Owing to the complexity of multicomponent gases,developing multifunctional catalysts for synergistic removal of benzene and toluene remains challenging.The spinel MMn_(2)O_(4)(M=Co,Ni,or Cu)catalysts were successfully...Owing to the complexity of multicomponent gases,developing multifunctional catalysts for synergistic removal of benzene and toluene remains challenging.The spinel MMn_(2)O_(4)(M=Co,Ni,or Cu)catalysts were successfully synthesized via the sol–gel method and tested for their catalytic performance for simultaneous degradation of benzene and toluene.The CuMn_(2)O_(4)sample exhibited the best catalytic performance,the conversion of benzene reached 100%at 350℃,and toluene conversion reached 100%at 250℃.XRD,N_(2)adsorption-desorption,HRTEM-EDS,ED-XRF,Raman spectroscopy,H_(2)-TPR,NH_(3)-TPD,O_(2)-TPD and XPS were used to characterize the physical and chemical properties of MMn_(2)O_(4)catalysts.The excellent redox properties,high concentration of surface Mn4+,and adsorption of oxygen species over the CuMn_(2)O_(4)sample facilitated the simultaneous and efficient removal of benzene and toluene.Additionally,in situ DRIFTS illustrated the intermediate species and reaction mechanism for the synergetic catalytic oxidation of benzene and toluene.Notably,as an effective catalytic material,spinel oxide exhibited excellent synergistic degradation performance for benzene and toluene,providing some insight for the development of efficient multicomponent VOC catalysts.展开更多
Wet flue gas desulfurization(WFGD)could effectively reduce sulfur dioxide emission.However,magnesium sulfite(MgSO_(3)),a by-product of desulfurization,was easy to result in secondary pollution.In this study,the solid ...Wet flue gas desulfurization(WFGD)could effectively reduce sulfur dioxide emission.However,magnesium sulfite(MgSO_(3)),a by-product of desulfurization,was easy to result in secondary pollution.In this study,the solid catalyst Co-Bent(bentonite supported cobalt)was prepared by blending method for MgSO_(3) oxidation with bentonite as the carrier and cobalt as the active component.At the calcination temperature of 550℃ and the Co loading level of 3 wt.%,the catalyst showed excellent catalytic performance for the oxidation of high concentration MgSO_(3) slurry,and the oxidation rate of MgSO_(3) was 0.13 mol/(L·h).The research indicated that the active component was uniformly distributed within porous structure of the catalyst as Co_(3)O_(4),which facilitated the oxidation of SO_(3)^(2-) catalyzed by Co_(3)O_(4).Kinetic researches indicated the oxidation rate of MgSO_(3) was influenced by the catalyst dosage,the reaction temperature,the solution pH,the airflow rate,and the SO_(3)^(2-) concentration.Additionally,after recycling experiments,the regenerated catalyst retained its high catalytic performance for the MgSO_(3) oxidation.The reaction mechanism for the catalytic oxidation of MgSO_(3) by Co-Bent catalyst was also proposed.The generation of active free radicals(OH·,SO_(4)^(-)·,SO_(3)^(-)·,SO_(5)^(-)·)accelerated the MgSO_(3) oxidation.These results provide theoretical support for the treatment of MgSO_(3) and the development of durable catalyst.展开更多
Perovskite oxides have been widely applied as an effective catalyst in heterogeneous catalysis.However,the rational design of active catalysts has been restricted by the lack of understanding of the electronic structu...Perovskite oxides have been widely applied as an effective catalyst in heterogeneous catalysis.However,the rational design of active catalysts has been restricted by the lack of understanding of the electronic structure.The correlations between surface properties and bulk electronic structure have been ignored.Herein,a simple handler of LaFeO_(3)with diluted HNO3 was employed to tune the electronic structure and catalytic properties.Experimental analysis and theoretical calculations elucidate that acid etching could raise the Fe valence and enhance Fe-O covalency in the octahedral structure,thereby lessening charge transfer energy.Enhanced Fe-O covalency could lower oxygen vacancy formation energy and enhance oxygen mobility.In-situ DRIFTS results indicated the inherent adsorption capability of Toluene and CO molecules has been greatly improved owing to higher Fe-O covalency.As compared,the catalysts after acid etching exhibited higher catalytic activity,and the T_(90)had a great reduction of 45 and 58℃ for toluene and CO oxidation,respectively.A deeper understanding of electronic structure in perovskite oxides may inspire the design of high-performance catalysts.展开更多
Herein,we fabricate an embedding structure at the interface between Pt nanoparticles(NPs)and CeO_(2)-{100}nanocubes with surface defect sites(CeO_(2)-SDS)through quenching and gas bubbling-assisted membrane reduction ...Herein,we fabricate an embedding structure at the interface between Pt nanoparticles(NPs)and CeO_(2)-{100}nanocubes with surface defect sites(CeO_(2)-SDS)through quenching and gas bubbling-assisted membrane reduction methods.The in-situ substitution of Pt NPs for atomic-layer Ce lattice significantly increases the amount of reactive oxygen species from 133.68μmol/g to 199.44μmol/g.As a result,the distinctive geometric structure of Pt/CeO_(2)-SDS catalyst substantially improves the catalytic activity and stability for soot oxidation compared with the catalyst with no quenching process,i.e.,its T_(50)and TOF values are 332°C and 2.915 h^(-1),respectively.Combined with the results of experimental investigations and density functional theory calculations,it is unveiled that the unique embedding structure of Pt/CeO_(2)-SDS catalyst can facilitate significantly electron transfer from Pt to the CeO_(2)-{100}support,and induce the formation of interfacial[Ce-O_(x)-Pt_(2)]bond chains,which plays a crucial role in enhancing the key step of soot oxidation through the dual activation of surface lattice oxygen and molecular O_(2).Such a fundamental revelation of the interfacial electronic transmission and corresponding modification strategy contributes a novel opportunity to develop high-efficient and stable noble metal catalysts at the atomic level.展开更多
By introduction of hydrogen peroxide into the reaction system of ZrOCl_(2)·8H_(2)O and K14[As_(2)W_(19)O_(67)(H_(2)O)],a novel polyoxometalate K_(8)Na_(19.5)H_(0.5)[Zr_(2)(O_(2))_(2)(β-AsVW_(10)O_(38))]4·68...By introduction of hydrogen peroxide into the reaction system of ZrOCl_(2)·8H_(2)O and K14[As_(2)W_(19)O_(67)(H_(2)O)],a novel polyoxometalate K_(8)Na_(19.5)H_(0.5)[Zr_(2)(O_(2))_(2)(β-AsVW_(10)O_(38))]4·68H_(2)O(1)has been successfully obtained via one-pot method and systematically characterized by IR,XPS,solid UV spectra,PXRD pattern,and TGA analysis.The analysis of X-ray crystallography exhibits that compound 1 crystallizes in the triclinic space group P-1 and presents a novel square-shaped Zr-substituted tetrameric polyoxometalate.The catalytic oxidation of sulfides by 1 are carried out,which demonstrate that 1 exhibits a good performance for the catalytic oxidation of sulfides to sulfones with high conversion(100%)and high selectivity(100%).展开更多
A novel tetra-europium(III)-containing antimonotungstate,Na_(8.2)[H_(2)N(CH_(3))_(2)]_(9)[Na_(10.8)(tar)_(4)(H_(2)O)_(20)(Eu_(2)Sb_(2)W_(21)O_(72))_(2)]·44.5H_(2)O(EuSbW,H_(4)tar=dl-tartaric acid),has been synthe...A novel tetra-europium(III)-containing antimonotungstate,Na_(8.2)[H_(2)N(CH_(3))_(2)]_(9)[Na_(10.8)(tar)_(4)(H_(2)O)_(20)(Eu_(2)Sb_(2)W_(21)O_(72))_(2)]·44.5H_(2)O(EuSbW,H_(4)tar=dl-tartaric acid),has been synthesized and characterized.The dimeric polyoxoanion of EuSbW consists of two Dawson-like{Eu_(2)Sb_(2)W_(21)}units bridged by four dl-tartaric acid ligands.The adjacent carboxyl and hydroxy groups in each tartaric acid simultaneously chelate with W and Eu atoms from different{Eu_(2)Sb_(2)W_(21)}units,thereby forming the dimeric structure.EuSbW represents an extremely rare polyoxometalate where four tartaric acid ligands function as connectors to bridge two{Eu_(2)Sb_(2)W_(21)}units.Additionally,EuSbW exhibits excellent catalytic activity and reusability in the oxidation of thioethers and alcohols,achieving 100%conversion and>99%selectivity for various thioethers,and 85–100%conversion with 90–99%selectivity for diverse alcohols under mild conditions.展开更多
Volatile organic compounds(VOCs)exhausted from industrial processes are the major atmospheric pollutants,which could destroy the ecological environment and make hazards to human health seriously.Catalytic oxidation is...Volatile organic compounds(VOCs)exhausted from industrial processes are the major atmospheric pollutants,which could destroy the ecological environment and make hazards to human health seriously.Catalytic oxidation is regarded as the most competitive strategy for the efficient elimination of low-concentration VOCs.Supported noble metal catalysts are preferred catalysts due to their excellent low-temperature catalytic activity.To further lower the cost of catalysts,single atom catalysts(SAC)have been fabricated and extensively studied for application in VOCs oxidation due to their 100%atom-utilization efficiency and unique catalytic performance.In this review,we comprehensively summarize the recent advances in supported noble metal(e.g.,Pt,Pd,Au,and Ag)catalysts and SAC for VOCs oxidation since 2015.Firstly,this paper focuses on some important influencing factors that affect the activity of supported noble metal catalysts,including particle size,valence state and dispersion of noble metals,properties of the support,metal oxide/ion modification,preparation method,and pretreatment conditions of catalysts.Secondly,we briefly summarize the catalytic performance of SAC for typical VOCs.Finally,we conclude the key influencing factors and provide the prospects and challenges of VOCs oxidation.展开更多
Sulfur dioxide(SO_(2))frequently coexist with volatile organic compounds(VOCs)in exhaust gas.The competitive adsorption of SO_(2) and VOCs can adversely affect the efficiency of catalytic combustion,leading to catalys...Sulfur dioxide(SO_(2))frequently coexist with volatile organic compounds(VOCs)in exhaust gas.The competitive adsorption of SO_(2) and VOCs can adversely affect the efficiency of catalytic combustion,leading to catalyst poisoning and irreversible loss of activity.To investigate the impact of sulfur poisoning on the catalysts,we prepared the MnO_(2)/Beta zeolite,and a corresponding series of sulfur-poisoned catalysts through in-situ thermal decomposition of(NH_(4))_(2)SO_(4).The decrease in toluene catalytic activity of poisoned MnO_(2)/Beta zeolite primarily results from the conversion of the active species MnO_(2) to MnSO_(4).However,the crystal structure and the porous structure of MnO_(2)/Beta zeolite were stable,and original structure was still maintained when 1.6%(mass)sulfur species were introduced.Furthermore,the extra-framework Al of Beta zeolite could capture sulfur species to generate Al2(SO_(4))_(3),thereby reducing sulfur species from reacting with Mn^(4+) active sites.The combination of sulfur and Beta zeolite was found to directly produce new strong-acid sites,thus effectively compensating for the effect of reduced Mn4+active species on the catalytic activity.展开更多
Concurrent activation of lattice oxygen(O_L)and molecular oxygen(O_(2))is crucial for the efficient catalytic oxidation of biomass-derived molecules over metal oxides.Herein,we report that the introduction of ultralow...Concurrent activation of lattice oxygen(O_L)and molecular oxygen(O_(2))is crucial for the efficient catalytic oxidation of biomass-derived molecules over metal oxides.Herein,we report that the introduction of ultralow-loading of Ru single atoms(0.42 wt%)into Mn_(2)O_(3)matrix(0.4%Ru-Mn_(2)O_(3))greatly boosts its catalytic activity for the aerobic oxidation of 5-hydroxymethylfurfural(HMF)to 2,5-furandicarboxylic acid(FDCA).The FDCA productivity over the 0.4%Ru-Mn_(2)O_(3)(5.4 mmol_(FDCA)g_(cat)h^(-1))is 4.9 times higher than the Mn_(2)O_(3).Especially,this FDCAproductivity is also significantly higher than that of existing Ru and Mn-based catalysts.Experimental and theoretical investigations discovered that the Ru single atom facilitated the formation of oxygen vacancy(O_(v))in the catalyst,which synergistically weakened the Mn-O bond and promoted the activation of O_L.The co-presence of Ru single atoms and O_(v)also promote the adsorption and activation of both O_(2)and HMF.Consequently,the dehydrogenation reaction energy barrier of the rate-determining step was reduced via both the O_L and chemisorbed O_(2)dehydrogenation pathways,thus boosting the catalytic oxidation reactions.展开更多
An efficient and novel approach is proposed for oxidative arylation of bio-based furfuryl alcohol(FA)to aryl furans(AFs),a versatile monomer of photoelectric materials,in the presence of UiO-67-Pd(F)with phenanthrolin...An efficient and novel approach is proposed for oxidative arylation of bio-based furfuryl alcohol(FA)to aryl furans(AFs),a versatile monomer of photoelectric materials,in the presence of UiO-67-Pd(F)with phenanthroline/bipyridine,and poly-F substituted phenyl ligands as the mixture linkers.The results of control experiments and theoretical calculations reveal that the–F on the phenyl linkers efficiently tunes the electron-deficient nature of Pd through the Zr_(6) clusters bridges,which favors the adsorption and activation of the furan ring.Furthermore,the conjugation of different nitrogen-containing ligands facilitates Pd coordination for the Heck-type insertion and subsequent electrophilic palladation,respectively.As a result,the oxidative arylation of FA derivatives is substantially enhanced because of these electronic and steric synergistic effects.Under the optimized conditions,72.2%FA conversion and 74.8%mono aryl furan(MAF)selectivity are shown in the Heck-type insertion.Meanwhile,85.3%of MAF is converted,affording 74.8%selectivity of final product(AFs)in the subsequent electrophilic palladation reaction.This process efficiency is remarkably higher than that with homogeneous catalysts.In addition,furan-benzene polymer obtained from the halogen-free synthesis catalyzed by UiO-67-Pd(F)show significantly better properties than that from conventional Suzuki coupling method.Therefore,the present work provides a new insight for useful AFs synthesis by oxidative arylation of bio-furan via rational tunning the metal center micro-environment of heterogeneous catalyst.展开更多
Creating a new low-temperature catalyst in decreasing the emission of volatile organic compounds(VOCs)has great significance under different industrial production situations.In particular,the Zr-UiO-66 is optimized by...Creating a new low-temperature catalyst in decreasing the emission of volatile organic compounds(VOCs)has great significance under different industrial production situations.In particular,the Zr-UiO-66 is optimized by different amounts of cerium,which not only enhances the physicochemical stability but also increases the number of active sites of Ce_(x)Zr_(y)UiO-66.Furthermore,the catalysts with Co_(3)O_(4)nanoparticles supported on Ce_(x)Zr_(y)UiO-66 were successfully prepared via impregnation method.In the process of toluene degradation,the Co/Ce_(1)Zr_(2)-Ui0-66 attains a 90%conversion rate at 210℃with a space velocity of 60000 mL/(g·h)and toluene concentration at 1000×10^(-6).Meanwhile,the carbon dioxide selectivity reaches 100%at 218℃.The Co/Ce_(1)Zr_(2)-UiO-66 shows great water resistance(3 vol%H_(2)O).Multiple characterization methods were used to figure out the physicochemical properties of the catalysts.It is found that the addition of an appropriate amount of cerium can enhance stability of UiO-66 and surface lattice oxygen proportion.Additionally,the stronger electron transfer between Ce^(4+)and Co^(2+)enables the Co/Ce_(1)Zr_(2)-UiO-66 to possess more active surface oxygen species and Co_(3)+cationic species in all samples.展开更多
Volatile organic compounds(VOCs)can cause atmospheric environmental problems such as haze and photochemical smog,which seriously restrict the sustainable development of the environment and threaten human health.Effect...Volatile organic compounds(VOCs)can cause atmospheric environmental problems such as haze and photochemical smog,which seriously restrict the sustainable development of the environment and threaten human health.Effective and comprehensive implementation of VOC prevention is an arduous task.Catalytic oxidation can achieve VOC removal with low energy costs and high efficiency.This review presents representative research progress in thermal or photothermal catalysis over the past ten years,concentrating on various catalysts with distinctive morphologies and structures designed and prepared for investigating single-or multi-component VOC purification,synergetic elimination of VOCs and NO_(x),and VOCs resource utilization.Furthermore,the influence mechanisms of H_(2)O,CO_(2),and SO_(2)on the catalytic stability are summarized.The activity and stability of the catalysts affect their lifespan and cost of use.In particular,for supported noble-metal catalysts with poor stability,some unique design strategies have been summarized for the efficient removal of VOCs while balancing low noble-metal usage and optimized catalytic performance.Finally,the scientific problems and future research directions are presented.Coordinated treatment of atmospheric pollutants and greenhouse gases should be considered.This study is expected to provide profound insights into the design of catalysts with high activity,selectivity,and stability,as well as air pollution control via catalytic methods.展开更多
Co-based catalysts are the most promising catalysts in catalytic oxidation of volatile organic compounds(VOCs).Precious metal doping is adopted to improve the catalytic activity of toluene on Co_(3)O_(4) catalysts,but...Co-based catalysts are the most promising catalysts in catalytic oxidation of volatile organic compounds(VOCs).Precious metal doping is adopted to improve the catalytic activity of toluene on Co_(3)O_(4) catalysts,but greatly increases its cost along with it.It is found that doping a small amount of rare earth(Ce,Pr,Sm and Nd)can dramatically promote the catalytic activity of Co_(3)O_(4).Especially,the Nd-doped Co_(3)O_(4) catalyst exhibits excellent catalytic activity with a toluene removal rate of 90% at 162.1℃,which is even better than that of Pt-doped Co_(3)O_(4).Compared with other rare earth metal doping,the Nd doping leads to a higher ratio of Co^(3+)/Co^(2+) and has more oxygen vacancies.The in situ diffuse reflectance infrared Fourier transform spectroscopy(DRIFTS)experiments show that the lattice oxygen of Nd-Co sample can be utilized at a quite low temperature,while that of pure Co_(3)O_(4) cannot engage in oxidation reaction when the temperature is below 200℃,which visually demonstrates the main reason for the improved catalytic performance of Nd-Co catalyst.展开更多
Alkali metal potassium was beneficial to the electronic regulation and structural stability of transition metal oxides.Herein,K ions were introduced into manganese oxides by different methods to improve the degradatio...Alkali metal potassium was beneficial to the electronic regulation and structural stability of transition metal oxides.Herein,K ions were introduced into manganese oxides by different methods to improve the degradation efficiency of toluene.The results of activity experiments indicated that KMnO_(4)-HT(HT:Hydrothermal method)exhibited outstanding low-temperature catalytic activity,and 90%conversion of toluene can be achieved at 243℃,which was 41℃and 43℃lower than that of KNO_(3)-HT and Mn-HT,respectively.The largest specific surface area was observed on KMnO_(4)-HT,facilitating the adsorption of toluene.The formation of cryptomelane structure over KMnO_(4)-HT could contribute to higher content of Mn^(3+)and lattice oxygen(Olatt),excellent low-temperature reducibility,and high oxygen mobility,which could increase the catalytic performance.Furthermore,two distinct degradation pathways were inferred.PathwayⅠ(KMnO_(4)-HT):toluene→benzyl→benzoic acid→carbonate→CO_(2)and H2O;PathwayⅡ(Mn-HT):toluene→benzyl alcohol→benzoic acid→phenol→maleic anhydride→CO_(2)and H2O.Fewer intermediates were detected on KMnO_(4)-HT,indicating its stronger oxidation capacity of toluene,which was originated from the doping of K^(+)and the interaction between K-O-Mn.More intermediates were observed on Mn-HT,which can be attributed to the weaker oxidation ability of pure Mn.The results indicated that the doping of K^(+)can improve the catalytic oxidation capacity of toluene,resulting in promoted degradation of intermediates during the oxidation of toluene.展开更多
Polyoxometalates(POMs),as a class of multinuclear clusters,are polymerized of oxygen and early high-valent transition metals(e.g.,Mo,W,V and Nb).Based on the geometry of heteroatoms and the ratio of heteroatoms to coo...Polyoxometalates(POMs),as a class of multinuclear clusters,are polymerized of oxygen and early high-valent transition metals(e.g.,Mo,W,V and Nb).Based on the geometry of heteroatoms and the ratio of heteroatoms to coordination atoms,POMs can be classified into six classical configurations including Keggin-type,Dawson-type,Anderson-type,Waugh-type,Silverton-type,and Lindqvist-type.They exhibit the diverse structures and versatile properties,which enrich their applications in catalysis,medicine,electrochemistry,magnetism,and so on.The chemistry of POMs is an important branch of inorganic chemistry with a history of more than 200 years.It intersects with physical chemistry,analytical chemistry,structural chemistry,biochemistry,environmental chemistry,material chemistry and many other fields.Modern chemistry of POMs has developed from single POMs synthesis to controllable molecular design synthesis,from simple POMs monomer to high-dimensional,high-core and other novel structure clusters constructed with POMs as building units.Especially,POMs are considered as electron stores due to their strong ability to bear and release electrons,indicating they have redox properties.Therefore,POMs have received increasing attentions as redox heterogeneous catalysts.To resolve the problem of the high solubility of POMs,the design synthesis and performance research of functional complexes with POMs as inorganic ligands or non-coordination templates have become one of hot spots.The encapsulation of POMs into the crystalline architecture results in multifunctional hybrid materials,which combine the merits of POMs and the organic frameworks to achieve specific properties.With the increase of consciousness for environmental protection,green oxidants such as hydrogen peroxide and oxygen are utilized as main oxidants for the oxidation.The combination of POMs-based materials with environment friendly oxidants can efficiently catalyze various oxidation reactions,such as epoxidation of olefin,oxidation of sulfurcontaining compounds,oxidation of alcohols,oxidation of alkanes and so on.In this paper,an overview of recent advances of POMs in catalytic oxidation was presented.展开更多
Due to the presence of nitrogen,nitrogen-containing volatile organic compounds(NVOCs) are more difficult to remove than conventional volatile organic compounds(VOCs).Both catalytic activity and N_(2)selectivity should...Due to the presence of nitrogen,nitrogen-containing volatile organic compounds(NVOCs) are more difficult to remove than conventional volatile organic compounds(VOCs).Both catalytic activity and N_(2)selectivity should be considered in the design of suitable catalysts.A series of Ag/Ce-Zr solid solution(Ag/CZ)catalysts were prepared and applied to the catalytic oxidation of N,N-dimethylformamide(DMF).Redox ability and acidity were regulated by modifying the Zr content.The introduction of Zr promoted the formation of active oxygen species until the molar ratio of Zr reached 0.5,after which the formation decreased.Moreover,adding Zr increased the number of weak and medium acidic sites,which significantly improved DMF adsorption.The improved DMF adsorption hindered the combination of nitrogen and active oxygen,thus reducing the generation of NO_(x)effectively.Therefore,the Ag/CZ(5:5) catalyst,with suitable redox ability and acidity,exhibited the highest activity(T_(90)=176℃),the lowest elimination temperature of organic compounds(T=255℃),satisfactory N_(2)yield(95%-75% in the range of 240-400℃),and outstanding stability under both common and humid conditions(at least50 h).The reaction mechanism was investigated based on the in situ diffuse reflectance infrared Fourier transform spectroscopy(DRIFTS) results.During the catalytic oxidation of DMF,the surface lattice oxygen directly participated in the dehydrogenation and dissociation of the C(O)-N bonds.The generated dimethylamine(DMA) was then oxidized by active oxygen species to form the final product.展开更多
The Mn-Ce-Fe mixed oxide(MCFe)was prepared by co-precipitation and the catalytic performance was tested by using 1,2-dichlorobenzene(1,2-DCB)and furan as model molecules of PCDD/F.The effect of O_(2)concentration,SO_(...The Mn-Ce-Fe mixed oxide(MCFe)was prepared by co-precipitation and the catalytic performance was tested by using 1,2-dichlorobenzene(1,2-DCB)and furan as model molecules of PCDD/F.The effect of O_(2)concentration,SO_(2) and NO on the catalytic activity was studied.At 270℃,the MCFe oxide catalyst presents significant simultaneous removal efficiency of 75.25%and 100%for 1,2-DCB and furan,respectively.Brunauer-Emmett-Teller(BET)method(BET),X-ray diffraction(XRD),scanning electron microscopy(SEM),X-ray photoelectron spectroscopy(XPS),Fourier transform infrared spectroscopy(FTIR),H_2-temperature programmed reduction(H_(2)-TPR),NH_(3)-temperature programmed desorption(NH_3-TPD)and O_(2)-TPD were used to characterize the catalysts before and after the reaction.Competition tests suggest that the oxidation behavior of furan occurred prior to that of 1,2-DCB.According to the intermediate products detected by gas chromatography-mass spectrometry(GC-MS),the by-products include chlorinated hydrocarbons,long-chain hydrocarbons,ketone,etc.Possible catalytic oxidation reaction paths are proposed.展开更多
The catalytic oxidation of volatile organic compounds(VOCs)is of considerable significance for the sustainable development of the chemical industry;thus,considerable efforts have been devoted to the exploration of eff...The catalytic oxidation of volatile organic compounds(VOCs)is of considerable significance for the sustainable development of the chemical industry;thus,considerable efforts have been devoted to the exploration of efficient catalysts for use in this reaction.In this regard,the development and utilization of single-atom catalysts(SACs)in VOCs decomposition is a rapidly expanding research area.SACs can be employed as potential catalysts for oxidizing VOC molecules due to their optimal utilization efficiency,unique atomic bonding structures,and unsaturated orbits.Progress has been achieved,while the challenges surrounding precise regulation of the microstructures of SACs for improving their low-temperature efficiency,stability,and product selectivity under practical conditions are remaining.Therefore,elucidating structure-performance relationships and establishing intrinsic modulating mechanisms are urgently required for guiding researchers on how to synthesize effective and stable functional SACs proactively.Herein,recent advances in the design and synthesis of functional SACs for application in the catalytic oxidation of VOCs are summarized.The experimental and theoretical studies revealing higher efficiency,stability,and selectivity of as-prepared functional SACs are being highlighted.Accordingly,the future perspectives in terms of promising catalysts with multi-sized composite active sites and the illustration of intrinsic mechanism are proposed.The rapid intelligent screening of applicable SACs and their industrial applications are also discussed.展开更多
NH_(3) in ambient air directly leads to an increase in the aerosol content in the air. These substances lead to the formation of haze to various environmental problems after atmospheric circulation and diffusion. Cont...NH_(3) in ambient air directly leads to an increase in the aerosol content in the air. These substances lead to the formation of haze to various environmental problems after atmospheric circulation and diffusion. Controlling NH_(3) emissions caused by ammonia escaping from mobile and industrial sources can effectively reduce the NH_(3) content in ambient air. Among the various NH_(3) removal methods, the selective catalytic oxygen method (NH_(3)-SCO) is committed to oxidizing NH_(3) to environmentally harmless H_(2)O and N_(2);therefore, it is the most valuable and ideal ammonia removal method. In this review, the characteristics of loaded and core-shell catalysts in NH_(3)-SCO have been reviewed in the context of catalyst structure-activity relationships, and the H_(2)O resistance and SO2 resistance of the catalysts are discussed in the context of practical application conditions. Then the effects of the valence state of the active center, oxygen species on the catalyst surface, dispersion of the active center and acidic sites on the catalyst performance are discussed comprehensively. Finally, the shortcomings of the existing catalysts are summarized and the catalyst development is discussed based on the existing studies.展开更多
Biomass-derived platform molecules,such as furfural,are abundant and renewable feedstock for valuable chemical production.It is critical to synthesize highly efficient photocatalysts for selective oxidation under visi...Biomass-derived platform molecules,such as furfural,are abundant and renewable feedstock for valuable chemical production.It is critical to synthesize highly efficient photocatalysts for selective oxidation under visible light.The Er@K-C_(3)N_(4)/UiO-66-NH_(2) catalyst was synthesized using a straight-forward hydrothermal technique,and exhibited exceptional efficiency in the photocatalytic oxidation of furfural to furoic acid.The catalyst was thoroughly characterized,confirming the effective adjustment of the band gap energy of Er@K-C_(3)N_(4)/UiO-66-NH_(2).Upon the optimized reaction conditions,the conversion rate of furfural reached 89.3%,with a corresponding yield of furoic acid at 79.8%.The primary reactive oxygen species was identified as·O_(2)^(-) from ESR spectra and scavenger tests.The incorporation of Er and K into the catalyst enhanced the photogenerated carriers transfer rate,hence increasing the separating efficiency of photogenerated electron-hole pairs.This study expands the potential applications of rare earth element doped g-C_(3)N_(4) in the photocatalytic selective oxidation of furfurans.展开更多
基金supported by the National Natural Science Foundation of China(Nos.22206146,22006079,and U21A20524)the Fundamental Research Funds for the Central Universities,the Youth Innovation Promotion Association of Chinese Academy of Sciences,the Fundamental Research Program of Shanxi Province(No.202103021223280)+1 种基金the Special Fund for Science and Technology Innovation Teams of Shanxi Province(No.202204051002026)the Natural Science Foundation of Shandong Province(No.ZR2021QB133).
文摘Owing to the complexity of multicomponent gases,developing multifunctional catalysts for synergistic removal of benzene and toluene remains challenging.The spinel MMn_(2)O_(4)(M=Co,Ni,or Cu)catalysts were successfully synthesized via the sol–gel method and tested for their catalytic performance for simultaneous degradation of benzene and toluene.The CuMn_(2)O_(4)sample exhibited the best catalytic performance,the conversion of benzene reached 100%at 350℃,and toluene conversion reached 100%at 250℃.XRD,N_(2)adsorption-desorption,HRTEM-EDS,ED-XRF,Raman spectroscopy,H_(2)-TPR,NH_(3)-TPD,O_(2)-TPD and XPS were used to characterize the physical and chemical properties of MMn_(2)O_(4)catalysts.The excellent redox properties,high concentration of surface Mn4+,and adsorption of oxygen species over the CuMn_(2)O_(4)sample facilitated the simultaneous and efficient removal of benzene and toluene.Additionally,in situ DRIFTS illustrated the intermediate species and reaction mechanism for the synergetic catalytic oxidation of benzene and toluene.Notably,as an effective catalytic material,spinel oxide exhibited excellent synergistic degradation performance for benzene and toluene,providing some insight for the development of efficient multicomponent VOC catalysts.
基金supported by the State Key Laboratory of Urban Water Resource and Environment,Harbin Institute of Technology (No. 2022TS10)the Taishan Industrial Experts Programthe Natural Science Foundation of Shandong Province of China (No. ZR2023ME212).
文摘Wet flue gas desulfurization(WFGD)could effectively reduce sulfur dioxide emission.However,magnesium sulfite(MgSO_(3)),a by-product of desulfurization,was easy to result in secondary pollution.In this study,the solid catalyst Co-Bent(bentonite supported cobalt)was prepared by blending method for MgSO_(3) oxidation with bentonite as the carrier and cobalt as the active component.At the calcination temperature of 550℃ and the Co loading level of 3 wt.%,the catalyst showed excellent catalytic performance for the oxidation of high concentration MgSO_(3) slurry,and the oxidation rate of MgSO_(3) was 0.13 mol/(L·h).The research indicated that the active component was uniformly distributed within porous structure of the catalyst as Co_(3)O_(4),which facilitated the oxidation of SO_(3)^(2-) catalyzed by Co_(3)O_(4).Kinetic researches indicated the oxidation rate of MgSO_(3) was influenced by the catalyst dosage,the reaction temperature,the solution pH,the airflow rate,and the SO_(3)^(2-) concentration.Additionally,after recycling experiments,the regenerated catalyst retained its high catalytic performance for the MgSO_(3) oxidation.The reaction mechanism for the catalytic oxidation of MgSO_(3) by Co-Bent catalyst was also proposed.The generation of active free radicals(OH·,SO_(4)^(-)·,SO_(3)^(-)·,SO_(5)^(-)·)accelerated the MgSO_(3) oxidation.These results provide theoretical support for the treatment of MgSO_(3) and the development of durable catalyst.
基金the National Natural Science Foundation of China(Nos.22376178,22322606,22276105)the National Key Research and Development Program of China(No.2022YFC3704300)the Beijing Natural Science Foundation(No.8222054).
文摘Perovskite oxides have been widely applied as an effective catalyst in heterogeneous catalysis.However,the rational design of active catalysts has been restricted by the lack of understanding of the electronic structure.The correlations between surface properties and bulk electronic structure have been ignored.Herein,a simple handler of LaFeO_(3)with diluted HNO3 was employed to tune the electronic structure and catalytic properties.Experimental analysis and theoretical calculations elucidate that acid etching could raise the Fe valence and enhance Fe-O covalency in the octahedral structure,thereby lessening charge transfer energy.Enhanced Fe-O covalency could lower oxygen vacancy formation energy and enhance oxygen mobility.In-situ DRIFTS results indicated the inherent adsorption capability of Toluene and CO molecules has been greatly improved owing to higher Fe-O covalency.As compared,the catalysts after acid etching exhibited higher catalytic activity,and the T_(90)had a great reduction of 45 and 58℃ for toluene and CO oxidation,respectively.A deeper understanding of electronic structure in perovskite oxides may inspire the design of high-performance catalysts.
基金supported by the Beijing Nova Program(No.20220484215)National Key Research and Development Program of China(Nos.2022YFB3504100,2022YFB3506200,2021YFA1500300 and 2022YFA1500146)National Natural Science Foundation of China(Nos.22376217,22208373,22272090 and 22272106)。
文摘Herein,we fabricate an embedding structure at the interface between Pt nanoparticles(NPs)and CeO_(2)-{100}nanocubes with surface defect sites(CeO_(2)-SDS)through quenching and gas bubbling-assisted membrane reduction methods.The in-situ substitution of Pt NPs for atomic-layer Ce lattice significantly increases the amount of reactive oxygen species from 133.68μmol/g to 199.44μmol/g.As a result,the distinctive geometric structure of Pt/CeO_(2)-SDS catalyst substantially improves the catalytic activity and stability for soot oxidation compared with the catalyst with no quenching process,i.e.,its T_(50)and TOF values are 332°C and 2.915 h^(-1),respectively.Combined with the results of experimental investigations and density functional theory calculations,it is unveiled that the unique embedding structure of Pt/CeO_(2)-SDS catalyst can facilitate significantly electron transfer from Pt to the CeO_(2)-{100}support,and induce the formation of interfacial[Ce-O_(x)-Pt_(2)]bond chains,which plays a crucial role in enhancing the key step of soot oxidation through the dual activation of surface lattice oxygen and molecular O_(2).Such a fundamental revelation of the interfacial electronic transmission and corresponding modification strategy contributes a novel opportunity to develop high-efficient and stable noble metal catalysts at the atomic level.
基金financially supported by the National Natural Science Foundation of China(No.22071043).
文摘By introduction of hydrogen peroxide into the reaction system of ZrOCl_(2)·8H_(2)O and K14[As_(2)W_(19)O_(67)(H_(2)O)],a novel polyoxometalate K_(8)Na_(19.5)H_(0.5)[Zr_(2)(O_(2))_(2)(β-AsVW_(10)O_(38))]4·68H_(2)O(1)has been successfully obtained via one-pot method and systematically characterized by IR,XPS,solid UV spectra,PXRD pattern,and TGA analysis.The analysis of X-ray crystallography exhibits that compound 1 crystallizes in the triclinic space group P-1 and presents a novel square-shaped Zr-substituted tetrameric polyoxometalate.The catalytic oxidation of sulfides by 1 are carried out,which demonstrate that 1 exhibits a good performance for the catalytic oxidation of sulfides to sulfones with high conversion(100%)and high selectivity(100%).
基金supported by the Natural Science Foundation of Jiangxi Province(20232ACB213005).
文摘A novel tetra-europium(III)-containing antimonotungstate,Na_(8.2)[H_(2)N(CH_(3))_(2)]_(9)[Na_(10.8)(tar)_(4)(H_(2)O)_(20)(Eu_(2)Sb_(2)W_(21)O_(72))_(2)]·44.5H_(2)O(EuSbW,H_(4)tar=dl-tartaric acid),has been synthesized and characterized.The dimeric polyoxoanion of EuSbW consists of two Dawson-like{Eu_(2)Sb_(2)W_(21)}units bridged by four dl-tartaric acid ligands.The adjacent carboxyl and hydroxy groups in each tartaric acid simultaneously chelate with W and Eu atoms from different{Eu_(2)Sb_(2)W_(21)}units,thereby forming the dimeric structure.EuSbW represents an extremely rare polyoxometalate where four tartaric acid ligands function as connectors to bridge two{Eu_(2)Sb_(2)W_(21)}units.Additionally,EuSbW exhibits excellent catalytic activity and reusability in the oxidation of thioethers and alcohols,achieving 100%conversion and>99%selectivity for various thioethers,and 85–100%conversion with 90–99%selectivity for diverse alcohols under mild conditions.
基金supported by Beijing Natural Science Foundation(No.8244060)China Postdoctoral Science Foundation(No.2023M730143)+3 种基金the National Natural Science Foundation of China(No.22425601)the National Key R&D Program of China(No.2023YFB3810801)Beijing Nova Program(No.20240484659)the R&D Program of Beijing Municipal Education Commission(No.KZ202210005011).
文摘Volatile organic compounds(VOCs)exhausted from industrial processes are the major atmospheric pollutants,which could destroy the ecological environment and make hazards to human health seriously.Catalytic oxidation is regarded as the most competitive strategy for the efficient elimination of low-concentration VOCs.Supported noble metal catalysts are preferred catalysts due to their excellent low-temperature catalytic activity.To further lower the cost of catalysts,single atom catalysts(SAC)have been fabricated and extensively studied for application in VOCs oxidation due to their 100%atom-utilization efficiency and unique catalytic performance.In this review,we comprehensively summarize the recent advances in supported noble metal(e.g.,Pt,Pd,Au,and Ag)catalysts and SAC for VOCs oxidation since 2015.Firstly,this paper focuses on some important influencing factors that affect the activity of supported noble metal catalysts,including particle size,valence state and dispersion of noble metals,properties of the support,metal oxide/ion modification,preparation method,and pretreatment conditions of catalysts.Secondly,we briefly summarize the catalytic performance of SAC for typical VOCs.Finally,we conclude the key influencing factors and provide the prospects and challenges of VOCs oxidation.
基金supported by the National Natural Science Foundation of China(21577094)the Zhejiang Public Welfare Technology Research Project(LGG19B070003).
文摘Sulfur dioxide(SO_(2))frequently coexist with volatile organic compounds(VOCs)in exhaust gas.The competitive adsorption of SO_(2) and VOCs can adversely affect the efficiency of catalytic combustion,leading to catalyst poisoning and irreversible loss of activity.To investigate the impact of sulfur poisoning on the catalysts,we prepared the MnO_(2)/Beta zeolite,and a corresponding series of sulfur-poisoned catalysts through in-situ thermal decomposition of(NH_(4))_(2)SO_(4).The decrease in toluene catalytic activity of poisoned MnO_(2)/Beta zeolite primarily results from the conversion of the active species MnO_(2) to MnSO_(4).However,the crystal structure and the porous structure of MnO_(2)/Beta zeolite were stable,and original structure was still maintained when 1.6%(mass)sulfur species were introduced.Furthermore,the extra-framework Al of Beta zeolite could capture sulfur species to generate Al2(SO_(4))_(3),thereby reducing sulfur species from reacting with Mn^(4+) active sites.The combination of sulfur and Beta zeolite was found to directly produce new strong-acid sites,thus effectively compensating for the effect of reduced Mn4+active species on the catalytic activity.
基金financially supported by National Natural Science Foundation of China(22208137 and 22068022)Yunnan Fundamental Research Projects(202101BE070001-033,202401AT070825,202201BE070001007 and 202301AV070005)。
文摘Concurrent activation of lattice oxygen(O_L)and molecular oxygen(O_(2))is crucial for the efficient catalytic oxidation of biomass-derived molecules over metal oxides.Herein,we report that the introduction of ultralow-loading of Ru single atoms(0.42 wt%)into Mn_(2)O_(3)matrix(0.4%Ru-Mn_(2)O_(3))greatly boosts its catalytic activity for the aerobic oxidation of 5-hydroxymethylfurfural(HMF)to 2,5-furandicarboxylic acid(FDCA).The FDCA productivity over the 0.4%Ru-Mn_(2)O_(3)(5.4 mmol_(FDCA)g_(cat)h^(-1))is 4.9 times higher than the Mn_(2)O_(3).Especially,this FDCAproductivity is also significantly higher than that of existing Ru and Mn-based catalysts.Experimental and theoretical investigations discovered that the Ru single atom facilitated the formation of oxygen vacancy(O_(v))in the catalyst,which synergistically weakened the Mn-O bond and promoted the activation of O_L.The co-presence of Ru single atoms and O_(v)also promote the adsorption and activation of both O_(2)and HMF.Consequently,the dehydrogenation reaction energy barrier of the rate-determining step was reduced via both the O_L and chemisorbed O_(2)dehydrogenation pathways,thus boosting the catalytic oxidation reactions.
文摘An efficient and novel approach is proposed for oxidative arylation of bio-based furfuryl alcohol(FA)to aryl furans(AFs),a versatile monomer of photoelectric materials,in the presence of UiO-67-Pd(F)with phenanthroline/bipyridine,and poly-F substituted phenyl ligands as the mixture linkers.The results of control experiments and theoretical calculations reveal that the–F on the phenyl linkers efficiently tunes the electron-deficient nature of Pd through the Zr_(6) clusters bridges,which favors the adsorption and activation of the furan ring.Furthermore,the conjugation of different nitrogen-containing ligands facilitates Pd coordination for the Heck-type insertion and subsequent electrophilic palladation,respectively.As a result,the oxidative arylation of FA derivatives is substantially enhanced because of these electronic and steric synergistic effects.Under the optimized conditions,72.2%FA conversion and 74.8%mono aryl furan(MAF)selectivity are shown in the Heck-type insertion.Meanwhile,85.3%of MAF is converted,affording 74.8%selectivity of final product(AFs)in the subsequent electrophilic palladation reaction.This process efficiency is remarkably higher than that with homogeneous catalysts.In addition,furan-benzene polymer obtained from the halogen-free synthesis catalyzed by UiO-67-Pd(F)show significantly better properties than that from conventional Suzuki coupling method.Therefore,the present work provides a new insight for useful AFs synthesis by oxidative arylation of bio-furan via rational tunning the metal center micro-environment of heterogeneous catalyst.
基金Project supported by National Natural Science Foundation of China(22076180)Youth Innovation Promotion Association of CAS(2019376)Chongqing Bayu Scholar Program(Young Scholar,YS2020048)。
文摘Creating a new low-temperature catalyst in decreasing the emission of volatile organic compounds(VOCs)has great significance under different industrial production situations.In particular,the Zr-UiO-66 is optimized by different amounts of cerium,which not only enhances the physicochemical stability but also increases the number of active sites of Ce_(x)Zr_(y)UiO-66.Furthermore,the catalysts with Co_(3)O_(4)nanoparticles supported on Ce_(x)Zr_(y)UiO-66 were successfully prepared via impregnation method.In the process of toluene degradation,the Co/Ce_(1)Zr_(2)-Ui0-66 attains a 90%conversion rate at 210℃with a space velocity of 60000 mL/(g·h)and toluene concentration at 1000×10^(-6).Meanwhile,the carbon dioxide selectivity reaches 100%at 218℃.The Co/Ce_(1)Zr_(2)-UiO-66 shows great water resistance(3 vol%H_(2)O).Multiple characterization methods were used to figure out the physicochemical properties of the catalysts.It is found that the addition of an appropriate amount of cerium can enhance stability of UiO-66 and surface lattice oxygen proportion.Additionally,the stronger electron transfer between Ce^(4+)and Co^(2+)enables the Co/Ce_(1)Zr_(2)-UiO-66 to possess more active surface oxygen species and Co_(3)+cationic species in all samples.
文摘Volatile organic compounds(VOCs)can cause atmospheric environmental problems such as haze and photochemical smog,which seriously restrict the sustainable development of the environment and threaten human health.Effective and comprehensive implementation of VOC prevention is an arduous task.Catalytic oxidation can achieve VOC removal with low energy costs and high efficiency.This review presents representative research progress in thermal or photothermal catalysis over the past ten years,concentrating on various catalysts with distinctive morphologies and structures designed and prepared for investigating single-or multi-component VOC purification,synergetic elimination of VOCs and NO_(x),and VOCs resource utilization.Furthermore,the influence mechanisms of H_(2)O,CO_(2),and SO_(2)on the catalytic stability are summarized.The activity and stability of the catalysts affect their lifespan and cost of use.In particular,for supported noble-metal catalysts with poor stability,some unique design strategies have been summarized for the efficient removal of VOCs while balancing low noble-metal usage and optimized catalytic performance.Finally,the scientific problems and future research directions are presented.Coordinated treatment of atmospheric pollutants and greenhouse gases should be considered.This study is expected to provide profound insights into the design of catalysts with high activity,selectivity,and stability,as well as air pollution control via catalytic methods.
基金Project supported by the Sichuan Provincial Science and Technology Agency Support Projects(2020YFG0066)Young Talent Team Science and Technology Innovation Project of Sichuan Province(2020JDTD0005)。
文摘Co-based catalysts are the most promising catalysts in catalytic oxidation of volatile organic compounds(VOCs).Precious metal doping is adopted to improve the catalytic activity of toluene on Co_(3)O_(4) catalysts,but greatly increases its cost along with it.It is found that doping a small amount of rare earth(Ce,Pr,Sm and Nd)can dramatically promote the catalytic activity of Co_(3)O_(4).Especially,the Nd-doped Co_(3)O_(4) catalyst exhibits excellent catalytic activity with a toluene removal rate of 90% at 162.1℃,which is even better than that of Pt-doped Co_(3)O_(4).Compared with other rare earth metal doping,the Nd doping leads to a higher ratio of Co^(3+)/Co^(2+) and has more oxygen vacancies.The in situ diffuse reflectance infrared Fourier transform spectroscopy(DRIFTS)experiments show that the lattice oxygen of Nd-Co sample can be utilized at a quite low temperature,while that of pure Co_(3)O_(4) cannot engage in oxidation reaction when the temperature is below 200℃,which visually demonstrates the main reason for the improved catalytic performance of Nd-Co catalyst.
基金supported by the National Natural Science Foundation of China(No.21872096)Scientific Research Project of Liaoning Provincial Department of Education(No.LJKMZ20220788)+2 种基金Zhongyuan Yingcai Jihua(No.ZYYCYU202012183)the Academic Leader of Henan Institute of Urban Construction(No.YCJXSJSDTR202204)the Doctoral Research Start-up Project of Henan University of Urban Construction(No.990/Q2017011)。
文摘Alkali metal potassium was beneficial to the electronic regulation and structural stability of transition metal oxides.Herein,K ions were introduced into manganese oxides by different methods to improve the degradation efficiency of toluene.The results of activity experiments indicated that KMnO_(4)-HT(HT:Hydrothermal method)exhibited outstanding low-temperature catalytic activity,and 90%conversion of toluene can be achieved at 243℃,which was 41℃and 43℃lower than that of KNO_(3)-HT and Mn-HT,respectively.The largest specific surface area was observed on KMnO_(4)-HT,facilitating the adsorption of toluene.The formation of cryptomelane structure over KMnO_(4)-HT could contribute to higher content of Mn^(3+)and lattice oxygen(Olatt),excellent low-temperature reducibility,and high oxygen mobility,which could increase the catalytic performance.Furthermore,two distinct degradation pathways were inferred.PathwayⅠ(KMnO_(4)-HT):toluene→benzyl→benzoic acid→carbonate→CO_(2)and H2O;PathwayⅡ(Mn-HT):toluene→benzyl alcohol→benzoic acid→phenol→maleic anhydride→CO_(2)and H2O.Fewer intermediates were detected on KMnO_(4)-HT,indicating its stronger oxidation capacity of toluene,which was originated from the doping of K^(+)and the interaction between K-O-Mn.More intermediates were observed on Mn-HT,which can be attributed to the weaker oxidation ability of pure Mn.The results indicated that the doping of K^(+)can improve the catalytic oxidation capacity of toluene,resulting in promoted degradation of intermediates during the oxidation of toluene.
基金supported by the Doctoral Scientific Research Foundation of Weifang University(2023BS13)the Project of Weifang Science and Technology Development Program(2022GX 020 and 2022GX021)+1 种基金the National Natural Science Foundation of China(22001032)the Doctoral Scientific Research Foundation of Weifang Vocational College(Preparation and electrochemical properties of high performance polyoxometallatebased lithium-ion battery anode materials)
文摘Polyoxometalates(POMs),as a class of multinuclear clusters,are polymerized of oxygen and early high-valent transition metals(e.g.,Mo,W,V and Nb).Based on the geometry of heteroatoms and the ratio of heteroatoms to coordination atoms,POMs can be classified into six classical configurations including Keggin-type,Dawson-type,Anderson-type,Waugh-type,Silverton-type,and Lindqvist-type.They exhibit the diverse structures and versatile properties,which enrich their applications in catalysis,medicine,electrochemistry,magnetism,and so on.The chemistry of POMs is an important branch of inorganic chemistry with a history of more than 200 years.It intersects with physical chemistry,analytical chemistry,structural chemistry,biochemistry,environmental chemistry,material chemistry and many other fields.Modern chemistry of POMs has developed from single POMs synthesis to controllable molecular design synthesis,from simple POMs monomer to high-dimensional,high-core and other novel structure clusters constructed with POMs as building units.Especially,POMs are considered as electron stores due to their strong ability to bear and release electrons,indicating they have redox properties.Therefore,POMs have received increasing attentions as redox heterogeneous catalysts.To resolve the problem of the high solubility of POMs,the design synthesis and performance research of functional complexes with POMs as inorganic ligands or non-coordination templates have become one of hot spots.The encapsulation of POMs into the crystalline architecture results in multifunctional hybrid materials,which combine the merits of POMs and the organic frameworks to achieve specific properties.With the increase of consciousness for environmental protection,green oxidants such as hydrogen peroxide and oxygen are utilized as main oxidants for the oxidation.The combination of POMs-based materials with environment friendly oxidants can efficiently catalyze various oxidation reactions,such as epoxidation of olefin,oxidation of sulfurcontaining compounds,oxidation of alcohols,oxidation of alkanes and so on.In this paper,an overview of recent advances of POMs in catalytic oxidation was presented.
基金financially supported by the Fundamental Research Funds for the Central UniversitiesNational Key Research and Development Program of China (Nos.2023YFA1508500,2023YFC3707500 and 2022YFB3504200)the National Natural Science Foundation of China (Nos.22106101 and U21A20326)。
文摘Due to the presence of nitrogen,nitrogen-containing volatile organic compounds(NVOCs) are more difficult to remove than conventional volatile organic compounds(VOCs).Both catalytic activity and N_(2)selectivity should be considered in the design of suitable catalysts.A series of Ag/Ce-Zr solid solution(Ag/CZ)catalysts were prepared and applied to the catalytic oxidation of N,N-dimethylformamide(DMF).Redox ability and acidity were regulated by modifying the Zr content.The introduction of Zr promoted the formation of active oxygen species until the molar ratio of Zr reached 0.5,after which the formation decreased.Moreover,adding Zr increased the number of weak and medium acidic sites,which significantly improved DMF adsorption.The improved DMF adsorption hindered the combination of nitrogen and active oxygen,thus reducing the generation of NO_(x)effectively.Therefore,the Ag/CZ(5:5) catalyst,with suitable redox ability and acidity,exhibited the highest activity(T_(90)=176℃),the lowest elimination temperature of organic compounds(T=255℃),satisfactory N_(2)yield(95%-75% in the range of 240-400℃),and outstanding stability under both common and humid conditions(at least50 h).The reaction mechanism was investigated based on the in situ diffuse reflectance infrared Fourier transform spectroscopy(DRIFTS) results.During the catalytic oxidation of DMF,the surface lattice oxygen directly participated in the dehydrogenation and dissociation of the C(O)-N bonds.The generated dimethylamine(DMA) was then oxidized by active oxygen species to form the final product.
基金Project supported by the Zhejiang Provincial Natural Science Foundation of China(LQ23E060002)the National Natural Science Foundation of China(51976192)。
文摘The Mn-Ce-Fe mixed oxide(MCFe)was prepared by co-precipitation and the catalytic performance was tested by using 1,2-dichlorobenzene(1,2-DCB)and furan as model molecules of PCDD/F.The effect of O_(2)concentration,SO_(2) and NO on the catalytic activity was studied.At 270℃,the MCFe oxide catalyst presents significant simultaneous removal efficiency of 75.25%and 100%for 1,2-DCB and furan,respectively.Brunauer-Emmett-Teller(BET)method(BET),X-ray diffraction(XRD),scanning electron microscopy(SEM),X-ray photoelectron spectroscopy(XPS),Fourier transform infrared spectroscopy(FTIR),H_2-temperature programmed reduction(H_(2)-TPR),NH_(3)-temperature programmed desorption(NH_3-TPD)and O_(2)-TPD were used to characterize the catalysts before and after the reaction.Competition tests suggest that the oxidation behavior of furan occurred prior to that of 1,2-DCB.According to the intermediate products detected by gas chromatography-mass spectrometry(GC-MS),the by-products include chlorinated hydrocarbons,long-chain hydrocarbons,ketone,etc.Possible catalytic oxidation reaction paths are proposed.
基金financially supported by the National Natural Science Foundation of China(Nos.22276145,2187613921922606)+1 种基金National Key R&D Program of China(No.2022YFB4101500)China Postdoctoral Science Foundation(No.2023M732783)。
文摘The catalytic oxidation of volatile organic compounds(VOCs)is of considerable significance for the sustainable development of the chemical industry;thus,considerable efforts have been devoted to the exploration of efficient catalysts for use in this reaction.In this regard,the development and utilization of single-atom catalysts(SACs)in VOCs decomposition is a rapidly expanding research area.SACs can be employed as potential catalysts for oxidizing VOC molecules due to their optimal utilization efficiency,unique atomic bonding structures,and unsaturated orbits.Progress has been achieved,while the challenges surrounding precise regulation of the microstructures of SACs for improving their low-temperature efficiency,stability,and product selectivity under practical conditions are remaining.Therefore,elucidating structure-performance relationships and establishing intrinsic modulating mechanisms are urgently required for guiding researchers on how to synthesize effective and stable functional SACs proactively.Herein,recent advances in the design and synthesis of functional SACs for application in the catalytic oxidation of VOCs are summarized.The experimental and theoretical studies revealing higher efficiency,stability,and selectivity of as-prepared functional SACs are being highlighted.Accordingly,the future perspectives in terms of promising catalysts with multi-sized composite active sites and the illustration of intrinsic mechanism are proposed.The rapid intelligent screening of applicable SACs and their industrial applications are also discussed.
基金the National Natural Science Foundation of China(No.52000093)Yunnan Fundamental Research Projects(No.202101BE070001-001)National Engineering Laboratory for Mobile Source Emission Control Technology(No.NELMS2019B03).
文摘NH_(3) in ambient air directly leads to an increase in the aerosol content in the air. These substances lead to the formation of haze to various environmental problems after atmospheric circulation and diffusion. Controlling NH_(3) emissions caused by ammonia escaping from mobile and industrial sources can effectively reduce the NH_(3) content in ambient air. Among the various NH_(3) removal methods, the selective catalytic oxygen method (NH_(3)-SCO) is committed to oxidizing NH_(3) to environmentally harmless H_(2)O and N_(2);therefore, it is the most valuable and ideal ammonia removal method. In this review, the characteristics of loaded and core-shell catalysts in NH_(3)-SCO have been reviewed in the context of catalyst structure-activity relationships, and the H_(2)O resistance and SO2 resistance of the catalysts are discussed in the context of practical application conditions. Then the effects of the valence state of the active center, oxygen species on the catalyst surface, dispersion of the active center and acidic sites on the catalyst performance are discussed comprehensively. Finally, the shortcomings of the existing catalysts are summarized and the catalyst development is discussed based on the existing studies.
基金supported by Natural Science Foundation of Shandong Province(ZR2022MB049)National Natural Science Foundation of China(22078174)。
文摘Biomass-derived platform molecules,such as furfural,are abundant and renewable feedstock for valuable chemical production.It is critical to synthesize highly efficient photocatalysts for selective oxidation under visible light.The Er@K-C_(3)N_(4)/UiO-66-NH_(2) catalyst was synthesized using a straight-forward hydrothermal technique,and exhibited exceptional efficiency in the photocatalytic oxidation of furfural to furoic acid.The catalyst was thoroughly characterized,confirming the effective adjustment of the band gap energy of Er@K-C_(3)N_(4)/UiO-66-NH_(2).Upon the optimized reaction conditions,the conversion rate of furfural reached 89.3%,with a corresponding yield of furoic acid at 79.8%.The primary reactive oxygen species was identified as·O_(2)^(-) from ESR spectra and scavenger tests.The incorporation of Er and K into the catalyst enhanced the photogenerated carriers transfer rate,hence increasing the separating efficiency of photogenerated electron-hole pairs.This study expands the potential applications of rare earth element doped g-C_(3)N_(4) in the photocatalytic selective oxidation of furfurans.
