydroxyacetone production, the modeled yields of formaldehyde（HCHO） were twice higher than the experimental results. The discrepancy was ascribed to the existence of unconsidered non-HCHO forming channels in the chemistry of CH3-UC（=CH2）OO, which account for approx. 50%. In addition, the production of hydroxyacetone and HCHO were affected by water vapor as well as the initial NO/MACR ratio. The yields of HCHO were higher under humid conditions than that under dry condition. The yields of hydroxyacetone were higher under humid conditions at low-NOx level, while lower at high-NOxlevel. The reasonable explanation for the lower hydroxyacetone yield under humid conditions at high-NOx level is that water vapor promotes the production of Umethacrolein nitrate in the reaction of HOCH2 C（CH3）（OO）CHO with NO due to the peroxy radical-water complex formation, which was evidenced by calculational results. And the minimum equilibrium constant of this water complex formation was estimated to be 1.89 × 10 （-18） cm3/molecule. These results provide new insights into the MACR oxidation mechanism and the effects of water vapor.
文摘Heteropoly compounds with the general formula Cs1Mo.5X＋H3-o.5xP1.2MOllVO4o （M = Fe, Co, Ni, Cu or Zn） and CslCuyH3_2yP1.2MO11VO40 （y = 0.1, 0.3 or 0.7） were synthesized and then used as catalysts for the selective oxidation of methacrolein to methacrylic acid. The effects of the transition metals on the structure and activity of the catalysts were investigated. FTIR spectra showed that the transition metal-doped catalysts main- tained the Keggin structure of the undoped catalysts. X-ray diffraction results indicated that before calcination, the catalysts doped with Fe and Cu had cubic secondary structures, while the catalysts doped with Co, Ni or Zn had both triclinic and cubic phases and the Co-doped catalyst had the highest content of the triclinic form. Thermal treatment can decrease the content of the triclinic phase. NH3 temperature-programmed desorption and H2 tem- perature-programmed reduction results showed that the transition metals changed the acid and redox properties of the catalysts. The addition of Fe or Cu had positive effects on the activities of the catalyst which is due to the improvement of the electron transfer between the Fe or Cu and the Mo. The effects of the copper content on structure and catalytic activity were also investigated. The CSlCUo.3H2P1.2MO11VO40 catalyst had the best performance for the selective oxidation of methacrolein to methacrylic acid.
文摘Ionic liquid（IL）,[bmim]PF6,was used in the reaction of one-step oxidative esterification from methacrolein to methyl methacrylate. It was found that ionic liquid not only increased the selectivity of methyl methacrylate but also inhibited its polymerization. The selectivity of methyl methacrylate was increased from 45% to 100% with ionic liquid. The experiment results showed that the content of ionic liquid had no effects on the selectivity of methyl methacrylate in a certain range of IL concentration,which indicated that ionic liquid could be used as a potential inhibitor of polymerization. [WT5HZ]
文摘Mixed oxide catalyst Cs 0 1 Fe 2Co 6BiMnMo 12 O x was prepared by the interprecipitation method,then the catalyst was calcined at different temperature.Selective oxidation of isobutene was carried out in a fixed bed reactor.The results showed that the catalyst has high catalytic activity.Under the optimum reaction conditions (n( C = 4)∶n(O 2)=1∶2 1∶4,space velocity=180h 1 ,T=360℃),the yield of methacrolein and methacrylic reached 80%,8%,respectively.The total yields of liquid products(methacrolein,methacrylic acid and acetic acid)reached about 90%.
