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
Electrochemical oxidation of 5-hydroxymethylfurfural(HMFOR),featuring favorable thermodynamics,presents a promising alternative to the conventional oxygen evolution reaction for energy-saving hydrogen(H_(2))production...Electrochemical oxidation of 5-hydroxymethylfurfural(HMFOR),featuring favorable thermodynamics,presents a promising alternative to the conventional oxygen evolution reaction for energy-saving hydrogen(H_(2))production coupled with biomass upgrading.However,the multiple proton-coupled electron transfer steps in HMFOR result in sluggish kinetics,highlighting the development of highly efficient electrocatalysts.Herein,a high-entropy amorphous MoCrCoNiZn-S grown on nickel foam(HEAS@NF)is constructed via a metal organic framework-derived strategy to efficiently convert HMF to 2,5-furandicarboxylic acid(FDCA).The abundant active sites on the HEAS@NF facilitate the structural evolution to oxyhydroxides that possess strong reducibility for HMF dehydrogenation,leading to superior HMFOR performance compared to sulfides with fewer metal elements.In situ electrochemical impedance spectroscopy results confirm significantly favored kinetics to HMFOR over OER on the HEAS@NF,resulting in a remarkable98%HMF conversion,with FDCA yield and Faradaic efficiency of 98%and 94%even at a concentrated 100 mM HMF.A two-electrode flow electrolyzer equipped with the bifunctional HEAS@NF enables simultaneous cathodic H2and anodic FDCA production with an electricity saving of 10.8%.This study presents an effective strategy to inspire the exploration of high-entropy catalysts for biomass-assisted H2production.展开更多
The direct oxidation of cyclohexane to adipic acid(AA)without the use of HNO_(3)is important but still challenging.Herein,hierarchical manganese-containing TS-1 zeolite(HMTS)was prepared using an improved direct synth...The direct oxidation of cyclohexane to adipic acid(AA)without the use of HNO_(3)is important but still challenging.Herein,hierarchical manganese-containing TS-1 zeolite(HMTS)was prepared using an improved direct synthesis method,in which titanium and manganese coexist within the zeolite matrix,as characterized by X-ray diffraction,X-ray photoelectron spectroscopy,transmission electron microscopy,ultraviolet,extended X-ray absorption fine structure etc.The introduction of matrix Mn species(Mn^(3+),Mn^(4+))not only increased the surface oxygen vacancies,but also generated medium-strong acid sites,which endowed HMTS catalysts with the ability to efficiently activate oxygen and facilitate substrate coordination.On HMTS-3,one-pot oxidation of cyclohexane at 140℃and 2 MPa O_(2)gave 81.6%conversion and 71.5%AA selectivity,the highest value obtained at present.Control experiments with single-component samples confirmed that matrix Ti^(4+)catalyzed the conversion of cyclohexane to a mixture of cyclohexanone and cyclohexanol(KA oil),and matrix Mn favored the conversion of KA oil to AA.The synergy between matrix Ti and Mn inside the hierarchical structure were the key factor for the superior activity.Specifically,the matrix Ti^(4+)might activate oxygen to form Ti-O_(2)2-which facilitated the activation of the C-H bond of cyclohexane.The activation of O_(2)on matrix Mn^(3+)formed Mn^(4+)-O_(2)-favoring the breaking of the C-C bond of cyclohexanone.The hierarchical structure not only exposed more active sites and promoted mass transfer,but also provided a better microenvironment for the matrix Mn to synergize with the matrix Ti,which facilitated the overall reaction.This work demonstrated the practical application potential of HMTS and provided useful insights into the direct oxidation of cyclohexane to AA.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
Al_(2)O_(3)scale-forming materials are highly desirable for high-temperature oxidation resistance,and the for-mation of α-Al_(2)O_(3)scales with low-angle grain boundaries(LAGBs)will increase their service lifetime.H...Al_(2)O_(3)scale-forming materials are highly desirable for high-temperature oxidation resistance,and the for-mation of α-Al_(2)O_(3)scales with low-angle grain boundaries(LAGBs)will increase their service lifetime.However,the synthesis of LAGBs is a considerable challenge.Herein,a novel methodology for engineering in situ α-Al_(2)O_(3)with LAGBs is designed,capitalizing on preferential nucleation.This approach employs a dual-stage preoxidation process,initiating with the selective nucleation of α-Al_(2)O_(3)under extremely low oxygen partial pressures,followed by the growth of these nuclei into a dense,protective oxide layer un-der marginally higher oxygen partial pressures.Based on this method,an α-Al_(2)O_(3)film with LAGBs is finally obtained,which significantly improves the oxidation resistance.This study not only paves the way for advanced materials to improve durability in high-temperature environments but also provides novel insight into the mechanisms of α-Al_(2)O_(3)film formation and growth under controlled oxidative conditions.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
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financially supported by the National Natural Science Foundation of China(No.22275138 and 22271219)
文摘Electrochemical oxidation of 5-hydroxymethylfurfural(HMFOR),featuring favorable thermodynamics,presents a promising alternative to the conventional oxygen evolution reaction for energy-saving hydrogen(H_(2))production coupled with biomass upgrading.However,the multiple proton-coupled electron transfer steps in HMFOR result in sluggish kinetics,highlighting the development of highly efficient electrocatalysts.Herein,a high-entropy amorphous MoCrCoNiZn-S grown on nickel foam(HEAS@NF)is constructed via a metal organic framework-derived strategy to efficiently convert HMF to 2,5-furandicarboxylic acid(FDCA).The abundant active sites on the HEAS@NF facilitate the structural evolution to oxyhydroxides that possess strong reducibility for HMF dehydrogenation,leading to superior HMFOR performance compared to sulfides with fewer metal elements.In situ electrochemical impedance spectroscopy results confirm significantly favored kinetics to HMFOR over OER on the HEAS@NF,resulting in a remarkable98%HMF conversion,with FDCA yield and Faradaic efficiency of 98%and 94%even at a concentrated 100 mM HMF.A two-electrode flow electrolyzer equipped with the bifunctional HEAS@NF enables simultaneous cathodic H2and anodic FDCA production with an electricity saving of 10.8%.This study presents an effective strategy to inspire the exploration of high-entropy catalysts for biomass-assisted H2production.
文摘The direct oxidation of cyclohexane to adipic acid(AA)without the use of HNO_(3)is important but still challenging.Herein,hierarchical manganese-containing TS-1 zeolite(HMTS)was prepared using an improved direct synthesis method,in which titanium and manganese coexist within the zeolite matrix,as characterized by X-ray diffraction,X-ray photoelectron spectroscopy,transmission electron microscopy,ultraviolet,extended X-ray absorption fine structure etc.The introduction of matrix Mn species(Mn^(3+),Mn^(4+))not only increased the surface oxygen vacancies,but also generated medium-strong acid sites,which endowed HMTS catalysts with the ability to efficiently activate oxygen and facilitate substrate coordination.On HMTS-3,one-pot oxidation of cyclohexane at 140℃and 2 MPa O_(2)gave 81.6%conversion and 71.5%AA selectivity,the highest value obtained at present.Control experiments with single-component samples confirmed that matrix Ti^(4+)catalyzed the conversion of cyclohexane to a mixture of cyclohexanone and cyclohexanol(KA oil),and matrix Mn favored the conversion of KA oil to AA.The synergy between matrix Ti and Mn inside the hierarchical structure were the key factor for the superior activity.Specifically,the matrix Ti^(4+)might activate oxygen to form Ti-O_(2)2-which facilitated the activation of the C-H bond of cyclohexane.The activation of O_(2)on matrix Mn^(3+)formed Mn^(4+)-O_(2)-favoring the breaking of the C-C bond of cyclohexanone.The hierarchical structure not only exposed more active sites and promoted mass transfer,but also provided a better microenvironment for the matrix Mn to synergize with the matrix Ti,which facilitated the overall reaction.This work demonstrated the practical application potential of HMTS and provided useful insights into the direct oxidation of cyclohexane to AA.
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financially supported by the National Program for Support of Top-notch Young Professionals,the Natural Science Foundation of Shaanxi Province(No.2023JC-XJ-04)the Postdoc-toral Innovative Talent Support Program(No.BX2021238)the National Natural Science Foundation of China(No.U22A20110).
文摘Al_(2)O_(3)scale-forming materials are highly desirable for high-temperature oxidation resistance,and the for-mation of α-Al_(2)O_(3)scales with low-angle grain boundaries(LAGBs)will increase their service lifetime.However,the synthesis of LAGBs is a considerable challenge.Herein,a novel methodology for engineering in situ α-Al_(2)O_(3)with LAGBs is designed,capitalizing on preferential nucleation.This approach employs a dual-stage preoxidation process,initiating with the selective nucleation of α-Al_(2)O_(3)under extremely low oxygen partial pressures,followed by the growth of these nuclei into a dense,protective oxide layer un-der marginally higher oxygen partial pressures.Based on this method,an α-Al_(2)O_(3)film with LAGBs is finally obtained,which significantly improves the oxidation resistance.This study not only paves the way for advanced materials to improve durability in high-temperature environments but also provides novel insight into the mechanisms of α-Al_(2)O_(3)film formation and growth under controlled oxidative conditions.
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.
