The removal of NO from oxy-fuel combustion is typically incorporated in sour gas compression purification process. This process involves the oxidation of NO to NO2 at a high pressure of 1–3 MPa, followed by absorptio...The removal of NO from oxy-fuel combustion is typically incorporated in sour gas compression purification process. This process involves the oxidation of NO to NO2 at a high pressure of 1–3 MPa, followed by absorption of NO2 by water. In this pressure range, the NO conversion rates calculated using the existing kinetic constants are often higher than those obtained experimentally. This study aimed to achieve the regression of kinetic parameters of NO oxidation based on the existing experimental results and theoretical models.Based on three existing NO oxidation mechanisms, first, the expressions for NO conversion against residence time were derived. By minimizing the mean-square errors of NO conversion ratio, the optimum kinetic rate constants were obtained. Without considering the reverse reaction for NO oxidation, similar mean-square errors for NO conversion ratio were calculated. Considering the reverse reaction for NO oxidation based on the termolecular reaction mechanism, the minimum mean-square error for NO conversion ratio was obtained. Thus, the optimum NO oxidation rate in the pressure range 0.1–3 MPa can be expressed as follows:-d[NO]/dt=d[NO2]/dt=0.0026[NO]2[O2]-0.0034[NO2]2 Detailed elementary reactions for N2/NO/NO2/O2 system were established to simulate the NO oxidation rate. A sensitivity analysis showed that the critical elementary reaction is 2 NO + O2? 2 NO2. However, the simulated NO conversions at a high pressure of 10–30 bar are still higher than the experimental values and similar to those obtained from the models without considering the reverse reaction for NO oxidation.展开更多
Iron oxide nanoparticles supported on zirconia were prepared by precipitation-deposition method and characterized by XRD, SEM, FT-IR, TGA/DTA, surface area and particle size analysis. Catalytic activities of the catal...Iron oxide nanoparticles supported on zirconia were prepared by precipitation-deposition method and characterized by XRD, SEM, FT-IR, TGA/DTA, surface area and particle size analysis. Catalytic activities of the catalysts were tested in the gas-phase conversion of cyclohexanol in a fixed-bed flow type, Pyrex glass reactor, at 433 - 463 K. Major detected products were cyclohexanone, cyclohexene and benzene, depending on the used catalyst. The rate of reaction was significantly raised by the introduction of molecular oxygen in the feed gas, thereby suggesting the oxidation of cyclohexanol to cyclohexanone. Furthermore, the catalytic activity of iron oxide nanoparticles supported on zirconia treated with hydrogen at 553 K for 2 hours, was more selective and better than the unreduced iron oxide nanoparticles supported on zirconia, in the gas-phase oxidation of cyclohexanol to cyclohexanone. Experimental results showed that there was no leaching of metal, and that the catalyst was thus truly heterogeneous.展开更多
Hexafluoropropylene oxide(HFPO)is a crucial fluorinated chemical mainly synthesized from hexafluoropropylene(HFP)through the oxidation of oxygen.However,the reaction network and kinetic characteristics are not fully u...Hexafluoropropylene oxide(HFPO)is a crucial fluorinated chemical mainly synthesized from hexafluoropropylene(HFP)through the oxidation of oxygen.However,the reaction network and kinetic characteristics are not fully understood yet,resulting in a lack of theoretical basis for synthesis process improvement.Here,the free radical reaction mechanism and complete reaction network involved in the noncatalytic oxidation of HFP to synthesize HFPO was explored by density functional theory.Transition state theory was employed to calculate the intrinsic reaction rate constants for elementary reactions.Based on theoretical reaction rate ratios,reaction pathways were selected,and a simplified reaction network was derived.It was found that byproducts were formed owing to the decomposition of HFPO and subsequent reactions with excessive oxygen while oxygen tended to participate more in the main reaction under oxygen-deficient conditions.The variations in reaction pathways occurring at different HFP/oxygen molar ratios was well elucidated by comparing with experimental data.This research establishes a robust theoretical foundation for optimizing and regulating the synthesis of HFPO.展开更多
In order to remove gas-phase mercury and NOx from flue gas, experimental studies on flue gas mercury oxidation removal and denitration of Guizhou anthracite combustion with NH4Br addition were carried out. The influen...In order to remove gas-phase mercury and NOx from flue gas, experimental studies on flue gas mercury oxidation removal and denitration of Guizhou anthracite combustion with NH4Br addition were carried out. The influence of NH4Br addition on the ignition temperature and combustion characteristics was studied using a thermogravimetric analyzer. The effects of the NHaBr addition amount on gas-phase mercury oxidation and removal were investigated in a bench scale of 6 kW fluidized bed combustor （FBC）. Mercury concentrations in flue gas were determined by the Ontario hydro method （OHM） and the mercury mass balance was obtained. Results show that the NH4Br addition has little influence on the ignition temperature of Guizhou anthracite. With the mercury mass balance of 95.47%, the proportion of particulate mercury Hg^p, gaseous mercury Hg^0 and Hg^2＋ are 75.28%, 11.60% and 13. 12%, respectively, as raw coal combustion. The high particulate mercury Hg^p in flue gas is caused by the high unburned carbon content in fly ash. When the NH4Br addition amount increases from 0 to 0. 3%, the concentration of gaseous Hg^0 and Hg^2＋ in flue gas decreases continuously, leading to the Hg^p increase accordingly. The oxidation rate of Hg^0 is positively correlated to the Br addition amount. It demonstrates that coal combustion with NH4Br addition can promote Hg^0 oxidation and removal. NOx concentration in flue gas exhibits a descending trend with the NHaBr addition and the removal rate reaches 17.31% with the addition amount of 0.3%. Adding NH4Br to coal also plays a synergistic role in denitration.展开更多
To mitigate the impact of interdiffusion reactions between the silicide slurry and Ta12W alloy substrate during vacuum sintering process on the oxidation resistance of the silicide coating,a micro-arc oxidation pretre...To mitigate the impact of interdiffusion reactions between the silicide slurry and Ta12W alloy substrate during vacuum sintering process on the oxidation resistance of the silicide coating,a micro-arc oxidation pretreatment was employed to construct a Ta_(2)O_(5)ceramic layer on the Ta12W alloy surface.Subsequently,a slurry spraying-vacuum sintering method was used to prepare a Si-Cr-Ti-Zr coating on the pretreated substrate.Comparative studies were conducted on the microstructure,phase composition,and isothermal oxidation resistance(at 1600℃)of the as-prepared coatings with and without the micro-arc oxidation ceramic layer.The results show that the Ta_(2)O_(5)layer prepared at 400 V is more continuous and has smaller pores than that prepared at 350 V.After microarc oxidation pretreatment,the Si-Cr-Ti-Zr coating on Ta12W alloy consists of three distinct layers:an upper layer dominated by Ti_(5)Si_(3),Ta_(5)Si_(3),and ZrSi;a middle layer dominated by TaSi_(2);a coating/substrate interfacial reaction layer dominated by Ta_(5)Si_(3).Both the Si-Cr-Ti-Zr coatings with and without the Ta_(2)O_(5)ceramic layer do not fail after isothermal oxidation at 1600℃for 5 h.Notably,the addition of the Ta2O5 ceramic layer reduces the high-temperature oxidation rate of the coating.展开更多
TiB_(2)coatings can significantly enhance the high-temperature oxidation resistance of molybdenum,which would broaden the application range of molybdenum and alloys thereof.However,traditional methods for preparing Ti...TiB_(2)coatings can significantly enhance the high-temperature oxidation resistance of molybdenum,which would broaden the application range of molybdenum and alloys thereof.However,traditional methods for preparing TiB_(2)coatings have disadvantages such as high equipment costs,complicated processes,and highly toxic gas emissions.This paper proposes an environmentally friendly method,which requires inexpensive equipment and simple processing,for preparing TiB_(2)coating on molybdenum via electrophoretic deposition within Na3AlF6-based molten salts.The produced TiB_(2)layer had an approximate thickness of 60μm and exhibited high density,outstanding hardness(38.2 GPa)and robust adhesion strength(51 N).Additionally,high-temperature oxidation experiments revealed that,at900℃,the TiB_(2)coating provided effective protection to the molybdenum substrate against oxidation for 3 h.This result indicates that the TiB_(2)coating prepared on molybdenum using molten salt electrophoretic deposition possesses good high-temperature oxidation resistance.展开更多
Investigating structural and hydroxyl group effects in electrooxidation of alcohols to value-added products by solid-acid electrocatalysts is essential for upgrading biomass alcohols.Herein,we report efficient electro...Investigating structural and hydroxyl group effects in electrooxidation of alcohols to value-added products by solid-acid electrocatalysts is essential for upgrading biomass alcohols.Herein,we report efficient electrocatalytic oxidations of saturated alcohols(C_(1)-C_(6))to selectively form formate using Ni Co hydroxide(Ni Co-OH)derived Ni Co_(2)O_(4)solid-acid electrocatalysts with balanced Lewis acid(LASs)and Brønsted acid sites(BASs).Thermal treatment transforms BASs-rich(89.6%)Ni Co-OH into Ni Co_(2)O_(4)with nearly equal distribution of LASs(53.1%)and BASs(46.9%)which synergistically promote adsorption and activation of OH-and alcohol molecules for enhanced oxidation activity.In contrast,BASs-enriched Ni Co-OH facilitates formation of higher valence metal sites,beneficial for water oxidation.The combined experimental studies and theoretical calculation imply the oxidation ability of C1-C6alcohols increases as increased number of hydroxyl groups and decreased HOMO-LUMO gaps:methanol(C_(1))<ethylene glycol(C_(2))<glycerol(C3)<meso-erythritol(C4)<xylitol(C5)<sorbitol(C6),while the formate selectivity shows the opposite trend from 100 to 80%.This study unveils synergistic roles of LASs and BASs,as well as hydroxyl group effect in electro-upgrading of alcohols using solid-acid electrocatalysts.展开更多
Heterogeneous oxidation of gas-phase Hg 0 by nano-Fe 2 O 3 was investigated on a fixed bed reactor, and the effects of oxygen concentration, bed temperature, water vapour concentration and particle size have been disc...Heterogeneous oxidation of gas-phase Hg 0 by nano-Fe 2 O 3 was investigated on a fixed bed reactor, and the effects of oxygen concentration, bed temperature, water vapour concentration and particle size have been discussed. The results showed that Hg 0 could be oxidized by active oxygen atom on the surface of nano-Fe 2 O 3 as well as lattice oxygen in nano-Fe 2 O 3 . Among the factors that affect Hg 0 oxidation by nano-Fe 2 O 3 , bed temperature plays an important role. More than 40% of total mercury was oxidized at 300°C, however, the test temperature at 400°C could cause sintering of nano-catalyst, which led to a lower efficiency of Hg 0 oxidation. The increase of oxygen concentration could promote mercury oxidation and led to higher Hg 0 oxidation efficiency. No obvious mercury oxidation was detected in the pure N 2 atmosphere, which indicates that oxygen is required in the gas stream for mercury oxidation. The presence of water vapour showed different effects on mercury oxidation depending on its concentration. The lower content of water vapour could promote mercury oxidation, while the higher content of water vapour inhibits mercury oxidation.展开更多
Recent experimental results and kinetic modeling of fast flow gas-phase oxidation of methane and other lower alkanes to methanol and other oxygenates are discussed, alongside with prospects and possible areas for appl...Recent experimental results and kinetic modeling of fast flow gas-phase oxidation of methane and other lower alkanes to methanol and other oxygenates are discussed, alongside with prospects and possible areas for applications of the processes.展开更多
In this study, a hybrid process using non‐thermal plasma (NTP) and photocatalytic oxidation (PCO) was adopted for the degradation of gas‐phase toluene using TiO2 as the photocatalyst. To discover the synergetic effe...In this study, a hybrid process using non‐thermal plasma (NTP) and photocatalytic oxidation (PCO) was adopted for the degradation of gas‐phase toluene using TiO2 as the photocatalyst. To discover the synergetic effect between NTP and PCO, the performances of both sole (O3, UV, NTP, and PCO) and combined (O3 + TiO2, O3 + UV, NTP + UV, O3 + PCO, and NTP + PCO) processes were investigated from different perspectives, such as the toluene removal efficiency, selectivity of COx, mineralization rate, ozone utilization, and the generation of by‐products. The toluene removal efficiency of the combined NTP + PCO process was 80.2%, which was much higher than that of a sole degradation process such as NTP (18.8%) and PCO (13.4%). The selectivity of CO2 and the ozone utilization efficiency also significantly improved. The amount of by‐products in the gas phase and the carbon‐ based intermediates adsorbed on the catalyst surface dramatically reduced. The improvement in the overall performances of the combined NTP + PCO process was mainly ascribed to the efficient utilization of ozone in the photocatalytic oxidation, and the ozone further acting as an electron acceptor and scavenger, generating more hydroxyl radicals and reducing the recombination of electron‐ hole pairs.展开更多
Ag‐Cu‐Cl/BaCO3 catalysts with different Cl and Cu loadings, prepared by the reduction deposition impregnation method, were investigated for gas‐phase epoxidation of propylene by molecular oxygen and characterized b...Ag‐Cu‐Cl/BaCO3 catalysts with different Cl and Cu loadings, prepared by the reduction deposition impregnation method, were investigated for gas‐phase epoxidation of propylene by molecular oxygen and characterized by X‐ray diffraction, X‐ray photoelectron spectroscopy and O2 temperatureprogrammed desorption. Ag‐Cu‐Cl/BaCO3 catalyst with 0.036 wt% Cu and 0.060 wt% Cl exhibitedthe highest catalytic performance for gas‐phase epoxidation of propylene by molecular oxygen. Apropylene oxide selectivity of 83.7% and propylene conversion of 1.2% were achieved under thereaction conditions of 20% C3H6‐10% O2‐70% N2, 200 °C, 0.1 MPa and 3000 h?1. Increasing the Clloading allowed Ag to ensemble easier, whereas changing the Cu loading showed little effect on Agcrystallite size. The appropriate Cl loading of Ag‐Cu‐Cl/BaCO3 catalyst can reduce the dissociationadsorption of oxygen to atomic oxygen species leading to the combustion of propylene to CO2, whichbenefits epoxidation of propylene by molecular oxygen. Excessive Cl loading of Ag‐Cu‐Cl/BaCO3catalyst decreases propylene conversion and propylene oxide selectivity remarkably because of Clpoisoning. The appropriate Cu loading of Ag‐Cu‐Cl/BaCO3 catalyst is efficient for the epoxidation ofpropylene by molecular oxygen, and an excess Cu loading decreases propylene oxide selectivitybecause the aggregation of Cu species increases the exposed surfaces of Ag nanoparticles, whichwas shown by slight increases in atomic oxygen species adsorbed. The appropriate loadings of Cu and Cl of Ag‐Cu‐Cl/BaCO3 catalyst are important to strike the balance between molecular oxygen and atomic oxygen species to create a favorable epoxidation of propylene by molecular oxygen.展开更多
Molybdenum-based catalysts for the gas-phase oxidation of propylene with air were investigated. Various types of silica-supported molybdenum oxide and molybdenum-bismuth mixed oxide cata- lysts were prepared from inor...Molybdenum-based catalysts for the gas-phase oxidation of propylene with air were investigated. Various types of silica-supported molybdenum oxide and molybdenum-bismuth mixed oxide cata- lysts were prepared from inorganic and organometallic molybdenum precursors using wet impregnation and physical vapor deposition methods. The epoxidation activities of the prepared cata- lysts showed direct correlations with their nanostructures, which were identified using transmission electron microscopy. The appearance of a partly or fully crystalline molybdenum oxide phase, which interacted poorly with the silica support, decreased the selectivity for propylene oxide for- mation to below 10%; non-crystalline octahedrally coordinated molybdenum species anchored on the support gave propylene oxide formations greater than 55%, with 11% propylene conversion. Electrochemical characterization of molybdenum oxides with various morphologies showed the importance of structural defects. Direct promotion by bismuth of the epoxidation reactivities over molybdenum oxides is disputed.展开更多
TiO2 was prepared by sol-gel method using tetrabutyl titanate as precursor. TiO2 was loaded on Bi12TiO20. The photocatalyst with different TiO2 loading was calcined at 723 K. The photocatalytic activity of decompositi...TiO2 was prepared by sol-gel method using tetrabutyl titanate as precursor. TiO2 was loaded on Bi12TiO20. The photocatalyst with different TiO2 loading was calcined at 723 K. The photocatalytic activity of decomposition gaseous benzene was investigated in a batch reactor. The prepared photocatalyst was characterized by UV-vis diffuse reflectance. The result showed that TiO2/Bi12TiO20 absorbed much more ultraviolet light than Ti02 in the ultraviolet light region and showed red shift. The results indicated that the prepared photocatalyst can greatly promote the photocatalytic activity. The 2.0% TiO2/Bi12TiO20 system exhibited the highest photocatalytic activity.展开更多
Despite of considerable efforts on the MnO2-based catalytic combustion,the different structural and component requirements of MnO2 for gas-phase selective oxidation and complete oxidation largely remain unknown.By com...Despite of considerable efforts on the MnO2-based catalytic combustion,the different structural and component requirements of MnO2 for gas-phase selective oxidation and complete oxidation largely remain unknown.By comparing four types of MnO2 with different crystal structures(α,β,γandδ),γ-MnO2 was found to be the most efficient catalyst for both aerobic selective oxidation of ethanol and CO oxidation.The structural effect ofγ-MnO2 was further investigated by doping metal ions into the framework and by comparing the catalytic performance in the gas-phase aerobic oxidation of CO and ethanol.Among ten M-γ-MnO2 catalysts,Zn-γ-MnO2 showed the lowest temperature(160°C)for achieving 90%CO conversion.The CO oxidation activity of the M-γ-MnO2 catalysts was found to be more relevant to the surface acidity-basicity than the reducibility.In contrast,surface reducibility has been demonstrated to be more crucial in the gas-phase ethanol oxidation.Cu-γ-MnO2 with higher reducibility and more oxygen vacancies of Mn^2+/Mn^3+species exhibited higher catalytic activity in the selective ethanol oxidation.Cu-γ-MnO2 achieved the highest acetaldehyde yield(75%)and space-time-yield(5.4 g gcat^-1 h^-1)at 200°C,which are even comparable to the results obtained by the state-of-the-art silver and gold-containing catalysts.Characterization results and kinetic studies further suggest that the CO oxidation follows the lattice oxygen-based Mars-van Krevelen mechanism,whereas both surface lattice oxygen and adsorbed oxygen species involve in the ethanol activation.展开更多
Many researchers have studied the photocatalytic oxidation of trace levels of benzene,toluene and xy-lene in air over titania photocatalysts.However,atthe moment,the effectiveness of the photocatalytic oxidation is li...Many researchers have studied the photocatalytic oxidation of trace levels of benzene,toluene and xy-lene in air over titania photocatalysts.However,atthe moment,the effectiveness of the photocatalytic oxidation is limited by the deactivation of photocata-lysts.展开更多
The gas-phase synthesis of dimethyl carbonate (DMC) from methanol, carbon monoxide and oXygen has here Studied in a flow system at atomspheric Pressure. A series of Catalyst used in this reaCtion have been prepared an...The gas-phase synthesis of dimethyl carbonate (DMC) from methanol, carbon monoxide and oXygen has here Studied in a flow system at atomspheric Pressure. A series of Catalyst used in this reaCtion have been prepared and evaluated. The influence of trivared carbon supporters, alkaline metal Promoters and operation conditions on DMC opthesis reaction has been discussed. Under the conditions of 130℃, CO/O2=1 .96, SV=3340h-1, the space-time yield (STY) of DMC over PdCl2-CuCl2-CH3COOK/ac. catalyst is 217g/l-cat h,which is higher than what is published in the literatUre so far.展开更多
Up-and-coming high-temperature materials,refractory high entropy alloys,are suffering from lower oxidation resistance,restricting their applications in the aerospace field.In this study,two novel treatments of Al-depo...Up-and-coming high-temperature materials,refractory high entropy alloys,are suffering from lower oxidation resistance,restricting their applications in the aerospace field.In this study,two novel treatments of Al-deposited and remelted were developed to refine the microstructure and enhance the oxidation resistance of refractory high entropy alloy using electron beam freeform fabrication(EBF3).Finer and short-range ordering structures were observed in the remelted sample,whereas the Al-deposited sample showcased the formation of silicide and intermetallic phases.High-temperature cyclic and isothermal oxidation tests at 1000℃ were carried out.The total weight gain after 60 h of cyclic oxidation decreased by 17.49%and 30.46%for the remelted and deposited samples,respectively,compared to the as-cast state.Oxidation kinetics reveal an evident lower mass gain and oxidation rate in the treated samples.A multilayer oxide consisting of TiO_(2)+Al_(2)O_(3)+SiO_(2)+AlNbO_(4) was studied for its excellent oxidation resistance.The oxidation behavior of rutile,corundum and other oxides was analyzed using first principles calculations and chemical defect analysis.Overall,this research,which introduces novel treatments,offers promising insights for enhancing the inherent oxidation resistance of refractory high entropy alloys.展开更多
Carbon dioxide transformation to fuels or chemicals provides an attractive approach for its utilization as feedstock and its emission reduction. Herein, we report a gas-phase electrocatalytic reduction of CO2 in an el...Carbon dioxide transformation to fuels or chemicals provides an attractive approach for its utilization as feedstock and its emission reduction. Herein, we report a gas-phase electrocatalytic reduction of CO2 in an electrolytic cell, constructed using phosphoric acid-doped polybenz- imidazole （PBI） membrane, which allowed operation at 170 ℃ Pt/C and PtMo/C with variable ratio of Pt/Mo were studied as the cathode catalysts. The results showed that PtMo/C catalysts significantly enhanced CO formation and inhibited CH4 formation compared with Pt/C catalyst. Characterization by X-ray diffraction, X-ray photoelectron spectroscopy and transmission electron microscopy revealed that most Mo species existed as MoO3 in PtMo/C catalysts and the interaction between Pt and MoOx was likely responsible for the enhanced CO formation rate although these bicomponent catalysts in general had a larger particle size than Pt/C catalyst.展开更多
Pitch produced by the lique-faction of coal was divided into two frac-tions:soluble in toluene(TS)and insol-uble in toluene but soluble in pyridine(TI-PS),and their differences in molecu-lar structure and oxidation ac...Pitch produced by the lique-faction of coal was divided into two frac-tions:soluble in toluene(TS)and insol-uble in toluene but soluble in pyridine(TI-PS),and their differences in molecu-lar structure and oxidation activity were studied.Several different carbon materi-als were produced from them by oxida-tion in air(350℃,300 mL/min)fol-lowed by carbonization(1000℃ in Ar),and the effect of the cross-linked structure on their structure and sodium storage properties was investigated.The results showed that the two pitch fractions were obviously different after the air oxidation.The TS fraction with a low degree of condensation and abundant side chains had a stronger oxidation activity and thus introduced more cross-linked oxygen-containing functional groups C(O)―O which prevented carbon layer rearrangement during the carbonization.As a result,a disordered hard carbon with more defects was formed,which improved the electrochemical performance.Therefore,the carbon materials derived from TS(O-TS-1000)had an obvious disordered structure and a larger layer spacing,giving them better sodium storage perform-ance than those derived from the TI-PS fraction(O-TI-PS-1000).The specific capacity of O-TS-1000 was about 250 mAh/g at 20 mA/g,which was 1.67 times higher than that of O-TI-PS-1000(150 mAh/g).展开更多
基金Supported by the Shanghai Pujiang Program(16PJ1407900)
文摘The removal of NO from oxy-fuel combustion is typically incorporated in sour gas compression purification process. This process involves the oxidation of NO to NO2 at a high pressure of 1–3 MPa, followed by absorption of NO2 by water. In this pressure range, the NO conversion rates calculated using the existing kinetic constants are often higher than those obtained experimentally. This study aimed to achieve the regression of kinetic parameters of NO oxidation based on the existing experimental results and theoretical models.Based on three existing NO oxidation mechanisms, first, the expressions for NO conversion against residence time were derived. By minimizing the mean-square errors of NO conversion ratio, the optimum kinetic rate constants were obtained. Without considering the reverse reaction for NO oxidation, similar mean-square errors for NO conversion ratio were calculated. Considering the reverse reaction for NO oxidation based on the termolecular reaction mechanism, the minimum mean-square error for NO conversion ratio was obtained. Thus, the optimum NO oxidation rate in the pressure range 0.1–3 MPa can be expressed as follows:-d[NO]/dt=d[NO2]/dt=0.0026[NO]2[O2]-0.0034[NO2]2 Detailed elementary reactions for N2/NO/NO2/O2 system were established to simulate the NO oxidation rate. A sensitivity analysis showed that the critical elementary reaction is 2 NO + O2? 2 NO2. However, the simulated NO conversions at a high pressure of 10–30 bar are still higher than the experimental values and similar to those obtained from the models without considering the reverse reaction for NO oxidation.
文摘Iron oxide nanoparticles supported on zirconia were prepared by precipitation-deposition method and characterized by XRD, SEM, FT-IR, TGA/DTA, surface area and particle size analysis. Catalytic activities of the catalysts were tested in the gas-phase conversion of cyclohexanol in a fixed-bed flow type, Pyrex glass reactor, at 433 - 463 K. Major detected products were cyclohexanone, cyclohexene and benzene, depending on the used catalyst. The rate of reaction was significantly raised by the introduction of molecular oxygen in the feed gas, thereby suggesting the oxidation of cyclohexanol to cyclohexanone. Furthermore, the catalytic activity of iron oxide nanoparticles supported on zirconia treated with hydrogen at 553 K for 2 hours, was more selective and better than the unreduced iron oxide nanoparticles supported on zirconia, in the gas-phase oxidation of cyclohexanol to cyclohexanone. Experimental results showed that there was no leaching of metal, and that the catalyst was thus truly heterogeneous.
基金supported by the National Key Research&Development Program of China(2021YFB3803200)the National Natural Science Foundation of China(22288102).
文摘Hexafluoropropylene oxide(HFPO)is a crucial fluorinated chemical mainly synthesized from hexafluoropropylene(HFP)through the oxidation of oxygen.However,the reaction network and kinetic characteristics are not fully understood yet,resulting in a lack of theoretical basis for synthesis process improvement.Here,the free radical reaction mechanism and complete reaction network involved in the noncatalytic oxidation of HFP to synthesize HFPO was explored by density functional theory.Transition state theory was employed to calculate the intrinsic reaction rate constants for elementary reactions.Based on theoretical reaction rate ratios,reaction pathways were selected,and a simplified reaction network was derived.It was found that byproducts were formed owing to the decomposition of HFPO and subsequent reactions with excessive oxygen while oxygen tended to participate more in the main reaction under oxygen-deficient conditions.The variations in reaction pathways occurring at different HFP/oxygen molar ratios was well elucidated by comparing with experimental data.This research establishes a robust theoretical foundation for optimizing and regulating the synthesis of HFPO.
基金The National Natural Science Foundation of China(No.51376046,51076030)the National Key Technology R&D Program of China during the 12th Five-Year Plan Period(No.2012BAA02B01)+2 种基金the United Creative Foundation of Jiangsu Province(No.BY2013073-10)the Fundamental Research Funds for the Central Universitiesthe Scientific Innovation Research of College Graduates in Jiangsu Province(CXZZ13_0093,KYLX_0115,KYLX_0184)
文摘In order to remove gas-phase mercury and NOx from flue gas, experimental studies on flue gas mercury oxidation removal and denitration of Guizhou anthracite combustion with NH4Br addition were carried out. The influence of NH4Br addition on the ignition temperature and combustion characteristics was studied using a thermogravimetric analyzer. The effects of the NHaBr addition amount on gas-phase mercury oxidation and removal were investigated in a bench scale of 6 kW fluidized bed combustor （FBC）. Mercury concentrations in flue gas were determined by the Ontario hydro method （OHM） and the mercury mass balance was obtained. Results show that the NH4Br addition has little influence on the ignition temperature of Guizhou anthracite. With the mercury mass balance of 95.47%, the proportion of particulate mercury Hg^p, gaseous mercury Hg^0 and Hg^2＋ are 75.28%, 11.60% and 13. 12%, respectively, as raw coal combustion. The high particulate mercury Hg^p in flue gas is caused by the high unburned carbon content in fly ash. When the NH4Br addition amount increases from 0 to 0. 3%, the concentration of gaseous Hg^0 and Hg^2＋ in flue gas decreases continuously, leading to the Hg^p increase accordingly. The oxidation rate of Hg^0 is positively correlated to the Br addition amount. It demonstrates that coal combustion with NH4Br addition can promote Hg^0 oxidation and removal. NOx concentration in flue gas exhibits a descending trend with the NHaBr addition and the removal rate reaches 17.31% with the addition amount of 0.3%. Adding NH4Br to coal also plays a synergistic role in denitration.
基金National Natural Science Foundation of China(52071274)Key Research and Development Projects of Shaanxi Province(2023-YBGY-442)Science and Technology Nova Project-Innovative Talent Promotion Program of Shaanxi Province(2020KJXX-062)。
文摘To mitigate the impact of interdiffusion reactions between the silicide slurry and Ta12W alloy substrate during vacuum sintering process on the oxidation resistance of the silicide coating,a micro-arc oxidation pretreatment was employed to construct a Ta_(2)O_(5)ceramic layer on the Ta12W alloy surface.Subsequently,a slurry spraying-vacuum sintering method was used to prepare a Si-Cr-Ti-Zr coating on the pretreated substrate.Comparative studies were conducted on the microstructure,phase composition,and isothermal oxidation resistance(at 1600℃)of the as-prepared coatings with and without the micro-arc oxidation ceramic layer.The results show that the Ta_(2)O_(5)layer prepared at 400 V is more continuous and has smaller pores than that prepared at 350 V.After microarc oxidation pretreatment,the Si-Cr-Ti-Zr coating on Ta12W alloy consists of three distinct layers:an upper layer dominated by Ti_(5)Si_(3),Ta_(5)Si_(3),and ZrSi;a middle layer dominated by TaSi_(2);a coating/substrate interfacial reaction layer dominated by Ta_(5)Si_(3).Both the Si-Cr-Ti-Zr coatings with and without the Ta_(2)O_(5)ceramic layer do not fail after isothermal oxidation at 1600℃for 5 h.Notably,the addition of the Ta2O5 ceramic layer reduces the high-temperature oxidation rate of the coating.
基金supported by the Original Exploratory Program of the National Natural Science Foundation of China(No.52450012)。
文摘TiB_(2)coatings can significantly enhance the high-temperature oxidation resistance of molybdenum,which would broaden the application range of molybdenum and alloys thereof.However,traditional methods for preparing TiB_(2)coatings have disadvantages such as high equipment costs,complicated processes,and highly toxic gas emissions.This paper proposes an environmentally friendly method,which requires inexpensive equipment and simple processing,for preparing TiB_(2)coating on molybdenum via electrophoretic deposition within Na3AlF6-based molten salts.The produced TiB_(2)layer had an approximate thickness of 60μm and exhibited high density,outstanding hardness(38.2 GPa)and robust adhesion strength(51 N).Additionally,high-temperature oxidation experiments revealed that,at900℃,the TiB_(2)coating provided effective protection to the molybdenum substrate against oxidation for 3 h.This result indicates that the TiB_(2)coating prepared on molybdenum using molten salt electrophoretic deposition possesses good high-temperature oxidation resistance.
基金the financial support from the National Natural Science Foundation of China(52172110,52472231,52311530113)Shanghai"Science and Technology Innovation Action Plan"intergovernmental international science and technology cooperation project(23520710600)+1 种基金Science and Technology Commission of Shanghai Municipality(22DZ1205600)the Central Guidance on Science and Technology Development Fund of Zhejiang Province(2024ZY01011)。
文摘Investigating structural and hydroxyl group effects in electrooxidation of alcohols to value-added products by solid-acid electrocatalysts is essential for upgrading biomass alcohols.Herein,we report efficient electrocatalytic oxidations of saturated alcohols(C_(1)-C_(6))to selectively form formate using Ni Co hydroxide(Ni Co-OH)derived Ni Co_(2)O_(4)solid-acid electrocatalysts with balanced Lewis acid(LASs)and Brønsted acid sites(BASs).Thermal treatment transforms BASs-rich(89.6%)Ni Co-OH into Ni Co_(2)O_(4)with nearly equal distribution of LASs(53.1%)and BASs(46.9%)which synergistically promote adsorption and activation of OH-and alcohol molecules for enhanced oxidation activity.In contrast,BASs-enriched Ni Co-OH facilitates formation of higher valence metal sites,beneficial for water oxidation.The combined experimental studies and theoretical calculation imply the oxidation ability of C1-C6alcohols increases as increased number of hydroxyl groups and decreased HOMO-LUMO gaps:methanol(C_(1))<ethylene glycol(C_(2))<glycerol(C3)<meso-erythritol(C4)<xylitol(C5)<sorbitol(C6),while the formate selectivity shows the opposite trend from 100 to 80%.This study unveils synergistic roles of LASs and BASs,as well as hydroxyl group effect in electro-upgrading of alcohols using solid-acid electrocatalysts.
基金supported by the Scientific Funds for Outstanding Young Scientists of China(No.50525619)the National Natural Science Foundation of China(No.51078163,50706014)the National High Technology Research and Development Program(863)of China(No.2006AA05Z304)
文摘Heterogeneous oxidation of gas-phase Hg 0 by nano-Fe 2 O 3 was investigated on a fixed bed reactor, and the effects of oxygen concentration, bed temperature, water vapour concentration and particle size have been discussed. The results showed that Hg 0 could be oxidized by active oxygen atom on the surface of nano-Fe 2 O 3 as well as lattice oxygen in nano-Fe 2 O 3 . Among the factors that affect Hg 0 oxidation by nano-Fe 2 O 3 , bed temperature plays an important role. More than 40% of total mercury was oxidized at 300°C, however, the test temperature at 400°C could cause sintering of nano-catalyst, which led to a lower efficiency of Hg 0 oxidation. The increase of oxygen concentration could promote mercury oxidation and led to higher Hg 0 oxidation efficiency. No obvious mercury oxidation was detected in the pure N 2 atmosphere, which indicates that oxygen is required in the gas stream for mercury oxidation. The presence of water vapour showed different effects on mercury oxidation depending on its concentration. The lower content of water vapour could promote mercury oxidation, while the higher content of water vapour inhibits mercury oxidation.
基金support from Russian Foundation for Basic Research(Grant No 03-03-32105)is gratefully acknowledged.
文摘Recent experimental results and kinetic modeling of fast flow gas-phase oxidation of methane and other lower alkanes to methanol and other oxygenates are discussed, alongside with prospects and possible areas for applications of the processes.
基金supported by the National Key Research and Development Plan of China (2016YFC0204700)National Natural Science Foundation of China (NSFC-51578488)+3 种基金Zhejiang Provincial "151" Talents Program (2013)Key Project of Zhejiang Provincial Science and Technology Programthe Program for Zhejiang Leading Team of S&T Innovation (2013TD07)the Changjiang Scholar Incentive Program (2009)~~
文摘In this study, a hybrid process using non‐thermal plasma (NTP) and photocatalytic oxidation (PCO) was adopted for the degradation of gas‐phase toluene using TiO2 as the photocatalyst. To discover the synergetic effect between NTP and PCO, the performances of both sole (O3, UV, NTP, and PCO) and combined (O3 + TiO2, O3 + UV, NTP + UV, O3 + PCO, and NTP + PCO) processes were investigated from different perspectives, such as the toluene removal efficiency, selectivity of COx, mineralization rate, ozone utilization, and the generation of by‐products. The toluene removal efficiency of the combined NTP + PCO process was 80.2%, which was much higher than that of a sole degradation process such as NTP (18.8%) and PCO (13.4%). The selectivity of CO2 and the ozone utilization efficiency also significantly improved. The amount of by‐products in the gas phase and the carbon‐ based intermediates adsorbed on the catalyst surface dramatically reduced. The improvement in the overall performances of the combined NTP + PCO process was mainly ascribed to the efficient utilization of ozone in the photocatalytic oxidation, and the ozone further acting as an electron acceptor and scavenger, generating more hydroxyl radicals and reducing the recombination of electron‐ hole pairs.
基金supported by National Basic Research Program of China (2013CB933200)Commission of Science and Technology of Shanghai Municipality (15DZ1205305)~~
文摘Ag‐Cu‐Cl/BaCO3 catalysts with different Cl and Cu loadings, prepared by the reduction deposition impregnation method, were investigated for gas‐phase epoxidation of propylene by molecular oxygen and characterized by X‐ray diffraction, X‐ray photoelectron spectroscopy and O2 temperatureprogrammed desorption. Ag‐Cu‐Cl/BaCO3 catalyst with 0.036 wt% Cu and 0.060 wt% Cl exhibitedthe highest catalytic performance for gas‐phase epoxidation of propylene by molecular oxygen. Apropylene oxide selectivity of 83.7% and propylene conversion of 1.2% were achieved under thereaction conditions of 20% C3H6‐10% O2‐70% N2, 200 °C, 0.1 MPa and 3000 h?1. Increasing the Clloading allowed Ag to ensemble easier, whereas changing the Cu loading showed little effect on Agcrystallite size. The appropriate Cl loading of Ag‐Cu‐Cl/BaCO3 catalyst can reduce the dissociationadsorption of oxygen to atomic oxygen species leading to the combustion of propylene to CO2, whichbenefits epoxidation of propylene by molecular oxygen. Excessive Cl loading of Ag‐Cu‐Cl/BaCO3catalyst decreases propylene conversion and propylene oxide selectivity remarkably because of Clpoisoning. The appropriate Cu loading of Ag‐Cu‐Cl/BaCO3 catalyst is efficient for the epoxidation ofpropylene by molecular oxygen, and an excess Cu loading decreases propylene oxide selectivitybecause the aggregation of Cu species increases the exposed surfaces of Ag nanoparticles, whichwas shown by slight increases in atomic oxygen species adsorbed. The appropriate loadings of Cu and Cl of Ag‐Cu‐Cl/BaCO3 catalyst are important to strike the balance between molecular oxygen and atomic oxygen species to create a favorable epoxidation of propylene by molecular oxygen.
基金A support by VEGA grant 2/0129/13 is acknowledged by I.V.
文摘Molybdenum-based catalysts for the gas-phase oxidation of propylene with air were investigated. Various types of silica-supported molybdenum oxide and molybdenum-bismuth mixed oxide cata- lysts were prepared from inorganic and organometallic molybdenum precursors using wet impregnation and physical vapor deposition methods. The epoxidation activities of the prepared cata- lysts showed direct correlations with their nanostructures, which were identified using transmission electron microscopy. The appearance of a partly or fully crystalline molybdenum oxide phase, which interacted poorly with the silica support, decreased the selectivity for propylene oxide for- mation to below 10%; non-crystalline octahedrally coordinated molybdenum species anchored on the support gave propylene oxide formations greater than 55%, with 11% propylene conversion. Electrochemical characterization of molybdenum oxides with various morphologies showed the importance of structural defects. Direct promotion by bismuth of the epoxidation reactivities over molybdenum oxides is disputed.
文摘TiO2 was prepared by sol-gel method using tetrabutyl titanate as precursor. TiO2 was loaded on Bi12TiO20. The photocatalyst with different TiO2 loading was calcined at 723 K. The photocatalytic activity of decomposition gaseous benzene was investigated in a batch reactor. The prepared photocatalyst was characterized by UV-vis diffuse reflectance. The result showed that TiO2/Bi12TiO20 absorbed much more ultraviolet light than Ti02 in the ultraviolet light region and showed red shift. The results indicated that the prepared photocatalyst can greatly promote the photocatalytic activity. The 2.0% TiO2/Bi12TiO20 system exhibited the highest photocatalytic activity.
文摘Despite of considerable efforts on the MnO2-based catalytic combustion,the different structural and component requirements of MnO2 for gas-phase selective oxidation and complete oxidation largely remain unknown.By comparing four types of MnO2 with different crystal structures(α,β,γandδ),γ-MnO2 was found to be the most efficient catalyst for both aerobic selective oxidation of ethanol and CO oxidation.The structural effect ofγ-MnO2 was further investigated by doping metal ions into the framework and by comparing the catalytic performance in the gas-phase aerobic oxidation of CO and ethanol.Among ten M-γ-MnO2 catalysts,Zn-γ-MnO2 showed the lowest temperature(160°C)for achieving 90%CO conversion.The CO oxidation activity of the M-γ-MnO2 catalysts was found to be more relevant to the surface acidity-basicity than the reducibility.In contrast,surface reducibility has been demonstrated to be more crucial in the gas-phase ethanol oxidation.Cu-γ-MnO2 with higher reducibility and more oxygen vacancies of Mn^2+/Mn^3+species exhibited higher catalytic activity in the selective ethanol oxidation.Cu-γ-MnO2 achieved the highest acetaldehyde yield(75%)and space-time-yield(5.4 g gcat^-1 h^-1)at 200°C,which are even comparable to the results obtained by the state-of-the-art silver and gold-containing catalysts.Characterization results and kinetic studies further suggest that the CO oxidation follows the lattice oxygen-based Mars-van Krevelen mechanism,whereas both surface lattice oxygen and adsorbed oxygen species involve in the ethanol activation.
文摘Many researchers have studied the photocatalytic oxidation of trace levels of benzene,toluene and xy-lene in air over titania photocatalysts.However,atthe moment,the effectiveness of the photocatalytic oxidation is limited by the deactivation of photocata-lysts.
文摘The gas-phase synthesis of dimethyl carbonate (DMC) from methanol, carbon monoxide and oXygen has here Studied in a flow system at atomspheric Pressure. A series of Catalyst used in this reaCtion have been prepared and evaluated. The influence of trivared carbon supporters, alkaline metal Promoters and operation conditions on DMC opthesis reaction has been discussed. Under the conditions of 130℃, CO/O2=1 .96, SV=3340h-1, the space-time yield (STY) of DMC over PdCl2-CuCl2-CH3COOK/ac. catalyst is 217g/l-cat h,which is higher than what is published in the literatUre so far.
基金supported by the National Key Research and Development Program of China(Grant No.2022YFF0609000)National Natural Science Foundation of China(Grant Nos.52171034 and 52101037)Postdoctoral Fellowship Program of CPSFara(No.GZB20230944).
文摘Up-and-coming high-temperature materials,refractory high entropy alloys,are suffering from lower oxidation resistance,restricting their applications in the aerospace field.In this study,two novel treatments of Al-deposited and remelted were developed to refine the microstructure and enhance the oxidation resistance of refractory high entropy alloy using electron beam freeform fabrication(EBF3).Finer and short-range ordering structures were observed in the remelted sample,whereas the Al-deposited sample showcased the formation of silicide and intermetallic phases.High-temperature cyclic and isothermal oxidation tests at 1000℃ were carried out.The total weight gain after 60 h of cyclic oxidation decreased by 17.49%and 30.46%for the remelted and deposited samples,respectively,compared to the as-cast state.Oxidation kinetics reveal an evident lower mass gain and oxidation rate in the treated samples.A multilayer oxide consisting of TiO_(2)+Al_(2)O_(3)+SiO_(2)+AlNbO_(4) was studied for its excellent oxidation resistance.The oxidation behavior of rutile,corundum and other oxides was analyzed using first principles calculations and chemical defect analysis.Overall,this research,which introduces novel treatments,offers promising insights for enhancing the inherent oxidation resistance of refractory high entropy alloys.
基金supported by the Ministry of Science and Technology of China(Grant No:2012CB215500 and 2013CB933100)the National Natural Science Foundation of China(Grant No:21103178 and 21033009)
文摘Carbon dioxide transformation to fuels or chemicals provides an attractive approach for its utilization as feedstock and its emission reduction. Herein, we report a gas-phase electrocatalytic reduction of CO2 in an electrolytic cell, constructed using phosphoric acid-doped polybenz- imidazole （PBI） membrane, which allowed operation at 170 ℃ Pt/C and PtMo/C with variable ratio of Pt/Mo were studied as the cathode catalysts. The results showed that PtMo/C catalysts significantly enhanced CO formation and inhibited CH4 formation compared with Pt/C catalyst. Characterization by X-ray diffraction, X-ray photoelectron spectroscopy and transmission electron microscopy revealed that most Mo species existed as MoO3 in PtMo/C catalysts and the interaction between Pt and MoOx was likely responsible for the enhanced CO formation rate although these bicomponent catalysts in general had a larger particle size than Pt/C catalyst.
文摘Pitch produced by the lique-faction of coal was divided into two frac-tions:soluble in toluene(TS)and insol-uble in toluene but soluble in pyridine(TI-PS),and their differences in molecu-lar structure and oxidation activity were studied.Several different carbon materi-als were produced from them by oxida-tion in air(350℃,300 mL/min)fol-lowed by carbonization(1000℃ in Ar),and the effect of the cross-linked structure on their structure and sodium storage properties was investigated.The results showed that the two pitch fractions were obviously different after the air oxidation.The TS fraction with a low degree of condensation and abundant side chains had a stronger oxidation activity and thus introduced more cross-linked oxygen-containing functional groups C(O)―O which prevented carbon layer rearrangement during the carbonization.As a result,a disordered hard carbon with more defects was formed,which improved the electrochemical performance.Therefore,the carbon materials derived from TS(O-TS-1000)had an obvious disordered structure and a larger layer spacing,giving them better sodium storage perform-ance than those derived from the TI-PS fraction(O-TI-PS-1000).The specific capacity of O-TS-1000 was about 250 mAh/g at 20 mA/g,which was 1.67 times higher than that of O-TI-PS-1000(150 mAh/g).
