Investigation was made into the degradation of organic compounds by a dielectric barrier corona discharge （DBCD） system. The DBCD, consisting of a quartz tube, a concentric high voltage electrode and a net wrapped t...Investigation was made into the degradation of organic compounds by a dielectric barrier corona discharge （DBCD） system. The DBCD, consisting of a quartz tube, a concentric high voltage electrode and a net wrapped to the external wall （used as ground electrode）, was introduced to generate active species which were sprayed into the organic solution through an aerator fixed on the bottom of the tube. The effect of four factors-the discharge voltage, gas flow rate, solution conductivity, and pH of wastewater, on the degradation efficiency of phenol was assessed. The obtained results demonstrated that this process was an effective method for phenol degradation. The degradation rate was enhanced with the increase in power supplied. The degradation efficiency in alkaline conditions was higher than those in acid and neutral conditions. The optimal gas flow rate for phenol degradation in the system was 1.6 L/min, while the solution conductivity had little effect on the degradation.展开更多
Cupric oxide （CuO） and copper-cuprous oxide （Cu-Cu2O） nanoparticles were prepared by a simple hydrothermal method for the synthesis of diethyi carbonate （DEC） from ethanol. During these syntheses, varying NaOH a...Cupric oxide （CuO） and copper-cuprous oxide （Cu-Cu2O） nanoparticles were prepared by a simple hydrothermal method for the synthesis of diethyi carbonate （DEC） from ethanol. During these syntheses, varying NaOH and glucose concentrations were applied to explore and pinpoint the active species. It was found that PdCl2/CuO and PdCI2/Cu-Cu2O both catalysts exhibited good thermal stability and morphology. The results of catalytic tests showed that the catalysts prepared with 5 mol/L NaOH show superior catalytic performances because of their lower extent of agglomeration. It is noteworthy that the PdC12/Cu-Cu2O catalysts were the most active, especially the PdCl2/Cu-Cu2O catalyst prepared with 10 mmol glucose and having a higher Cu2O concentration. In Pd（ll）-Cu（II） （PdCl2/CuO） catalysts, there is an induction period, during which Pd（II） is reduced to Pd（0）, that must occur prior to electron transfer between Pd and Cu, and this can slow the catalytic reaction. To further pinpoint the active species, PdCl2/Cu-Cu2O catalysts with different Cu2O contents were prepared by controlling the dosages of glucose. The maximum DEC yield obtained with these catalysts was 151.9 mg.g-1.h-1, corresponding to an ethanol conversion of 7.2% and 97.9% DEC selectivity on an ethanol basis. Therefore, it was concluded that Cu＋ was the active species in this catalytic system, possibly because a higher proportion of Cu＋ reduces the Pd2＋ concentration and limits the CO oxidation side reaction, thus increasing DEC selectivity. In addition, Cu＋ promotes electron transfer between Pd and Cu without an induction period, which could also promote the catalytic activity.展开更多
A pilot-scale filtration system was adopted to prepare filter media with catalytic activity to remove manganese(Mn^(2+))and ammonium(NH_(4)^(+)-N).Three different combinations of oxidants(KMnO_(4)and K_(2)FeO_(4))and ...A pilot-scale filtration system was adopted to prepare filter media with catalytic activity to remove manganese(Mn^(2+))and ammonium(NH_(4)^(+)-N).Three different combinations of oxidants(KMnO_(4)and K_(2)FeO_(4))and reductants(MnSO_(4)and FeCl_(2))were used during the start-up period.Filter R3 started up by KMnO_(4)and FeCl_(2)(Mn^(7+)→MnO_(x))exhibited excellent catalytic property,and the NH_(4)^(+)-N and Mn^(2+)removal efficiency reached over 80%on the 10th and 35th days,respectively.Filter R1 started up by K_(2)FeO_(4)and MnSO_(4)(MnO_(x)←Mn^(2+))exhibited the worst catalytic property.Filter R2 started up by KMnO_(4)and MnSO_(4)(Mn^(7+)→MnO_(x)←Mn^(2+))were in between.According to Zeta potential results,the Mn-based oxides(MnO_(x))formed by Mn^(7+)→MnO_(x)performed the highest pHIEP and pHPZC.The higher the pHIEP and pHPZC,the more unfavorable the cation adsorption.However,it was inconsistent with its excellent Mn^(2+)and NH_(4)^(+)-N removal abilities,implying that catalytic oxidation played a key role.Combined with XRD and XPS analysis,the results showed that the MnO_(x)produced by the reduction of KMnO_(4)showed early formation of buserite crystals,high degree of amorphous,high content of Mn3+and lattice oxygen with the higher activity to form defects.The above results showed that MnO_(x)produced by the reduction of KMnO_(4)was more conducive to the formation of active species for catalytic oxidation of NH_(4)^(+)-N and Mn^(2+)removal.This study provides new insights on the formation mechanisms of the active MnO_(x)that could catalytic oxidation of NH_(4)^(+)-N and Mn^(2+).展开更多
Converting CO_(2) into value-added chemicals and fuels through various catalytic methods to lower the atmospheric CO_(2) concentration has been developed to be a crucial means to alleviate the energy shortage and amel...Converting CO_(2) into value-added chemicals and fuels through various catalytic methods to lower the atmospheric CO_(2) concentration has been developed to be a crucial means to alleviate the energy shortage and ameliorate the ever-fragile environment status. However, the complexity of the CO_(2) conversion reaction and the strong reduction conditions lead to the inevitable structural evolution, making it difficult for the prior design of suitable catalytic materials. Herein, to guide the rational design of efficient catalysts,we will be centered on the thermal, electro, and photo-induced structural evolution and active species identification during the CO_(2) conversion, including the in situ/operando characterization techniques monitoring the activation, steady, and deactivation stage of the catalysts as well as the inherent restructuring mechanism towards active species. Besides, the future challenges and opportunities on the merits of combining the structural evolution with the adsorbed intermediates recognized by ultra-fast spectroscopic techniques, simultaneously, the combination of theoretical simulation and the results of in situ experiments will also be addressed. This review can not only guide the identification of real active species, but also provide an approach to design the specific active species towards CO_(2) conversion, rather than only focusing on activity, for the purpose of practical industrial application.展开更多
Nanosized Ga-containing ZSM-5 zeolites were prepared via isomorphous substitution and impregnation followed by characterized using various techniques. The catalytic performance of the zeolites for the aromatization of...Nanosized Ga-containing ZSM-5 zeolites were prepared via isomorphous substitution and impregnation followed by characterized using various techniques. The catalytic performance of the zeolites for the aromatization of 1-hexene was investigated. The results indicate that isomorphous substitution promotes the incorporation of Ga heteroatoms into the framework along with the formation of extra-framework GaO;species（[GaO;]a） that have stronger interactions with the negative potential of the framework. In addition, based on the Py-IR results and catalytic performance, the [GaO;]aspecies with stronger Lewis acid sites produced a better synergism with moderate Br?nsted acid sites and thus improved the selectivity to aromatic compounds. However, the impregnation results in the formation of Ga;O;phase and small amounts of GaO;species that are mainly located on the external surface（[GaO;];）, which contribute to weaker Lewis acid sites due to weaker interactions with the zeolite framework. During 1-hexene aromatization, the nanosized Ga isomorphously substituted ZSM-5 zeolite samples（Gax-NZ5） exhibited better catalytic performance compared to the impregnated samples, and the highest aromatic yield（i.e.,65.4 wt%） was achieved over the Ga4.2-NZ5 sample, which contained with the highest Ga content.展开更多
Oxide-supported copper-containing materials have attracted considerable research attention as promising candidates for acrolein formation.Nevertheless,the elucidation of the structure-performance relationships for the...Oxide-supported copper-containing materials have attracted considerable research attention as promising candidates for acrolein formation.Nevertheless,the elucidation of the structure-performance relationships for these systems remains a scientific challenge.In this work,copper oxide clusters deposited on a high-surface-area silica support were synthesized via a deposition-precipitation approach and exhibited remarkable catalytic reactivity(up to 25.5%conversion and 66.8%selectivity)in the propylene-selective oxidation of acrolein at 300℃.Aberration-corrected high-angle annular dark-field scanning transmission electron microscopy combined with X-ray absorption fine structure measurements of the catalyst before and after the reaction confirmed the transformation of the small-sized copper oxide(CuO)clusters into cuprous oxide(Cu2O)clusters.With the aid of in situ X-ray diffraction and in situ dual beam Fourier transform infrared spectroscopy(DB-FTIR),the allyl intermediate(CH2=CHCH2*)was clearly observed,along with the as-formed Cu2O species.The intermediate can react with oxygen atoms from neighboring Cu2O species to form acrolein during the catalytic process,and the small-sized Cu2O clusters play a crucial role in the generation of acrolein via the selective oxidation of propylene.展开更多
Despite wide applications of noble metal-based catalysts in 5-hydroxymethylfurfural(HMF)oxidation,promoting the catalytic performance at low loading amounts still remains a significant challenge.Herein,a series of met...Despite wide applications of noble metal-based catalysts in 5-hydroxymethylfurfural(HMF)oxidation,promoting the catalytic performance at low loading amounts still remains a significant challenge.Herein,a series of metal oxide modified MO_(x)-Au/TiO_(2)(M=Fe,Co,Ni)catalysts with low Au loading amount of 0.5 wt%were synthesized.Addition of transition metal oxides promotes electron transfer and generation of the Au^(δ-)-O_(v)-Ti^(3+)interface.A combination study reveals that the dual-active site(Au^(δ-)-O_(v)-Ti^(3+))governs the catalytic performance of the ratedetermining step,namely hydroxyl group oxidation.Au^(δ-) site facilitates chemisorption and activation of O_(2) molecules.At the same time,O_(v)-Ti^(3+) site acts as the role of“killing two birds with one stone”:enhancing adsorption of both reactants,accelerating the activation and dissociation of H_(2)O,and facilitating activation of the adsorbed O_(2).Besides,superoxide radicals instead of base is the active oxygen species during the rate-determining step.On this basis,a FDCA yield of 71.2% was achieved under base-free conditions,complying with the“green chemistry”principle.This work provides a new strategy for the transition metal oxides modification of Au-based catalysts,which would be constructive for the rational design of other heterogeneous catalysts.展开更多
Two series of layered mixed oxides La4BaCu5-xMxO13+(M=Mn, Co, x=05) were prepared and characterized by means of XRD, XPS, O2TPD and chemical analysis. The results show that their structures are 5layered ABO3 perovskit...Two series of layered mixed oxides La4BaCu5-xMxO13+(M=Mn, Co, x=05) were prepared and characterized by means of XRD, XPS, O2TPD and chemical analysis. The results show that their structures are 5layered ABO3 perovskite, and the XPS and O2TPD investigation confirms that there exists synergistic effect between Cu ion and M when M ion is doped into the lattice of La4BaCu5O13+, and the synergistic effect between Mn and Cu is stronger than that of CuCo.展开更多
The effects of different Cd (Cadmium) levels on generation of active oxygen speceies(AOS) and H2O2-scavenging system in the leaves of Brassica campestris L. ssp. chinensiswere studied. The results showed that generat...The effects of different Cd (Cadmium) levels on generation of active oxygen speceies(AOS) and H2O2-scavenging system in the leaves of Brassica campestris L. ssp. chinensiswere studied. The results showed that generation rate, and H2O2 content were enhancedand malondialdehyde (MDA) content increased with the increase of Cd concentrations inthe growth medium. The activities of ascorbate peroxidase (APX), dehydroascorbatereductase (DR) and glutathione reductase (GR) were promoted by the addition of Cd.Exposed to Cd also increased the contents of ascorbate (AsA) and glutathione (GSH) in theleaves.展开更多
The distribution pattern of metals as active centers on a substrate can influence the peroxymonosulfate(PMS)activation and contaminants degradation.Herein,atomic layer deposition is applied to prepare Cu single atom(S...The distribution pattern of metals as active centers on a substrate can influence the peroxymonosulfate(PMS)activation and contaminants degradation.Herein,atomic layer deposition is applied to prepare Cu single atom(SA-Cu),cluster(C-Cu),and film(F-Cu)decorated MXene catalysts by regulating the number of deposition cycles.In comparison with SA-Cu-MXene(adsorption energy(E_(ads))=-4.236 eV)and F-Cu-MXene(E_(ads)=-3.548 eV),PMS is shown to adsorb preferably on the C-Cu-MXene surface for activation(E_(ads)=-5.435 eV),realizing higher utilization efficiency.More SO_(4)^(·-)are generated in C-Cu-MXene/PMS system with steady-state concentration and 1–3 orders of magnitude higher than those in the SA-Cu-MXene and F-Cu-MXene activated PMS systems.Particularly,the contribution of SO_(4)^(·-)oxidation to sulfamethoxazole(SMX)degradation followed the order,C-Cu-MXene(97.3%)>SA-Cu-MXene(90.4%)>FCu-MXene(71.9%),realizing the larger SMX degradation rate in the C-Cu-MXene/PMS system with the degradation rate constants(k)at 0.0485 min^(-1).Additionally,SMX degradation routes in C-Cu-MXene/PMS system are found with fewer toxic intermediates.Through this work,we highlighted the importance of guided design of heterogeneous catalysts in the PMS system.Appropriate metal distribution patterns need to be selected according to the actual water treatment demand.Metal sites could be then fully utilized to produce specific active species to improve the utilization efficiency of the oxidants.展开更多
In this study,the hydrothermal method was employed to grow submicron CuS on carbon cloth(CC),and the photoreduction method was used to grow Ag nanoparticles on the CuS submicron flowers,thus forming the Ag/CuS/CC cata...In this study,the hydrothermal method was employed to grow submicron CuS on carbon cloth(CC),and the photoreduction method was used to grow Ag nanoparticles on the CuS submicron flowers,thus forming the Ag/CuS/CC catalytic electrode.The application of Ag/CuS/CC electrode-coupled dielectric barrier discharge(DBD)plasma in the disinfection of pathogenic bacteria in water was studied.The Ag/CuS/CC electrode exhibits strong antibacterial activity,and under an external voltage of 30 V,the degradation efficiency of Bacillus subtilis reaches 99.99%within 15 min without regeneration.After five cycles,the inactivation rate of Bacillus subtilis reached 99.99%within 25 min.The practical applicability of the Ag/CuS/CC-coupled DBD system for treating actual wastewater was evaluated,and the changes in biological toxicity were investigated.The results indicate that the prepared Ag/CuS/CC coupled DBD has great potential for safe disinfection of pathogenic bacteria in water through integrated processes.展开更多
A process capable of simultaneously oxidizing NO, SO2, and Hg^0 was proposed, using a nigh-voltage and short-duration positive pulsed corona discharge. By focusing on NO, SO2, and Hg^0 oxidation efficiencies, the infl...A process capable of simultaneously oxidizing NO, SO2, and Hg^0 was proposed, using a nigh-voltage and short-duration positive pulsed corona discharge. By focusing on NO, SO2, and Hg^0 oxidation efficiencies, the influences of pulse peak voltage, pulse frequency, initial concentration, electrode number, residence time and water vapor addition were investigated. The results indicate that NO, SO2 and Hg^0 oxidation efficiencies depend primarily on the radicals （OH, HO2, O） and the active species （O3, H2O2, etc.） produced by the pulsed corona discharge. The NO, SO2 and Hg^0 oxidation efficiencies could be improved as pulse peak voltage, pulse frequency, electrode number and residence time increased, but they were reduced with increasing initial concentrations. By adding water vapor, the SO2 oxidation efficiency was improved remarkably, while the NO oxidation efficiency decreased slightly. In our experiments, the simultaneous NO, SO2, and Hg^0 oxidation efficiencies reached to 40%, 98%, and 55% with the initial concentrations 479 mg/m^3, 1040 mg/m^3, and 15.0 μg/m^3, respectively.展开更多
Efficient nitrogen fixation through a reactive plasma process attracts intense interest due to the environmental issues induced by the conventional Haber–Bosch method. In this work, we present a direct and simple fix...Efficient nitrogen fixation through a reactive plasma process attracts intense interest due to the environmental issues induced by the conventional Haber–Bosch method. In this work, we present a direct and simple fixation routine without any catalysts for nitrogen in open air using an atmospheric-pressure pin-to-solution plasma electrolytic system. Nitrate, nitrite, and ammonia as the nitrogen-derived chemicals in solution were analyzed as indicators under various discharge conditions to estimate the energy efficiency of this process. The results show that the nitrogen fixation process was much more efficient by the pin-positive discharge compared to the negative one. N chemicals preferred to be formed when the solution was of negative polarity. It was also found that, with the help of solution circulation, the energy efficiency was enhanced compared to that of static liquid. However, an inverse trend was observed with the increase of the discharge current. Further study by optical emission spectroscopy indicates the important roles of active N2* and water vapour and their derived species near the plasma–water interface in the fixation process.展开更多
A comparative study of the needle-to-liquid plasma in the continuous mode with DC and AC excitations is detailed in this paper. All plasmas studied here are shown to be glow discharges. This study is based on measurem...A comparative study of the needle-to-liquid plasma in the continuous mode with DC and AC excitations is detailed in this paper. All plasmas studied here are shown to be glow discharges. This study is based on measurements of several key parameters, including electrical energy, optical emission intensities of active species, rotational and vibrational temperatures, and temperatures of the needle and liquid electrodes. AC plasmas can produce 1.2～5 times higher excited state active species than DC plasmas under the same dissipated power. AC excited liquid plasmas have the highest energy utilization efficiency among the three systems （AC excited plasmas, DC excited plasmas with water anode and DC excited plasmas with water cathode）; most of the energy is used to produce useful species rather than to heat the electrodes and plasmas.展开更多
Water splitting is important to the conversion and storage of renewable energy,but slow kinetics of the oxygen evolution reaction(OER)greatly limits its utility.Here,under visible light illumination,the p-n WO_(3)/SnS...Water splitting is important to the conversion and storage of renewable energy,but slow kinetics of the oxygen evolution reaction(OER)greatly limits its utility.Here,under visible light illumination,the p-n WO_(3)/SnSe_(2)(WS)heterojunction significantly activates OER catalysis of CoFe-layered double hydroxide(CF)/carbon nanotubes(CNTs).Specifically,the catalyst achieves an overpotential of 224 mV at 10 mA cm^(-2)and a small Tafel slope of 47 mV dec^(-1),superior to RuO_(2)and most previously reported transition metal-based OER catalysts.The p-n WS heterojunction shows strong light absorption to produce photogenerated carriers.The photogenerated holes are trapped by CF to suppresses the charge recombination and facilitate charge transfer,which accelerates OER kinetics and boost the activity for the OER.This work highlights the possibility of using heterojunctions to activate OER catalysis and advances the design of energy-efficient catalysts for water oxidation systems using solar energy.展开更多
The bactericidal effect on the representative type of Gram-negative Escherichia coli（E.coli） and Gram-positive Bacillus subtilis in drinking water was investigated in this paper by using dielectric barrier discharge...The bactericidal effect on the representative type of Gram-negative Escherichia coli（E.coli） and Gram-positive Bacillus subtilis in drinking water was investigated in this paper by using dielectric barrier discharge（DBD） advanced oxidation technology.The sterilizing rates under different conditions of reaction time t,input voltage V,p H value,and initial concentration of bacteria C_0 were investigated to figure out the optimum sterilization conditions.Our observations and comparisons of cell morphology alteration by scanning electron microscopy and transmission electron microscopy revealed the sterilization mechanisms.The results showed that the sterilizing rate increased obviously with the extension of reaction time t and the rise of input voltage V.The optimal sterilization effect was achieved when the p H value was 7.1.As the initial concentration of bacteria rose,the sterilizing rate decreased.When the input voltage was 2.2 k V and the initial concentration of bacteria was relatively low,the sterilizing rate almost reached 100% after a certain treatment time in neutral aqueous solution.The reasons for the great damage of cell structure and the killing of bacteria are the oxidation of O_3,OH and the accumulation of active species produced by DBD.The article provides a certain theoretical and experimental basis for DBD application in water pollution treatment.展开更多
Activation and surface reactions of CO and H2 on ZnO powders and nanoplates under CO hydrogenation reaction conditions were(quasi) in situ studied using temperature programmed surface reaction spectra, diffuse reflect...Activation and surface reactions of CO and H2 on ZnO powders and nanoplates under CO hydrogenation reaction conditions were(quasi) in situ studied using temperature programmed surface reaction spectra, diffuse reflectance Fourier transform infrared spectroscopy, inelastic neutron scattering spectroscopy and electron paramagnetic resonance. CO undergoes disproportion reaction to produce gaseous CO2 and surface carbon adatoms, and adsorbs to form surface formate species. H2 adsorption forms dominant irreversibly-adsorbed surface hydroxyl groups and interstitial H species and very minor surface Zn-H species. Surface formate species and hydroxyl groups react to produce CO2 and H2, while surface carbon adatoms are hydrogenated by surface Zn-H species sequentially to produce CH(a), CH2(a), CH3(a)and eventually gaseous CH4. The ZnO nanoplates, exposing a higher fraction of Zn-ZnO(0001) and OZnO(000–1) polar facets, are more active than the ZnO powders to catalyze CO hydrogenation to CH4.These results provide fundamental understanding of the reaction mechanisms and structural effects of CO hydrogenation reaction catalyzed by ZnO-based catalysts.展开更多
The organic compounds of p-nitrophenol （PNP） solution was treated by the active species generated in a stirred reactor by an atmospheric pressure plasma jet （APPJ）. The emission intensities of hydroxyl （OH）, oxy...The organic compounds of p-nitrophenol （PNP） solution was treated by the active species generated in a stirred reactor by an atmospheric pressure plasma jet （APPJ）. The emission intensities of hydroxyl （OH）, oxygen （O）, nitric oxide （NO）, hydrogen （H） and molecular （N2） were measured by optical emission spectroscopy （OES）. The relations between the flow rates of the PNP solution and degradation, the degradation effects and initial pH value of the solution were also investigated. Experimental results show that there exist intense emissions of O （777.1 nm）, N（337.1 nm）, OH （306-310 nm） and NO band （200-290 nm） in the region of plasma. Given the treatment time and gas flow rate, the degradation increased as a function of discharge energy and solution flow rate, respectively. The solution flow rate for the most efficient degradation ranged from 1.414 m/s to 1.702 m/s, and contributed very little when it exceeded 2.199 m/s. This indicates the existence of diffusion-controlled reactions at a low solution flow rate and activation- controlled reactions at a high solution flow rate. Moreover, increasing or decreasing the initial pH value of neutral PNP solution （pH=5.95） could improve the degradation efficiency. Treated by APPJ, the PNP solutions with different initial pH values of 5.95, 7.47 and 2.78 turned more acidic in the end, while the neutral solution had the lowest degradation efficiency. This work clearly demonstrates the close coupling of active species, photolysis of ultraviolet, the organic solution flow rate and the initial pH value, and thus is helpful in the study of the mechanism and application of plasma in wastewater treatment.展开更多
Catalytic oxidation of toluene over noble metal catalysts is a representative reaction for elimination of volatile organic compounds(VOCs).However,to fully understand the activation of molecular oxygen and the role of...Catalytic oxidation of toluene over noble metal catalysts is a representative reaction for elimination of volatile organic compounds(VOCs).However,to fully understand the activation of molecular oxygen and the role of active oxygen species generated in this reaction is still a challenging target.Herein,MgO nanosheets and single-atom Pt loaded MgO(Pt SA/MgO)nanosheets were synthesized and used as catalysts in toluene oxidation.The activation process of molecular oxygen and oxidation performance on the two catalysts were contrastively investigated.The Pt SA/MgO exhibited significantly enhanced catalytic activity compared to MgO.The oxygen vacancies can be easily generated on the Pt SA/MgO surface,which facilitate the activation of molecular oxygen and the formation of active oxygen species.Based on the experimental data and theoretical calculations,an active oxygen species promoted oxidation mechanism for toluene was proposed.In the presence of H2O,the molecular oxygen is more favorable to be dissociated to generate•OH on the oxygen vacancies of the Pt SA/MgO surface,which is the dominant active oxygen species.We anticipate that this work may shed light on further investigation of t10.1007/s12274-020-2765-1he oxidation mechanism of toluene and other VOCs over noble metal catalysts.展开更多
Hierarchical ZSM-5(HZ)molecular sieves based on fly ash were synthesized using a method combining water heat treatment with step-by-step calcination.The coupling catalysts between La_(1-x)Ce_(x)Mn_(0.8)-Ni_(0.2)O_(3)(...Hierarchical ZSM-5(HZ)molecular sieves based on fly ash were synthesized using a method combining water heat treatment with step-by-step calcination.The coupling catalysts between La_(1-x)Ce_(x)Mn_(0.8)-Ni_(0.2)O_(3)(x≤0.5)perovskites and HZ were prepared through the impregnation method,which were characterized by X-ray diffraction(XRD),scanning electron microscopy(SEM),high-resolution transmission electron microscopy(HRTEM),N_(2)adsorption,X-ray photoelectron spectroscopy(XPS),NH3-temperature programmed desoprtion(NH3-TPD),H_(2)-temperature programmed reduction(H_(2)-TPR)and O_(2)-TPD techniques and investigated regarding pentanal oxidation at 120-390℃to explore the effects of Ce doping on the catalytic activity and the active oxygen species of the coupling catalysts,meanwhile,the reaction mechanism and pathway of pentanal oxidation were also studied.The results reveal that Ce substitution at La sites can change the electronic interactions between all the elements and promote the electronic transfer among La,Ce,Ni,Mn and HZ,influencing directly the physicochemical characteristics of the catalysts.Moreover,the amount and transfer ability of surface adsorbed oxygen(O_(2)-and O-)regarded as the reactive oxygen species and the low temperature reducibility are the main influence factors in pentanal oxidation.Additionally,La_(0.8)Ce_(0.2)Mn_(0.8)Ni_(0.2)O_(3)/HZ exhibits the best catalytic activity and deep oxidation capacity as well as a better water resistance due to its larger amount of surface adsorbed oxygen species and higher low temperature reducibility.What’s more,appropriate Ce substitution can significantly enhance the amount of O_(2)-ions,which can distinctly enhance the catalytic activity of the catalyst,and moderate acid strength and appropriate acid amount can also facilitate the improvement of the pentanal oxidation activity.It is found that there is a synergic catalytic effect between surface acidity and redox ability of the catalyst.According to the in situ DRIFTS and GC/MS analyses,pentanal can be oxidized gradually to CO_(2)and H_(2)O by the surface oxygen species with the form of adsorption in air following the Langmuir-Hinshelwood(L-H)reaction mechanism.Two reaction pathways for the pentanal oxidation process are proposed,and the conversion of the formates to carbonates may be one of the main rate-determining steps.展开更多
基金supported by Ministry of Education of the People's Republic of China (20070141004)
文摘Investigation was made into the degradation of organic compounds by a dielectric barrier corona discharge （DBCD） system. The DBCD, consisting of a quartz tube, a concentric high voltage electrode and a net wrapped to the external wall （used as ground electrode）, was introduced to generate active species which were sprayed into the organic solution through an aerator fixed on the bottom of the tube. The effect of four factors-the discharge voltage, gas flow rate, solution conductivity, and pH of wastewater, on the degradation efficiency of phenol was assessed. The obtained results demonstrated that this process was an effective method for phenol degradation. The degradation rate was enhanced with the increase in power supplied. The degradation efficiency in alkaline conditions was higher than those in acid and neutral conditions. The optimal gas flow rate for phenol degradation in the system was 1.6 L/min, while the solution conductivity had little effect on the degradation.
基金supported by the National Natural Science Foundation of China(21106054)~~
文摘Cupric oxide （CuO） and copper-cuprous oxide （Cu-Cu2O） nanoparticles were prepared by a simple hydrothermal method for the synthesis of diethyi carbonate （DEC） from ethanol. During these syntheses, varying NaOH and glucose concentrations were applied to explore and pinpoint the active species. It was found that PdCl2/CuO and PdCI2/Cu-Cu2O both catalysts exhibited good thermal stability and morphology. The results of catalytic tests showed that the catalysts prepared with 5 mol/L NaOH show superior catalytic performances because of their lower extent of agglomeration. It is noteworthy that the PdC12/Cu-Cu2O catalysts were the most active, especially the PdCl2/Cu-Cu2O catalyst prepared with 10 mmol glucose and having a higher Cu2O concentration. In Pd（ll）-Cu（II） （PdCl2/CuO） catalysts, there is an induction period, during which Pd（II） is reduced to Pd（0）, that must occur prior to electron transfer between Pd and Cu, and this can slow the catalytic reaction. To further pinpoint the active species, PdCl2/Cu-Cu2O catalysts with different Cu2O contents were prepared by controlling the dosages of glucose. The maximum DEC yield obtained with these catalysts was 151.9 mg.g-1.h-1, corresponding to an ethanol conversion of 7.2% and 97.9% DEC selectivity on an ethanol basis. Therefore, it was concluded that Cu＋ was the active species in this catalytic system, possibly because a higher proportion of Cu＋ reduces the Pd2＋ concentration and limits the CO oxidation side reaction, thus increasing DEC selectivity. In addition, Cu＋ promotes electron transfer between Pd and Cu without an induction period, which could also promote the catalytic activity.
基金supported by the National Natural Science Foundation of China(No.52000145)the Youth Innovation Team of Shaanxi Universities,China(No.2019No.19)+1 种基金the Key Scientific Research Projects of Education Department of Shaanxi Province,China(No.22JY035)the Project of Youth Talent Lift Program of Shaanxi Association for Science and Technology,China(No.20230447).
文摘A pilot-scale filtration system was adopted to prepare filter media with catalytic activity to remove manganese(Mn^(2+))and ammonium(NH_(4)^(+)-N).Three different combinations of oxidants(KMnO_(4)and K_(2)FeO_(4))and reductants(MnSO_(4)and FeCl_(2))were used during the start-up period.Filter R3 started up by KMnO_(4)and FeCl_(2)(Mn^(7+)→MnO_(x))exhibited excellent catalytic property,and the NH_(4)^(+)-N and Mn^(2+)removal efficiency reached over 80%on the 10th and 35th days,respectively.Filter R1 started up by K_(2)FeO_(4)and MnSO_(4)(MnO_(x)←Mn^(2+))exhibited the worst catalytic property.Filter R2 started up by KMnO_(4)and MnSO_(4)(Mn^(7+)→MnO_(x)←Mn^(2+))were in between.According to Zeta potential results,the Mn-based oxides(MnO_(x))formed by Mn^(7+)→MnO_(x)performed the highest pHIEP and pHPZC.The higher the pHIEP and pHPZC,the more unfavorable the cation adsorption.However,it was inconsistent with its excellent Mn^(2+)and NH_(4)^(+)-N removal abilities,implying that catalytic oxidation played a key role.Combined with XRD and XPS analysis,the results showed that the MnO_(x)produced by the reduction of KMnO_(4)showed early formation of buserite crystals,high degree of amorphous,high content of Mn3+and lattice oxygen with the higher activity to form defects.The above results showed that MnO_(x)produced by the reduction of KMnO_(4)was more conducive to the formation of active species for catalytic oxidation of NH_(4)^(+)-N and Mn^(2+)removal.This study provides new insights on the formation mechanisms of the active MnO_(x)that could catalytic oxidation of NH_(4)^(+)-N and Mn^(2+).
基金the National Natural Science Foundation of China(No.22209120)the China Postdoctoral Science Foundation (No.2022M722364) for financial support。
文摘Converting CO_(2) into value-added chemicals and fuels through various catalytic methods to lower the atmospheric CO_(2) concentration has been developed to be a crucial means to alleviate the energy shortage and ameliorate the ever-fragile environment status. However, the complexity of the CO_(2) conversion reaction and the strong reduction conditions lead to the inevitable structural evolution, making it difficult for the prior design of suitable catalytic materials. Herein, to guide the rational design of efficient catalysts,we will be centered on the thermal, electro, and photo-induced structural evolution and active species identification during the CO_(2) conversion, including the in situ/operando characterization techniques monitoring the activation, steady, and deactivation stage of the catalysts as well as the inherent restructuring mechanism towards active species. Besides, the future challenges and opportunities on the merits of combining the structural evolution with the adsorbed intermediates recognized by ultra-fast spectroscopic techniques, simultaneously, the combination of theoretical simulation and the results of in situ experiments will also be addressed. This review can not only guide the identification of real active species, but also provide an approach to design the specific active species towards CO_(2) conversion, rather than only focusing on activity, for the purpose of practical industrial application.
基金supported by the National Natural Science Foundation of China(Nos.21276067 and 21676074)Programs of International S&T cooperation(No.2014DFR41110)
文摘Nanosized Ga-containing ZSM-5 zeolites were prepared via isomorphous substitution and impregnation followed by characterized using various techniques. The catalytic performance of the zeolites for the aromatization of 1-hexene was investigated. The results indicate that isomorphous substitution promotes the incorporation of Ga heteroatoms into the framework along with the formation of extra-framework GaO;species（[GaO;]a） that have stronger interactions with the negative potential of the framework. In addition, based on the Py-IR results and catalytic performance, the [GaO;]aspecies with stronger Lewis acid sites produced a better synergism with moderate Br?nsted acid sites and thus improved the selectivity to aromatic compounds. However, the impregnation results in the formation of Ga;O;phase and small amounts of GaO;species that are mainly located on the external surface（[GaO;];）, which contribute to weaker Lewis acid sites due to weaker interactions with the zeolite framework. During 1-hexene aromatization, the nanosized Ga isomorphously substituted ZSM-5 zeolite samples（Gax-NZ5） exhibited better catalytic performance compared to the impregnated samples, and the highest aromatic yield（i.e.,65.4 wt%） was achieved over the Ga4.2-NZ5 sample, which contained with the highest Ga content.
文摘Oxide-supported copper-containing materials have attracted considerable research attention as promising candidates for acrolein formation.Nevertheless,the elucidation of the structure-performance relationships for these systems remains a scientific challenge.In this work,copper oxide clusters deposited on a high-surface-area silica support were synthesized via a deposition-precipitation approach and exhibited remarkable catalytic reactivity(up to 25.5%conversion and 66.8%selectivity)in the propylene-selective oxidation of acrolein at 300℃.Aberration-corrected high-angle annular dark-field scanning transmission electron microscopy combined with X-ray absorption fine structure measurements of the catalyst before and after the reaction confirmed the transformation of the small-sized copper oxide(CuO)clusters into cuprous oxide(Cu2O)clusters.With the aid of in situ X-ray diffraction and in situ dual beam Fourier transform infrared spectroscopy(DB-FTIR),the allyl intermediate(CH2=CHCH2*)was clearly observed,along with the as-formed Cu2O species.The intermediate can react with oxygen atoms from neighboring Cu2O species to form acrolein during the catalytic process,and the small-sized Cu2O clusters play a crucial role in the generation of acrolein via the selective oxidation of propylene.
基金support of State Key Laboratory of Chemical Engineering (No.SKL-ChE-20A02)the support of International Clean Energy Talent Program by China Scholarship Council.
文摘Despite wide applications of noble metal-based catalysts in 5-hydroxymethylfurfural(HMF)oxidation,promoting the catalytic performance at low loading amounts still remains a significant challenge.Herein,a series of metal oxide modified MO_(x)-Au/TiO_(2)(M=Fe,Co,Ni)catalysts with low Au loading amount of 0.5 wt%were synthesized.Addition of transition metal oxides promotes electron transfer and generation of the Au^(δ-)-O_(v)-Ti^(3+)interface.A combination study reveals that the dual-active site(Au^(δ-)-O_(v)-Ti^(3+))governs the catalytic performance of the ratedetermining step,namely hydroxyl group oxidation.Au^(δ-) site facilitates chemisorption and activation of O_(2) molecules.At the same time,O_(v)-Ti^(3+) site acts as the role of“killing two birds with one stone”:enhancing adsorption of both reactants,accelerating the activation and dissociation of H_(2)O,and facilitating activation of the adsorbed O_(2).Besides,superoxide radicals instead of base is the active oxygen species during the rate-determining step.On this basis,a FDCA yield of 71.2% was achieved under base-free conditions,complying with the“green chemistry”principle.This work provides a new strategy for the transition metal oxides modification of Au-based catalysts,which would be constructive for the rational design of other heterogeneous catalysts.
文摘Two series of layered mixed oxides La4BaCu5-xMxO13+(M=Mn, Co, x=05) were prepared and characterized by means of XRD, XPS, O2TPD and chemical analysis. The results show that their structures are 5layered ABO3 perovskite, and the XPS and O2TPD investigation confirms that there exists synergistic effect between Cu ion and M when M ion is doped into the lattice of La4BaCu5O13+, and the synergistic effect between Mn and Cu is stronger than that of CuCo.
文摘The effects of different Cd (Cadmium) levels on generation of active oxygen speceies(AOS) and H2O2-scavenging system in the leaves of Brassica campestris L. ssp. chinensiswere studied. The results showed that generation rate, and H2O2 content were enhancedand malondialdehyde (MDA) content increased with the increase of Cd concentrations inthe growth medium. The activities of ascorbate peroxidase (APX), dehydroascorbatereductase (DR) and glutathione reductase (GR) were promoted by the addition of Cd.Exposed to Cd also increased the contents of ascorbate (AsA) and glutathione (GSH) in theleaves.
基金the National Natural Science Foundation of China(52100156)the Natural Science Foundation of Tianjin(21JCQNJC00400)the Shenzhen Science and Technology Program(GJHZ20200731095801005 and JCYJ20200109150210400)for financial support to this research.
文摘The distribution pattern of metals as active centers on a substrate can influence the peroxymonosulfate(PMS)activation and contaminants degradation.Herein,atomic layer deposition is applied to prepare Cu single atom(SA-Cu),cluster(C-Cu),and film(F-Cu)decorated MXene catalysts by regulating the number of deposition cycles.In comparison with SA-Cu-MXene(adsorption energy(E_(ads))=-4.236 eV)and F-Cu-MXene(E_(ads)=-3.548 eV),PMS is shown to adsorb preferably on the C-Cu-MXene surface for activation(E_(ads)=-5.435 eV),realizing higher utilization efficiency.More SO_(4)^(·-)are generated in C-Cu-MXene/PMS system with steady-state concentration and 1–3 orders of magnitude higher than those in the SA-Cu-MXene and F-Cu-MXene activated PMS systems.Particularly,the contribution of SO_(4)^(·-)oxidation to sulfamethoxazole(SMX)degradation followed the order,C-Cu-MXene(97.3%)>SA-Cu-MXene(90.4%)>FCu-MXene(71.9%),realizing the larger SMX degradation rate in the C-Cu-MXene/PMS system with the degradation rate constants(k)at 0.0485 min^(-1).Additionally,SMX degradation routes in C-Cu-MXene/PMS system are found with fewer toxic intermediates.Through this work,we highlighted the importance of guided design of heterogeneous catalysts in the PMS system.Appropriate metal distribution patterns need to be selected according to the actual water treatment demand.Metal sites could be then fully utilized to produce specific active species to improve the utilization efficiency of the oxidants.
基金funded by the National College Student Innovation and Entrepreneurship Training Program(No.GJ202323011)。
文摘In this study,the hydrothermal method was employed to grow submicron CuS on carbon cloth(CC),and the photoreduction method was used to grow Ag nanoparticles on the CuS submicron flowers,thus forming the Ag/CuS/CC catalytic electrode.The application of Ag/CuS/CC electrode-coupled dielectric barrier discharge(DBD)plasma in the disinfection of pathogenic bacteria in water was studied.The Ag/CuS/CC electrode exhibits strong antibacterial activity,and under an external voltage of 30 V,the degradation efficiency of Bacillus subtilis reaches 99.99%within 15 min without regeneration.After five cycles,the inactivation rate of Bacillus subtilis reached 99.99%within 25 min.The practical applicability of the Ag/CuS/CC-coupled DBD system for treating actual wastewater was evaluated,and the changes in biological toxicity were investigated.The results indicate that the prepared Ag/CuS/CC coupled DBD has great potential for safe disinfection of pathogenic bacteria in water through integrated processes.
基金supported by the Science and Technology Research of Department of Education of China (No. 0305,03087)
文摘A process capable of simultaneously oxidizing NO, SO2, and Hg^0 was proposed, using a nigh-voltage and short-duration positive pulsed corona discharge. By focusing on NO, SO2, and Hg^0 oxidation efficiencies, the influences of pulse peak voltage, pulse frequency, initial concentration, electrode number, residence time and water vapor addition were investigated. The results indicate that NO, SO2 and Hg^0 oxidation efficiencies depend primarily on the radicals （OH, HO2, O） and the active species （O3, H2O2, etc.） produced by the pulsed corona discharge. The NO, SO2 and Hg^0 oxidation efficiencies could be improved as pulse peak voltage, pulse frequency, electrode number and residence time increased, but they were reduced with increasing initial concentrations. By adding water vapor, the SO2 oxidation efficiency was improved remarkably, while the NO oxidation efficiency decreased slightly. In our experiments, the simultaneous NO, SO2, and Hg^0 oxidation efficiencies reached to 40%, 98%, and 55% with the initial concentrations 479 mg/m^3, 1040 mg/m^3, and 15.0 μg/m^3, respectively.
基金partly supported by National Natural Science Foundation of China (No. 11975061)the Technology Innovation and Application Development Project of Chongqing (No. cstc2019jscx-msxmX0041)+1 种基金the Construction Committee Project of Chongqing (No. 2018-1-3-6)the Fundamental Research Funds for the Central Universities (No. 2019CDQYDQ034)。
文摘Efficient nitrogen fixation through a reactive plasma process attracts intense interest due to the environmental issues induced by the conventional Haber–Bosch method. In this work, we present a direct and simple fixation routine without any catalysts for nitrogen in open air using an atmospheric-pressure pin-to-solution plasma electrolytic system. Nitrate, nitrite, and ammonia as the nitrogen-derived chemicals in solution were analyzed as indicators under various discharge conditions to estimate the energy efficiency of this process. The results show that the nitrogen fixation process was much more efficient by the pin-positive discharge compared to the negative one. N chemicals preferred to be formed when the solution was of negative polarity. It was also found that, with the help of solution circulation, the energy efficiency was enhanced compared to that of static liquid. However, an inverse trend was observed with the increase of the discharge current. Further study by optical emission spectroscopy indicates the important roles of active N2* and water vapour and their derived species near the plasma–water interface in the fixation process.
基金supported by National Natural Science Foundation of China(No.51207027)Scientific Research Foundation for the Returned Overseas Chinese Scholars,State Education Ministry of China
文摘A comparative study of the needle-to-liquid plasma in the continuous mode with DC and AC excitations is detailed in this paper. All plasmas studied here are shown to be glow discharges. This study is based on measurements of several key parameters, including electrical energy, optical emission intensities of active species, rotational and vibrational temperatures, and temperatures of the needle and liquid electrodes. AC plasmas can produce 1.2～5 times higher excited state active species than DC plasmas under the same dissipated power. AC excited liquid plasmas have the highest energy utilization efficiency among the three systems （AC excited plasmas, DC excited plasmas with water anode and DC excited plasmas with water cathode）; most of the energy is used to produce useful species rather than to heat the electrodes and plasmas.
基金the National Natural Science Foundation of China(No.41807213)the Hydrogeo-logical Survey Project of Huangshui River(No.DD20190331).
文摘Water splitting is important to the conversion and storage of renewable energy,but slow kinetics of the oxygen evolution reaction(OER)greatly limits its utility.Here,under visible light illumination,the p-n WO_(3)/SnSe_(2)(WS)heterojunction significantly activates OER catalysis of CoFe-layered double hydroxide(CF)/carbon nanotubes(CNTs).Specifically,the catalyst achieves an overpotential of 224 mV at 10 mA cm^(-2)and a small Tafel slope of 47 mV dec^(-1),superior to RuO_(2)and most previously reported transition metal-based OER catalysts.The p-n WS heterojunction shows strong light absorption to produce photogenerated carriers.The photogenerated holes are trapped by CF to suppresses the charge recombination and facilitate charge transfer,which accelerates OER kinetics and boost the activity for the OER.This work highlights the possibility of using heterojunctions to activate OER catalysis and advances the design of energy-efficient catalysts for water oxidation systems using solar energy.
基金supported by the Science and Technology Support Project Plan and Social Development of Jiangsu Province,China(No.BE2011732)the Science and Technology Support Project Plan and Social Development of Zhenjiang,Jiangsu Province,China(No.SH2012013)
文摘The bactericidal effect on the representative type of Gram-negative Escherichia coli（E.coli） and Gram-positive Bacillus subtilis in drinking water was investigated in this paper by using dielectric barrier discharge（DBD） advanced oxidation technology.The sterilizing rates under different conditions of reaction time t,input voltage V,p H value,and initial concentration of bacteria C_0 were investigated to figure out the optimum sterilization conditions.Our observations and comparisons of cell morphology alteration by scanning electron microscopy and transmission electron microscopy revealed the sterilization mechanisms.The results showed that the sterilizing rate increased obviously with the extension of reaction time t and the rise of input voltage V.The optimal sterilization effect was achieved when the p H value was 7.1.As the initial concentration of bacteria rose,the sterilizing rate decreased.When the input voltage was 2.2 k V and the initial concentration of bacteria was relatively low,the sterilizing rate almost reached 100% after a certain treatment time in neutral aqueous solution.The reasons for the great damage of cell structure and the killing of bacteria are the oxidation of O_3,OH and the accumulation of active species produced by DBD.The article provides a certain theoretical and experimental basis for DBD application in water pollution treatment.
基金the National Key R&D Program of Ministry of Science and Technology of China(2017YFB0602205)the National Natural Science Foundation of China(21525313,91745202,91945301)+4 种基金the Chinese Academy of Sciencesthe Changjiang Scholars Program of Ministry of Education of Chinathe financial support of the China Scholarship Councilsupported by the Scientific User Facilities Division,Office of Basic Energy Sciences,US DOE,under Contract No.DE-AC0500OR22725 with UT Battelle,LLCsupported by the U.S.Department of Energy,Office of Science,Office of Basic Energy Sciences,Chemical Sciences,Geosciences,and Biosciences Division,Catalysis Science Program。
文摘Activation and surface reactions of CO and H2 on ZnO powders and nanoplates under CO hydrogenation reaction conditions were(quasi) in situ studied using temperature programmed surface reaction spectra, diffuse reflectance Fourier transform infrared spectroscopy, inelastic neutron scattering spectroscopy and electron paramagnetic resonance. CO undergoes disproportion reaction to produce gaseous CO2 and surface carbon adatoms, and adsorbs to form surface formate species. H2 adsorption forms dominant irreversibly-adsorbed surface hydroxyl groups and interstitial H species and very minor surface Zn-H species. Surface formate species and hydroxyl groups react to produce CO2 and H2, while surface carbon adatoms are hydrogenated by surface Zn-H species sequentially to produce CH(a), CH2(a), CH3(a)and eventually gaseous CH4. The ZnO nanoplates, exposing a higher fraction of Zn-ZnO(0001) and OZnO(000–1) polar facets, are more active than the ZnO powders to catalyze CO hydrogenation to CH4.These results provide fundamental understanding of the reaction mechanisms and structural effects of CO hydrogenation reaction catalyzed by ZnO-based catalysts.
基金supported by National Natural Science Foundation of China(Nos.11274092,11105039,11205201)the Changzhou Science and Technology Support Projects,Changzhou,China(No.CJ20130008)the Nantong Science and Technology Support Project,Nantong,China(No.BK2014024)
文摘The organic compounds of p-nitrophenol （PNP） solution was treated by the active species generated in a stirred reactor by an atmospheric pressure plasma jet （APPJ）. The emission intensities of hydroxyl （OH）, oxygen （O）, nitric oxide （NO）, hydrogen （H） and molecular （N2） were measured by optical emission spectroscopy （OES）. The relations between the flow rates of the PNP solution and degradation, the degradation effects and initial pH value of the solution were also investigated. Experimental results show that there exist intense emissions of O （777.1 nm）, N（337.1 nm）, OH （306-310 nm） and NO band （200-290 nm） in the region of plasma. Given the treatment time and gas flow rate, the degradation increased as a function of discharge energy and solution flow rate, respectively. The solution flow rate for the most efficient degradation ranged from 1.414 m/s to 1.702 m/s, and contributed very little when it exceeded 2.199 m/s. This indicates the existence of diffusion-controlled reactions at a low solution flow rate and activation- controlled reactions at a high solution flow rate. Moreover, increasing or decreasing the initial pH value of neutral PNP solution （pH=5.95） could improve the degradation efficiency. Treated by APPJ, the PNP solutions with different initial pH values of 5.95, 7.47 and 2.78 turned more acidic in the end, while the neutral solution had the lowest degradation efficiency. This work clearly demonstrates the close coupling of active species, photolysis of ultraviolet, the organic solution flow rate and the initial pH value, and thus is helpful in the study of the mechanism and application of plasma in wastewater treatment.
基金This work was financially supported by National Natural Science Foundation of China (Nos. 51808037, 21601136 and 21876010)the Science & Technology Development Fund of Tianjin Education Commission for Higher Education (No. 2018KJ126)the Fundamental Research Funds for the Central Universities (No. FRF-TP-16-060A1).
文摘Catalytic oxidation of toluene over noble metal catalysts is a representative reaction for elimination of volatile organic compounds(VOCs).However,to fully understand the activation of molecular oxygen and the role of active oxygen species generated in this reaction is still a challenging target.Herein,MgO nanosheets and single-atom Pt loaded MgO(Pt SA/MgO)nanosheets were synthesized and used as catalysts in toluene oxidation.The activation process of molecular oxygen and oxidation performance on the two catalysts were contrastively investigated.The Pt SA/MgO exhibited significantly enhanced catalytic activity compared to MgO.The oxygen vacancies can be easily generated on the Pt SA/MgO surface,which facilitate the activation of molecular oxygen and the formation of active oxygen species.Based on the experimental data and theoretical calculations,an active oxygen species promoted oxidation mechanism for toluene was proposed.In the presence of H2O,the molecular oxygen is more favorable to be dissociated to generate•OH on the oxygen vacancies of the Pt SA/MgO surface,which is the dominant active oxygen species.We anticipate that this work may shed light on further investigation of t10.1007/s12274-020-2765-1he oxidation mechanism of toluene and other VOCs over noble metal catalysts.
基金Project supported by the National Key Research and Development Program of China(2017YFC0212606,2017YFC0211503,2016YFC0204102)the National Natural Science Foundation of China(51608500)。
文摘Hierarchical ZSM-5(HZ)molecular sieves based on fly ash were synthesized using a method combining water heat treatment with step-by-step calcination.The coupling catalysts between La_(1-x)Ce_(x)Mn_(0.8)-Ni_(0.2)O_(3)(x≤0.5)perovskites and HZ were prepared through the impregnation method,which were characterized by X-ray diffraction(XRD),scanning electron microscopy(SEM),high-resolution transmission electron microscopy(HRTEM),N_(2)adsorption,X-ray photoelectron spectroscopy(XPS),NH3-temperature programmed desoprtion(NH3-TPD),H_(2)-temperature programmed reduction(H_(2)-TPR)and O_(2)-TPD techniques and investigated regarding pentanal oxidation at 120-390℃to explore the effects of Ce doping on the catalytic activity and the active oxygen species of the coupling catalysts,meanwhile,the reaction mechanism and pathway of pentanal oxidation were also studied.The results reveal that Ce substitution at La sites can change the electronic interactions between all the elements and promote the electronic transfer among La,Ce,Ni,Mn and HZ,influencing directly the physicochemical characteristics of the catalysts.Moreover,the amount and transfer ability of surface adsorbed oxygen(O_(2)-and O-)regarded as the reactive oxygen species and the low temperature reducibility are the main influence factors in pentanal oxidation.Additionally,La_(0.8)Ce_(0.2)Mn_(0.8)Ni_(0.2)O_(3)/HZ exhibits the best catalytic activity and deep oxidation capacity as well as a better water resistance due to its larger amount of surface adsorbed oxygen species and higher low temperature reducibility.What’s more,appropriate Ce substitution can significantly enhance the amount of O_(2)-ions,which can distinctly enhance the catalytic activity of the catalyst,and moderate acid strength and appropriate acid amount can also facilitate the improvement of the pentanal oxidation activity.It is found that there is a synergic catalytic effect between surface acidity and redox ability of the catalyst.According to the in situ DRIFTS and GC/MS analyses,pentanal can be oxidized gradually to CO_(2)and H_(2)O by the surface oxygen species with the form of adsorption in air following the Langmuir-Hinshelwood(L-H)reaction mechanism.Two reaction pathways for the pentanal oxidation process are proposed,and the conversion of the formates to carbonates may be one of the main rate-determining steps.
