Refractory organic pollutants in water threaten human health and environmental safety,and advanced oxidation processes (AOPs) are effective for the degradation of these pollutants.Catalysts play vital role in AOPs,and...Refractory organic pollutants in water threaten human health and environmental safety,and advanced oxidation processes (AOPs) are effective for the degradation of these pollutants.Catalysts play vital role in AOPs,and Ce-based catalysts have exhibited excellent performance.Recently,the development and application of Ce-based catalysts in various AOPs have been reported.Our study conducts the first review in this rapid growing field.This paper clarifies the variety and properties of Ce-based catalysts.Their applications in different AOP systems (catalytic ozonation,photodegradation,Fenton-like reactions,sulfate radicalbased AOPs,and catalytic sonochemistry) are discussed.Different Ce-based catalysts suit different reaction systems and produce different active radicals.Finally,future research directions of Ce-based catalysts in AOP systems are suggested.展开更多
The development of solid frustrated Lewis pairs(FLPs)catalysts with porous structures is a promising strategy for advancing green hydrogenation technologies and has garnered significant attention.Leveraging the divers...The development of solid frustrated Lewis pairs(FLPs)catalysts with porous structures is a promising strategy for advancing green hydrogenation technologies and has garnered significant attention.Leveraging the diverse oxidation states and structural tunability of cerium-based metal-organic frameworks(Ce-MOFs),this study employed a competitive coordination strategy utilizing a single carboxylate functional group ligand to construct a series of MOF-808-X(X=-NH_(2),-OH,-Br,and-NO_(2))featuring rich solid-state FLPs for hydrogenation of unsaturated olefins.The-X functional group serves as a microenvironment,enhancing hydrogenation activity by modulating the electronic properties and acid-base characteristics of the FLP sites.The unique redox properties of elemental cerium facilitate the exposure of unsaturated Ce sites(Ce-CUS,Lewis acid(LA))and adjacent Ce-OH(Lewis base(LB))sites within the MOFs,generating abundant solid-state FLP(Ce-CUS/Ce-OH)sites.Experimental results demonstrate that Ce-CUS and Ce-OH interact with theσandσ^(*)orbitals of H-H,and this"push-pull"synergy promotes heterolytic cleavage of the H-H bond.The lone pair electrons of the electron-donating functional group are transmitted through the molecular backbone to the LB site,thereby increasing its strength and reducing the activation energy required for H_(2)heterolytic cleavage.Notably,at 100℃and 2 MPa H_(2),MOF-808-NH_(2)achieves complete conversion of styrene and dicyclopentadiene,significantly outperforming MOF-808.Based on in-situ analysis and density functional theory calculations,a plausible reaction mechanism is proposed.This research enriches the theoretical framework for unsaturated olefin hydrogenation catalysts and contributes to the development of efficient catalytic systems.展开更多
The construction of frustrated Lewis acid-base pairs(FLPs)in porous systems is very important for the field of industrial hydrogenation catalysis,but there is still a great challenge.Based on the Ce^(3+)/Ce^(4+)redox ...The construction of frustrated Lewis acid-base pairs(FLPs)in porous systems is very important for the field of industrial hydrogenation catalysis,but there is still a great challenge.Based on the Ce^(3+)/Ce^(4+)redox pairs and abundant defects in porous Ce-based metal-organic frameworks(Ce-MOFs),FLP sites consisting of ligand-defective Ce sites(Lewis acid,LA)and neighboring terminal O sites(Lewis base,LB)were constructed in situ by a simple vacuum thermal activation method in lamellar Ce-UiO-66-F.Defects/oxygen vacancies in the Ce-MOFs structure result in the difference in the electron cloud density between Ce and O,which is suitable for H-H hetero-cleavage and H-transfer in the dicyclopentadiene(DCPD)hydrogenation process.Particularly,Ce-UiO-66-F-200 achieved 96.9%conversion of DCPD and 97.8%selectivity of 8,9-dihydrodicyclopentadiene(8,9-DHDCPD)at 100℃ under 2MPa H2 for 10 h,which is 9.4 times higher than 10.2%conversion of DCPD over the unactivated Ce-UiO-66-F.This research promotes the understanding of solid MOFs-based porous FLPs for H_(2) activation,and encourages the in-depth investigation of surface solid FLPs to the whole material FLPs.展开更多
The three-way catalyst(TWC),as a promising approach to control automobile exhaust emission,has been widely studied and applied.However,it still suffers from the high light-off temperature and poor stability.Herein,we ...The three-way catalyst(TWC),as a promising approach to control automobile exhaust emission,has been widely studied and applied.However,it still suffers from the high light-off temperature and poor stability.Herein,we synthesized a multicomponent catalyst Rh/Cu-CeSn by using Cu metal doping to modify the Ce-based solid solution,which exhibited good TWC catalytic performance:the light-off temperatures for CO,NO,and C_(3)H_(6)conversion are 172℃,266℃,and 193℃,respectively.Moreover,the catalyst still maintained good activity after 12 h of the continuous reaction under high-temperature conditions.The experiments and mechanism studies reveal that due to the redox pair Cu^(+)/Cu^(2+),the Cu incorporation can effectively inhibit the Rh transition to the oxidation state and greatly enhance the catalytic activity and stability.This work provides a viable strategy for precise characteristic modulation of composite oxide supports during the fabrication of noble metal-based catalysts,which significantly reduces environmental pollution from energy applications.展开更多
Green hydrogen from water splitting has emerged as a critical energy vector with the potential to spearhead the global transition to a fossil fuel-independent society.The field of catalysis has been revolutionized by ...Green hydrogen from water splitting has emerged as a critical energy vector with the potential to spearhead the global transition to a fossil fuel-independent society.The field of catalysis has been revolutionized by single-atom catalysts(SACs),which exhibit unique and intricate interactions between atomically dispersed metal atoms and their supports.Recently,bimetallic SACs(bimSACs)have garnered significant attention for leveraging the synergistic functions of two metal ions coordinated on appropriately designed supports.BimSACs offer an avenue for rich metal–metal and metal–support cooperativity,potentially addressing current limitations of SACs in effectively furnishing transformations which involve synchronous proton–electron exchanges,substrate activation with reversible redox cycles,simultaneous multi-electron transfer,regulation of spin states,tuning of electronic properties,and cyclic transition states with low activation energies.This review aims to encapsulate the growing advancements in bimSACs,with an emphasis on their pivotal role in hydrogen generation via water splitting.We subsequently delve into advanced experimental methodologies for the elaborate characterization of SACs,elucidate their electronic properties,and discuss their local coordination environment.Overall,we present comprehensive discussion on the deployment of bimSACs in both hydrogen evolution reaction and oxygen evolution reaction,the two half-reactions of the water electrolysis process.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
Ni-based catalysts are widely applied in the hydrodeoxygenation of lignin derivatives via C-O cleavage for the production of cycloalkanes.However,they often have difficulty in achieving high activity under mild condit...Ni-based catalysts are widely applied in the hydrodeoxygenation of lignin derivatives via C-O cleavage for the production of cycloalkanes.However,they often have difficulty in achieving high activity under mild conditions and exhibit relatively poor stability,and rare studies focus on the cleavage of the stubborn interunit C-C linkages.To address this issue,we developed a Ni@AlPO_(4)/Al_(2)O_(3)catalyst in which the surface of Ni nanoparticles was decorated by AlPO_(4)species,demonstrating excellent catalytic activity and stability in the C-C and C-O cleavages.In the hydrodeoxygenation of guaiacol,this catalyst afforded99.1%conversion and 92.9%yield of cyclohexane under 1 MPa H_(2)at 230℃ for 2 h.More important,this catalyst maintained unchanged performance even after 6 runs with the conversion controlled at about50%,Mecha nistic investigations revealed that the moderate surface coverage of AlPO_(4)on Ni with the formation of Ni^(δ+)-AlPO_(4)interface significantly facilitated the conversion of methoxycyclohexanol and cyclohexanol to cyclohexane,whereas,excess coverage would also block the access to Ni site.Moreover,Ni@AlPO_(4)/Al_(2)O_(3)demonstrated broad applicability in the C-O cleavage of various typical lignin monomers and dimers into cycloalkanes.To our delight,this catalyst also displayed pretty good activity even in the simultaneous cleavage of C-C linkages and C-O bonds for the lignin-derived C-C dimers,achieving cycloalkanes as final products.As a consequence,a 27.1 wt%yield of monocycloalkanes was obtained in the depolymerization of poplar lignin with both C-C and C-O cleavages.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
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
Novel hydrogen storage materials have propelled progress in hydrogen storage technologies.Magnesium hydride(MgH_(2))is a highly promising candidate.Nevertheless,several drawbacks,including the need for elevated therma...Novel hydrogen storage materials have propelled progress in hydrogen storage technologies.Magnesium hydride(MgH_(2))is a highly promising candidate.Nevertheless,several drawbacks,including the need for elevated thermal conditions,sluggish dehydrogena-tion kinetics,and high thermodynamic stability,limit its practical application.One effective method of addressing these challenges is cata-lyst doping,which effectively boosts the hydrogen storage capability of Mg-based materials.Herein,we review recent advancements in catalyst-doped MgH_(2) composites,with particular focus on multicomponent and high-entropy catalysts.Structure-property relationships and catalytic mechanisms in these doping strategies are also summarized.Finally,based on existing challenges,we discuss future research directions for the development of Mg-based hydrogen storage systems.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
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
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
Low-concentration coal mine methane(LC-CMM),which is predominantly composed of methane,serves as a clean and low-carbon energy resource with significant potential for utilization.Utilizing LC-CMM as fuel for solid oxi...Low-concentration coal mine methane(LC-CMM),which is predominantly composed of methane,serves as a clean and low-carbon energy resource with significant potential for utilization.Utilizing LC-CMM as fuel for solid oxide fuel cells(SOFCs)represents an efficient and promising strategy for its effective utilization.However,direct application in Ni-based anodes induces carbon deposition,which severely degrades cell performance.Herein,a medium-entropy oxide Sr_(2)FeNi_(0.1)Cr_(0.3)Mn_(0.3)Mo_(0.3)O_(6−δ)(SFNCMM)was developed as an anode internal reforming catalyst.Following reduction treatment,FeNi_(3) nano-alloy particles precipitate on the surface of the material,thereby significantly enhancing its catalytic activity for LC-CMM reforming process.The catalyst achieved a methane conversion rate of 53.3%,demonstrating excellent catalytic performance.Electrochemical evaluations revealed that SFNCMM-Gd_(0.1)Ce_(0.9)O_(2−δ)(GDC)with a weight ratio of 7:3 exhibited superior electrochemical performance when employed as the anodic catalytic layer.With H_(2) and LC-CMM as fuels,the single cell achieved maximum power densities of 1467.32 and 1116.97 mW·cm^(−2) at 800℃,respectively,with corresponding polarization impedances of 0.17 and 1.35Ω·cm^(2).Furthermore,the single cell maintained stable operation for over 100 h under LC-CMM fueling without significant carbon deposition,confirming its robust resistance to carbon formation.These results underscore the potential of medium-entropy oxides as highly effective catalytic layers for mitigating carbon deposition in SOFCs.展开更多
A multifunctional porous organic polymer of POP-Nixantphos-PPh_(3)-PhSO_(3)Na was prepared by free radical tricopolymerization.Further loading of Pd(OAc)2 led to the catalyst of Pd/POP-Nixantphos-PPh_(3)-PhSO_(3)Na.In...A multifunctional porous organic polymer of POP-Nixantphos-PPh_(3)-PhSO_(3)Na was prepared by free radical tricopolymerization.Further loading of Pd(OAc)2 led to the catalyst of Pd/POP-Nixantphos-PPh_(3)-PhSO_(3)Na.In this catalyst,Nixantphos ligand moieties were employed to enhance the catalytic hydrocarboxylation activity of palladium.Additionally,PPh_(3)ligand moieties were utilized to construct a porous framework of catalyst that facilitated the dispersion of Pd nanoparticles as well as the diffusion of reactants and products.Furthermore,the incorporation of PhSO_(3)Na moieties improved the hydrophilicity of the support.With H_(2)O as the reaction solvent,under the initial CO pressure of 0.1 MPa,Pd/POP-Nixantphos-PPh3-PhSO3Na-catalyzed hydrocarboxylation of alkynes to afford the correspondingα,β-unsaturated carboxylic acids in good yields(76%~96%).Various alkynes,such as diaromatic alkynes,arylalkyl alkynes and dialkyl alkynes,worked well in the process.Additionally,the catalyst showed excellent recyclability with no significant yield loss over five cycles.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
基金supported by National Water Pollution Control and Treatment Science and Technology Major Project (No.2018ZX07110003)the National Natural Science Foundation of China (No.51779068)。
文摘Refractory organic pollutants in water threaten human health and environmental safety,and advanced oxidation processes (AOPs) are effective for the degradation of these pollutants.Catalysts play vital role in AOPs,and Ce-based catalysts have exhibited excellent performance.Recently,the development and application of Ce-based catalysts in various AOPs have been reported.Our study conducts the first review in this rapid growing field.This paper clarifies the variety and properties of Ce-based catalysts.Their applications in different AOP systems (catalytic ozonation,photodegradation,Fenton-like reactions,sulfate radicalbased AOPs,and catalytic sonochemistry) are discussed.Different Ce-based catalysts suit different reaction systems and produce different active radicals.Finally,future research directions of Ce-based catalysts in AOP systems are suggested.
文摘The development of solid frustrated Lewis pairs(FLPs)catalysts with porous structures is a promising strategy for advancing green hydrogenation technologies and has garnered significant attention.Leveraging the diverse oxidation states and structural tunability of cerium-based metal-organic frameworks(Ce-MOFs),this study employed a competitive coordination strategy utilizing a single carboxylate functional group ligand to construct a series of MOF-808-X(X=-NH_(2),-OH,-Br,and-NO_(2))featuring rich solid-state FLPs for hydrogenation of unsaturated olefins.The-X functional group serves as a microenvironment,enhancing hydrogenation activity by modulating the electronic properties and acid-base characteristics of the FLP sites.The unique redox properties of elemental cerium facilitate the exposure of unsaturated Ce sites(Ce-CUS,Lewis acid(LA))and adjacent Ce-OH(Lewis base(LB))sites within the MOFs,generating abundant solid-state FLP(Ce-CUS/Ce-OH)sites.Experimental results demonstrate that Ce-CUS and Ce-OH interact with theσandσ^(*)orbitals of H-H,and this"push-pull"synergy promotes heterolytic cleavage of the H-H bond.The lone pair electrons of the electron-donating functional group are transmitted through the molecular backbone to the LB site,thereby increasing its strength and reducing the activation energy required for H_(2)heterolytic cleavage.Notably,at 100℃and 2 MPa H_(2),MOF-808-NH_(2)achieves complete conversion of styrene and dicyclopentadiene,significantly outperforming MOF-808.Based on in-situ analysis and density functional theory calculations,a plausible reaction mechanism is proposed.This research enriches the theoretical framework for unsaturated olefin hydrogenation catalysts and contributes to the development of efficient catalytic systems.
基金supported by the National Key Research and Development Program of China(No.2021YFB3500700)the National Natural Science Foundation of China(No.51972024)+1 种基金Natural Science Foundation of Guangdong Province(No.2022A1515010185)Fundamental Research Funds for the Central Universities(No.FRFEYIT-23-07).
文摘The construction of frustrated Lewis acid-base pairs(FLPs)in porous systems is very important for the field of industrial hydrogenation catalysis,but there is still a great challenge.Based on the Ce^(3+)/Ce^(4+)redox pairs and abundant defects in porous Ce-based metal-organic frameworks(Ce-MOFs),FLP sites consisting of ligand-defective Ce sites(Lewis acid,LA)and neighboring terminal O sites(Lewis base,LB)were constructed in situ by a simple vacuum thermal activation method in lamellar Ce-UiO-66-F.Defects/oxygen vacancies in the Ce-MOFs structure result in the difference in the electron cloud density between Ce and O,which is suitable for H-H hetero-cleavage and H-transfer in the dicyclopentadiene(DCPD)hydrogenation process.Particularly,Ce-UiO-66-F-200 achieved 96.9%conversion of DCPD and 97.8%selectivity of 8,9-dihydrodicyclopentadiene(8,9-DHDCPD)at 100℃ under 2MPa H2 for 10 h,which is 9.4 times higher than 10.2%conversion of DCPD over the unactivated Ce-UiO-66-F.This research promotes the understanding of solid MOFs-based porous FLPs for H_(2) activation,and encourages the in-depth investigation of surface solid FLPs to the whole material FLPs.
基金supported by the financial aid from National Science and Technology Major Project of China(No.2020YFE0204500)National Natural Science Foundation of China(Nos.22020102003,22025506 and 11975301)Youth Innovation Promotion Association of the Chinese Academy of Sciences(No.2020286)。
文摘The three-way catalyst(TWC),as a promising approach to control automobile exhaust emission,has been widely studied and applied.However,it still suffers from the high light-off temperature and poor stability.Herein,we synthesized a multicomponent catalyst Rh/Cu-CeSn by using Cu metal doping to modify the Ce-based solid solution,which exhibited good TWC catalytic performance:the light-off temperatures for CO,NO,and C_(3)H_(6)conversion are 172℃,266℃,and 193℃,respectively.Moreover,the catalyst still maintained good activity after 12 h of the continuous reaction under high-temperature conditions.The experiments and mechanism studies reveal that due to the redox pair Cu^(+)/Cu^(2+),the Cu incorporation can effectively inhibit the Rh transition to the oxidation state and greatly enhance the catalytic activity and stability.This work provides a viable strategy for precise characteristic modulation of composite oxide supports during the fabrication of noble metal-based catalysts,which significantly reduces environmental pollution from energy applications.
基金support from the Czech Science Foundation,project EXPRO,No 19-27454Xsupport by the European Union under the REFRESH—Research Excellence For Region Sustainability and High-tech Industries project number CZ.10.03.01/00/22_003/0000048 via the Operational Programme Just Transition from the Ministry of the Environment of the Czech Republic+1 种基金Horizon Europe project EIC Pathfinder Open 2023,“GlaS-A-Fuels”(No.101130717)supported from ERDF/ESF,project TECHSCALE No.CZ.02.01.01/00/22_008/0004587).
文摘Green hydrogen from water splitting has emerged as a critical energy vector with the potential to spearhead the global transition to a fossil fuel-independent society.The field of catalysis has been revolutionized by single-atom catalysts(SACs),which exhibit unique and intricate interactions between atomically dispersed metal atoms and their supports.Recently,bimetallic SACs(bimSACs)have garnered significant attention for leveraging the synergistic functions of two metal ions coordinated on appropriately designed supports.BimSACs offer an avenue for rich metal–metal and metal–support cooperativity,potentially addressing current limitations of SACs in effectively furnishing transformations which involve synchronous proton–electron exchanges,substrate activation with reversible redox cycles,simultaneous multi-electron transfer,regulation of spin states,tuning of electronic properties,and cyclic transition states with low activation energies.This review aims to encapsulate the growing advancements in bimSACs,with an emphasis on their pivotal role in hydrogen generation via water splitting.We subsequently delve into advanced experimental methodologies for the elaborate characterization of SACs,elucidate their electronic properties,and discuss their local coordination environment.Overall,we present comprehensive discussion on the deployment of bimSACs in both hydrogen evolution reaction and oxygen evolution reaction,the two half-reactions of the water electrolysis process.
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.
基金supported by National Natural Science Foundation of China(22178258,22308254)China Postdoctoral Science Foundation(2023M742593,2024T170642)+1 种基金Independent Innova-tion Fund of Tianjin University(2024XQM-0021)the Open Fund of the Key Laboratory of Functional Molecular Solids(FMS2023006)。
文摘Ni-based catalysts are widely applied in the hydrodeoxygenation of lignin derivatives via C-O cleavage for the production of cycloalkanes.However,they often have difficulty in achieving high activity under mild conditions and exhibit relatively poor stability,and rare studies focus on the cleavage of the stubborn interunit C-C linkages.To address this issue,we developed a Ni@AlPO_(4)/Al_(2)O_(3)catalyst in which the surface of Ni nanoparticles was decorated by AlPO_(4)species,demonstrating excellent catalytic activity and stability in the C-C and C-O cleavages.In the hydrodeoxygenation of guaiacol,this catalyst afforded99.1%conversion and 92.9%yield of cyclohexane under 1 MPa H_(2)at 230℃ for 2 h.More important,this catalyst maintained unchanged performance even after 6 runs with the conversion controlled at about50%,Mecha nistic investigations revealed that the moderate surface coverage of AlPO_(4)on Ni with the formation of Ni^(δ+)-AlPO_(4)interface significantly facilitated the conversion of methoxycyclohexanol and cyclohexanol to cyclohexane,whereas,excess coverage would also block the access to Ni site.Moreover,Ni@AlPO_(4)/Al_(2)O_(3)demonstrated broad applicability in the C-O cleavage of various typical lignin monomers and dimers into cycloalkanes.To our delight,this catalyst also displayed pretty good activity even in the simultaneous cleavage of C-C linkages and C-O bonds for the lignin-derived C-C dimers,achieving cycloalkanes as final products.As a consequence,a 27.1 wt%yield of monocycloalkanes was obtained in the depolymerization of poplar lignin with both C-C and C-O cleavages.
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.
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.
基金financially supported by the National Key Research and Development Program of China (No. 2021YFB4000604)the National Natural Science Foundation of China (No. 52271220)+2 种基金the 111 Project (No. B12015)the Fundamental Research Funds for the Central UniversitiesHaihe Laboratory of Sustainable Chemical Transformations, Guangxi Collaborative Innovation Centre of Structure and Property for New Energy and Materials, Science Research and Technology Development Project of Guilin (No. 20210102-4)
文摘Novel hydrogen storage materials have propelled progress in hydrogen storage technologies.Magnesium hydride(MgH_(2))is a highly promising candidate.Nevertheless,several drawbacks,including the need for elevated thermal conditions,sluggish dehydrogena-tion kinetics,and high thermodynamic stability,limit its practical application.One effective method of addressing these challenges is cata-lyst doping,which effectively boosts the hydrogen storage capability of Mg-based materials.Herein,we review recent advancements in catalyst-doped MgH_(2) composites,with particular focus on multicomponent and high-entropy catalysts.Structure-property relationships and catalytic mechanisms in these doping strategies are also summarized.Finally,based on existing challenges,we discuss future research directions for the development of Mg-based hydrogen storage systems.
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.
基金supported by the National Key R&D Program of China(No.2024YFB4007501)the Natural Science Foundation of Jiangsu Province(No.BK20240109)the project of Jiangsu Key Laboratory for Clean Utilization of Carbon Resources(No.BM2024007).
文摘Low-concentration coal mine methane(LC-CMM),which is predominantly composed of methane,serves as a clean and low-carbon energy resource with significant potential for utilization.Utilizing LC-CMM as fuel for solid oxide fuel cells(SOFCs)represents an efficient and promising strategy for its effective utilization.However,direct application in Ni-based anodes induces carbon deposition,which severely degrades cell performance.Herein,a medium-entropy oxide Sr_(2)FeNi_(0.1)Cr_(0.3)Mn_(0.3)Mo_(0.3)O_(6−δ)(SFNCMM)was developed as an anode internal reforming catalyst.Following reduction treatment,FeNi_(3) nano-alloy particles precipitate on the surface of the material,thereby significantly enhancing its catalytic activity for LC-CMM reforming process.The catalyst achieved a methane conversion rate of 53.3%,demonstrating excellent catalytic performance.Electrochemical evaluations revealed that SFNCMM-Gd_(0.1)Ce_(0.9)O_(2−δ)(GDC)with a weight ratio of 7:3 exhibited superior electrochemical performance when employed as the anodic catalytic layer.With H_(2) and LC-CMM as fuels,the single cell achieved maximum power densities of 1467.32 and 1116.97 mW·cm^(−2) at 800℃,respectively,with corresponding polarization impedances of 0.17 and 1.35Ω·cm^(2).Furthermore,the single cell maintained stable operation for over 100 h under LC-CMM fueling without significant carbon deposition,confirming its robust resistance to carbon formation.These results underscore the potential of medium-entropy oxides as highly effective catalytic layers for mitigating carbon deposition in SOFCs.
文摘A multifunctional porous organic polymer of POP-Nixantphos-PPh_(3)-PhSO_(3)Na was prepared by free radical tricopolymerization.Further loading of Pd(OAc)2 led to the catalyst of Pd/POP-Nixantphos-PPh_(3)-PhSO_(3)Na.In this catalyst,Nixantphos ligand moieties were employed to enhance the catalytic hydrocarboxylation activity of palladium.Additionally,PPh_(3)ligand moieties were utilized to construct a porous framework of catalyst that facilitated the dispersion of Pd nanoparticles as well as the diffusion of reactants and products.Furthermore,the incorporation of PhSO_(3)Na moieties improved the hydrophilicity of the support.With H_(2)O as the reaction solvent,under the initial CO pressure of 0.1 MPa,Pd/POP-Nixantphos-PPh3-PhSO3Na-catalyzed hydrocarboxylation of alkynes to afford the correspondingα,β-unsaturated carboxylic acids in good yields(76%~96%).Various alkynes,such as diaromatic alkynes,arylalkyl alkynes and dialkyl alkynes,worked well in the process.Additionally,the catalyst showed excellent recyclability with no significant yield loss over five cycles.
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.
