Although bimetallic phosphide cocatalysts have attracted considerable interest in photocatalysis research owing to their advantageous thermodynamic characteristics,superstable and efficient cocatalysts have rarely bee...Although bimetallic phosphide cocatalysts have attracted considerable interest in photocatalysis research owing to their advantageous thermodynamic characteristics,superstable and efficient cocatalysts have rarely been produced through the modulation of their structure and composition.In this study,a series of bimetallic nickel-iron phosphide(Ni_(x)Fe_(2-x)P,where 0<x<2)cocatalysts with controllable structures and overpotentials were designed by adjusting the atomic ratio of Ni/Fe onto nonmetallic elemental red phosphorus(RP)for the photocatalytic selective oxidation of benzyl alcohol(BA)coupled with hydrogen production.The catalysts exhibited an outstanding photocatalytic activity for benzaldehyde and a high H_(2)yield.The RP regulated by bimetallic phosphide cocatalysts(Ni_(x)Fe_(2-x)P)demonstrated higher photocatalytic oxidation-reduction activity than that regulated by monometallic phosphide cocatalysts(Ni_(2)P and Fe2P).In particular,the RP regulated by Ni_(1.25)Fe_(0.75)P exhibited the best photocatalytic performance.In addition,experimental and theoretical calculations further illustrated that Ni_(1.25)Fe_(0.75)P,with the optimized electronic structure,possessed good electrical conductivity and provided strong adsorption and abundant active sites,thereby accelerating electron migration and lowering the reaction energy barrier of RP.This finding offers valuable insights into the rational design of highly effective cocatalysts aimed at optimizing the photocatalytic activity of composite photocatalysts.展开更多
The catalytic oxidation of HMF involves a cascading reaction with multiple intermediate products,making it crucial to enhance the oriented adsorption capacity of specific functional groups for accelerating the entire ...The catalytic oxidation of HMF involves a cascading reaction with multiple intermediate products,making it crucial to enhance the oriented adsorption capacity of specific functional groups for accelerating the entire process.To achieve the efficient selective oxidation of HMF to FDCA,a series of NiCo_(2)O_(4)catalysts with different morphologies,such as flaky,echinoids,pompon and corolla,were prepared and characterized by XRD,SEM,TEM,BET,XPS,and FTIR.Among the four catalysts,flaky NiCo_(2)O_(4)exhibited the most excellent catalytic activity and stability,with a FDCA yield of 60.1%within 12 h at 80℃without alkali participation.The excellent performance of flaky NiCo_(2)O_(4)catalyst is attributed to the oxygen vacancies and acid sites generated by the exposed(400)facets.The oxygen vacancies and acid sites on the catalyst surface can precisely adsorb-CHO and-CH_(2)-OH of HMF,respectively,and this synergistic effect promotes the efficient production of FDCA.This work is of great significance for fundamentally study the effect of micro-topography or crystal-plane reaction properties on surfaces.展开更多
Silicon-carbide-fiber-reinforced silicon-carbide-ceramic-based matrix(SiC/SiC)composites possess excellent properties such as low density,high strength and high temperature resistance,showing a potential application f...Silicon-carbide-fiber-reinforced silicon-carbide-ceramic-based matrix(SiC/SiC)composites possess excellent properties such as low density,high strength and high temperature resistance,showing a potential application for structural components in the aerospace field,but their oxidation behavior remains largely unknown.In this study,Yb_(2)Si_(2)O_(7)modified SiC/SiC(SiC/SiC-Yb_(2)Si_(2)O_(7))mini-composites were prepared by introducing Yb_(2)Si_(2)O_(7)as anti-oxidation phase into SiC fiber bundles via Sol-Gel and depositing SiC matrix by chemical vapor deposition(CVD).Influence of Yb_(2)Si_(2)O_(7)on microstructure,mechanical property and oxidation behavior of SiC/SiC mini-composites was investigated.The results showed that after oxidation in air at 1200 and 1400℃for 50 h,the tensile strength retentions of SiC/SiC mini-composites were 77%and 69%,respectively,and the fracture morphology exhibited flat.The Yb_(2)Si_(2)O_(7)introduced by Sol-Gel partially distributed in layers,contributing to the toughening of the material.On the fracture surface,there was interlayer debonding,which extended energy dissipation mechanism of SiC/SiC mini-composites.Tensile strength of SiC/SiC-Yb_(2)Si_(2)O_(7)mini-composites at room temperature was 484 MPa.After oxidation in air at 1200 and 1400℃for 50 h,the tensile strengths decreased to 425 and 374 MPa,resulting in retention rates of 88%and 77%,respectively.It displayed typical non-brittle fracture characteristics.The interface oxygen content of SiC/SiC mini-composites at the fracture surface was higher than that of SiC/SiC-Yb_(2)Si_(2)O_(7)mini-composites,indicating that introduction of Yb_(2)Si_(2)O_(7)could alleviate oxygen diffusion towards the interface,and therefore improve the oxidation resistance of SiC/SiC-Yb_(2)Si_(2)O_(7)mini-composites.展开更多
Photoelectrochemical water oxidation(PEC-WO)as a green and sustainable route to produce H_(2)O_(2)has attracted extensive attentions.However,water oxidation to H_(2)O_(2)via a 2e^(-) pathway is thermodynamically more ...Photoelectrochemical water oxidation(PEC-WO)as a green and sustainable route to produce H_(2)O_(2)has attracted extensive attentions.However,water oxidation to H_(2)O_(2)via a 2e^(-) pathway is thermodynamically more difficult than to O_(2)via a 4e^(-)pathway.Herein,with a series of BiVO_(4)-based photoanodes,the decisive factors determining the PEC activity and selectivity are elucidated,combining a comprehensive experimental and theoretical investigations.It is discovered that the ZnO/BiVO_(4)photoanode(ZnO/BVO)forms a Type-Ⅱheterojunction in energy level alignment.The accelerated photogenerated charge separation/transfer dynamics generates denser surface holes and higher surface photovoltage.Therefore,the activity of water oxidation reaction is promoted.The selectivity of PEC-WO to H_(2)O_(2)is found to be potential-dependent,i.e.,at the lower potentials(PEC-dominated),surface hole density determines the selectivity;and at the higher potentials(electrochemical-dominated),surface reaction barriers govern the selectivity.For the ZnO/BVO heterojunction photoanode,the higher surface hole density facilitates the generation of OH·and the subsequent OH·/OH·coupling to form H_(2)O_(2),thus rising up with potentials;at the higher potentials,the 2-electron pathway barrier over ZnO/BVO surface is lower than over BVO surface,which benefits from the electronic structure regulation by the underlying ZnO alleviating the over-strong adsorption of^(*)OH on BVO,thus,the two-electron pathway to produce H_(2)O_(2)is more favored than on BVO surface.This work highlights the crucial role of band energy structure of semiconductors on both PEC reaction activity and selectivity,and the knowledge gained is expected to be extended to other photoeletrochemical reactions.展开更多
Herein,a first-principles investigation was innovatively conducted to research the surface oxidation of ZnS-like sphalerite in the absence and presence of H_(2)O .The findings showed that single O_(2) was preferred to...Herein,a first-principles investigation was innovatively conducted to research the surface oxidation of ZnS-like sphalerite in the absence and presence of H_(2)O .The findings showed that single O_(2) was preferred to be dissociated adsorption on sphalerite surface by generating SAO and Zn AO bonds,and the S atom on the surface was the most energy-supported site for O_(2) adsorption,on which a≡Zn-O-S-O-Zn≡structure will be formed.However,dissociated adsorption of single H_(2)O will not happen.It was preferred to be adsorbed on the top Zn atom on sphalerite surface in molecular form through Zn-O bond.Besides,sphalerite oxidation can occur as if O_(2) was present regardless of the presence of H_(2)O ,and when H_(2)O and O_(2) coexisted,the formation of sulfur oxide(SO_(2) )needed a lower energy barrier and it was easier to form on sphalerite surface than that only O_(2) existed.In the absence of H_(2)O ,when SO_(2) was generated,further oxidation of which would form neutral zinc sulfate.In the presence of H_(2)O ,the formation of SO_(2) on sphalerite surface was easier and the rate of further oxidation to form sulfate was also greater.Consequently,the occurrence of sphalerite oxidation was accelerated.展开更多
The expandable graphite(EG)modified TiO_(2) nanocomposites were prepared by the high shearmethod using the TiO_(2) nanoparticles(NPs)and EG as precursors,in which the amount of EG doped in TiO_(2) was 10 wt.%.Followed...The expandable graphite(EG)modified TiO_(2) nanocomposites were prepared by the high shearmethod using the TiO_(2) nanoparticles(NPs)and EG as precursors,in which the amount of EG doped in TiO_(2) was 10 wt.%.Followed by the impregnation method,adjusting the pH of the solution to 10,and using the electrostatic adsorption to achieve spatial confinement,the Pt elementswere mainly distributed on the exposed TiO_(2),thus generating the Pt/10EG-TiO_(2)-10 catalyst.The best CO oxidation activity with the excellent resistance to H_(2)O and SO_(2) was obtained over the Pt/10EG-TiO_(2)-10 catalyst:CO conversion after 36 hr of the reaction was ca.85%under the harsh condition of 10 vol.%H_(2)O and 100 ppm SO_(2) at a high gaseous hourly space velocity(GHSV)of 400,000 hr−1.Physicochemical properties of the catalystswere characterized by various techniques.The results showed that the electrostatic adsorption,which riveted the Pt elements mainly on the exposed TiO_(2) of the support surface,reduced the dispersion of Pt NPs on EG and achieved the effective dispersion of Pt NPs,hence significantly improving CO oxidation activity over the Pt/10EG-TiO_(2)-10 catalyst.The 10 wt.%EG doped in TiO_(2) caused the TiO_(2) support to form a more hydrophobic surface,which reduced the adsorption of H_(2)O and SO_(2) on the catalyst,greatly inhibited deposition of the TiOSO_(4) and formation of the PtSO4 species as well as suppressed the oxidation of SO_(2),thus resulting in an improvement in the resistance to H_(2)O and SO_(2) of the Pt/10EG-TiO_(2)-10 catalyst.展开更多
The oxygen evolution reaction(OER)serves as a fundamental half–reaction in the electrolysis of water for hydrogen production,which is restricted by the sluggish OER reaction kinetics and unable to be practically appl...The oxygen evolution reaction(OER)serves as a fundamental half–reaction in the electrolysis of water for hydrogen production,which is restricted by the sluggish OER reaction kinetics and unable to be practically applied.The traditional lattice oxygen oxidation mechanism(LOM)offers an advantageous route by circumventing the formation of M-OOH^(*)in the adsorption evolution mechanism(AEM),thus enhancing the reaction kinetics of the OER but resulting in possible structural destabilization due to the decreased M–O bond order.Fortunately,the asymmetry of tetrahedral and octahedral sites in transition metal spinel oxides permits the existence of non-bonding oxygen,which could be activated by rational band structure design for direct O-O coupling,where the M–O bond maintains its initial bond order.Here,non-bonding oxygen was introduced into NiFe_(2)O_(4)via annealing in an oxygen-deficient atmosphere.Then,in-situ grown sulfate species on octahedral nickel sites significantly improved the reactivity of the non-bonding oxygen electrons,thereby facilitating the transformation of the redox center from metal to oxygen.LOM based on non-bonding oxygen(LOMNB)was successfully activated within NiFe_(2)O_(4),exhibiting a low overpotential of 206 mV to achieve a current density of 10 mA cm^(-2)and excellent durability of stable operation for over 150 h.Additionally,catalysts featuring varying band structures were synthesized for comparative analysis,and it was found that the reversible redox processes of non-bonding oxygen and the accumulation of non-bonding oxygen species containing 2p holes are critical prerequisites for triggering and sustaining the LOMNB pathway in transition metal spinel oxides.These findings may provide valuable insights for the future development of spinel-oxide-based LOM catalysts.展开更多
Plastics are ubiquitous in human life and pose certain hazards to the environment and human body.The increasing amount of CO_(2)in the atmosphere will lead to the greenhouse effect.Therefore,it is urgent to treat micr...Plastics are ubiquitous in human life and pose certain hazards to the environment and human body.The increasing amount of CO_(2)in the atmosphere will lead to the greenhouse effect.Therefore,it is urgent to treat microplastic waste and CO_(2)by using environmentally friendly and efficient technologies.In this work,we developed an efficient photoelectrocatalytic system composed of Ni single atoms(Ni SAs)supported by P,N-doped amorphous NiFe_(2)O_(4)(Ni SAs/A-P-N-NFO)as anode and Ag nanoparticles(Ag NPs)supported by CuO/Cu_(2)O nanocubes(Ag NPs@CuO/Cu_(2)O NCs)as cathode for microplastic oxidation and CO_(2)reduction.The Ni SAs/A-P-N-NFO was synthesized by calcination-H_(2)reduction method,and it achieved a Faraday efficiency of 93%for the oxidation reaction of poly(ethylene terephthalate)(PET)solution under AM 1.5 G light.As a photocathode,the synthesized Ag NPs@CuO/Cu_(2)O NCs was utilized to reduce CO_(2)to ethylene and CO at 1.5 V vs.RHE with selectivity of 42%and 55%,respectively.This work shows that the photoelectrocatalysis,as an environmentally friendly technology,is a feasible strategy for reducing the environmental and biological hazards of light plastics,as well as for efficient CO_(2)reduction.展开更多
Electrocatalytic toluene(TL)oxidation to produce benzoic acid(BAC)process is largely hindered due to sluggish kinetics associated with the transformation of the rate-determining step,because of weak TL adsorption and ...Electrocatalytic toluene(TL)oxidation to produce benzoic acid(BAC)process is largely hindered due to sluggish kinetics associated with the transformation of the rate-determining step,because of weak TL adsorption and high rate-determining step energy barrier for difficult to dehydrogenate.Herein,we report Mn_(x)Ce_(1-x)O_(2)/CNT catalyst for accelerated reaction kinetics.Theoretical and experimental studies indicate that Ce sites promote TL adsorption and polyvalent Mn modulates the electronic structure of Ce sites reducing the rate-determining step energy barrier.This results in increasing^(*)C_(6)H_(5)CH_(2)coverage and effectively accelerating TL oxidation reaction(TOR)kinetics.Excitingly,the Faraday efficiency(FE)and BAC yield of optimized Mn_(0.6)Ce_(0.4)O_(2)/CNT at 2.6 V vs.RHE could reach 85.9%and 653.9 mg h^(-1)cm^(-2),respectively.In addition,the Mn_(0.6)Ce_(0.4)O_(2)/CNT displays a high selectivity of 96.3%for BAC.Combining the TL oxidation reaction with hydrogen evolution reaction,the anion exchange membrane electrolyzer of Mn_(0.6)Ce_(0.4)O_(2)/CNT(+)||Pt/C(-)can reach 100 mA cm^(-2)at the voltage of 3.0 V,in which the BAC yield is 579.4 mg h^(-1)cm^(-2)and the FE is 83.6%.This work achieved high selectivity of TOR at industrial-relevant current densities of 100 mA cm^(-2)at the low voltage for the first time.展开更多
Most studies have shown that oxygen vacancies on Ce_(x)Zr_(1-x)O_(2) solid solution are important for enhancing the catalytic oxidation performance.However,a handful of studies investigated the different roles of surf...Most studies have shown that oxygen vacancies on Ce_(x)Zr_(1-x)O_(2) solid solution are important for enhancing the catalytic oxidation performance.However,a handful of studies investigated the different roles of surface and subsurface oxygen vacancies on the performance and mechanisms of catalysts.Herein,a series of zirconium doping on CeO_(2) samples(CeO_(2),Ce_(0.95)Zr_(0.05)O_(2),and Ce_(0.8)5Zr_(0.15)O_(2))with various surface-to-subsurface oxygen vacancies ratios have been synthesized and applied in toluene catalytic oxidation.The obtained Ce_(0.95)Zr_(0.05)O_(2) exhibits an excellent catalytic performance with a 90%toluene conversion at 295℃,which is 68℃lower than that of CeO_(2).Additionally,the obtained Ce_(0.95)Zr_(0.05)O_(2)catalyst also exhibited good catalytic stability and water resistance.The XRD and HRTEM results show that Zr ions are incorporated into CeO_(2) lattice,forming Ce_(x)Zr_(1-x)O_(2) solid solution.Temperature-programmed experiments reveal that Ce_(0.95)Zr_(0.05)O_(2) shows excellent lowtemperature reducibility and abundant surface oxygen species.In-situ DRIFTS tests were used to probe the reaction mechanism,and the function of Zr doping in promoting the activation of oxygen was further determined.Density functional theory(DFT)calculations indicate that the vacancy formation energy and O_(2) adsorption energy are both lower on Ce_(0.95)Zr_(0.05)O_(2),confirming the reason for its superior catalytic performance.展开更多
The oxidation behavior of Ni-based superalloy GH4742 exposed to water vapor was investigated at 900-1100℃for 50 h in Ar+20%H_(2)O,with Ar+20%O_(2)included for comparison.The presence of H_(2)O is adverse to formation...The oxidation behavior of Ni-based superalloy GH4742 exposed to water vapor was investigated at 900-1100℃for 50 h in Ar+20%H_(2)O,with Ar+20%O_(2)included for comparison.The presence of H_(2)O is adverse to formation of continuous Cr_(2)O_(3)oxide layer but contributes to generation of big voids.Based on this,Ni^(2+)and Co^(2+)are more easily to diffuse towards the outermost oxide layer(OOL),forming non-protective Ni-and Co-rich oxides with high proportion.This leads to a higher weight gain in Ar+20%H_(2)O than that in Ar+20%O_(2).At elevated temperatures,the spallation of oxide scale occurs while the consumption of Cr is reduced in Ar+20%H_(2)O,and the contents of Ni-and Co-rich oxides at this moment are reduced in the OOL.The oxidation mechanism was also discussed.展开更多
The existence and risk of emerging organic contaminants(EOCs)have been under consideration and paid much effort to degrade these pollutants.Fenton system is one of the most widely used technologies to solve this probl...The existence and risk of emerging organic contaminants(EOCs)have been under consideration and paid much effort to degrade these pollutants.Fenton system is one of the most widely used technologies to solve this problem.The original Fenton system relies on the hydroxyl radicals produced by Fe(Ⅱ)/H_(2)O_(2) to oxidize the organic contaminants.However,the application of the Fenton system is limited by its low iron cycling efficiency and the high risks of hydrogen peroxide transportation and storage.The introduction of external energy(including light and electricity etc.)can effectively promote the Fe(Ⅲ)/Fe(Ⅱ)cycle and the reduction of oxygen to produce hydrogen peroxide in situ.This review introduces three in-situ Fenton systems,which are electro-Fenton,Photo-Fenton,and chemical reaction.The mechanism,influencing factors,and catalysts of these three in-situ Fenton systems in degrading EOCs are discussed systematically.This review strengthens the understanding of Fenton and in-situ Fenton systems in degradation,offering further insight into the real application of the in-situ Fenton system in the removal of EOCs.展开更多
Direct methanol fuel cell technology recently becomes the focus of both academic and engineering circles,which stimulates the exploitation and utilization of advanced electrode catalysts with high activity and long li...Direct methanol fuel cell technology recently becomes the focus of both academic and engineering circles,which stimulates the exploitation and utilization of advanced electrode catalysts with high activity and long lifespan.Herein,we demonstrate a robust bottom-up approach to the spatial construction of three-dimensional(3D) spinel manganese-cobalt oxide-modified N-doped graphene nanoarchitectures decorated with ultrasmall Pt nanoparticles(Pt/MnCo_(2)O_(4)-NG) via a controllable selfassembly process.The incorporation of MnCo_(2)O_(4)nanocrystals provides abundant hydroxyl sources to promote the oxidative removal of CO-like byproducts on Pt sites,while the existence of 3D porous N-doped graphene networks facilitates the transportation of both ions and electrons in the hybrid system,thus giving rise to remarkable synergetic coupling effects during the methanol oxidation process.Consequently,the optimized Pt/MnCo_(2)O_(4)-NG nano architecture expres ses exceptional electrocatalytic properties with a large electrochemically active surface area of 99.5 m^(2)·g^(-1),a high mass activity of1508.3 mA·mg^(-1),strong toxicity resistance and reliable long-term durability,which have obvious competitive advantages over those of conventional Pt/carbon black,Pt/carbon nano tube,Pt/graphene,and Pt/N-doped graphene catalysts with the same Pt usage.展开更多
Hydrogen sulfide(H_(2)S) not only presents significant environmental concerns but also induces severe corrosion in industrial equipment,even at low concentrations.Among various technologies,the selective oxidation of ...Hydrogen sulfide(H_(2)S) not only presents significant environmental concerns but also induces severe corrosion in industrial equipment,even at low concentrations.Among various technologies,the selective oxidation of hydrogen sulfide(SOH_(2)S) to elemental sulfur(S) has emerged as a sustainable and environmentally friendly solution.Due to its unique properties,iron oxide has been extensively investigated as a catalyst for SOH_(2)S;however,rapid deactivation has remained a significant drawback.The causes of iron oxide-based catalysts deactivation mechanisms in SOH_(2)S,including sulfur or sulfate deposition,the transformation of iron species,sintering and excessive oxygen vacancy formation,and active site loss,are thoroughly examined in this review.By focusing on the deactivation mechanisms,this review aims to provide valuable insights into enhancing the stability and efficiency of iron-based catalysts for SOH_(2)S.展开更多
This study investigated the impact of surface degradation caused by oxygen(O)and nitrogen(N)ele-ments in the environmental atmosphere on the service failure of nearly lamellar TNM alloy.The results show that oxidation...This study investigated the impact of surface degradation caused by oxygen(O)and nitrogen(N)ele-ments in the environmental atmosphere on the service failure of nearly lamellar TNM alloy.The results show that oxidation-induced phase transformations at the surface and subsurface regions strongly af-fect the alloy’s tensile properties at high temperatures.The precipitation of Al_(2)O_(3),which disrupts the integrity of the Ti_(2)AlN layer,has a weaker deformation resistance capacity compared to the Z-phase.Un-der stress conditions,numerous dislocations concentrate at the Al_(2)O_(3)phase,causing Al_(2)O_(3)particles to easily detach and initiating crack nucleation at the Z-phase/Al_(2)O_(3)interface.This is the origin of oxidation failure.Cracks nucleate at the Al_(2)O_(3)detachment region,propagate,and connect with surface microcracks induced by the rough and loose outer oxide layer structure.This leads to the rapid propagation of cracks into the subsurface.The consumption ofβ-stabilizing elements at the surface,along with the internal dif-fusion of O and N elements into the subsurface region,results in the formation of the hard brittle Z-phase at the subsurface lamellar structure and a transition fromβ0 toα2 at the lamellar colony boundaries.The precipitation ofα2 and Z-phase also accelerates crack propagation.In summary,the failure mode shifts from toughness fracture to brittle fracture.展开更多
A general,facile and eco-friendly iron catalysis enables oxidation of unstrained tertiary aromatic alcohols to ketones through C-C bond cleavage even with H_(2)O_(2) as the oxidant.Notably,this transformation can tole...A general,facile and eco-friendly iron catalysis enables oxidation of unstrained tertiary aromatic alcohols to ketones through C-C bond cleavage even with H_(2)O_(2) as the oxidant.Notably,this transformation can tolerate oxidation-labile functional groups.The robustness of this method is further demonstrated on the late-stage oxidation of complex bioactive molecules.展开更多
Rare earth elements have been widely applied in various sectors.Bastnaesite and monazite are crucial rare earth minerals,and flotation is a vital technique for recovering fine-grained rare earth minerals and separatin...Rare earth elements have been widely applied in various sectors.Bastnaesite and monazite are crucial rare earth minerals,and flotation is a vital technique for recovering fine-grained rare earth minerals and separating them from associated gangue minerals such as fluorite and apatite.Flotation collectors play a key role in selectively adsorbing valuable minerals,enhancing their surface hydrophobicity,which has prompted considerable research interest.However,the interaction between minerals and reagents relies on the reactivity and selectivity of the reagent groups,as well as the reactive properties of the surface atoms of the minerals.This study proposes the use of H_(2)O_(2)oxidation to enhance the flotation process of rare earth minerals.The flotation experiments demonstrated that pre-adding H_(2)O_(2)before introducing the flotation collector significantly improved the grade and recovery of rare earth concentrates.The adsorption mechanisms of 2-hydroxy-3-naphthyl hydroxamic acid collector on rare earth mineral surfaces before and after H_(2)O_(2)pre-oxidation were studied.The 2-hydroxy-3-naphthyl hydroxamic acid interacts with Ce^(3+)on the surface of unoxidized rare earth minerals,forming chelate compounds with five-membered ring structures.The H_(2)O_(2)exhibited potent oxidizing properties and oxidized the Ce^(3+)on the bastnaesite and monazite surfaces to more stable Ce^(4+),which demonstrated stronger binding capability with hydroxamic acid.展开更多
Tuning oxygen vacancy(VO)in metal oxides catalysts that efficiently activates O_(2)molecule to promote oxidation reactions remains challenging.Herein,transition metal(M=Mn,Co,and Mo)doping was used to moderate the coo...Tuning oxygen vacancy(VO)in metal oxides catalysts that efficiently activates O_(2)molecule to promote oxidation reactions remains challenging.Herein,transition metal(M=Mn,Co,and Mo)doping was used to moderate the coordination environment of VO in La_(2)FeMO_(6)and promote activity for selective oxidation of hydrogen sulfide(H_(2)S).Various techniques reveal that the introduction of Mn and Co forms the homogeneous double perovskite phase,which results in the formation of asymmetric VO.Although these asymmetric VO are more difficult to form than symmetric Fe-VO-Fe due to the shorter bond distance and stronger bond strength of Fe-O,they are more conducive to the dissociation of O_(2)molecules.Among them,the formed rich Fe-VO-Mn sites from the alternate substitution of Mn to Fe boosted the activation of O_(2)molecules of Mn-substituted LaFeO_(3).Therefore,enhanced catalytic activity and outstanding sulfur selectivity were achieved as a result of promoted oxygen mobility and reducibility.This work provides an attractive strategy for rational design of advanced oxidation catalysts.展开更多
The rapid deactivation of cost-effective MnO_(2)-based catalysts in humid air limits their application in practice,and the identification of the role of water in an oxidation process is significant for developing wate...The rapid deactivation of cost-effective MnO_(2)-based catalysts in humid air limits their application in practice,and the identification of the role of water in an oxidation process is significant for developing water-resistant MnO_(2)-based catalysts.Here,CuMnO_(2)showed a20.3%HCHO conversion in 10 hr at room temperature in humid air with relative humidity of 40%,but deactivated in 3 hr in dry air.The excellent activity and stability of HCHO oxidation in humid air were attributed to the positive effect of H_(2)O on HCHO oxidation to the H_(2)O-HOCH_(2)OH supermolecule assemblies via hydrogen bonds formed on CuMnO_(2).H_(2)O-HOCH_(2)OH supermolecule assemblies tend to be oxidized to carbonate,which is further oxidized to CO_(2).Furthermore,CuMnO_(2)exhibited a much poorer activity of CO oxidation in humid air,but the CO conversion was still 100%in 10 hr in dry air.H_(2)O showed a competitive adsorption effect to CO on CuMnO_(2).CuMnO_(2)could be applied in HCHO elimination in humid air and CO elimination in dry air.展开更多
High-temperature oxidation behavior of ferrovanadium(FeV_(2)O_(4))and ferrochrome(FeCr_(2)O_(4))spinels is crucial for the application of spinel as an energy material,as well as for the clean usage of high-chromium va...High-temperature oxidation behavior of ferrovanadium(FeV_(2)O_(4))and ferrochrome(FeCr_(2)O_(4))spinels is crucial for the application of spinel as an energy material,as well as for the clean usage of high-chromium vanadium slag.Herein,the nonisothermal oxidation behavior of FeV_(2)O_(4)and FeCr_(2)O_(4)prepared by high-temperature solid-state reaction was examined by thermogravimetry and X-ray diffraction(XRD)at heating rates of 5,10,and 15 K/min.The apparent activation energy was determined by the Kissinger-Akahira-Sunose(KAS)method,whereas the mechanism function was elucidated by the Malek method.Moreover,in-situ XRD was conducted to deduce the phase transformation of the oxidation mechanism for FeV_(2)O_(4)and FeCr_(2)O_(4).The results reveal a gradual increase in the overall apparent activation energies for FeV_(2)O_(4)and FeCr_(2)O_(4)during oxidation.Four stages of the oxidation process are observed based on the oxidation conversion rate of each compound.The oxidation mechanisms of FeV_(2)O_(4)and FeCr_(2)O_(4)are complex and have distinct mechanisms.In particular,the chemical reaction controls the entire oxidation process for FeV_(2)O_(4),whereas that for FeCr_(2)O_(4)transitions from a three-dimensional diffusion model to a chemical reaction model.According to the in-situ XRD results,numerous intermediate products are observed during the oxidation process of both compounds,eventually resulting in the final products FeVO_(4)and V2O_(5)for FeV_(2)O_(4)and Fe_(2)O_(3)and Cr_(2)O_(3)for FeCr_(2)O_(4),respectively.展开更多
文摘Although bimetallic phosphide cocatalysts have attracted considerable interest in photocatalysis research owing to their advantageous thermodynamic characteristics,superstable and efficient cocatalysts have rarely been produced through the modulation of their structure and composition.In this study,a series of bimetallic nickel-iron phosphide(Ni_(x)Fe_(2-x)P,where 0<x<2)cocatalysts with controllable structures and overpotentials were designed by adjusting the atomic ratio of Ni/Fe onto nonmetallic elemental red phosphorus(RP)for the photocatalytic selective oxidation of benzyl alcohol(BA)coupled with hydrogen production.The catalysts exhibited an outstanding photocatalytic activity for benzaldehyde and a high H_(2)yield.The RP regulated by bimetallic phosphide cocatalysts(Ni_(x)Fe_(2-x)P)demonstrated higher photocatalytic oxidation-reduction activity than that regulated by monometallic phosphide cocatalysts(Ni_(2)P and Fe2P).In particular,the RP regulated by Ni_(1.25)Fe_(0.75)P exhibited the best photocatalytic performance.In addition,experimental and theoretical calculations further illustrated that Ni_(1.25)Fe_(0.75)P,with the optimized electronic structure,possessed good electrical conductivity and provided strong adsorption and abundant active sites,thereby accelerating electron migration and lowering the reaction energy barrier of RP.This finding offers valuable insights into the rational design of highly effective cocatalysts aimed at optimizing the photocatalytic activity of composite photocatalysts.
基金supported by the Swedish Energy Agency(P47500-1)the National Key R&D Program of China(2020YFA0710200)+2 种基金the National Natural Science Foundation of China(22378401 and U22A20416)the financial support from STINT(CH2019-8287)financial support from the European Union and Swedish Energy Agency(P2020-90066).
文摘The catalytic oxidation of HMF involves a cascading reaction with multiple intermediate products,making it crucial to enhance the oriented adsorption capacity of specific functional groups for accelerating the entire process.To achieve the efficient selective oxidation of HMF to FDCA,a series of NiCo_(2)O_(4)catalysts with different morphologies,such as flaky,echinoids,pompon and corolla,were prepared and characterized by XRD,SEM,TEM,BET,XPS,and FTIR.Among the four catalysts,flaky NiCo_(2)O_(4)exhibited the most excellent catalytic activity and stability,with a FDCA yield of 60.1%within 12 h at 80℃without alkali participation.The excellent performance of flaky NiCo_(2)O_(4)catalyst is attributed to the oxygen vacancies and acid sites generated by the exposed(400)facets.The oxygen vacancies and acid sites on the catalyst surface can precisely adsorb-CHO and-CH_(2)-OH of HMF,respectively,and this synergistic effect promotes the efficient production of FDCA.This work is of great significance for fundamentally study the effect of micro-topography or crystal-plane reaction properties on surfaces.
基金National Natural Science Foundation of China(52222202)National Key R&D Program of China(2022YFB3707700)+2 种基金Project of Shanghai Science and Technology Innovation Action Plan(21511104800)Shanghai Pilot Program for Basic Research-Chinese Academy of Science,Shanghai Branch(JCYJ-SHFY-2021-001)Science Center for Gas Turbine Project(P2022-B-Ⅳ-001-001)。
文摘Silicon-carbide-fiber-reinforced silicon-carbide-ceramic-based matrix(SiC/SiC)composites possess excellent properties such as low density,high strength and high temperature resistance,showing a potential application for structural components in the aerospace field,but their oxidation behavior remains largely unknown.In this study,Yb_(2)Si_(2)O_(7)modified SiC/SiC(SiC/SiC-Yb_(2)Si_(2)O_(7))mini-composites were prepared by introducing Yb_(2)Si_(2)O_(7)as anti-oxidation phase into SiC fiber bundles via Sol-Gel and depositing SiC matrix by chemical vapor deposition(CVD).Influence of Yb_(2)Si_(2)O_(7)on microstructure,mechanical property and oxidation behavior of SiC/SiC mini-composites was investigated.The results showed that after oxidation in air at 1200 and 1400℃for 50 h,the tensile strength retentions of SiC/SiC mini-composites were 77%and 69%,respectively,and the fracture morphology exhibited flat.The Yb_(2)Si_(2)O_(7)introduced by Sol-Gel partially distributed in layers,contributing to the toughening of the material.On the fracture surface,there was interlayer debonding,which extended energy dissipation mechanism of SiC/SiC mini-composites.Tensile strength of SiC/SiC-Yb_(2)Si_(2)O_(7)mini-composites at room temperature was 484 MPa.After oxidation in air at 1200 and 1400℃for 50 h,the tensile strengths decreased to 425 and 374 MPa,resulting in retention rates of 88%and 77%,respectively.It displayed typical non-brittle fracture characteristics.The interface oxygen content of SiC/SiC mini-composites at the fracture surface was higher than that of SiC/SiC-Yb_(2)Si_(2)O_(7)mini-composites,indicating that introduction of Yb_(2)Si_(2)O_(7)could alleviate oxygen diffusion towards the interface,and therefore improve the oxidation resistance of SiC/SiC-Yb_(2)Si_(2)O_(7)mini-composites.
基金financially supported by the National Natural Science Foundation of China(22478211,22179067,22372017)the Major Fundamental Research Program of Natural Science Foundation of Shandong Province(ZR2022ZD10)。
文摘Photoelectrochemical water oxidation(PEC-WO)as a green and sustainable route to produce H_(2)O_(2)has attracted extensive attentions.However,water oxidation to H_(2)O_(2)via a 2e^(-) pathway is thermodynamically more difficult than to O_(2)via a 4e^(-)pathway.Herein,with a series of BiVO_(4)-based photoanodes,the decisive factors determining the PEC activity and selectivity are elucidated,combining a comprehensive experimental and theoretical investigations.It is discovered that the ZnO/BiVO_(4)photoanode(ZnO/BVO)forms a Type-Ⅱheterojunction in energy level alignment.The accelerated photogenerated charge separation/transfer dynamics generates denser surface holes and higher surface photovoltage.Therefore,the activity of water oxidation reaction is promoted.The selectivity of PEC-WO to H_(2)O_(2)is found to be potential-dependent,i.e.,at the lower potentials(PEC-dominated),surface hole density determines the selectivity;and at the higher potentials(electrochemical-dominated),surface reaction barriers govern the selectivity.For the ZnO/BVO heterojunction photoanode,the higher surface hole density facilitates the generation of OH·and the subsequent OH·/OH·coupling to form H_(2)O_(2),thus rising up with potentials;at the higher potentials,the 2-electron pathway barrier over ZnO/BVO surface is lower than over BVO surface,which benefits from the electronic structure regulation by the underlying ZnO alleviating the over-strong adsorption of^(*)OH on BVO,thus,the two-electron pathway to produce H_(2)O_(2)is more favored than on BVO surface.This work highlights the crucial role of band energy structure of semiconductors on both PEC reaction activity and selectivity,and the knowledge gained is expected to be extended to other photoeletrochemical reactions.
基金supported by the Postdoctoral Fellowship Program(Grade A)of China Postdoctoral Science Foundation(No.BX20240429)the National Science and Technology Major Project of the Ministry of Science and Technology of China(No.2024ZD1004007)+3 种基金the National Key R&D Program of China(Nos.2022YFC2904502 and 2022YFC2904501)the National Natural Science Foundation of China(No.52204298)the Major Science and Technology Projects in Yunnan Province(No.202202AB080012)the High Performance Computing Center of Central South University。
文摘Herein,a first-principles investigation was innovatively conducted to research the surface oxidation of ZnS-like sphalerite in the absence and presence of H_(2)O .The findings showed that single O_(2) was preferred to be dissociated adsorption on sphalerite surface by generating SAO and Zn AO bonds,and the S atom on the surface was the most energy-supported site for O_(2) adsorption,on which a≡Zn-O-S-O-Zn≡structure will be formed.However,dissociated adsorption of single H_(2)O will not happen.It was preferred to be adsorbed on the top Zn atom on sphalerite surface in molecular form through Zn-O bond.Besides,sphalerite oxidation can occur as if O_(2) was present regardless of the presence of H_(2)O ,and when H_(2)O and O_(2) coexisted,the formation of sulfur oxide(SO_(2) )needed a lower energy barrier and it was easier to form on sphalerite surface than that only O_(2) existed.In the absence of H_(2)O ,when SO_(2) was generated,further oxidation of which would form neutral zinc sulfate.In the presence of H_(2)O ,the formation of SO_(2) on sphalerite surface was easier and the rate of further oxidation to form sulfate was also greater.Consequently,the occurrence of sphalerite oxidation was accelerated.
基金supported by the National Key R&D Program of China (No.2017YFC0210303).
文摘The expandable graphite(EG)modified TiO_(2) nanocomposites were prepared by the high shearmethod using the TiO_(2) nanoparticles(NPs)and EG as precursors,in which the amount of EG doped in TiO_(2) was 10 wt.%.Followed by the impregnation method,adjusting the pH of the solution to 10,and using the electrostatic adsorption to achieve spatial confinement,the Pt elementswere mainly distributed on the exposed TiO_(2),thus generating the Pt/10EG-TiO_(2)-10 catalyst.The best CO oxidation activity with the excellent resistance to H_(2)O and SO_(2) was obtained over the Pt/10EG-TiO_(2)-10 catalyst:CO conversion after 36 hr of the reaction was ca.85%under the harsh condition of 10 vol.%H_(2)O and 100 ppm SO_(2) at a high gaseous hourly space velocity(GHSV)of 400,000 hr−1.Physicochemical properties of the catalystswere characterized by various techniques.The results showed that the electrostatic adsorption,which riveted the Pt elements mainly on the exposed TiO_(2) of the support surface,reduced the dispersion of Pt NPs on EG and achieved the effective dispersion of Pt NPs,hence significantly improving CO oxidation activity over the Pt/10EG-TiO_(2)-10 catalyst.The 10 wt.%EG doped in TiO_(2) caused the TiO_(2) support to form a more hydrophobic surface,which reduced the adsorption of H_(2)O and SO_(2) on the catalyst,greatly inhibited deposition of the TiOSO_(4) and formation of the PtSO4 species as well as suppressed the oxidation of SO_(2),thus resulting in an improvement in the resistance to H_(2)O and SO_(2) of the Pt/10EG-TiO_(2)-10 catalyst.
文摘The oxygen evolution reaction(OER)serves as a fundamental half–reaction in the electrolysis of water for hydrogen production,which is restricted by the sluggish OER reaction kinetics and unable to be practically applied.The traditional lattice oxygen oxidation mechanism(LOM)offers an advantageous route by circumventing the formation of M-OOH^(*)in the adsorption evolution mechanism(AEM),thus enhancing the reaction kinetics of the OER but resulting in possible structural destabilization due to the decreased M–O bond order.Fortunately,the asymmetry of tetrahedral and octahedral sites in transition metal spinel oxides permits the existence of non-bonding oxygen,which could be activated by rational band structure design for direct O-O coupling,where the M–O bond maintains its initial bond order.Here,non-bonding oxygen was introduced into NiFe_(2)O_(4)via annealing in an oxygen-deficient atmosphere.Then,in-situ grown sulfate species on octahedral nickel sites significantly improved the reactivity of the non-bonding oxygen electrons,thereby facilitating the transformation of the redox center from metal to oxygen.LOM based on non-bonding oxygen(LOMNB)was successfully activated within NiFe_(2)O_(4),exhibiting a low overpotential of 206 mV to achieve a current density of 10 mA cm^(-2)and excellent durability of stable operation for over 150 h.Additionally,catalysts featuring varying band structures were synthesized for comparative analysis,and it was found that the reversible redox processes of non-bonding oxygen and the accumulation of non-bonding oxygen species containing 2p holes are critical prerequisites for triggering and sustaining the LOMNB pathway in transition metal spinel oxides.These findings may provide valuable insights for the future development of spinel-oxide-based LOM catalysts.
文摘Plastics are ubiquitous in human life and pose certain hazards to the environment and human body.The increasing amount of CO_(2)in the atmosphere will lead to the greenhouse effect.Therefore,it is urgent to treat microplastic waste and CO_(2)by using environmentally friendly and efficient technologies.In this work,we developed an efficient photoelectrocatalytic system composed of Ni single atoms(Ni SAs)supported by P,N-doped amorphous NiFe_(2)O_(4)(Ni SAs/A-P-N-NFO)as anode and Ag nanoparticles(Ag NPs)supported by CuO/Cu_(2)O nanocubes(Ag NPs@CuO/Cu_(2)O NCs)as cathode for microplastic oxidation and CO_(2)reduction.The Ni SAs/A-P-N-NFO was synthesized by calcination-H_(2)reduction method,and it achieved a Faraday efficiency of 93%for the oxidation reaction of poly(ethylene terephthalate)(PET)solution under AM 1.5 G light.As a photocathode,the synthesized Ag NPs@CuO/Cu_(2)O NCs was utilized to reduce CO_(2)to ethylene and CO at 1.5 V vs.RHE with selectivity of 42%and 55%,respectively.This work shows that the photoelectrocatalysis,as an environmentally friendly technology,is a feasible strategy for reducing the environmental and biological hazards of light plastics,as well as for efficient CO_(2)reduction.
基金supported by the National Natural Science Foundation of China(52272222)the Taishan Scholar Young Talent Program(tsqn201909114,tsqn201909123)the University Youth Innovation Team of Shandong Province(202201010318)。
文摘Electrocatalytic toluene(TL)oxidation to produce benzoic acid(BAC)process is largely hindered due to sluggish kinetics associated with the transformation of the rate-determining step,because of weak TL adsorption and high rate-determining step energy barrier for difficult to dehydrogenate.Herein,we report Mn_(x)Ce_(1-x)O_(2)/CNT catalyst for accelerated reaction kinetics.Theoretical and experimental studies indicate that Ce sites promote TL adsorption and polyvalent Mn modulates the electronic structure of Ce sites reducing the rate-determining step energy barrier.This results in increasing^(*)C_(6)H_(5)CH_(2)coverage and effectively accelerating TL oxidation reaction(TOR)kinetics.Excitingly,the Faraday efficiency(FE)and BAC yield of optimized Mn_(0.6)Ce_(0.4)O_(2)/CNT at 2.6 V vs.RHE could reach 85.9%and 653.9 mg h^(-1)cm^(-2),respectively.In addition,the Mn_(0.6)Ce_(0.4)O_(2)/CNT displays a high selectivity of 96.3%for BAC.Combining the TL oxidation reaction with hydrogen evolution reaction,the anion exchange membrane electrolyzer of Mn_(0.6)Ce_(0.4)O_(2)/CNT(+)||Pt/C(-)can reach 100 mA cm^(-2)at the voltage of 3.0 V,in which the BAC yield is 579.4 mg h^(-1)cm^(-2)and the FE is 83.6%.This work achieved high selectivity of TOR at industrial-relevant current densities of 100 mA cm^(-2)at the low voltage for the first time.
基金supported by the National Natural Science Foundation(No.51678291)the Basic Science(Natural Science)Research in Higher Education in Jiangsu Province(No.23KJA610003)the High-level Scientific Research Foundation for the introduction of talent in Nanjing Institute of Technology(No.YKJ201999)。
文摘Most studies have shown that oxygen vacancies on Ce_(x)Zr_(1-x)O_(2) solid solution are important for enhancing the catalytic oxidation performance.However,a handful of studies investigated the different roles of surface and subsurface oxygen vacancies on the performance and mechanisms of catalysts.Herein,a series of zirconium doping on CeO_(2) samples(CeO_(2),Ce_(0.95)Zr_(0.05)O_(2),and Ce_(0.8)5Zr_(0.15)O_(2))with various surface-to-subsurface oxygen vacancies ratios have been synthesized and applied in toluene catalytic oxidation.The obtained Ce_(0.95)Zr_(0.05)O_(2) exhibits an excellent catalytic performance with a 90%toluene conversion at 295℃,which is 68℃lower than that of CeO_(2).Additionally,the obtained Ce_(0.95)Zr_(0.05)O_(2)catalyst also exhibited good catalytic stability and water resistance.The XRD and HRTEM results show that Zr ions are incorporated into CeO_(2) lattice,forming Ce_(x)Zr_(1-x)O_(2) solid solution.Temperature-programmed experiments reveal that Ce_(0.95)Zr_(0.05)O_(2) shows excellent lowtemperature reducibility and abundant surface oxygen species.In-situ DRIFTS tests were used to probe the reaction mechanism,and the function of Zr doping in promoting the activation of oxygen was further determined.Density functional theory(DFT)calculations indicate that the vacancy formation energy and O_(2) adsorption energy are both lower on Ce_(0.95)Zr_(0.05)O_(2),confirming the reason for its superior catalytic performance.
基金supported by the National Key R&D Program of China(No.2021YFB3700400)National Natural Science Foundation of China(Nos.52074030,51904021,52174294).
文摘The oxidation behavior of Ni-based superalloy GH4742 exposed to water vapor was investigated at 900-1100℃for 50 h in Ar+20%H_(2)O,with Ar+20%O_(2)included for comparison.The presence of H_(2)O is adverse to formation of continuous Cr_(2)O_(3)oxide layer but contributes to generation of big voids.Based on this,Ni^(2+)and Co^(2+)are more easily to diffuse towards the outermost oxide layer(OOL),forming non-protective Ni-and Co-rich oxides with high proportion.This leads to a higher weight gain in Ar+20%H_(2)O than that in Ar+20%O_(2).At elevated temperatures,the spallation of oxide scale occurs while the consumption of Cr is reduced in Ar+20%H_(2)O,and the contents of Ni-and Co-rich oxides at this moment are reduced in the OOL.The oxidation mechanism was also discussed.
基金supported by the National Natural Science Foundation of China(No.21906056No.22176060)+2 种基金the Undergraduate Training Program on Innovation and Entrepreneurship(S202110251087)the Science and Technology Commission of Shanghai Municipality(22ZR1418600)Shanghai Municipal Science and Technology(No.20DZ2250400).
文摘The existence and risk of emerging organic contaminants(EOCs)have been under consideration and paid much effort to degrade these pollutants.Fenton system is one of the most widely used technologies to solve this problem.The original Fenton system relies on the hydroxyl radicals produced by Fe(Ⅱ)/H_(2)O_(2) to oxidize the organic contaminants.However,the application of the Fenton system is limited by its low iron cycling efficiency and the high risks of hydrogen peroxide transportation and storage.The introduction of external energy(including light and electricity etc.)can effectively promote the Fe(Ⅲ)/Fe(Ⅱ)cycle and the reduction of oxygen to produce hydrogen peroxide in situ.This review introduces three in-situ Fenton systems,which are electro-Fenton,Photo-Fenton,and chemical reaction.The mechanism,influencing factors,and catalysts of these three in-situ Fenton systems in degrading EOCs are discussed systematically.This review strengthens the understanding of Fenton and in-situ Fenton systems in degradation,offering further insight into the real application of the in-situ Fenton system in the removal of EOCs.
基金financially supported by the National Natural Science Foundation of China (Nos.22209037 and 51802077)the Fundamental Research Funds for the Central Universities (No.B220202042)。
文摘Direct methanol fuel cell technology recently becomes the focus of both academic and engineering circles,which stimulates the exploitation and utilization of advanced electrode catalysts with high activity and long lifespan.Herein,we demonstrate a robust bottom-up approach to the spatial construction of three-dimensional(3D) spinel manganese-cobalt oxide-modified N-doped graphene nanoarchitectures decorated with ultrasmall Pt nanoparticles(Pt/MnCo_(2)O_(4)-NG) via a controllable selfassembly process.The incorporation of MnCo_(2)O_(4)nanocrystals provides abundant hydroxyl sources to promote the oxidative removal of CO-like byproducts on Pt sites,while the existence of 3D porous N-doped graphene networks facilitates the transportation of both ions and electrons in the hybrid system,thus giving rise to remarkable synergetic coupling effects during the methanol oxidation process.Consequently,the optimized Pt/MnCo_(2)O_(4)-NG nano architecture expres ses exceptional electrocatalytic properties with a large electrochemically active surface area of 99.5 m^(2)·g^(-1),a high mass activity of1508.3 mA·mg^(-1),strong toxicity resistance and reliable long-term durability,which have obvious competitive advantages over those of conventional Pt/carbon black,Pt/carbon nano tube,Pt/graphene,and Pt/N-doped graphene catalysts with the same Pt usage.
基金supported by Thailand Science Research and Innovation Fund Chulalongkorn University,Thailand(IND66210014)。
文摘Hydrogen sulfide(H_(2)S) not only presents significant environmental concerns but also induces severe corrosion in industrial equipment,even at low concentrations.Among various technologies,the selective oxidation of hydrogen sulfide(SOH_(2)S) to elemental sulfur(S) has emerged as a sustainable and environmentally friendly solution.Due to its unique properties,iron oxide has been extensively investigated as a catalyst for SOH_(2)S;however,rapid deactivation has remained a significant drawback.The causes of iron oxide-based catalysts deactivation mechanisms in SOH_(2)S,including sulfur or sulfate deposition,the transformation of iron species,sintering and excessive oxygen vacancy formation,and active site loss,are thoroughly examined in this review.By focusing on the deactivation mechanisms,this review aims to provide valuable insights into enhancing the stability and efficiency of iron-based catalysts for SOH_(2)S.
基金supported by the National Science and Technology Major Project(No.J2019-VI-0011-0125)Shaanxi Provincial Innovation Capacity Support Plan(No.2023-CX-TD-47)the ND Basic Research Funds of NPU(No.G2022WD).
文摘This study investigated the impact of surface degradation caused by oxygen(O)and nitrogen(N)ele-ments in the environmental atmosphere on the service failure of nearly lamellar TNM alloy.The results show that oxidation-induced phase transformations at the surface and subsurface regions strongly af-fect the alloy’s tensile properties at high temperatures.The precipitation of Al_(2)O_(3),which disrupts the integrity of the Ti_(2)AlN layer,has a weaker deformation resistance capacity compared to the Z-phase.Un-der stress conditions,numerous dislocations concentrate at the Al_(2)O_(3)phase,causing Al_(2)O_(3)particles to easily detach and initiating crack nucleation at the Z-phase/Al_(2)O_(3)interface.This is the origin of oxidation failure.Cracks nucleate at the Al_(2)O_(3)detachment region,propagate,and connect with surface microcracks induced by the rough and loose outer oxide layer structure.This leads to the rapid propagation of cracks into the subsurface.The consumption ofβ-stabilizing elements at the surface,along with the internal dif-fusion of O and N elements into the subsurface region,results in the formation of the hard brittle Z-phase at the subsurface lamellar structure and a transition fromβ0 toα2 at the lamellar colony boundaries.The precipitation ofα2 and Z-phase also accelerates crack propagation.In summary,the failure mode shifts from toughness fracture to brittle fracture.
基金the Natural Science Foundation of China(No.21776139)the“Qing Lan Project”Young and Middle-aged Academic Leaders of Jiangsu Provincial Colleges and Universities,and the Priority Academic Program Development of Jiangsu Higher Education Institutions.
文摘A general,facile and eco-friendly iron catalysis enables oxidation of unstrained tertiary aromatic alcohols to ketones through C-C bond cleavage even with H_(2)O_(2) as the oxidant.Notably,this transformation can tolerate oxidation-labile functional groups.The robustness of this method is further demonstrated on the late-stage oxidation of complex bioactive molecules.
基金financially supported by the National Natural Science Foundation of China(No.52174236)Fundamental Research Funds for the Central Universities(No.FRF-DF-23-001)the Natural Science Foundation of Inner Mongolia of China(Nos.2024MS05061 and 2023LHMS05050)。
文摘Rare earth elements have been widely applied in various sectors.Bastnaesite and monazite are crucial rare earth minerals,and flotation is a vital technique for recovering fine-grained rare earth minerals and separating them from associated gangue minerals such as fluorite and apatite.Flotation collectors play a key role in selectively adsorbing valuable minerals,enhancing their surface hydrophobicity,which has prompted considerable research interest.However,the interaction between minerals and reagents relies on the reactivity and selectivity of the reagent groups,as well as the reactive properties of the surface atoms of the minerals.This study proposes the use of H_(2)O_(2)oxidation to enhance the flotation process of rare earth minerals.The flotation experiments demonstrated that pre-adding H_(2)O_(2)before introducing the flotation collector significantly improved the grade and recovery of rare earth concentrates.The adsorption mechanisms of 2-hydroxy-3-naphthyl hydroxamic acid collector on rare earth mineral surfaces before and after H_(2)O_(2)pre-oxidation were studied.The 2-hydroxy-3-naphthyl hydroxamic acid interacts with Ce^(3+)on the surface of unoxidized rare earth minerals,forming chelate compounds with five-membered ring structures.The H_(2)O_(2)exhibited potent oxidizing properties and oxidized the Ce^(3+)on the bastnaesite and monazite surfaces to more stable Ce^(4+),which demonstrated stronger binding capability with hydroxamic acid.
文摘Tuning oxygen vacancy(VO)in metal oxides catalysts that efficiently activates O_(2)molecule to promote oxidation reactions remains challenging.Herein,transition metal(M=Mn,Co,and Mo)doping was used to moderate the coordination environment of VO in La_(2)FeMO_(6)and promote activity for selective oxidation of hydrogen sulfide(H_(2)S).Various techniques reveal that the introduction of Mn and Co forms the homogeneous double perovskite phase,which results in the formation of asymmetric VO.Although these asymmetric VO are more difficult to form than symmetric Fe-VO-Fe due to the shorter bond distance and stronger bond strength of Fe-O,they are more conducive to the dissociation of O_(2)molecules.Among them,the formed rich Fe-VO-Mn sites from the alternate substitution of Mn to Fe boosted the activation of O_(2)molecules of Mn-substituted LaFeO_(3).Therefore,enhanced catalytic activity and outstanding sulfur selectivity were achieved as a result of promoted oxygen mobility and reducibility.This work provides an attractive strategy for rational design of advanced oxidation catalysts.
基金supported by the National Natural Science Foundation of China (Nos. 21976198 and 21777175)the National Key Research and Development Program of China (No. 2018YFA0901200)。
文摘The rapid deactivation of cost-effective MnO_(2)-based catalysts in humid air limits their application in practice,and the identification of the role of water in an oxidation process is significant for developing water-resistant MnO_(2)-based catalysts.Here,CuMnO_(2)showed a20.3%HCHO conversion in 10 hr at room temperature in humid air with relative humidity of 40%,but deactivated in 3 hr in dry air.The excellent activity and stability of HCHO oxidation in humid air were attributed to the positive effect of H_(2)O on HCHO oxidation to the H_(2)O-HOCH_(2)OH supermolecule assemblies via hydrogen bonds formed on CuMnO_(2).H_(2)O-HOCH_(2)OH supermolecule assemblies tend to be oxidized to carbonate,which is further oxidized to CO_(2).Furthermore,CuMnO_(2)exhibited a much poorer activity of CO oxidation in humid air,but the CO conversion was still 100%in 10 hr in dry air.H_(2)O showed a competitive adsorption effect to CO on CuMnO_(2).CuMnO_(2)could be applied in HCHO elimination in humid air and CO elimination in dry air.
基金This work was supported by the National Natural Science Foundation of China(No.52004044)the Natural Science Foundation of Chongqing,China(Nos.cstb2022nscqmsx0801 and cstc2021jcyj-msxmx0882)+2 种基金the Foundation of Chongqing University of Science and Technology(No.ckrc2022030)the Graduate Research Innovation Project of Chongqing University of Science and Technology(No.YKJCX2220216)the National Undergraduate Training Program for Innovation and Entrepreneurship(No.202311551007).
文摘High-temperature oxidation behavior of ferrovanadium(FeV_(2)O_(4))and ferrochrome(FeCr_(2)O_(4))spinels is crucial for the application of spinel as an energy material,as well as for the clean usage of high-chromium vanadium slag.Herein,the nonisothermal oxidation behavior of FeV_(2)O_(4)and FeCr_(2)O_(4)prepared by high-temperature solid-state reaction was examined by thermogravimetry and X-ray diffraction(XRD)at heating rates of 5,10,and 15 K/min.The apparent activation energy was determined by the Kissinger-Akahira-Sunose(KAS)method,whereas the mechanism function was elucidated by the Malek method.Moreover,in-situ XRD was conducted to deduce the phase transformation of the oxidation mechanism for FeV_(2)O_(4)and FeCr_(2)O_(4).The results reveal a gradual increase in the overall apparent activation energies for FeV_(2)O_(4)and FeCr_(2)O_(4)during oxidation.Four stages of the oxidation process are observed based on the oxidation conversion rate of each compound.The oxidation mechanisms of FeV_(2)O_(4)and FeCr_(2)O_(4)are complex and have distinct mechanisms.In particular,the chemical reaction controls the entire oxidation process for FeV_(2)O_(4),whereas that for FeCr_(2)O_(4)transitions from a three-dimensional diffusion model to a chemical reaction model.According to the in-situ XRD results,numerous intermediate products are observed during the oxidation process of both compounds,eventually resulting in the final products FeVO_(4)and V2O_(5)for FeV_(2)O_(4)and Fe_(2)O_(3)and Cr_(2)O_(3)for FeCr_(2)O_(4),respectively.
