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_2O_3 phase and small amounts of GaO^+species that are mainly located on the external surface([GaO^+]~b), 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
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
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
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
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
In this study,cyclohexene was used as a representative of olefin and catalyzed by CeY zeolites in a fixedbed reactor under mild conditions,and the influence of Ce species in hydride transfer reaction over CeY zeolites...In this study,cyclohexene was used as a representative of olefin and catalyzed by CeY zeolites in a fixedbed reactor under mild conditions,and the influence of Ce species in hydride transfer reaction over CeY zeolites was evaluated.CeY zeolites show more excellent hydride transfer properties than HY zeolite.Based on the results of almost identical Bronsted acid properties but not the product distributions for 0.075 CeY and 0.075 CeY(DC)samples,it should be suggested that the Bronsted acid strength and density are not the deciding factors to the hydride transfer reaction.A unique band at 1442 cm^-1 in situ FTIR spectroscopy spectra are assigned to pyridine complexes bonded to a class of active Ce species that could reversibly migrate from the core of SOD cages to its 6-rings mouth towards the supercages.These results provide valuable information that these active Ce species should play a synergistic role with the Bronsted acid sites in enhancing the hydride transfer reaction with a bimolecular mechanism over CeY zeolites.展开更多
Metal-based perovskite oxides have contributed significantly to the advanced oxidation processes(AOPs)due to their diverse active sites and excellent compositional/structural flexibility.In this study,we specially des...Metal-based perovskite oxides have contributed significantly to the advanced oxidation processes(AOPs)due to their diverse active sites and excellent compositional/structural flexibility.In this study,we specially designed a perovskite oxide with abundant oxygen vacancies,SrCo_(0.8)Fe_(0.2)O_(3)(SCF),and firstly applied it as a catalyst in peroxymonosulfate(PMS) activation towards organic pollutants degradation.The result revealed that the prepared SCF catalyst exhibited excellent performance on organic compounds degradation.Besides,SCF showed much better activity than La_(0.5)Sr_(0.5)Co_(0.8)Fe_(0.2)O_(3)(LSCF) in terms of reaction rate and stability for the degradation of the organic compounds.Based on the analysis of scanning electron microscope,transmission electron microscope,X-ray diffraction,N_(2) adsorption-desorption,X-ray photoelectron spectroscopy and electron paramagnetic resonance,it was confirmed that the perovskite catalysts with high content of Sr doping at A-site could effectively create a defect-rich surface and optimize its physicochemical properties,which was responsible for the excellent heterogeneous catalytic activity of SCF.SCF can generate three highly active species:~1 O_(2),SO_(4)^(-)· and ·OH in PMS activation,revealing the degradation process of organic compounds was a coupled multiple active species in both radical and nonradical pathway.Moreover,it was mainly in a radical pathway in the degradation through PMS activation on SCF and SO_(4)^(-)· radicals produced were the dominant species in SCF/PMS system.This study demonstrated that perovskite-type catalysts could enrich OVs efficiently by doping strategy and regulate the PMS activation towards sulfate radical-based AOPs.展开更多
A convenient method for methane(CH_(4))direct conversion to methanol(CH_(3)OH)is of great significance to use methane-rich resources,especially clathrates and stranded shale gas resources located in remote regions.The...A convenient method for methane(CH_(4))direct conversion to methanol(CH_(3)OH)is of great significance to use methane-rich resources,especially clathrates and stranded shale gas resources located in remote regions.Theoretically,the activation of CH_(4) and the selectivity to the CH_(3)OH product are challenging due to the extreme stability of CH_(4) and relatively high reactivity of CH_(3)OH.The state-of-the-art‘methane reforming-methanol synthesis’process adopts a two-step strategy to avoid the further reaction of CH_(3)OH under the harsh conditions required for CH_(4) activation.In the electrochemical field,researchers are trying to develop conversion pathways under mild conditions.They have found suitable catalysts to activate the C–H bonds in methane with the help of external charge and have designed the electrode reactions to continuously generate certain active oxygen species.These active oxygen species attack the activated methane and convert it to CH_(3)OH,with the benefit of avoiding over-oxidation of CH_(3)OH,and thus obtain a high conversion efficiency of CH_(4) to CH_(3)OH.This mini-review focuses on the advantages and challenges of electrochemical conversion of CH4 to CH_(3)OH,especially the strategies for supplying electro-generated active oxygen species in-situ to react with the activated methane.展开更多
The industrialization of oxidative coupling of methane(OCM)is restricted by the low once through yield of C_(2)hydrocarbons.Recently,the halogen-assisted OCM process has been attempted to overcome this issue,but the r...The industrialization of oxidative coupling of methane(OCM)is restricted by the low once through yield of C_(2)hydrocarbons.Recently,the halogen-assisted OCM process has been attempted to overcome this issue,but the reaction stability was poor due to the rapid loss of gas-phase halides or molten alkali halides.In this work,the barium salts,particularly barium halides(BaCl_(2)and BaF_(2)),were demonstrated to be efficient promoters to improve the OCM reactivity of La_(2)O_(3)/CaO catalyst by increasing both C_(2)selectivity and C_(2)H_(4)/C_(2)H_(6)ratio,and simultaneously achieving outstanding reaction stability.The promoting mechanism can be understood in two aspects.On the one hand,the introduction of barium salts increased the amount of surface electrophilic oxygen species,serving as the alkaline active sites for selective methane activation.On the other hand,the barium halide additives induced the in-situ formation of methyl halide intermediates facilitating C_(2)H_(6)dehydrogenation,and their intimate contact with catalyst substrate restricted the rapid halogen loss and thereby improved the catalytic stability.This work not only provides a class of efficient OCM catalyst,but also offers a highly stable halogen-assisted reaction strategy.展开更多
Metal phthalocyanine has been extensively studied as a catalyst for degradation of carbamazepine(CBZ).However,metal phthalocyanine tends to undergo their own dimerization or polymerization,thereby reducing their activ...Metal phthalocyanine has been extensively studied as a catalyst for degradation of carbamazepine(CBZ).However,metal phthalocyanine tends to undergo their own dimerization or polymerization,thereby reducing their activity points and affecting their catalytic properties.In this study,a catalytic system consisting of O-bridged iron perfluorophthalocyanine dimers(FePcF16-O-FePcF16),multi-walled carbon nanotubes(MWCNTs)and H2O_(2) was proposed.The results showed MWCNTs loaded with FePcF16-O-FePcF16 can achieve excellent degradation of CBZ with smaller dosages of FePcF16-O-FePcF16 and H2O_(2),and milder reaction temperatures.In addition,the results of experiments revealed the reaction mechanism of non-hydroxyl radicals.The highly oxidized high-valent iron-oxo(Fe(IV)=O)species was the main reactive species in the FePcF16-O-FePcF16/MWCNTs/H2O_(2) system.It is noteworthy that MWCNTs can improve the dispersion of FePcF16-O-FePcF16,contributing to the production of highly oxidized Fe(IV)=O.Then,the pathway of CBZ oxidative degradation was speculated,and the study results also provide new ideas for metal phthalocyanine-loaded carbon materials to degrade emerging pollutants.展开更多
In Algerian traditional medicine,Erica arborea(EA),Erica multiflora(EM)and Arbutus unedo(AU)are reported as antiseptic,diuretic,astringent,depurative,and to treat scalds and wounds.The methanolic extracts of their lea...In Algerian traditional medicine,Erica arborea(EA),Erica multiflora(EM)and Arbutus unedo(AU)are reported as antiseptic,diuretic,astringent,depurative,and to treat scalds and wounds.The methanolic extracts of their leaves and aerial parts were screened for enzyme inhibitory and cytotoxic activities.TLC and HPLC chromatographic profiles based on flavonoids allowed to easily distinguish between the three investigated species.Inhibitory展开更多
Heterojunction photocatalysts have shown considerable activities for organic pollutants degradation.However,the faint connection interface and inferior charge shift efficiency critically block the property of heteroju...Heterojunction photocatalysts have shown considerable activities for organic pollutants degradation.However,the faint connection interface and inferior charge shift efficiency critically block the property of heterojunction photocatalysis.Herein,Bi_(2)O_(2)S/NiFe_(2)O_(4) nanosheets heterojunction with ultrastrong inter-face interaction and high internal electric field are designed by an in-situ growth method.Tentative and theoretical consequences prove that the interfacial interaction and internal electric field not only act as the electron flow bridge but also decrease the electrons shift energy obstacle,thus speeding up electrons transfer and achieving effective spatial electron-hole separation.Therefore,a large amount of·O_(2)^(-)and holes as active species were generated.Remarkably,Bi_(2)O_(2) S/NiFe_(2)O_(4) establishes a considerably boosted photocatalytic performance for tetracycline degradation(0.032 min^(-1)),which is about 14.2-fold and 7.8-fold of the pristine BOS and NFO,respectively.This work provides a promising motivation for modulating charge transfer by interface control and internal electric field to boost photocatalytic performance.展开更多
Hydroxyl radicals(·OH) generated on anode play a vital role in electrochemical oxidation(EO) of organic pollutants for water treatment. Inspired by the four-electron oxygen evolution reaction(OER), we supposed an...Hydroxyl radicals(·OH) generated on anode play a vital role in electrochemical oxidation(EO) of organic pollutants for water treatment. Inspired by the four-electron oxygen evolution reaction(OER), we supposed an anode-selection strategy to stabilize deeply oxidized states(*O and*OOH) which are beneficial to generating·OH. To verify the hypothesis, a candidate anode component(MIL-101(Cr), a well-known metal-organic framework with active variable-valence transition metal centers) was used to coat Ti/TiO_(2)plate to fabricate anodes. Compared to TiO_(2)(101) plane on undecorated anode surface, fast and complete removal of aniline and phenol, and improved energy utilization were achieved on MIL-101(Cr)-coatedTi/TiO_(2)anode. Mechanism investigation, including pollutant degradation pathways, showed the predominate contribution(69.60%–75.13%) of·OH in pollutant mineralization. Density functional theory(DFT)computations indicated Cr site in MIL-101(Cr) was more conducive to stabilizing*O and*OOH, leading to thermodynamical spontaneous generation of·OH. This work opens up an exciting avenue to explore·OH production, and supplies a useful guidance to the development of anode materials for EO process.展开更多
Given the grim situation of global warming and energy crisis,replacing traditional energy conversions based on carbon cycle with water cycle is a sustainable development trend.The synergistic electrocatalysis for valu...Given the grim situation of global warming and energy crisis,replacing traditional energy conversions based on carbon cycle with water cycle is a sustainable development trend.The synergistic electrocatalysis for value-added chemical production through oxygen species(O_(ads):OH^(*),O^(*),and OOH^(*))and the active hydrogen species(H_(ads))derived from water splitting powered by“green”electricity from renewable energy resource(wind,solar,etc.)is a promising manner,because of its reduced energy consumption and emission and high Faradaic efficiency.The study and summarization of catalytic mechanism of synergistic electrocatalysis are particularly significant,but are rarely involved.In this review,recent progress of various synergistic electrocatalysis systems for generating valuable products based on water cycle is systematically summarized.Importantly,the catalytic mechanism of synergistic electrocatalysis and the positive effect of O_(ads) and H_(ads) species produced by water splitting during the synergistic electrocatalytsis are detailedly elucidated.Furthermore,the regulation of water-derived O_(ads) and H_(ads) species for achieving efficient matchability of synergistic electrocatalysis is emphatically discussed.Finally,we propose the limitations and future goals of this synergistic system based on water cycle.This review is guidance for design of synergistic electrocatalysis architectures for producing valuable substances based on water cycle.展开更多
Series of Fe/Cu-SSZ-13 catalysts with different Fe loading content were synthesized by simple one-pot strategy.The obtained catalysts were subjected to selective catalytic reduction(SCR)of NO x with NH 3 and were char...Series of Fe/Cu-SSZ-13 catalysts with different Fe loading content were synthesized by simple one-pot strategy.The obtained catalysts were subjected to selective catalytic reduction(SCR)of NO x with NH 3 and were characterized by various techniques.The results show that Fe 0.63/Cu 1.50-SSZ-13 catalyst with proper Fe content exhibits excellent catalytic activity with widest operation temperature window from 160 to 580℃,excellent hydrothermal stability as well as good resistance to sulfur poisoning when compared with Cu-SSZ-13,signifying its great potential for practical applications.Further characterizations reveal that the synthesized Fe/Cu-SSZ-13 catalysts present typical chabazite(CHA)structure with good crystallinity,while isolated Cu^2+and monomeric Fe 3+are revealed as the predominant copper and iron species.At low temperatures,isolated Cu^2+species act as primary active sites for SCR reaction,while monomeric Fe^3+species provide sufficient active sites for sustain the SCR activity at high temperature.Moreover,Fe over doping would lead to the damage of zeolite structure,destruction of isolated Cu^2+site,as well as the formation of highly oxidizing Fe2O3,thus causing deterioration of catalytic performances.展开更多
This review article provides a new insight on the application of cerium oxide(CeO_(2))-metal oxide nanocomposites as catalyst with enhanced reducibility and improved oxygen(O_(2))storage capacity,especially in the var...This review article provides a new insight on the application of cerium oxide(CeO_(2))-metal oxide nanocomposites as catalyst with enhanced reducibility and improved oxygen(O_(2))storage capacity,especially in the varying chemical reaction processes including combustion,oxidation,epoxidation and redox.The CeO_(2)-metal oxide interaction plays an important role in controlling particle size,O_(2) availability and coke resistance properties of the catalyst.Strong metal oxide-CeO_(2) interaction also assists in generating small and highly dispersed particles,resists sintering of catalyst particles during the catalysis process,and consequently improves the O_(2) availability of the catalyst.Indeed,CeO_(2) not only provides an active support to heterogeneous catalyst,but also creates a new active site at the metal-support interface to produce stronger nanoparticle bonding through the surface O_(2) vacancy.This consequently produces a heterogeneous catalytic system with promising reaction rate and catalytic stability in many industrial applications such as CO_(2) hydrogenation,CO oxidatio n,biodiesel productio n,gas reduction,photocatalytic and methane steam reforming.展开更多
Z-Schemc photocatalysts as a research locus pertomi strong redox capability and high photocatalytic peribnnance.WO3/KNbO3 photocatalysts were fabricated by ball milling method,and performed higlier photocatalytic acti...Z-Schemc photocatalysts as a research locus pertomi strong redox capability and high photocatalytic peribnnance.WO3/KNbO3 photocatalysts were fabricated by ball milling method,and performed higlier photocatalytic activity in liquid degradation(rhodamine B,methylene blue and bisphenol A),compared with WO3 or KNbO3 monomer.This is due to that Z-scheme heterojunction is lonned between WO3 and KNbO3,and the holes photo-excited in valence band of KNbO?are quickly combined with the electrons in conduction band of WO3.The electrons accumulated in conduction band of KNbO3 show high reducibility,thereby reducing O2 to·O 2-,and the holes in valence band of WO3 show high oxidative to oxidize H2O to·OH,respectively.Furthermore,it is proved by means of electron spin resonaiice(ESR)spectra,terephthalic acid photolumiiiescence probing technique(TA・PL),and UV-Vis absorption spectra of nitroblue tetrazolium.This work indicates that the iabrication of Z-scheme structure can improve the photocatalytic activity by efficiently separating the photogenerated electrons and holes in the photocatalytic reaction system,which is helpful to deeply understand the migration mechanism of photoexcited cairier(band-band transfer and Z-scheme transfer)in heterojunction photocatalysts.展开更多
The temperature of waste gas in refuse transfer station,airport smoking area,and RTO terminal is low,which needs deep oxidation.Catalytic ozonation is one of the most effective treatment techniques in these scenarios....The temperature of waste gas in refuse transfer station,airport smoking area,and RTO terminal is low,which needs deep oxidation.Catalytic ozonation is one of the most effective treatment techniques in these scenarios.In this study,we reported that catalysts were modified under the condition of mag-netic field to simulate the low temperature dynamic conditions of low concentration toluene for catalytic ozonation.This paper aims to explore the relationship between oxygen vacancy and active oxygen species,and the specific pathways of toluene oxidation.The study found that citric acid can enhance the syner-gistic effect between Mn and Ce,and promote the generation of oxygen vacancies.The surface molecule adsorption oxygen is more conducive to catalytic oxidation than subsurface atom adsorption oxygen.Fi-nally,we proposed the main pathways of toluene in this reaction system,which runs through the whole process of the reaction.展开更多
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_2O_3 phase and small amounts of GaO^+species that are mainly located on the external surface([GaO^+]~b), 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.
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.
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.
基金Project supported by the National Natural Science Foundation of China(21902068,U1662135)PetroChina Company Limited(KYWX-18-011)Scientific Research Project of Education Department of Liaoning Province(L2019035)。
文摘In this study,cyclohexene was used as a representative of olefin and catalyzed by CeY zeolites in a fixedbed reactor under mild conditions,and the influence of Ce species in hydride transfer reaction over CeY zeolites was evaluated.CeY zeolites show more excellent hydride transfer properties than HY zeolite.Based on the results of almost identical Bronsted acid properties but not the product distributions for 0.075 CeY and 0.075 CeY(DC)samples,it should be suggested that the Bronsted acid strength and density are not the deciding factors to the hydride transfer reaction.A unique band at 1442 cm^-1 in situ FTIR spectroscopy spectra are assigned to pyridine complexes bonded to a class of active Ce species that could reversibly migrate from the core of SOD cages to its 6-rings mouth towards the supercages.These results provide valuable information that these active Ce species should play a synergistic role with the Bronsted acid sites in enhancing the hydride transfer reaction with a bimolecular mechanism over CeY zeolites.
基金supported by the National Key Research and Development Program of China (Project No.2018YFB1502903)。
文摘Metal-based perovskite oxides have contributed significantly to the advanced oxidation processes(AOPs)due to their diverse active sites and excellent compositional/structural flexibility.In this study,we specially designed a perovskite oxide with abundant oxygen vacancies,SrCo_(0.8)Fe_(0.2)O_(3)(SCF),and firstly applied it as a catalyst in peroxymonosulfate(PMS) activation towards organic pollutants degradation.The result revealed that the prepared SCF catalyst exhibited excellent performance on organic compounds degradation.Besides,SCF showed much better activity than La_(0.5)Sr_(0.5)Co_(0.8)Fe_(0.2)O_(3)(LSCF) in terms of reaction rate and stability for the degradation of the organic compounds.Based on the analysis of scanning electron microscope,transmission electron microscope,X-ray diffraction,N_(2) adsorption-desorption,X-ray photoelectron spectroscopy and electron paramagnetic resonance,it was confirmed that the perovskite catalysts with high content of Sr doping at A-site could effectively create a defect-rich surface and optimize its physicochemical properties,which was responsible for the excellent heterogeneous catalytic activity of SCF.SCF can generate three highly active species:~1 O_(2),SO_(4)^(-)· and ·OH in PMS activation,revealing the degradation process of organic compounds was a coupled multiple active species in both radical and nonradical pathway.Moreover,it was mainly in a radical pathway in the degradation through PMS activation on SCF and SO_(4)^(-)· radicals produced were the dominant species in SCF/PMS system.This study demonstrated that perovskite-type catalysts could enrich OVs efficiently by doping strategy and regulate the PMS activation towards sulfate radical-based AOPs.
基金support from National Science Foundation of China(No.22075012).
文摘A convenient method for methane(CH_(4))direct conversion to methanol(CH_(3)OH)is of great significance to use methane-rich resources,especially clathrates and stranded shale gas resources located in remote regions.Theoretically,the activation of CH_(4) and the selectivity to the CH_(3)OH product are challenging due to the extreme stability of CH_(4) and relatively high reactivity of CH_(3)OH.The state-of-the-art‘methane reforming-methanol synthesis’process adopts a two-step strategy to avoid the further reaction of CH_(3)OH under the harsh conditions required for CH_(4) activation.In the electrochemical field,researchers are trying to develop conversion pathways under mild conditions.They have found suitable catalysts to activate the C–H bonds in methane with the help of external charge and have designed the electrode reactions to continuously generate certain active oxygen species.These active oxygen species attack the activated methane and convert it to CH_(3)OH,with the benefit of avoiding over-oxidation of CH_(3)OH,and thus obtain a high conversion efficiency of CH_(4) to CH_(3)OH.This mini-review focuses on the advantages and challenges of electrochemical conversion of CH4 to CH_(3)OH,especially the strategies for supplying electro-generated active oxygen species in-situ to react with the activated methane.
基金financially supported by the National Natural Science Foundation of China(22178390,21961132026)the Key Research and Development Plan of Shandong Province(2018GGX107011)the Natural Science Foundation of Shandong Province(ZR2017BB020)。
文摘The industrialization of oxidative coupling of methane(OCM)is restricted by the low once through yield of C_(2)hydrocarbons.Recently,the halogen-assisted OCM process has been attempted to overcome this issue,but the reaction stability was poor due to the rapid loss of gas-phase halides or molten alkali halides.In this work,the barium salts,particularly barium halides(BaCl_(2)and BaF_(2)),were demonstrated to be efficient promoters to improve the OCM reactivity of La_(2)O_(3)/CaO catalyst by increasing both C_(2)selectivity and C_(2)H_(4)/C_(2)H_(6)ratio,and simultaneously achieving outstanding reaction stability.The promoting mechanism can be understood in two aspects.On the one hand,the introduction of barium salts increased the amount of surface electrophilic oxygen species,serving as the alkaline active sites for selective methane activation.On the other hand,the barium halide additives induced the in-situ formation of methyl halide intermediates facilitating C_(2)H_(6)dehydrogenation,and their intimate contact with catalyst substrate restricted the rapid halogen loss and thereby improved the catalytic stability.This work not only provides a class of efficient OCM catalyst,but also offers a highly stable halogen-assisted reaction strategy.
基金the National Natural Science Foundation of China(No.51703201)Zhejiang Provincial Natural Science Foundation of China(No.LQ17E030003)。
文摘Metal phthalocyanine has been extensively studied as a catalyst for degradation of carbamazepine(CBZ).However,metal phthalocyanine tends to undergo their own dimerization or polymerization,thereby reducing their activity points and affecting their catalytic properties.In this study,a catalytic system consisting of O-bridged iron perfluorophthalocyanine dimers(FePcF16-O-FePcF16),multi-walled carbon nanotubes(MWCNTs)and H2O_(2) was proposed.The results showed MWCNTs loaded with FePcF16-O-FePcF16 can achieve excellent degradation of CBZ with smaller dosages of FePcF16-O-FePcF16 and H2O_(2),and milder reaction temperatures.In addition,the results of experiments revealed the reaction mechanism of non-hydroxyl radicals.The highly oxidized high-valent iron-oxo(Fe(IV)=O)species was the main reactive species in the FePcF16-O-FePcF16/MWCNTs/H2O_(2) system.It is noteworthy that MWCNTs can improve the dispersion of FePcF16-O-FePcF16,contributing to the production of highly oxidized Fe(IV)=O.Then,the pathway of CBZ oxidative degradation was speculated,and the study results also provide new ideas for metal phthalocyanine-loaded carbon materials to degrade emerging pollutants.
文摘In Algerian traditional medicine,Erica arborea(EA),Erica multiflora(EM)and Arbutus unedo(AU)are reported as antiseptic,diuretic,astringent,depurative,and to treat scalds and wounds.The methanolic extracts of their leaves and aerial parts were screened for enzyme inhibitory and cytotoxic activities.TLC and HPLC chromatographic profiles based on flavonoids allowed to easily distinguish between the three investigated species.Inhibitory
基金the financial support by the National Natural Science Foundation of China as general projects(Grant Nos.51779068,52070066,52211530084,42277059,and 22006029)Tianjin Commission of Science and Technology as key technologies R&D projects(No.21YFSNSN00250)+1 种基金Doctoral Inno-vation Project of Hebei Province(CXZZBS2023031)the Royal Society/International Exchanges 2021 Cost Share/NSFC(Grant No.IEC\NSFC\211142).
文摘Heterojunction photocatalysts have shown considerable activities for organic pollutants degradation.However,the faint connection interface and inferior charge shift efficiency critically block the property of heterojunction photocatalysis.Herein,Bi_(2)O_(2)S/NiFe_(2)O_(4) nanosheets heterojunction with ultrastrong inter-face interaction and high internal electric field are designed by an in-situ growth method.Tentative and theoretical consequences prove that the interfacial interaction and internal electric field not only act as the electron flow bridge but also decrease the electrons shift energy obstacle,thus speeding up electrons transfer and achieving effective spatial electron-hole separation.Therefore,a large amount of·O_(2)^(-)and holes as active species were generated.Remarkably,Bi_(2)O_(2) S/NiFe_(2)O_(4) establishes a considerably boosted photocatalytic performance for tetracycline degradation(0.032 min^(-1)),which is about 14.2-fold and 7.8-fold of the pristine BOS and NFO,respectively.This work provides a promising motivation for modulating charge transfer by interface control and internal electric field to boost photocatalytic performance.
基金supported by the National Natrual Science of China (NSFC, Nos. 51978341, 52070100 and 52011530433)the Natural Science Foundation of Jiangsu Province of China (No. BK20190087)Jiangsu Key Laboratory of New Power Batteries, and a project funded by the Priority Academic Program Development (PAPD) of Jiangsu Higher Education Institutions。
文摘Hydroxyl radicals(·OH) generated on anode play a vital role in electrochemical oxidation(EO) of organic pollutants for water treatment. Inspired by the four-electron oxygen evolution reaction(OER), we supposed an anode-selection strategy to stabilize deeply oxidized states(*O and*OOH) which are beneficial to generating·OH. To verify the hypothesis, a candidate anode component(MIL-101(Cr), a well-known metal-organic framework with active variable-valence transition metal centers) was used to coat Ti/TiO_(2)plate to fabricate anodes. Compared to TiO_(2)(101) plane on undecorated anode surface, fast and complete removal of aniline and phenol, and improved energy utilization were achieved on MIL-101(Cr)-coatedTi/TiO_(2)anode. Mechanism investigation, including pollutant degradation pathways, showed the predominate contribution(69.60%–75.13%) of·OH in pollutant mineralization. Density functional theory(DFT)computations indicated Cr site in MIL-101(Cr) was more conducive to stabilizing*O and*OOH, leading to thermodynamical spontaneous generation of·OH. This work opens up an exciting avenue to explore·OH production, and supplies a useful guidance to the development of anode materials for EO process.
基金the National Natural Science Foundation of China(Nos.U20A20250,22171074,91961111,and 21901064)the Heilongjiang Provincial Natural Science Foundation of China(No.YQ2021B009)+1 种基金the Reform and Development Fund Project of Local University supported by the Central Government(Outstanding Youth Program)the Basic Research Fund of Heilongjiang University in Heilongjiang Province(No.2021-KYYWF-0031).
文摘Given the grim situation of global warming and energy crisis,replacing traditional energy conversions based on carbon cycle with water cycle is a sustainable development trend.The synergistic electrocatalysis for value-added chemical production through oxygen species(O_(ads):OH^(*),O^(*),and OOH^(*))and the active hydrogen species(H_(ads))derived from water splitting powered by“green”electricity from renewable energy resource(wind,solar,etc.)is a promising manner,because of its reduced energy consumption and emission and high Faradaic efficiency.The study and summarization of catalytic mechanism of synergistic electrocatalysis are particularly significant,but are rarely involved.In this review,recent progress of various synergistic electrocatalysis systems for generating valuable products based on water cycle is systematically summarized.Importantly,the catalytic mechanism of synergistic electrocatalysis and the positive effect of O_(ads) and H_(ads) species produced by water splitting during the synergistic electrocatalytsis are detailedly elucidated.Furthermore,the regulation of water-derived O_(ads) and H_(ads) species for achieving efficient matchability of synergistic electrocatalysis is emphatically discussed.Finally,we propose the limitations and future goals of this synergistic system based on water cycle.This review is guidance for design of synergistic electrocatalysis architectures for producing valuable substances based on water cycle.
基金the Key Program of Science Technology Department of Zhejiang Province(No.2018C03037)the Scientific Research Fund of Nanjing Institute of Technology(No.YKJ2019111)。
文摘Series of Fe/Cu-SSZ-13 catalysts with different Fe loading content were synthesized by simple one-pot strategy.The obtained catalysts were subjected to selective catalytic reduction(SCR)of NO x with NH 3 and were characterized by various techniques.The results show that Fe 0.63/Cu 1.50-SSZ-13 catalyst with proper Fe content exhibits excellent catalytic activity with widest operation temperature window from 160 to 580℃,excellent hydrothermal stability as well as good resistance to sulfur poisoning when compared with Cu-SSZ-13,signifying its great potential for practical applications.Further characterizations reveal that the synthesized Fe/Cu-SSZ-13 catalysts present typical chabazite(CHA)structure with good crystallinity,while isolated Cu^2+and monomeric Fe 3+are revealed as the predominant copper and iron species.At low temperatures,isolated Cu^2+species act as primary active sites for SCR reaction,while monomeric Fe^3+species provide sufficient active sites for sustain the SCR activity at high temperature.Moreover,Fe over doping would lead to the damage of zeolite structure,destruction of isolated Cu^2+site,as well as the formation of highly oxidizing Fe2O3,thus causing deterioration of catalytic performances.
基金the Universiti Malaya Research Grant(UMRG RP044A-17AET)for the financial support。
文摘This review article provides a new insight on the application of cerium oxide(CeO_(2))-metal oxide nanocomposites as catalyst with enhanced reducibility and improved oxygen(O_(2))storage capacity,especially in the varying chemical reaction processes including combustion,oxidation,epoxidation and redox.The CeO_(2)-metal oxide interaction plays an important role in controlling particle size,O_(2) availability and coke resistance properties of the catalyst.Strong metal oxide-CeO_(2) interaction also assists in generating small and highly dispersed particles,resists sintering of catalyst particles during the catalysis process,and consequently improves the O_(2) availability of the catalyst.Indeed,CeO_(2) not only provides an active support to heterogeneous catalyst,but also creates a new active site at the metal-support interface to produce stronger nanoparticle bonding through the surface O_(2) vacancy.This consequently produces a heterogeneous catalytic system with promising reaction rate and catalytic stability in many industrial applications such as CO_(2) hydrogenation,CO oxidatio n,biodiesel productio n,gas reduction,photocatalytic and methane steam reforming.
基金Supported by the National Natural Science Foundation of China(Nos.51472005,51772118 and 21607027)the Natural Science Foundation of Anhui Province,China(No.1608085QB37)+3 种基金the Open Project Program of the State Key Laboratory of Photocatalysis on Energy and Environment,Fuzhou University,China(No.SKLPEE-KF201804)the Natural Science Foundation of Educational Conunittee of Anhui Province,China(Nos.KJ2018A0387 and KJ2019A0601)the Project of Aiiliui Province tor Excellent Young Talents in Universities,Cliina(No.gxyq2019029)the Graduate Innovation Foundation of Huaibei Nonnal University,China(No.ycx201901003)。
文摘Z-Schemc photocatalysts as a research locus pertomi strong redox capability and high photocatalytic peribnnance.WO3/KNbO3 photocatalysts were fabricated by ball milling method,and performed higlier photocatalytic activity in liquid degradation(rhodamine B,methylene blue and bisphenol A),compared with WO3 or KNbO3 monomer.This is due to that Z-scheme heterojunction is lonned between WO3 and KNbO3,and the holes photo-excited in valence band of KNbO?are quickly combined with the electrons in conduction band of WO3.The electrons accumulated in conduction band of KNbO3 show high reducibility,thereby reducing O2 to·O 2-,and the holes in valence band of WO3 show high oxidative to oxidize H2O to·OH,respectively.Furthermore,it is proved by means of electron spin resonaiice(ESR)spectra,terephthalic acid photolumiiiescence probing technique(TA・PL),and UV-Vis absorption spectra of nitroblue tetrazolium.This work indicates that the iabrication of Z-scheme structure can improve the photocatalytic activity by efficiently separating the photogenerated electrons and holes in the photocatalytic reaction system,which is helpful to deeply understand the migration mechanism of photoexcited cairier(band-band transfer and Z-scheme transfer)in heterojunction photocatalysts.
基金financially supported by the Scientific Research Project of Guangzhou City(No.201804020026)the National Nat-ural Science Foundation of China(Nos.51878293,21777047)+1 种基金the National Key Research and Development Program of China(No.2018YFB0605200)the Natural Science Foundation of Guang-dong Province(No.2017B090901049).
文摘The temperature of waste gas in refuse transfer station,airport smoking area,and RTO terminal is low,which needs deep oxidation.Catalytic ozonation is one of the most effective treatment techniques in these scenarios.In this study,we reported that catalysts were modified under the condition of mag-netic field to simulate the low temperature dynamic conditions of low concentration toluene for catalytic ozonation.This paper aims to explore the relationship between oxygen vacancy and active oxygen species,and the specific pathways of toluene oxidation.The study found that citric acid can enhance the syner-gistic effect between Mn and Ce,and promote the generation of oxygen vacancies.The surface molecule adsorption oxygen is more conducive to catalytic oxidation than subsurface atom adsorption oxygen.Fi-nally,we proposed the main pathways of toluene in this reaction system,which runs through the whole process of the reaction.
