With ongoing global warming and increasing energy demands,the CH_(4)-CO_(2)reforming reaction(dry reforming of methane,DRM)has garnered significant attention as a promising carbon capture and utilization technology.Ni...With ongoing global warming and increasing energy demands,the CH_(4)-CO_(2)reforming reaction(dry reforming of methane,DRM)has garnered significant attention as a promising carbon capture and utilization technology.Nickel-based catalysts are renowned for their outstanding activity and selectivity in this process.The impact of metal-support interaction(MSI),on Ni-based catalyst performance has been extensively researched and debated recently.This paper reviews the recent research progress of MSI on Ni-based catalysts and their characterization and modulation strategies in catalytic reactions.From the perspective of MSI,the effects of different carriers(metal oxides,carbon materials and molecular sieves,etc.)are introduced on the dispersion and surface structure of Ni active metal particles,and the effect of MSI on the activity and stability of DRM reactions on Ni-based catalysts is discussed in detail.Future research should focus on better understanding and controlling MSI to improve the performance and durability of nickel-based catalysts in CH_(4)-CO_(2)reforming,advancing cleaner energy technologies.展开更多
Photothermal catalytic methane dry reforming(DRM)technology can convert greenhouse gases(i.e.CH_(4)and CO_(2))into syngas(i.e.H_(2)and CO),providing more opportunities for reducing the greenhouse effect and achieving ...Photothermal catalytic methane dry reforming(DRM)technology can convert greenhouse gases(i.e.CH_(4)and CO_(2))into syngas(i.e.H_(2)and CO),providing more opportunities for reducing the greenhouse effect and achieving carbon neutrality.In the DRM field,Ni-based catalysts attract wide attention due to their low cost and high activity.However,the carbon deposition over Ni-based catalysts always leads to rapid deactivation,which is still a main challenge.To improve the long-term stability of Ni-based catalysts,this work proposes a carbon-atom-diffusion strategy under photothermal conditions and investigates its effect on a Zn-doped Ni-based photothermal catalyst(Ni_(3)Zn@CeO_(2)).The photothermal catalytic behavior of Ni_(3)Zn@CeO_(2)can maintain more than 70 h in DRM reaction.And the photocatalytic DRM activity of Ni_(3)Zn@CeO_(2)is 1.2 times higher than thermal catalytic activity.Density functional theory(DFT)calculation and experimental characterizations indicate that Ni_(3)Zn promotes the diffusion of carbon atoms into the Ni_(3)Zn to form the Ni_(3)ZnC0.7 phase with body-centered cubic(bcc)structure,thus inhibiting carbon deposition.Further,in-situ diffuse reflectance infrared Fourier transform(DRIFT)spectroscopy and DFT calculation prove Ni_(3)Zn@CeO_(2)benefits the CH_(4)activation and inhibits the carbon deposition during the DRM process.Through inducing carbon atoms diffusion within the Ni_(3)Zn lattice,this work provides a straightforward and feasible strategy for achieving efficient photothermal catalytic DRM and even other CH_(4)conversion implementations with long-term stability.展开更多
Nickel-based catalysts have emerged as crucial components in alkaline oxygen evolution reactions(OER)due to their exceptional catalytic performance and unique structural properties.However,the understanding of their c...Nickel-based catalysts have emerged as crucial components in alkaline oxygen evolution reactions(OER)due to their exceptional catalytic performance and unique structural properties.However,the understanding of their catalytic mechanisms remains incomplete.This review systematically explores the various types of Ni-based catalysts,including metal-organic frameworks(MOFs),perovskites,and layered double hydroxides(LDHs),while emphasizing their performance metrics.We critically assess the application of advanced in situ characterization techniques,such as in situ Raman spectroscopy and X-ray absorption spectroscopy(XAS),in elucidating the structural evolution and active species during the OER process.By addressing the interplay between catalyst structure and performance,this review aims to provide insights that drive future research efforts toward the optimization of Ni-based catalysts for sustainable hydrogen production.Key areas for potential research advancements are also identified.展开更多
S and Co co-doped carbon catalysts were prepared via pyrolysis of MOF-71 and thiourea mixtures at 800℃at a mass ratio of MOF-71 to thiourea of 1:0.1 to effectively activate peroxymonosulfate(PMS)for methylene blue(MB...S and Co co-doped carbon catalysts were prepared via pyrolysis of MOF-71 and thiourea mixtures at 800℃at a mass ratio of MOF-71 to thiourea of 1:0.1 to effectively activate peroxymonosulfate(PMS)for methylene blue(MB)degradation.The effects of two different mixing routes were identified on the MB degradation performance.Particularly,the catalyst obtained by the alcohol solvent evaporation(MOF-AEP)mixing route could degrade 95.60%MB(50 mg/L)within 4 min(degradation rate:K=0.78 min^(-1)),which was faster than that derived from the direct grinding method(MOF-DGP,80.97%,K=0.39 min^(-1)).X-ray photoelectron spectroscopy revealed that the Co-S content of MOF-AEP(43.39at%)was less than that of MOF-DGP(54.73at%),and the proportion of C-S-C in MOF-AEP(13.56at%)was higher than that of MOF-DGP(10.67at%).Density functional theory calculations revealed that the adsorption energy of Co for PMS was -2.94 eV when sulfur was doped as C-S-C on the carbon skeleton,which was higher than that when sulfur was doped next to cobalt in the form of Co-S bond(-2.86 eV).Thus,the C-S-C sites might provide more contributions to activate PMS compared with Co-S.Furthermore,the degradation parameters,including pH and MOF-AEP dosage,were investigated.Finally,radical quenching experiments and electron paramagnetic resonance(EPR)measurements revealed that ^(1)O_(2)might be the primary catalytic species,whereas·O~(2-)might be the secondary one in degrading MB.展开更多
The pursuit of alternative fuel generation technologies has gained momentum due to the diminishing reserves of fossil fuels and global warming from increased CO_(2)emission.Among the proposed methods,the hydrogenation...The pursuit of alternative fuel generation technologies has gained momentum due to the diminishing reserves of fossil fuels and global warming from increased CO_(2)emission.Among the proposed methods,the hydrogenation of CO_(2)to produce marketable carbon-based products like methanol and ethanol is a practical approach that offers great potential to reduce CO_(2)emissions.Although significant volumes of methanol are currently produced from CO_(2),developing highly efficient and stable catalysts is crucial for further enhancing conversion and selectivity,thereby reducing process costs.An in-depth examination of the differences and similarities in the reaction pathways for methanol and ethanol production highlights the key factors that drive C-C coupling.Identifying these factors guides us toward developing more effective catalysts for ethanol synthesis.In this paper,we explore how different catalysts,through the production of various intermediates,can initiate the synthesis of methanol or ethanol.The catalytic mechanisms proposed by spectroscopic techniques and theoretical calculations,including operando X-ray methods,FTIR analysis,and DFT calculations,are summarized and presented.The following discussion explores the structural properties and composition of catalysts that influence C-C coupling and optimize the conversion rate of CO_(2)into ethanol.Lastly,the review examines recent catalysts employed for selective methanol and ethanol production,focusing on single-atom catalysts.展开更多
The efficient hydrogenolysis of esters to alkanes is the key protocol for producing advanced biofuels from renewable plant oils or fats.Due to the low reactivity of the carbonyl group in esters,a high reaction tempera...The efficient hydrogenolysis of esters to alkanes is the key protocol for producing advanced biofuels from renewable plant oils or fats.Due to the low reactivity of the carbonyl group in esters,a high reaction temperature(>250℃)is the prerequisite to ensure high conversion of esters.Here,we report a highly dispersed MoO_(x)-Ru/C bimetallic catalyst for the efficient hydrogenolysis of esters to alkanes under 150°C.The optimal catalyst exhibits>99%conversion of methyl stearate and 99%selectivity to diesel-range alkanes,reaching a high rate of up to 2.0 mmol gcat^(–1)h^(–1),5 times higher than that of Ru/C catalyst(MoO_(x)/C is inert).Integrated experimental and theoretical investigations attribute the high performance to the abundant MoO_(x)-Ru interfacial sites on the catalyst surface,which offers high activity for the C–O cleavage of esters.Furthermore,the dispersed MoO_(x)species significantly weaken the hydrocracking activity of the metallic Ru for C–C bonds,thus yielding alkane products without carbon loss.This study provides a facile and novel strategy for the design of high-performance heterogeneous catalysts for the hydrodeoxygenation of biomass-derived esters to alkane products.展开更多
To improve the catalytic performance of La_(0.6)Sr_(0.4)Co_(0.2)Fe_(0.8)O_(3)(LSCF)towards carbon soot,we utilized the impregnation method to incorporate Ag into the prepared LSCF catalyst.We conducted a series of cha...To improve the catalytic performance of La_(0.6)Sr_(0.4)Co_(0.2)Fe_(0.8)O_(3)(LSCF)towards carbon soot,we utilized the impregnation method to incorporate Ag into the prepared LSCF catalyst.We conducted a series of characterization tests and evaluated the soot catalytic activity of the composite catalyst by comparing it with the LaCoO_(3) group,LaFeO_(3) group,and catalyst-free group.The results indicate that the Ag-LSCF composite catalyst exhibits the highest soot catalytic activity,with the characteristic temperature values of 376.3,431.1,and 473.9℃at 10%,50%,and 90%carbon soot conversion,respectively.These values are 24.8,20.2,and 23.1℃lower than those of the LSCF group.This also shows that LSCF can improve the catalytic activity of soot after compounding with Ag,and reflects the necessity of using catalysts in soot combustion reaction.XPS characterization and BET test show that Ag-LSCF has more abundant surface-adsorbed oxygen species,larger specific surface area and pore volume than LSCF,which also proves that Ag-LSCF has higher soot catalytic activity.展开更多
The microstructure of single crystal superalloy is relatively simple,consisting primarily ofγdendrites andγ/γ′eutectics.During the directional solidification process of Ni-based single crystal superalloys,withdraw...The microstructure of single crystal superalloy is relatively simple,consisting primarily ofγdendrites andγ/γ′eutectics.During the directional solidification process of Ni-based single crystal superalloys,withdrawal rate is a critical parameter affecting the spatial distribution ofγ/γ′eutectic along gravity direction.The results show that theγ/γ′eutectic fraction of the upper platform surface is always higher than that of the lower one,regardless of withdrawal rate.As the withdrawal rate decreases,there is a significant increase inγ/γ′eutectic fraction on the upper surface,while it decreases on the lower surface.The upward accumulation ofγ/γ′eutectic becomes more severe as the withdrawal rate decreases.It is also found that the percentage of Al+Ta is positively correlated with theγ/γ′eutectic fraction.Thermo-solute convection of Al and Ta solutes in the solidification front is the prime reason for the non-uniform distribution of eutectic.The non-uniform distribution ofγ/γ′eutectic cannot be eliminated even after subsequent solution heat treatment,resulting in excess eutectic on the upper surface and thus leading to the scrapping of the blade.展开更多
Exploiting non-precious metal catalysts with excellent oxygen reduction reaction(ORR)performance for energy devices is paramount essential for the green and sustainable society development.Herein,low-cost,high-perform...Exploiting non-precious metal catalysts with excellent oxygen reduction reaction(ORR)performance for energy devices is paramount essential for the green and sustainable society development.Herein,low-cost,high-performance biomass-derived ORR catalysts with an asymmetric Fe-N_(3)P configuration was prepared by a simple pyrolysis-etching technique,where carboxymethyl cellulose(CMC)was used as the carbon source,urea and 1,10-phenanthroline iron complex(FePhen)as additives,and Na_(3)PO_(4)as the phosphorus dopant and a pore-forming agent.The CMC-derived FeNPC catalyst displayed a large specific area(BET:1235 m^(2)g^(-1))with atomically dispersed Fe-N_(3)P active sites,which exhibited superior ORR activity and stability in alkaline solution(E_(1/2)=0.90 V vs.RHE)and Zn-air batteries(P_(max)=149 mW cm^(-2))to commercial Pt/C catalyst(E_(1/2)=0.87 V,P_(max)=118 mW cm^(-2))under similar experimental conditions.This work provides a feasible and costeffective route toward highly efficient ORR catalysts and their application to Zn-air batteries for energy conversion.展开更多
NH_(3)-SCR(SCR:Selective catalytic reduction)is an effective technology for the de-NO_(x)process from both mobile and stationary pollution sources,and the most commonly used catalysts are the vanadia-based catalysts.A...NH_(3)-SCR(SCR:Selective catalytic reduction)is an effective technology for the de-NO_(x)process from both mobile and stationary pollution sources,and the most commonly used catalysts are the vanadia-based catalysts.An innovative V_(2)O_(5)-CeO_(2)/TaTiO_(x)catalyst for NO_(x)removal was prepared in this study.The influences of Ce and Ta in the V_(2)O_(5)-CeO_(2)/TaTiO_(x)catalyst on the SCR performance and physicochemical properties were investigated.The V_(2)O_(5)-CeO_(2)/TaTiO_(x)catalyst not only exhibited excellent SCR activity in a wide temperature window,but also presented strong resistance to H_(2)Oand SO_(2)at 275◦C.A series of characterizationmethods was used to study the catalysts,including H2-temperature programmed reduction,X-ray photoelectron spectroscopy,NH_(3)-temperature programmed desorption,etc.It was discovered that a synergistic effect existed between Ce and Ta species.The introduction of Ce and Ta enlarged the specific surface area,increased the amount of acid sites and the ratio of Ce^(3+),(V^(3+)+V^(4+))and Oα,and strengthened the redox capability which were related to synergistic effect between Ce and Ta species,significantly improving the NH_(3)-SCR activity.展开更多
Catalyst–support interaction plays a crucial role in improving the catalytic activity of oxygen evolution reaction(OER).Here we modulate the catalyst–support interaction in polyaniline-supported Ni_(3)Fe oxide(Ni_(3...Catalyst–support interaction plays a crucial role in improving the catalytic activity of oxygen evolution reaction(OER).Here we modulate the catalyst–support interaction in polyaniline-supported Ni_(3)Fe oxide(Ni_(3)Fe oxide/PANI)with a robust hetero-interface,which significantly improves oxygen evolution activities with an overpotential of 270 mV at 10 mA cm^(-2)and specific activity of 2.08 mA cm_(ECSA)^(-2)at overpotential of 300 mV,3.84-fold that of Ni_(3)Fe oxide.It is revealed that the catalyst–support interaction between Ni_(3)Fe oxide and PANI support enhances the Ni–O covalency via the interfacial Ni–N bond,thus promoting the charge and mass transfer on Ni_(3)Fe oxide.Considering the excellent activity and stability,rechargeable Zn-air batteries with optimum Ni_(3)Fe oxide/PANI are assembled,delivering a low charge voltage of 1.95 V to cycle for 400 h at 10 mA cm^(-2).The regulation of the effect of catalyst–support interaction on catalytic activity provides new possibilities for the future design of highly efficient OER catalysts.展开更多
The microstructure evolution and deformation mechanism of a DZ125 superalloy during high-temperature creep were studied by means of microstructure observation and creep-property tests.The results show that at the init...The microstructure evolution and deformation mechanism of a DZ125 superalloy during high-temperature creep were studied by means of microstructure observation and creep-property tests.The results show that at the initial stage of high-temperature creep,two sets of dislocations with different Burgers vectors move and meet inγmatrix channels,and react to form a quadrilateral dislocation network.Andγ′phases with raft-like microstructure are generated after the formation of dislocation networks.As creep progresses,the quadrilateral dislocation network is gradually transformed into hexagonal and quadrilateral dislocation networks.During steady stage of creep,the superalloy undergoes deformation with the mechanism that a great number of dislocations slip and climb in the matrix across the raft-likeγ′phases.At the later stage of creep,the raft-likeγ′phases are sheared by dislocations at the breakage of dislocation networks,and then alternate slip occurs,which distorts and breaks the raft-likeγ′/γphases,resulting in the accumulation of micropores at the raft-likeγ′/γinterfaces and the formation of microcracks.As creep continues,the microcracks continue to expand until creep fracture occurs,which is the damage and fracture mechanism of the alloy at the later stage of creep at high temperature.展开更多
Anion-exchange membrane water electrolyzers(AEMWEs)for green hydrogen production have received intensive attention due to their feasibility of using earth-abundant NiFe-based catalysts.By introducing a third metal int...Anion-exchange membrane water electrolyzers(AEMWEs)for green hydrogen production have received intensive attention due to their feasibility of using earth-abundant NiFe-based catalysts.By introducing a third metal into NiFe-based catalysts to construct asymmetrical M-NiFe units,the d-orbital and electronic structures can be adjusted,which is an important strategy to achieve sufficient oxygen evolution reaction(OER)performance in AEMWEs.Herein,the ternary NiFeM(M:La,Mo)catalysts featured with distinct M-NiFe units and varying d-orbitals are reported in this work.Experimental and theoretical calculation results reveal that the doping of La leads to optimized hybridization between d orbital in NiFeM and 2p in oxygen,resulting in enhanced adsorption strength of oxygen intermediates,and reduced rate-determining step energy barrier,which is responsible for the enhanced OER performance.More critically,the obtained NiFeLa catalyst only requires 1.58 V to reach 1 A cm^(−2) in an anion exchange membrane electrolyzer and demonstrates excellent long-term stability of up to 600 h.展开更多
Transformation of urea and glycerol to glycerol carbonate is an environmental friendly and economical process.Catalysts play an indispensable role in the process.Although many catalysts have been developed,the perform...Transformation of urea and glycerol to glycerol carbonate is an environmental friendly and economical process.Catalysts play an indispensable role in the process.Although many catalysts have been developed,the performance of the catalysts still cannot meet the needs of industrialization.In this paper,research progress of the homogeneous and heterogeneous catalysts of the reaction over the past 20 years were reviewed systematically.According to the types and active centers of catalysts,the catalysts were classified systematically and analyzed in detail.The typical reaction mechanisms were also summarized.The research and development direction of catalysts is made more explicit through systematic classification and mechanism analysis.The article reveals more novel catalysts have been designed and used for the reaction,such as mixed metal oxides with special structures,solid wastes and non-metallic materials.This work summarized the current state of research and prospected possible routes for design of novel catalysts.It is hoped that this review can provide some references for developing efficient catalysts.展开更多
The current single-atom catalysts(SACs)for medicine still suffer from the limited active site density.Here,we develop a synthetic method capable of increasing both the metal loading and mass-specific activity of SACs ...The current single-atom catalysts(SACs)for medicine still suffer from the limited active site density.Here,we develop a synthetic method capable of increasing both the metal loading and mass-specific activity of SACs by exchanging zinc with iron.The constructed iron SACs(h^(3)-FNC)with a high metal loading of 6.27 wt%and an optimized adjacent Fe distance of~4 A exhibit excellent oxidase-like catalytic performance without significant activity decay after being stored for six months and promising antibacterial effects.Attractively,a“density effect”has been found at a high-enough metal doping amount,at which individual active sites become close enough to interact with each other and alter the electronic structure,resulting in significantly boosted intrinsic activity of single-atomic iron sites in h^(3)-FNCs by 2.3 times compared to low-and medium-loading SACs.Consequently,the overall catalytic activity of h^(3)-FNC is highly improved,with mass activity and metal mass-specific activity that are,respectively,66 and 315 times higher than those of commercial Pt/C.In addition,h^(3)-FNCs demonstrate efficiently enhanced capability in catalyzing oxygen reduction into superoxide anion(O_(2)·^(−))and glutathione(GSH)depletion.Both in vitro and in vivo assays demonstrate the superior antibacterial efficacy of h^(3)-FNCs in promoting wound healing.This work presents an intriguing activity-enhancement effect in catalysts and exhibits impressive therapeutic efficacy in combating bacterial infections.展开更多
Understanding the influence of HCl on the NH_(3)-selective catalytic reduction reaction mechanism is crucial for designing highly efficient denitrification catalysts.The formation of chlorate species on the surface of...Understanding the influence of HCl on the NH_(3)-selective catalytic reduction reaction mechanism is crucial for designing highly efficient denitrification catalysts.The formation of chlorate species on the surface of the synthesized SbCeO_(x)catalyst,induced by HCl,significantly enhances low-temperature activity,as evidenced by a 30%increase in NO conversion at 155℃.Furthermore,it improves N_(2)selectivity at high temperatures,with a notable 17%increase observed at 405℃.Both experimental results and density functional theory calculations confirm that chlorate species form at Ce sites.This formation facilitates the creation of oxygen vacancies,boosting the oxygen exchange capacity.It also increases NH_(3)adsorption at the Ce sites,promotes the formation of Sb-OH,and reduces competitive OH adsorption on these sites.Notably,compared with the reaction mechanism without HCl,the presence of chlorate species enhances NH_(3)adsorption and activation,which is vital for subsequent catalytic reactions.展开更多
Carbon nanotubes(CNTs)supported CoB and CoBSn catalysts were synthesized for hydrogen production via NaBH4 hydrolysis.The roles of Sn-promoter and the effect of CNTs treatment on CoB catalysts were evaluated and discu...Carbon nanotubes(CNTs)supported CoB and CoBSn catalysts were synthesized for hydrogen production via NaBH4 hydrolysis.The roles of Sn-promoter and the effect of CNTs treatment on CoB catalysts were evaluated and discussed.It is found that after the addition of Sn promoter,the specific surface area and the generation of active CoB phase are increased,while the oxidation treatment of CNTs results in more loading amounts of active components and enrichment of electron at active sites as well as large surface area.Consequently,the Sn-doped CoB catalysts supported on CNTs with oxidation treatment exhibits a significantly improved activity with a high H_(2)generation rate of 2640 mL/(min·g).Meanwhile,this catalyst shows a low activation energy of 43.7 kJ/mol and relatively high reusability.展开更多
By simplifying catalyst-product separation and reducing phosphorus waste,heterogeneous hydroformylation offers a more sustainable alternative to homogeneous processes.However,heterogeneous hydroformylation catalysts d...By simplifying catalyst-product separation and reducing phosphorus waste,heterogeneous hydroformylation offers a more sustainable alternative to homogeneous processes.However,heterogeneous hydroformylation catalysts developed thus far still suffer from the issues of much lower activity and metal leaching,which severely hinder their practical application.Here,we demonstrate that incorporating phosphorus(P)atoms into graphitic carbon nitride(PCN)supports facilitates charge transfer from Rh to the PCN support,thus largely enhancing electronic metal-support interactions(EMSIs).In the styrene hydroformylation reaction,the activity of Rh_(1)/PCN single-atom catalysts(SACs)with varying P contents exhibited a volcano-shaped relationship with P doping,where the Rh_(1)/PCN SAC with optimal P doping showed exceptional activity,approximately 5.8-and 3.3-fold greater than that of the Rh_(1)/g-C_(3)N_(4)SAC without P doping and the industrial homogeneous catalyst HRh(CO)(PPh_(3))_(3),respectively.In addition,the optimal Rh_(1)/PCN SAC catalyst also demonstrated largely enhanced multicycle stability without any visible metal aggregation owing to the increased EMSIs,which sharply differed from the severe metal aggregation of large nanoparticles on the Rh_(1)/g-C_(3)N_(4)SAC.Mechan-istic studies revealed that the enhanced catalytic performance could be attributed to electron-deficient Rh species,which reduced CO adsorption while simultaneously promoting alkene adsorption through increased EMSIs.These findings suggest that tuning EMSIs is an effective way to achieve SACs with high activity and durability.展开更多
Direct ethanol fuel cells(DEFCs)are a promising alternative to conventional energy sources,offering high energy density,environmental sustainability,and operational safety.Compared to methanol fuel cells,DEFCs exhibit...Direct ethanol fuel cells(DEFCs)are a promising alternative to conventional energy sources,offering high energy density,environmental sustainability,and operational safety.Compared to methanol fuel cells,DEFCs exhibit lower toxicity and a more mature preparation process.Unlike hydrogen fuel cells,DEFCs provide superior storage and transport feasibility,as well as cost-effectiveness,significantly enhancing their commercial viability.However,the stable C-C bond in ethanol creates a high activation energy barrier,often resulting in incomplete electrooxidation.Current commercial platinum(Pt)-and palladium(Pd)-based catalysts demonstrate low C-C bond cleavage efficiency(<7.5%),severely limiting DEFC energy output and power density.Furthermore,high catalyst costs and insufficient activity impede large-scale commercialization.Recent advances in DEFC anode catalyst design have focused on optimizing material composition and elucidating catalytic mechanisms.This review systematically examines developments in ethanol electrooxidation catalysts over the past five years,highlighting strategies to improve C1 pathway selectivity and C-C bond activation.Key approaches,such as alloying,nanostructure engineering,and interfacial synergy effects,are discussed alongside their mechanistic implications.Finally,we outline current challenges and future prospects for DEFC commercialization.展开更多
基金supported by the Natural Science Foundation of Shanxi Province(202203021221155)the Foundation of National Key Laboratory of High Efficiency and Low Carbon Utilization of Coal(J23-24-902)。
文摘With ongoing global warming and increasing energy demands,the CH_(4)-CO_(2)reforming reaction(dry reforming of methane,DRM)has garnered significant attention as a promising carbon capture and utilization technology.Nickel-based catalysts are renowned for their outstanding activity and selectivity in this process.The impact of metal-support interaction(MSI),on Ni-based catalyst performance has been extensively researched and debated recently.This paper reviews the recent research progress of MSI on Ni-based catalysts and their characterization and modulation strategies in catalytic reactions.From the perspective of MSI,the effects of different carriers(metal oxides,carbon materials and molecular sieves,etc.)are introduced on the dispersion and surface structure of Ni active metal particles,and the effect of MSI on the activity and stability of DRM reactions on Ni-based catalysts is discussed in detail.Future research should focus on better understanding and controlling MSI to improve the performance and durability of nickel-based catalysts in CH_(4)-CO_(2)reforming,advancing cleaner energy technologies.
文摘Photothermal catalytic methane dry reforming(DRM)technology can convert greenhouse gases(i.e.CH_(4)and CO_(2))into syngas(i.e.H_(2)and CO),providing more opportunities for reducing the greenhouse effect and achieving carbon neutrality.In the DRM field,Ni-based catalysts attract wide attention due to their low cost and high activity.However,the carbon deposition over Ni-based catalysts always leads to rapid deactivation,which is still a main challenge.To improve the long-term stability of Ni-based catalysts,this work proposes a carbon-atom-diffusion strategy under photothermal conditions and investigates its effect on a Zn-doped Ni-based photothermal catalyst(Ni_(3)Zn@CeO_(2)).The photothermal catalytic behavior of Ni_(3)Zn@CeO_(2)can maintain more than 70 h in DRM reaction.And the photocatalytic DRM activity of Ni_(3)Zn@CeO_(2)is 1.2 times higher than thermal catalytic activity.Density functional theory(DFT)calculation and experimental characterizations indicate that Ni_(3)Zn promotes the diffusion of carbon atoms into the Ni_(3)Zn to form the Ni_(3)ZnC0.7 phase with body-centered cubic(bcc)structure,thus inhibiting carbon deposition.Further,in-situ diffuse reflectance infrared Fourier transform(DRIFT)spectroscopy and DFT calculation prove Ni_(3)Zn@CeO_(2)benefits the CH_(4)activation and inhibits the carbon deposition during the DRM process.Through inducing carbon atoms diffusion within the Ni_(3)Zn lattice,this work provides a straightforward and feasible strategy for achieving efficient photothermal catalytic DRM and even other CH_(4)conversion implementations with long-term stability.
基金supported by the Fundamental Research Funds for the Central Universities(20822041H4082).
文摘Nickel-based catalysts have emerged as crucial components in alkaline oxygen evolution reactions(OER)due to their exceptional catalytic performance and unique structural properties.However,the understanding of their catalytic mechanisms remains incomplete.This review systematically explores the various types of Ni-based catalysts,including metal-organic frameworks(MOFs),perovskites,and layered double hydroxides(LDHs),while emphasizing their performance metrics.We critically assess the application of advanced in situ characterization techniques,such as in situ Raman spectroscopy and X-ray absorption spectroscopy(XAS),in elucidating the structural evolution and active species during the OER process.By addressing the interplay between catalyst structure and performance,this review aims to provide insights that drive future research efforts toward the optimization of Ni-based catalysts for sustainable hydrogen production.Key areas for potential research advancements are also identified.
基金financially supported by the National Natural Science Foundation of China(Nos.51602018 and 51902018)the Natural Science Foundation of Beijing Municipality(No.2154052)+3 种基金the China Postdoctoral Science Foundation(No.2014M560044)the Fundamental Research Funds for the Central Universities(No.FRF-MP-20-22)USTB Research Center for International People-to-people Exchange in Science,Technology and Civilization(No.2022KFYB007)Education and Teaching Reform Foundation at University of Science and Technology Beijing(Nos.2023JGC027,KC2022QYW06,and KC2022TS09)。
文摘S and Co co-doped carbon catalysts were prepared via pyrolysis of MOF-71 and thiourea mixtures at 800℃at a mass ratio of MOF-71 to thiourea of 1:0.1 to effectively activate peroxymonosulfate(PMS)for methylene blue(MB)degradation.The effects of two different mixing routes were identified on the MB degradation performance.Particularly,the catalyst obtained by the alcohol solvent evaporation(MOF-AEP)mixing route could degrade 95.60%MB(50 mg/L)within 4 min(degradation rate:K=0.78 min^(-1)),which was faster than that derived from the direct grinding method(MOF-DGP,80.97%,K=0.39 min^(-1)).X-ray photoelectron spectroscopy revealed that the Co-S content of MOF-AEP(43.39at%)was less than that of MOF-DGP(54.73at%),and the proportion of C-S-C in MOF-AEP(13.56at%)was higher than that of MOF-DGP(10.67at%).Density functional theory calculations revealed that the adsorption energy of Co for PMS was -2.94 eV when sulfur was doped as C-S-C on the carbon skeleton,which was higher than that when sulfur was doped next to cobalt in the form of Co-S bond(-2.86 eV).Thus,the C-S-C sites might provide more contributions to activate PMS compared with Co-S.Furthermore,the degradation parameters,including pH and MOF-AEP dosage,were investigated.Finally,radical quenching experiments and electron paramagnetic resonance(EPR)measurements revealed that ^(1)O_(2)might be the primary catalytic species,whereas·O~(2-)might be the secondary one in degrading MB.
基金the Canadian NRCan OERD Energy Innovation Programthe Natural Sciences and Engineering Research Council of Canada,and the Carbon Solution Program for their financial support.
文摘The pursuit of alternative fuel generation technologies has gained momentum due to the diminishing reserves of fossil fuels and global warming from increased CO_(2)emission.Among the proposed methods,the hydrogenation of CO_(2)to produce marketable carbon-based products like methanol and ethanol is a practical approach that offers great potential to reduce CO_(2)emissions.Although significant volumes of methanol are currently produced from CO_(2),developing highly efficient and stable catalysts is crucial for further enhancing conversion and selectivity,thereby reducing process costs.An in-depth examination of the differences and similarities in the reaction pathways for methanol and ethanol production highlights the key factors that drive C-C coupling.Identifying these factors guides us toward developing more effective catalysts for ethanol synthesis.In this paper,we explore how different catalysts,through the production of various intermediates,can initiate the synthesis of methanol or ethanol.The catalytic mechanisms proposed by spectroscopic techniques and theoretical calculations,including operando X-ray methods,FTIR analysis,and DFT calculations,are summarized and presented.The following discussion explores the structural properties and composition of catalysts that influence C-C coupling and optimize the conversion rate of CO_(2)into ethanol.Lastly,the review examines recent catalysts employed for selective methanol and ethanol production,focusing on single-atom catalysts.
文摘The efficient hydrogenolysis of esters to alkanes is the key protocol for producing advanced biofuels from renewable plant oils or fats.Due to the low reactivity of the carbonyl group in esters,a high reaction temperature(>250℃)is the prerequisite to ensure high conversion of esters.Here,we report a highly dispersed MoO_(x)-Ru/C bimetallic catalyst for the efficient hydrogenolysis of esters to alkanes under 150°C.The optimal catalyst exhibits>99%conversion of methyl stearate and 99%selectivity to diesel-range alkanes,reaching a high rate of up to 2.0 mmol gcat^(–1)h^(–1),5 times higher than that of Ru/C catalyst(MoO_(x)/C is inert).Integrated experimental and theoretical investigations attribute the high performance to the abundant MoO_(x)-Ru interfacial sites on the catalyst surface,which offers high activity for the C–O cleavage of esters.Furthermore,the dispersed MoO_(x)species significantly weaken the hydrocracking activity of the metallic Ru for C–C bonds,thus yielding alkane products without carbon loss.This study provides a facile and novel strategy for the design of high-performance heterogeneous catalysts for the hydrodeoxygenation of biomass-derived esters to alkane products.
文摘To improve the catalytic performance of La_(0.6)Sr_(0.4)Co_(0.2)Fe_(0.8)O_(3)(LSCF)towards carbon soot,we utilized the impregnation method to incorporate Ag into the prepared LSCF catalyst.We conducted a series of characterization tests and evaluated the soot catalytic activity of the composite catalyst by comparing it with the LaCoO_(3) group,LaFeO_(3) group,and catalyst-free group.The results indicate that the Ag-LSCF composite catalyst exhibits the highest soot catalytic activity,with the characteristic temperature values of 376.3,431.1,and 473.9℃at 10%,50%,and 90%carbon soot conversion,respectively.These values are 24.8,20.2,and 23.1℃lower than those of the LSCF group.This also shows that LSCF can improve the catalytic activity of soot after compounding with Ag,and reflects the necessity of using catalysts in soot combustion reaction.XPS characterization and BET test show that Ag-LSCF has more abundant surface-adsorbed oxygen species,larger specific surface area and pore volume than LSCF,which also proves that Ag-LSCF has higher soot catalytic activity.
基金Shenzhen Science and Technology Program(JSGG20220831092800001)。
文摘The microstructure of single crystal superalloy is relatively simple,consisting primarily ofγdendrites andγ/γ′eutectics.During the directional solidification process of Ni-based single crystal superalloys,withdrawal rate is a critical parameter affecting the spatial distribution ofγ/γ′eutectic along gravity direction.The results show that theγ/γ′eutectic fraction of the upper platform surface is always higher than that of the lower one,regardless of withdrawal rate.As the withdrawal rate decreases,there is a significant increase inγ/γ′eutectic fraction on the upper surface,while it decreases on the lower surface.The upward accumulation ofγ/γ′eutectic becomes more severe as the withdrawal rate decreases.It is also found that the percentage of Al+Ta is positively correlated with theγ/γ′eutectic fraction.Thermo-solute convection of Al and Ta solutes in the solidification front is the prime reason for the non-uniform distribution of eutectic.The non-uniform distribution ofγ/γ′eutectic cannot be eliminated even after subsequent solution heat treatment,resulting in excess eutectic on the upper surface and thus leading to the scrapping of the blade.
基金supported by the National Natural Science Foundation of China(No.21571062)the Program for Professor of Special Appointment(Eastern Scholar)at the Shanghai Institutions of Higher Learning to JGL,and the Fundamental Research Funds for the Central Universities(No.222201717003)。
文摘Exploiting non-precious metal catalysts with excellent oxygen reduction reaction(ORR)performance for energy devices is paramount essential for the green and sustainable society development.Herein,low-cost,high-performance biomass-derived ORR catalysts with an asymmetric Fe-N_(3)P configuration was prepared by a simple pyrolysis-etching technique,where carboxymethyl cellulose(CMC)was used as the carbon source,urea and 1,10-phenanthroline iron complex(FePhen)as additives,and Na_(3)PO_(4)as the phosphorus dopant and a pore-forming agent.The CMC-derived FeNPC catalyst displayed a large specific area(BET:1235 m^(2)g^(-1))with atomically dispersed Fe-N_(3)P active sites,which exhibited superior ORR activity and stability in alkaline solution(E_(1/2)=0.90 V vs.RHE)and Zn-air batteries(P_(max)=149 mW cm^(-2))to commercial Pt/C catalyst(E_(1/2)=0.87 V,P_(max)=118 mW cm^(-2))under similar experimental conditions.This work provides a feasible and costeffective route toward highly efficient ORR catalysts and their application to Zn-air batteries for energy conversion.
基金supported by the National Natural Science Foundation of China(Nos.22276182 and 22188102)the Natural Science Foundation of Fujian Province,China(No.2023J06048)the Youth Innovation Promotion Association of Chinese Academy of Sciences(No.2021303).
文摘NH_(3)-SCR(SCR:Selective catalytic reduction)is an effective technology for the de-NO_(x)process from both mobile and stationary pollution sources,and the most commonly used catalysts are the vanadia-based catalysts.An innovative V_(2)O_(5)-CeO_(2)/TaTiO_(x)catalyst for NO_(x)removal was prepared in this study.The influences of Ce and Ta in the V_(2)O_(5)-CeO_(2)/TaTiO_(x)catalyst on the SCR performance and physicochemical properties were investigated.The V_(2)O_(5)-CeO_(2)/TaTiO_(x)catalyst not only exhibited excellent SCR activity in a wide temperature window,but also presented strong resistance to H_(2)Oand SO_(2)at 275◦C.A series of characterizationmethods was used to study the catalysts,including H2-temperature programmed reduction,X-ray photoelectron spectroscopy,NH_(3)-temperature programmed desorption,etc.It was discovered that a synergistic effect existed between Ce and Ta species.The introduction of Ce and Ta enlarged the specific surface area,increased the amount of acid sites and the ratio of Ce^(3+),(V^(3+)+V^(4+))and Oα,and strengthened the redox capability which were related to synergistic effect between Ce and Ta species,significantly improving the NH_(3)-SCR activity.
基金Research Institute for Smart Energy(CDB2)the grant from the Research Institute for Advanced Manufacturing(CD8Z)+4 种基金the grant from the Carbon Neutrality Funding Scheme(WZ2R)at The Hong Kong Polytechnic Universitysupport from the Hong Kong Polytechnic University(CD9B,CDBZ and WZ4Q)the National Natural Science Foundation of China(22205187)Shenzhen Municipal Science and Technology Innovation Commission(JCYJ20230807140402006)Start-up Foundation for Introducing Talent of NUIST and Natural Science Foundation of Jiangsu Province of China(BK20230426).
文摘Catalyst–support interaction plays a crucial role in improving the catalytic activity of oxygen evolution reaction(OER).Here we modulate the catalyst–support interaction in polyaniline-supported Ni_(3)Fe oxide(Ni_(3)Fe oxide/PANI)with a robust hetero-interface,which significantly improves oxygen evolution activities with an overpotential of 270 mV at 10 mA cm^(-2)and specific activity of 2.08 mA cm_(ECSA)^(-2)at overpotential of 300 mV,3.84-fold that of Ni_(3)Fe oxide.It is revealed that the catalyst–support interaction between Ni_(3)Fe oxide and PANI support enhances the Ni–O covalency via the interfacial Ni–N bond,thus promoting the charge and mass transfer on Ni_(3)Fe oxide.Considering the excellent activity and stability,rechargeable Zn-air batteries with optimum Ni_(3)Fe oxide/PANI are assembled,delivering a low charge voltage of 1.95 V to cycle for 400 h at 10 mA cm^(-2).The regulation of the effect of catalyst–support interaction on catalytic activity provides new possibilities for the future design of highly efficient OER catalysts.
基金Guizhou Province Science and Technology Plan Project(QKHJC-ZK[2024]yiban604)Guizhou Province Science and Technology Plan Project(CXTD[2021]008)+4 种基金Bijie City Science and Technology Project(BKLH[2023]9)Technology Project of Bijie City(BKLH[2023]36)Natural Science Research Project of Guizhou Higher Education Institutions of China(QJJ[2023]047)Science and Technology Project of Guizhou Department of Transportation(2022-121-011)Sanmenxia City Science and Technology Bureau Science and Technology Research Project(2022002005)。
文摘The microstructure evolution and deformation mechanism of a DZ125 superalloy during high-temperature creep were studied by means of microstructure observation and creep-property tests.The results show that at the initial stage of high-temperature creep,two sets of dislocations with different Burgers vectors move and meet inγmatrix channels,and react to form a quadrilateral dislocation network.Andγ′phases with raft-like microstructure are generated after the formation of dislocation networks.As creep progresses,the quadrilateral dislocation network is gradually transformed into hexagonal and quadrilateral dislocation networks.During steady stage of creep,the superalloy undergoes deformation with the mechanism that a great number of dislocations slip and climb in the matrix across the raft-likeγ′phases.At the later stage of creep,the raft-likeγ′phases are sheared by dislocations at the breakage of dislocation networks,and then alternate slip occurs,which distorts and breaks the raft-likeγ′/γphases,resulting in the accumulation of micropores at the raft-likeγ′/γinterfaces and the formation of microcracks.As creep continues,the microcracks continue to expand until creep fracture occurs,which is the damage and fracture mechanism of the alloy at the later stage of creep at high temperature.
基金financially supported by the National Natural Science Foundation of China(22309137,22279095)Open subject project State Key Laboratory of New Textile Materials and Advanced Processing Technologies(FZ2023001).
文摘Anion-exchange membrane water electrolyzers(AEMWEs)for green hydrogen production have received intensive attention due to their feasibility of using earth-abundant NiFe-based catalysts.By introducing a third metal into NiFe-based catalysts to construct asymmetrical M-NiFe units,the d-orbital and electronic structures can be adjusted,which is an important strategy to achieve sufficient oxygen evolution reaction(OER)performance in AEMWEs.Herein,the ternary NiFeM(M:La,Mo)catalysts featured with distinct M-NiFe units and varying d-orbitals are reported in this work.Experimental and theoretical calculation results reveal that the doping of La leads to optimized hybridization between d orbital in NiFeM and 2p in oxygen,resulting in enhanced adsorption strength of oxygen intermediates,and reduced rate-determining step energy barrier,which is responsible for the enhanced OER performance.More critically,the obtained NiFeLa catalyst only requires 1.58 V to reach 1 A cm^(−2) in an anion exchange membrane electrolyzer and demonstrates excellent long-term stability of up to 600 h.
基金supported by Fundamental Research Program of Shanxi Province(202203021221303)。
文摘Transformation of urea and glycerol to glycerol carbonate is an environmental friendly and economical process.Catalysts play an indispensable role in the process.Although many catalysts have been developed,the performance of the catalysts still cannot meet the needs of industrialization.In this paper,research progress of the homogeneous and heterogeneous catalysts of the reaction over the past 20 years were reviewed systematically.According to the types and active centers of catalysts,the catalysts were classified systematically and analyzed in detail.The typical reaction mechanisms were also summarized.The research and development direction of catalysts is made more explicit through systematic classification and mechanism analysis.The article reveals more novel catalysts have been designed and used for the reaction,such as mixed metal oxides with special structures,solid wastes and non-metallic materials.This work summarized the current state of research and prospected possible routes for design of novel catalysts.It is hoped that this review can provide some references for developing efficient catalysts.
基金supported by the National Key Research and Development Program of China(Grant No.2022YFB3804500)the National Natural Science Foundation of China(Grant No.52202352,22335006)+4 种基金the Shanghai Municipal Health Commission(Grant No.20224Y0010)the CAMS Innovation Fund for Medical Sciences(Grant No.2021-I2M-5-012)the Basic Research Program of Shanghai Municipal Government(Grant No.21JC1406000)the Fundamental Research Funds for the Central Universities(Grant No.22120230237,2023-3-YB-11,22120220618)the Basic Research Program of Shanghai Municipal Government(23DX1900200).
文摘The current single-atom catalysts(SACs)for medicine still suffer from the limited active site density.Here,we develop a synthetic method capable of increasing both the metal loading and mass-specific activity of SACs by exchanging zinc with iron.The constructed iron SACs(h^(3)-FNC)with a high metal loading of 6.27 wt%and an optimized adjacent Fe distance of~4 A exhibit excellent oxidase-like catalytic performance without significant activity decay after being stored for six months and promising antibacterial effects.Attractively,a“density effect”has been found at a high-enough metal doping amount,at which individual active sites become close enough to interact with each other and alter the electronic structure,resulting in significantly boosted intrinsic activity of single-atomic iron sites in h^(3)-FNCs by 2.3 times compared to low-and medium-loading SACs.Consequently,the overall catalytic activity of h^(3)-FNC is highly improved,with mass activity and metal mass-specific activity that are,respectively,66 and 315 times higher than those of commercial Pt/C.In addition,h^(3)-FNCs demonstrate efficiently enhanced capability in catalyzing oxygen reduction into superoxide anion(O_(2)·^(−))and glutathione(GSH)depletion.Both in vitro and in vivo assays demonstrate the superior antibacterial efficacy of h^(3)-FNCs in promoting wound healing.This work presents an intriguing activity-enhancement effect in catalysts and exhibits impressive therapeutic efficacy in combating bacterial infections.
文摘Understanding the influence of HCl on the NH_(3)-selective catalytic reduction reaction mechanism is crucial for designing highly efficient denitrification catalysts.The formation of chlorate species on the surface of the synthesized SbCeO_(x)catalyst,induced by HCl,significantly enhances low-temperature activity,as evidenced by a 30%increase in NO conversion at 155℃.Furthermore,it improves N_(2)selectivity at high temperatures,with a notable 17%increase observed at 405℃.Both experimental results and density functional theory calculations confirm that chlorate species form at Ce sites.This formation facilitates the creation of oxygen vacancies,boosting the oxygen exchange capacity.It also increases NH_(3)adsorption at the Ce sites,promotes the formation of Sb-OH,and reduces competitive OH adsorption on these sites.Notably,compared with the reaction mechanism without HCl,the presence of chlorate species enhances NH_(3)adsorption and activation,which is vital for subsequent catalytic reactions.
基金supported by National Natural Science Foundation of China(22276144).
文摘Carbon nanotubes(CNTs)supported CoB and CoBSn catalysts were synthesized for hydrogen production via NaBH4 hydrolysis.The roles of Sn-promoter and the effect of CNTs treatment on CoB catalysts were evaluated and discussed.It is found that after the addition of Sn promoter,the specific surface area and the generation of active CoB phase are increased,while the oxidation treatment of CNTs results in more loading amounts of active components and enrichment of electron at active sites as well as large surface area.Consequently,the Sn-doped CoB catalysts supported on CNTs with oxidation treatment exhibits a significantly improved activity with a high H_(2)generation rate of 2640 mL/(min·g).Meanwhile,this catalyst shows a low activation energy of 43.7 kJ/mol and relatively high reusability.
基金supported by the Petrochemical Research Institute Foundation(21-CB-09-01)the National Natural Science Foundation of China(22302186,22025205)+1 种基金the China Postdoctoral Science Foundation(2022M713030,2023T160618)the Fundamental Research Funds for the Central Universities(WK2060000058,WK2060000038).
文摘By simplifying catalyst-product separation and reducing phosphorus waste,heterogeneous hydroformylation offers a more sustainable alternative to homogeneous processes.However,heterogeneous hydroformylation catalysts developed thus far still suffer from the issues of much lower activity and metal leaching,which severely hinder their practical application.Here,we demonstrate that incorporating phosphorus(P)atoms into graphitic carbon nitride(PCN)supports facilitates charge transfer from Rh to the PCN support,thus largely enhancing electronic metal-support interactions(EMSIs).In the styrene hydroformylation reaction,the activity of Rh_(1)/PCN single-atom catalysts(SACs)with varying P contents exhibited a volcano-shaped relationship with P doping,where the Rh_(1)/PCN SAC with optimal P doping showed exceptional activity,approximately 5.8-and 3.3-fold greater than that of the Rh_(1)/g-C_(3)N_(4)SAC without P doping and the industrial homogeneous catalyst HRh(CO)(PPh_(3))_(3),respectively.In addition,the optimal Rh_(1)/PCN SAC catalyst also demonstrated largely enhanced multicycle stability without any visible metal aggregation owing to the increased EMSIs,which sharply differed from the severe metal aggregation of large nanoparticles on the Rh_(1)/g-C_(3)N_(4)SAC.Mechan-istic studies revealed that the enhanced catalytic performance could be attributed to electron-deficient Rh species,which reduced CO adsorption while simultaneously promoting alkene adsorption through increased EMSIs.These findings suggest that tuning EMSIs is an effective way to achieve SACs with high activity and durability.
基金supported by the National Natural Science Foundation of China(22472023,22202037)the Jilin Province Science and Technology Development Program(20250102077JC)the Fundamental Research Funds for the Central Universities(2412024QD014,2412023QD019).
文摘Direct ethanol fuel cells(DEFCs)are a promising alternative to conventional energy sources,offering high energy density,environmental sustainability,and operational safety.Compared to methanol fuel cells,DEFCs exhibit lower toxicity and a more mature preparation process.Unlike hydrogen fuel cells,DEFCs provide superior storage and transport feasibility,as well as cost-effectiveness,significantly enhancing their commercial viability.However,the stable C-C bond in ethanol creates a high activation energy barrier,often resulting in incomplete electrooxidation.Current commercial platinum(Pt)-and palladium(Pd)-based catalysts demonstrate low C-C bond cleavage efficiency(<7.5%),severely limiting DEFC energy output and power density.Furthermore,high catalyst costs and insufficient activity impede large-scale commercialization.Recent advances in DEFC anode catalyst design have focused on optimizing material composition and elucidating catalytic mechanisms.This review systematically examines developments in ethanol electrooxidation catalysts over the past five years,highlighting strategies to improve C1 pathway selectivity and C-C bond activation.Key approaches,such as alloying,nanostructure engineering,and interfacial synergy effects,are discussed alongside their mechanistic implications.Finally,we outline current challenges and future prospects for DEFC commercialization.
