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
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
Structural regulation of Pd-based electrocatalytic hydrodechlorination(EHDC)catalyst for constructing high-efficient cathode materials with low noble metal content and high atom utilization is crucial but still challe...Structural regulation of Pd-based electrocatalytic hydrodechlorination(EHDC)catalyst for constructing high-efficient cathode materials with low noble metal content and high atom utilization is crucial but still challenging.Herein,a support electron inductive effect of Pd-Mn/Ni foam catalyst was proposed via in-situ Mn doping to optimize the electronic structure of the Ni foam(NF),which can inductive regulation of Pd for improving the EHDC performance.The mass activity and current efficiency of Pd-Mn/NF catalyst are 2.91 and 1.34 times superior to that of Pd/NF with 2,4-dichlorophenol as model compound,respectively.The Mn-doped interlayer optimized the electronic structure of Pd by bringing the d-state closer to the Fermi level than Pd on the NF surface,which optimizied the binding of EHDC intermediates.Additionally,the Mn-doped interlayer acted as a promoter for generating H∗and accelerating the EHDC reaction.This work presents a simple and effective regulation strategy for constructing high-efficient cathode catalyst for the EHDC of chlorinated organic compounds.展开更多
Carbon-supported mercury catalysts are extensivelyemployed in calcium carbide-based polyvinyl chloride(PVC)industries,but the usage of mercury-based catalysts can pose an environmental threat due to the release of mer...Carbon-supported mercury catalysts are extensivelyemployed in calcium carbide-based polyvinyl chloride(PVC)industries,but the usage of mercury-based catalysts can pose an environmental threat due to the release of mercury into the surrounding area during the operation period.In this study,a highly active and stable mercury-based catalyst was developed,utilizing the nitrogen atom of the support as the anchor site to enhance the interaction between active sites(HgCl_(2))and the carbon support(N-AC).Thermal loss rate testing and thermogravimetric analysis results demonstrate that,compared to commercial activated carbon,N-doped carbon can effectively increase the heat stability of HgCl_(2).The obtained mercury-based catalysts(HgCl_(2)/N-AC)exhibit significant catalytic performance,achieving 2.5 times the C2H2 conversion of conventional HgCl_(2)/AC catalysts.Experimental analysis combined with theoretical calculations reveals that,contrary to the Eley-Rideal(ER)mechanism of HgCl_(2)/AC,the HgCl_(2)/N-AC catalyst follows the Langmuir-Hinshelwood(LH)adsorption mechanism.The nitrogen sites and HgCl_(2) on the catalyst enhance the adsorption capabilities of the HCl and C2H2,thereby improving the catalytic performance.Based on the modification of the active center by these solid ligands,the loading amount of HgCl_(2) on the catalyst can be further reduced from the current 6.5%to 3%.Considering the absence of successful industrial applications for mercury-free catalysts,and based on the current annual consumption of commercial mercury chloride catalysts in the PVC industry,the widespread adoption of this technology could annually reduce the usage of chlorine mercury by 500 tons,making a notable contribution to mercury compliance,reduction,and emissions control in China.It also serves as a bridge between mercury-free and low-mercury catalysts.Moreover,this solid ligand technology can assist in the application research of mercury-free catalysts.展开更多
Maintaining high metal dispersion of supported metal catalysts to achieve superior reactivity under harsh conditions poses one of the main challenges for their practical applications.Constructing and regulating the st...Maintaining high metal dispersion of supported metal catalysts to achieve superior reactivity under harsh conditions poses one of the main challenges for their practical applications.Constructing and regulating the strong metal-support interactions(SMSI)by diverse methodologies has emerged as one of the promising approaches to fabricating robust supported metal catalysts.In this study,we report an L-ascorbic acid(AA)-inducing strategy to generate SMSI on a titania-supported gold(Au)catalyst after high-temperature treatment in an inert atmosphere(600℃,N_(2)).The AA-induced SMSI can efficiently stabilize Au nanoparticles(NPs)and preserve their catalytic performance.The detailed study reveals that the key to realizing this SMSI is the generation of oxygen vacancies within the TiO_(2) support induced by the adsorbed AA,which drives the formation of the Ti Oxpermeable layer onto the Au NPs.The strategy could be extended to TiO_(2)-supported Au catalysts with different crystal phases and platinum group metals,such as Pt,Pd,and Rh.This work offers a promising novel route to design stable and efficient supported noble metal catalysts by constructing SMSI using simple reducing organic adsorbent.展开更多
Herein,three supported catalysts,CuO/Al_(2)O_(3),CeO_(2)/Al_(2)O_(3),and CuO-CeO_(2)/Al_(2)O_(3),were synthesized by the convenient impregnation method to reveal the effect of CeO_(2)addition on catalytic performance ...Herein,three supported catalysts,CuO/Al_(2)O_(3),CeO_(2)/Al_(2)O_(3),and CuO-CeO_(2)/Al_(2)O_(3),were synthesized by the convenient impregnation method to reveal the effect of CeO_(2)addition on catalytic performance and reaction mechanism for toluene oxidation.Compared with CuO/Al_(2)O_(3),the T_(50)and T_(90)(the temperatures at 50%and 90%toluene conversion,respectively)of CuO-CeO_(2)/Al_(2)O_(3)were reduced by 33 and 39°C,respectively.N_(2)adsorptiondesorption experiment,XRD,SEM,EDS mapping,Raman,EPR,H_(2)-TPR,O_(2)-TPD,XPS,NH_(3)-TPD,Toluene-TPD,and in-situ DRIFTS were conducted to characterize these catalysts.The excellent catalytic performance of CuO-CeO_(2)/Al_(2)O_(3)could be attributed to its strong coppercerium interaction and high oxygen vacancies concentration.Moreover,in-situ DRIFTS proved that CuO-CeO_(2)/Al_(2)O_(3)promoted the conversion of toluene to benzoate and accelerated the deep degradation path of toluene.This work provided valuable insights into the development of efficient and economical catalysts for volatile organic compounds.展开更多
Volatile organic compounds(VOCs)exhausted from industrial processes are the major atmospheric pollutants,which could destroy the ecological environment and make hazards to human health seriously.Catalytic oxidation is...Volatile organic compounds(VOCs)exhausted from industrial processes are the major atmospheric pollutants,which could destroy the ecological environment and make hazards to human health seriously.Catalytic oxidation is regarded as the most competitive strategy for the efficient elimination of low-concentration VOCs.Supported noble metal catalysts are preferred catalysts due to their excellent low-temperature catalytic activity.To further lower the cost of catalysts,single atom catalysts(SAC)have been fabricated and extensively studied for application in VOCs oxidation due to their 100%atom-utilization efficiency and unique catalytic performance.In this review,we comprehensively summarize the recent advances in supported noble metal(e.g.,Pt,Pd,Au,and Ag)catalysts and SAC for VOCs oxidation since 2015.Firstly,this paper focuses on some important influencing factors that affect the activity of supported noble metal catalysts,including particle size,valence state and dispersion of noble metals,properties of the support,metal oxide/ion modification,preparation method,and pretreatment conditions of catalysts.Secondly,we briefly summarize the catalytic performance of SAC for typical VOCs.Finally,we conclude the key influencing factors and provide the prospects and challenges of VOCs oxidation.展开更多
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
Xylitol,one of the top twelve chemical building blocks,is commercially synthesized through the xylose hy-drogenation reaction using a metal catalyst.Biochar has emerged as an eco-efficient catalyst support material.In...Xylitol,one of the top twelve chemical building blocks,is commercially synthesized through the xylose hy-drogenation reaction using a metal catalyst.Biochar has emerged as an eco-efficient catalyst support material.In this study,biochar derived from corn stover(BCS)was first used as a metal catalyst support material for xylose hydrogenation into xylitol.The catalyst was prepared by carbonizing corn stover(CS),impregnating the resulting biochar with metal,and reducing the metal-impregnated BCS.The catalyst characteristics were comprehensively explored.The Ru/BCS catalyst was employed in xylose conversion to xylitol at different process temperatures(100-160℃),retention times(3-12 h),H_(2)pressures(2-5 MPa),and Ru contents(1-5%).The highest xylitol yield(87.0 wt.%)and selectivity(91.6%)were derived at 120℃ for 6 h under 4 MPa H_(2)using 5%Ru.Interestingly,the Ru/BCS catalyst showed high stability under the promising process condition.Additionally,xylitol production from hydrolysates enriched with CS xylose was subsequently explored.On the other hand,the catalyst characterization results revealed that the superior catalytic efficiency of 5Ru/BCS was mainly due to the metal nanoparticles embedded in the biochar.Additionally,BCS proved to be an outstanding support material for a bimetallic hydrogenation catalyst(Ru-Ni/BCS).Therefore,these results indicate that BCS can be a competitive support material for metal hydrogenation catalysts,enhancing environmental friendliness and potentially being employed in industrial-scale xylitol production.展开更多
Supported metal catalysts are the backbone of heterogeneous catalysis,playing a crucial role in the modern chemical industry.Metal-support interactions(MSIs)are known important in determining the catalytic performance...Supported metal catalysts are the backbone of heterogeneous catalysis,playing a crucial role in the modern chemical industry.Metal-support interactions(MSIs)are known important in determining the catalytic performance of supported metal catalysts.This is particularly true for single-atom catalysts(SACs)and pseudo-single-atom catalysts(pseudo-SACs),where all metal atoms are dispersed on,and interact directly with the support.Consequently,the MSI of SACs and pseudo-SACs are theoretically more sensitive to modulation compared to that of traditional nanoparticle catalysts.In this work,we experimentally demonstrated this hypothesis by an observed size-dependent MSI modulation.We fabricated CoFe_(2)O_(4) supported Pt pseudo-SACs and nanoparticle catalysts,followed by a straightforward water treatment process.It was found that the covalent strong metal-support interaction(CMSI)in pseudo-SACs can be weakened,leading to a significant activity improvement in methane combustion reaction.This finding aligns with our recent observation of CoFe_(2)O_(4) supported Pt SACs.By contrast,the MSI in Pt nanoparticle catalyst was barely affected by the water treatment,giving rise to almost unchanged catalytic performance.This work highlights the critical role of metal size in determining the MSI modulation,offering a novel strategy for tuning the catalytic performance of SACs and pseudo-SACs by fine-tuning their MSIs.展开更多
Developing cost-effective and high-performance catalyst systems for dry reforming of methane(DRM)is crucial for producing hydrogen(H_(2))sustainably.Herein,we investigate using iron(Fe)as a promoter and major alumina ...Developing cost-effective and high-performance catalyst systems for dry reforming of methane(DRM)is crucial for producing hydrogen(H_(2))sustainably.Herein,we investigate using iron(Fe)as a promoter and major alumina support in Ni-based catalysts to improve their DRM performance.The addition of iron as a promotor was found to add reducible iron species along with reducible NiO species,enhance the basicity and induce the deposition of oxidizable carbon.By incorporating 1 wt.%Fe into a 5Ni/10ZrAl catalyst,a higher CO_(2) interaction and formation of reducible"NiO-species having strong interaction with support"was observed,which led to an∼80%H_(2) yield in 420 min of Time on Stream(TOS).Further increasing the Fe content to 2 wt.%led to the formation of additional reducible iron oxide species and a noticeable rise in H_(2) yield up to 84%.Despite the severe weight loss on Fe-promoted catalysts,high H_(2) yield was maintained due to the proper balance between the rate of CH_(4) decomposition and the rate of carbon deposit diffusion.Finally,incorporating 3 wt.%Fe into the 5Ni/10ZrAl catalyst resulted in the highest CO_(2) interaction,wide presence of reducible NiO-species,minimumgraphitic deposit and an 87%H_(2) yield.Our findings suggest that ironpromoted zirconia-alumina-supported Ni catalysts can be a cheap and excellent catalytic system for H_(2) production via DRM.展开更多
High density polyethylene(HDPE)pyrolysis and in-line oxidative steam reforming was carried out in a two-step reaction system consisting of a conical spouted bed reactor and a fluidized bed reactor.Continuous plastic p...High density polyethylene(HDPE)pyrolysis and in-line oxidative steam reforming was carried out in a two-step reaction system consisting of a conical spouted bed reactor and a fluidized bed reactor.Continuous plastic pyrolysis was conducted at 550℃ and the volatiles formed were fed in-line to the oxidative steam reforming step(space-time 3.12 gcat min gHDPE−1;ER=0.2 and steam/plastic=3)operating at 700℃.The influence Ni based reforming catalyst support(Al_(2)O_(3),ZrO_(2),SiO_(2))and promoter(CeO_(2),La_(2)O_(3))have on HDPE pyrolysis volatiles conversion and H_(2) production was assessed.The catalysts were prepared by the wet impregnation and they were characterized by means of N_(2) adsorption-desorption,X-ray fluorescence,temperature-programmed reduction and X-ray powder diffraction.A preliminary study on coke deposition and the deterioration of catalysts properties was carried out,by analyzing the tested catalysts through temperature programmed oxidation of coke,transmission electron microscopy,and N_(2) adsorption-desorption.Among the supports tested,ZrO_(2) showed the best performance,attaining conversion and H_(2) production values of 92.2% and 12.8 wt%,respectively.Concerning promoted catalysts,they led to similar conversion values(around 90%),but significant differences were observed in H_(2) production.Thus,higher H_(2) productions were obtained on the Ni/La_(2)O_(3)-Al_(2)O_(3) catalyst(12.1 wt%)than on CeO_(2) promoted catalysts due to La_(2)O_(3) capability for enhancing water adsorption on the catalyst surface.展开更多
SAPO-5 zeolite supported RuMn was a highly efficient catalyst for the aqueous-phase selective hydrodeoxygenation of guaiacol to cyclohexanol.The optimal catalyst achieved a high cyclohexanol yield of 93.7%at full guai...SAPO-5 zeolite supported RuMn was a highly efficient catalyst for the aqueous-phase selective hydrodeoxygenation of guaiacol to cyclohexanol.The optimal catalyst achieved a high cyclohexanol yield of 93.7%at full guaiacol conversion under mild conditions,with a high TOF of 920 h^(-1).Moreover,the catalyst displayed remarkable performance for the hydrogenation of phenol to cyclohexanol,where a 100%yield of cyclohexanol was obtained at a phenol-to-Ru molar ratio of about 17900.In particular,the catalyst exhibited excellent recyclability and could be recycled for 20 times without obvious activity loss.The as-prepared RuMn/SAPO-5 catalyst exhibited higher performance than most of the reported Rubased catalysts.展开更多
Single-atom catalysts(SACs)are promising for oxygen reduction reaction(ORR)on account of their excellent catalytic activity and maximum utilization of atoms.However,due to the complicated preparation processes and exp...Single-atom catalysts(SACs)are promising for oxygen reduction reaction(ORR)on account of their excellent catalytic activity and maximum utilization of atoms.However,due to the complicated preparation processes and expensive reagents used,the cost of SACs is usually too high to put into practical application.The development of cost-effective and sustainable SACs remains a great challenge.Herein,a low-cost method employing biomass is designed to prepare efficient single-atom Fe-N-C catalysts(SA-Fe-N-C).Benefiting from the confinement effect of porous carbon support and the coordination effect of glucose,SA-Fe-N-C is derived from cheap flour by the two-step pyrolysis.Atomically dispersed Fe atoms exist in the form of Fe-N_(x),which acts as active sites for ORR.The catalyst shows outstanding activity with a half-wave potential(E_(1/2))of 0.86 V,which is better than that of Pt/C(0.84 V).Additionally,the catalyst also exhibits superior stability.The ORR catalyzed by SA-Fe-N-C proceeds via an efficient 4e transfer pathway.The high performance of SA-Fe-N-C also benefits from its porous structure,extremely high specific surface area(1450.1 m^(2)/g),and abundant micropores,which are conducive to increasing the density of active sites and fully exposing them.This work provides a cost-effective strategy to synthesize SACs from cheap biomass,achieving a balance between performance and cost.展开更多
Dual-atom catalysts(DACs),a natural extension of single-atom catalysts(SACs),have emerged as a prominent focal point in the field of heterogeneous catalysis,particularly in the context of chemical and energy conversio...Dual-atom catalysts(DACs),a natural extension of single-atom catalysts(SACs),have emerged as a prominent focal point in the field of heterogeneous catalysis,particularly in the context of chemical and energy conversion processes.Despite the fact that the catalytic activity of DACs is significantly modulated by the electronic structure of the catalyst,understanding how electron spin states are affected by variations in topology and geometric structure remains challenging and relatively unexplored.Herein,we propose the rational design of stable DACs composed of two iron atoms anchored on pristine graphdiyne(GDY),Fe_(2)-GDYn.A comprehensive and systematic investigation was carried out to elucidate the electronic configuration and spin states involved in the deliberate convergence towards the magnetic ground state,with the aim of uncovering the structure-spin relationship.Through an in-depth analysis of spin populations,electronic localization/delocalization,and the chemical bonding characteristics of the central metal atoms and the GDY skeleton,it was revealed that the spin coupling between the two iron atoms is preponderantly dictated by adjacent short-range Fe-Fe interactions.Conversely,spin decoupling can be attributed to the long-rangeπ-bond component within the linkage.Moreover,geometric and chemical bonding asymmetries were found to induce orbital and spin splitting in iron atoms possessing an electronic configuration of d8.These findings provide important insights into the relationship between topology and spin,thereby presenting novel strategies for the rational design of spin-manipulated DACs.展开更多
Two kinds of oxide-zeolite composite support,Ce-beta and Zr-beta were prepared by a simple wet impregnation method and adopted for the preparation of palladium-based catalysts for catalytic oxidation of methane.The Pd...Two kinds of oxide-zeolite composite support,Ce-beta and Zr-beta were prepared by a simple wet impregnation method and adopted for the preparation of palladium-based catalysts for catalytic oxidation of methane.The Pd/6.8Zr-beta catalyst showed superiormethane oxidation performance,achieving T_(50) and T90 of 417℃ and 451℃,respectively,together with robust hydrothermal stability.Kinetic analysis has shown that incorporating Zr into the catalyst significantly enhanced its efficiency,nearly tripling the turnover frequency(TOF)for methane combustion compared to the Pd/beta catalyst.This enhanced performance was attributed to the dispersion of Zr on the zeolite surface,which not only promoted the formation of active PdO sites but also helped maintain the high Pd^(2+)content via facilitating the oxygen migration during the reaction,thus improving both the catalyst’s activity and stability.In the Pd/8.6Ce-beta catalyst,doped CeO_(2) tended to aggregate in the zeolite’s pores,adversely affecting the catalyst’s efficiency.This aggregation promoted the formation of inactive Pd^(4+) species,a result of the enhanced metal-support interaction.This finding is critical for understanding the implications of dopant selection in the design of high-activity methane oxidation catalysts.展开更多
Wet flue gas desulfurization(WFGD)could effectively reduce sulfur dioxide emission.However,magnesium sulfite(MgSO_(3)),a by-product of desulfurization,was easy to result in secondary pollution.In this study,the solid ...Wet flue gas desulfurization(WFGD)could effectively reduce sulfur dioxide emission.However,magnesium sulfite(MgSO_(3)),a by-product of desulfurization,was easy to result in secondary pollution.In this study,the solid catalyst Co-Bent(bentonite supported cobalt)was prepared by blending method for MgSO_(3) oxidation with bentonite as the carrier and cobalt as the active component.At the calcination temperature of 550℃ and the Co loading level of 3 wt.%,the catalyst showed excellent catalytic performance for the oxidation of high concentration MgSO_(3) slurry,and the oxidation rate of MgSO_(3) was 0.13 mol/(L·h).The research indicated that the active component was uniformly distributed within porous structure of the catalyst as Co_(3)O_(4),which facilitated the oxidation of SO_(3)^(2-) catalyzed by Co_(3)O_(4).Kinetic researches indicated the oxidation rate of MgSO_(3) was influenced by the catalyst dosage,the reaction temperature,the solution pH,the airflow rate,and the SO_(3)^(2-) concentration.Additionally,after recycling experiments,the regenerated catalyst retained its high catalytic performance for the MgSO_(3) oxidation.The reaction mechanism for the catalytic oxidation of MgSO_(3) by Co-Bent catalyst was also proposed.The generation of active free radicals(OH·,SO_(4)^(-)·,SO_(3)^(-)·,SO_(5)^(-)·)accelerated the MgSO_(3) oxidation.These results provide theoretical support for the treatment of MgSO_(3) and the development of durable catalyst.展开更多
Pd-based catalysts have been extensively studied in the catalytic oxidation of methane,but their longterm stability and water resistance are unsatisfactory as the active sites are susceptible to water toxicity.The add...Pd-based catalysts have been extensively studied in the catalytic oxidation of methane,but their longterm stability and water resistance are unsatisfactory as the active sites are susceptible to water toxicity.The addition of Pt to Pd-based catalysts is found to be the most effective and promising method.However,distinct states of existence of Pt can affect the catalytic performance to different degrees,even negatively.Therefore,the impact mechanism of Pt on Pd-based catalysts needs to be further understood.In this work,A-site defective La_(0.9)AlO_(x)perovskite was used as a support,and the state of Pt in catalysts was regulated by adjusting the introducing sequence of Pd and Pt,It is found that only when Pt is introduced preferentially,the activity and water resistance of the bimetal can be improved.Combining a series of characterization results of the fresh catalysts,reduced catalysts,and the samples after reduction and use,it is found that the higher Pt^(2+)content in the catalyst is the main reason for promoting bimetallic properties,while more Pt0has an inhibitory effect.This work provides a new understanding of the promotion effect of Pt on Pd-Pt bimetal in the catalytic oxidation reaction of methane.展开更多
In this work,atomic Co catalysts are anchored on a three-dimensional(3D)interconnected g-C_(3)N_(4)(SACo-CN)through Co-N coordination,which exhibit efficient charge carrier transition and low activation energy barrier...In this work,atomic Co catalysts are anchored on a three-dimensional(3D)interconnected g-C_(3)N_(4)(SACo-CN)through Co-N coordination,which exhibit efficient charge carrier transition and low activation energy barriers for peroxymonosulfate(PMS).The incorporation of Co atoms extends the absorption spectrum and enhances the photoelectron-hole separation efficiency of the SACo-CN samples.The 3D interconnected structure,combined with the synergistic interplay between Co-N coordination and visible light irradiation,results in SACo-CN catalysts demonstrating excellent catalytic activity and stability for PMS activation.This leads to a degradation rate of 98.8%for oxytetracycline(OTC)within 30 min under visible light.The research proposes three potential mineralization pathways with eight intermediates,leading to a significant decrease in the toxicity of the intermediates.This work provides a facile and promising approach for the preparation of metal single atom catalysts with highly efficient PMS activation performance.展开更多
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.
基金supported by the National Natural Science Foundation of China(Nos.22178388 and 22108306)Taishan Scholars Program of Shandong Province(No.tsqn201909065)Chongqing Science and Technology Bureau(No.cstc2019jscx-gksb X0032).
文摘Structural regulation of Pd-based electrocatalytic hydrodechlorination(EHDC)catalyst for constructing high-efficient cathode materials with low noble metal content and high atom utilization is crucial but still challenging.Herein,a support electron inductive effect of Pd-Mn/Ni foam catalyst was proposed via in-situ Mn doping to optimize the electronic structure of the Ni foam(NF),which can inductive regulation of Pd for improving the EHDC performance.The mass activity and current efficiency of Pd-Mn/NF catalyst are 2.91 and 1.34 times superior to that of Pd/NF with 2,4-dichlorophenol as model compound,respectively.The Mn-doped interlayer optimized the electronic structure of Pd by bringing the d-state closer to the Fermi level than Pd on the NF surface,which optimizied the binding of EHDC intermediates.Additionally,the Mn-doped interlayer acted as a promoter for generating H∗and accelerating the EHDC reaction.This work presents a simple and effective regulation strategy for constructing high-efficient cathode catalyst for the EHDC of chlorinated organic compounds.
基金supported by the National Key Research and Development Program of China(2024YFC3907904).
文摘Carbon-supported mercury catalysts are extensivelyemployed in calcium carbide-based polyvinyl chloride(PVC)industries,but the usage of mercury-based catalysts can pose an environmental threat due to the release of mercury into the surrounding area during the operation period.In this study,a highly active and stable mercury-based catalyst was developed,utilizing the nitrogen atom of the support as the anchor site to enhance the interaction between active sites(HgCl_(2))and the carbon support(N-AC).Thermal loss rate testing and thermogravimetric analysis results demonstrate that,compared to commercial activated carbon,N-doped carbon can effectively increase the heat stability of HgCl_(2).The obtained mercury-based catalysts(HgCl_(2)/N-AC)exhibit significant catalytic performance,achieving 2.5 times the C2H2 conversion of conventional HgCl_(2)/AC catalysts.Experimental analysis combined with theoretical calculations reveals that,contrary to the Eley-Rideal(ER)mechanism of HgCl_(2)/AC,the HgCl_(2)/N-AC catalyst follows the Langmuir-Hinshelwood(LH)adsorption mechanism.The nitrogen sites and HgCl_(2) on the catalyst enhance the adsorption capabilities of the HCl and C2H2,thereby improving the catalytic performance.Based on the modification of the active center by these solid ligands,the loading amount of HgCl_(2) on the catalyst can be further reduced from the current 6.5%to 3%.Considering the absence of successful industrial applications for mercury-free catalysts,and based on the current annual consumption of commercial mercury chloride catalysts in the PVC industry,the widespread adoption of this technology could annually reduce the usage of chlorine mercury by 500 tons,making a notable contribution to mercury compliance,reduction,and emissions control in China.It also serves as a bridge between mercury-free and low-mercury catalysts.Moreover,this solid ligand technology can assist in the application research of mercury-free catalysts.
基金supported by the National Natural Science Foundation of China(NSFC)the Japan Society for the Promotion of Science(JSPS)under the Joint Research Program(Nos.NSFC21961142006 and JPJSJRP20191804)+3 种基金NSFC(Nos.U22A20394 and 22375200)the DICP.CAS-Cardiff Joint Research Units(No.121421ZYLH20230008)the International Partnership Program of Chinese Academy of Sciences(No.028GJHZ2023097GC)the China Postdoctoral Science Foundation(No.2022M723086)。
文摘Maintaining high metal dispersion of supported metal catalysts to achieve superior reactivity under harsh conditions poses one of the main challenges for their practical applications.Constructing and regulating the strong metal-support interactions(SMSI)by diverse methodologies has emerged as one of the promising approaches to fabricating robust supported metal catalysts.In this study,we report an L-ascorbic acid(AA)-inducing strategy to generate SMSI on a titania-supported gold(Au)catalyst after high-temperature treatment in an inert atmosphere(600℃,N_(2)).The AA-induced SMSI can efficiently stabilize Au nanoparticles(NPs)and preserve their catalytic performance.The detailed study reveals that the key to realizing this SMSI is the generation of oxygen vacancies within the TiO_(2) support induced by the adsorbed AA,which drives the formation of the Ti Oxpermeable layer onto the Au NPs.The strategy could be extended to TiO_(2)-supported Au catalysts with different crystal phases and platinum group metals,such as Pt,Pd,and Rh.This work offers a promising novel route to design stable and efficient supported noble metal catalysts by constructing SMSI using simple reducing organic adsorbent.
基金supported by the Science and Technology Program of Guangzhou,China(No.202002020020)the National Natural Science Foundation of China(Nos.51878292 and 42002035).
文摘Herein,three supported catalysts,CuO/Al_(2)O_(3),CeO_(2)/Al_(2)O_(3),and CuO-CeO_(2)/Al_(2)O_(3),were synthesized by the convenient impregnation method to reveal the effect of CeO_(2)addition on catalytic performance and reaction mechanism for toluene oxidation.Compared with CuO/Al_(2)O_(3),the T_(50)and T_(90)(the temperatures at 50%and 90%toluene conversion,respectively)of CuO-CeO_(2)/Al_(2)O_(3)were reduced by 33 and 39°C,respectively.N_(2)adsorptiondesorption experiment,XRD,SEM,EDS mapping,Raman,EPR,H_(2)-TPR,O_(2)-TPD,XPS,NH_(3)-TPD,Toluene-TPD,and in-situ DRIFTS were conducted to characterize these catalysts.The excellent catalytic performance of CuO-CeO_(2)/Al_(2)O_(3)could be attributed to its strong coppercerium interaction and high oxygen vacancies concentration.Moreover,in-situ DRIFTS proved that CuO-CeO_(2)/Al_(2)O_(3)promoted the conversion of toluene to benzoate and accelerated the deep degradation path of toluene.This work provided valuable insights into the development of efficient and economical catalysts for volatile organic compounds.
基金supported by Beijing Natural Science Foundation(No.8244060)China Postdoctoral Science Foundation(No.2023M730143)+3 种基金the National Natural Science Foundation of China(No.22425601)the National Key R&D Program of China(No.2023YFB3810801)Beijing Nova Program(No.20240484659)the R&D Program of Beijing Municipal Education Commission(No.KZ202210005011).
文摘Volatile organic compounds(VOCs)exhausted from industrial processes are the major atmospheric pollutants,which could destroy the ecological environment and make hazards to human health seriously.Catalytic oxidation is regarded as the most competitive strategy for the efficient elimination of low-concentration VOCs.Supported noble metal catalysts are preferred catalysts due to their excellent low-temperature catalytic activity.To further lower the cost of catalysts,single atom catalysts(SAC)have been fabricated and extensively studied for application in VOCs oxidation due to their 100%atom-utilization efficiency and unique catalytic performance.In this review,we comprehensively summarize the recent advances in supported noble metal(e.g.,Pt,Pd,Au,and Ag)catalysts and SAC for VOCs oxidation since 2015.Firstly,this paper focuses on some important influencing factors that affect the activity of supported noble metal catalysts,including particle size,valence state and dispersion of noble metals,properties of the support,metal oxide/ion modification,preparation method,and pretreatment conditions of catalysts.Secondly,we briefly summarize the catalytic performance of SAC for typical VOCs.Finally,we conclude the key influencing factors and provide the prospects and challenges of VOCs oxidation.
基金supported by 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 Specific League Funds from Mahidol University,and partially supported by Office of the Permanent Secretary,Ministry of Higher Education,Science,Research and Inno-vation(OPS MHESI),Thailand Science Research and Innovation(TSRI)(Grant No.RGNS 63-167).
文摘Xylitol,one of the top twelve chemical building blocks,is commercially synthesized through the xylose hy-drogenation reaction using a metal catalyst.Biochar has emerged as an eco-efficient catalyst support material.In this study,biochar derived from corn stover(BCS)was first used as a metal catalyst support material for xylose hydrogenation into xylitol.The catalyst was prepared by carbonizing corn stover(CS),impregnating the resulting biochar with metal,and reducing the metal-impregnated BCS.The catalyst characteristics were comprehensively explored.The Ru/BCS catalyst was employed in xylose conversion to xylitol at different process temperatures(100-160℃),retention times(3-12 h),H_(2)pressures(2-5 MPa),and Ru contents(1-5%).The highest xylitol yield(87.0 wt.%)and selectivity(91.6%)were derived at 120℃ for 6 h under 4 MPa H_(2)using 5%Ru.Interestingly,the Ru/BCS catalyst showed high stability under the promising process condition.Additionally,xylitol production from hydrolysates enriched with CS xylose was subsequently explored.On the other hand,the catalyst characterization results revealed that the superior catalytic efficiency of 5Ru/BCS was mainly due to the metal nanoparticles embedded in the biochar.Additionally,BCS proved to be an outstanding support material for a bimetallic hydrogenation catalyst(Ru-Ni/BCS).Therefore,these results indicate that BCS can be a competitive support material for metal hydrogenation catalysts,enhancing environmental friendliness and potentially being employed in industrial-scale xylitol production.
文摘Supported metal catalysts are the backbone of heterogeneous catalysis,playing a crucial role in the modern chemical industry.Metal-support interactions(MSIs)are known important in determining the catalytic performance of supported metal catalysts.This is particularly true for single-atom catalysts(SACs)and pseudo-single-atom catalysts(pseudo-SACs),where all metal atoms are dispersed on,and interact directly with the support.Consequently,the MSI of SACs and pseudo-SACs are theoretically more sensitive to modulation compared to that of traditional nanoparticle catalysts.In this work,we experimentally demonstrated this hypothesis by an observed size-dependent MSI modulation.We fabricated CoFe_(2)O_(4) supported Pt pseudo-SACs and nanoparticle catalysts,followed by a straightforward water treatment process.It was found that the covalent strong metal-support interaction(CMSI)in pseudo-SACs can be weakened,leading to a significant activity improvement in methane combustion reaction.This finding aligns with our recent observation of CoFe_(2)O_(4) supported Pt SACs.By contrast,the MSI in Pt nanoparticle catalyst was barely affected by the water treatment,giving rise to almost unchanged catalytic performance.This work highlights the critical role of metal size in determining the MSI modulation,offering a novel strategy for tuning the catalytic performance of SACs and pseudo-SACs by fine-tuning their MSIs.
基金The authors would like to extend their sincere appreciation to Researchers Supporting Project number (RSP2023R368)King Saud University,Riyadh,Saudi Arabia.RK,NP,VKS acknowledge Indus University,Ahmedabad,for supporting research.Dr.Ahmed I.Osman and Prof.David W.Rooney wish to acknowledge the support of The Bryden Centre project (Project ID VA5048)。
文摘Developing cost-effective and high-performance catalyst systems for dry reforming of methane(DRM)is crucial for producing hydrogen(H_(2))sustainably.Herein,we investigate using iron(Fe)as a promoter and major alumina support in Ni-based catalysts to improve their DRM performance.The addition of iron as a promotor was found to add reducible iron species along with reducible NiO species,enhance the basicity and induce the deposition of oxidizable carbon.By incorporating 1 wt.%Fe into a 5Ni/10ZrAl catalyst,a higher CO_(2) interaction and formation of reducible"NiO-species having strong interaction with support"was observed,which led to an∼80%H_(2) yield in 420 min of Time on Stream(TOS).Further increasing the Fe content to 2 wt.%led to the formation of additional reducible iron oxide species and a noticeable rise in H_(2) yield up to 84%.Despite the severe weight loss on Fe-promoted catalysts,high H_(2) yield was maintained due to the proper balance between the rate of CH_(4) decomposition and the rate of carbon deposit diffusion.Finally,incorporating 3 wt.%Fe into the 5Ni/10ZrAl catalyst resulted in the highest CO_(2) interaction,wide presence of reducible NiO-species,minimumgraphitic deposit and an 87%H_(2) yield.Our findings suggest that ironpromoted zirconia-alumina-supported Ni catalysts can be a cheap and excellent catalytic system for H_(2) production via DRM.
文摘High density polyethylene(HDPE)pyrolysis and in-line oxidative steam reforming was carried out in a two-step reaction system consisting of a conical spouted bed reactor and a fluidized bed reactor.Continuous plastic pyrolysis was conducted at 550℃ and the volatiles formed were fed in-line to the oxidative steam reforming step(space-time 3.12 gcat min gHDPE−1;ER=0.2 and steam/plastic=3)operating at 700℃.The influence Ni based reforming catalyst support(Al_(2)O_(3),ZrO_(2),SiO_(2))and promoter(CeO_(2),La_(2)O_(3))have on HDPE pyrolysis volatiles conversion and H_(2) production was assessed.The catalysts were prepared by the wet impregnation and they were characterized by means of N_(2) adsorption-desorption,X-ray fluorescence,temperature-programmed reduction and X-ray powder diffraction.A preliminary study on coke deposition and the deterioration of catalysts properties was carried out,by analyzing the tested catalysts through temperature programmed oxidation of coke,transmission electron microscopy,and N_(2) adsorption-desorption.Among the supports tested,ZrO_(2) showed the best performance,attaining conversion and H_(2) production values of 92.2% and 12.8 wt%,respectively.Concerning promoted catalysts,they led to similar conversion values(around 90%),but significant differences were observed in H_(2) production.Thus,higher H_(2) productions were obtained on the Ni/La_(2)O_(3)-Al_(2)O_(3) catalyst(12.1 wt%)than on CeO_(2) promoted catalysts due to La_(2)O_(3) capability for enhancing water adsorption on the catalyst surface.
基金supported by the Zhejiang Provincial Natural Science Foundation of China(LY23B060006 and LY18B060016).
文摘SAPO-5 zeolite supported RuMn was a highly efficient catalyst for the aqueous-phase selective hydrodeoxygenation of guaiacol to cyclohexanol.The optimal catalyst achieved a high cyclohexanol yield of 93.7%at full guaiacol conversion under mild conditions,with a high TOF of 920 h^(-1).Moreover,the catalyst displayed remarkable performance for the hydrogenation of phenol to cyclohexanol,where a 100%yield of cyclohexanol was obtained at a phenol-to-Ru molar ratio of about 17900.In particular,the catalyst exhibited excellent recyclability and could be recycled for 20 times without obvious activity loss.The as-prepared RuMn/SAPO-5 catalyst exhibited higher performance than most of the reported Rubased catalysts.
基金Project(52174338)supported by the National Natural Science Foundation of ChinaProjects(2022JJ20086,2021JJ30796)supported by the Natural Science Foundation of Hunan Province,China+1 种基金Project(2023CXQD005)supported by the Central South University Innovation-Driven Research Programme,ChinaProject(23B0841)supported by the Education Department of Hunan Provincial Government,China。
文摘Single-atom catalysts(SACs)are promising for oxygen reduction reaction(ORR)on account of their excellent catalytic activity and maximum utilization of atoms.However,due to the complicated preparation processes and expensive reagents used,the cost of SACs is usually too high to put into practical application.The development of cost-effective and sustainable SACs remains a great challenge.Herein,a low-cost method employing biomass is designed to prepare efficient single-atom Fe-N-C catalysts(SA-Fe-N-C).Benefiting from the confinement effect of porous carbon support and the coordination effect of glucose,SA-Fe-N-C is derived from cheap flour by the two-step pyrolysis.Atomically dispersed Fe atoms exist in the form of Fe-N_(x),which acts as active sites for ORR.The catalyst shows outstanding activity with a half-wave potential(E_(1/2))of 0.86 V,which is better than that of Pt/C(0.84 V).Additionally,the catalyst also exhibits superior stability.The ORR catalyzed by SA-Fe-N-C proceeds via an efficient 4e transfer pathway.The high performance of SA-Fe-N-C also benefits from its porous structure,extremely high specific surface area(1450.1 m^(2)/g),and abundant micropores,which are conducive to increasing the density of active sites and fully exposing them.This work provides a cost-effective strategy to synthesize SACs from cheap biomass,achieving a balance between performance and cost.
文摘Dual-atom catalysts(DACs),a natural extension of single-atom catalysts(SACs),have emerged as a prominent focal point in the field of heterogeneous catalysis,particularly in the context of chemical and energy conversion processes.Despite the fact that the catalytic activity of DACs is significantly modulated by the electronic structure of the catalyst,understanding how electron spin states are affected by variations in topology and geometric structure remains challenging and relatively unexplored.Herein,we propose the rational design of stable DACs composed of two iron atoms anchored on pristine graphdiyne(GDY),Fe_(2)-GDYn.A comprehensive and systematic investigation was carried out to elucidate the electronic configuration and spin states involved in the deliberate convergence towards the magnetic ground state,with the aim of uncovering the structure-spin relationship.Through an in-depth analysis of spin populations,electronic localization/delocalization,and the chemical bonding characteristics of the central metal atoms and the GDY skeleton,it was revealed that the spin coupling between the two iron atoms is preponderantly dictated by adjacent short-range Fe-Fe interactions.Conversely,spin decoupling can be attributed to the long-rangeπ-bond component within the linkage.Moreover,geometric and chemical bonding asymmetries were found to induce orbital and spin splitting in iron atoms possessing an electronic configuration of d8.These findings provide important insights into the relationship between topology and spin,thereby presenting novel strategies for the rational design of spin-manipulated DACs.
基金supported by the National Natural Science Foundation of China(Nos.U20B6004 and 22072179)。
文摘Two kinds of oxide-zeolite composite support,Ce-beta and Zr-beta were prepared by a simple wet impregnation method and adopted for the preparation of palladium-based catalysts for catalytic oxidation of methane.The Pd/6.8Zr-beta catalyst showed superiormethane oxidation performance,achieving T_(50) and T90 of 417℃ and 451℃,respectively,together with robust hydrothermal stability.Kinetic analysis has shown that incorporating Zr into the catalyst significantly enhanced its efficiency,nearly tripling the turnover frequency(TOF)for methane combustion compared to the Pd/beta catalyst.This enhanced performance was attributed to the dispersion of Zr on the zeolite surface,which not only promoted the formation of active PdO sites but also helped maintain the high Pd^(2+)content via facilitating the oxygen migration during the reaction,thus improving both the catalyst’s activity and stability.In the Pd/8.6Ce-beta catalyst,doped CeO_(2) tended to aggregate in the zeolite’s pores,adversely affecting the catalyst’s efficiency.This aggregation promoted the formation of inactive Pd^(4+) species,a result of the enhanced metal-support interaction.This finding is critical for understanding the implications of dopant selection in the design of high-activity methane oxidation catalysts.
基金supported by the State Key Laboratory of Urban Water Resource and Environment,Harbin Institute of Technology (No. 2022TS10)the Taishan Industrial Experts Programthe Natural Science Foundation of Shandong Province of China (No. ZR2023ME212).
文摘Wet flue gas desulfurization(WFGD)could effectively reduce sulfur dioxide emission.However,magnesium sulfite(MgSO_(3)),a by-product of desulfurization,was easy to result in secondary pollution.In this study,the solid catalyst Co-Bent(bentonite supported cobalt)was prepared by blending method for MgSO_(3) oxidation with bentonite as the carrier and cobalt as the active component.At the calcination temperature of 550℃ and the Co loading level of 3 wt.%,the catalyst showed excellent catalytic performance for the oxidation of high concentration MgSO_(3) slurry,and the oxidation rate of MgSO_(3) was 0.13 mol/(L·h).The research indicated that the active component was uniformly distributed within porous structure of the catalyst as Co_(3)O_(4),which facilitated the oxidation of SO_(3)^(2-) catalyzed by Co_(3)O_(4).Kinetic researches indicated the oxidation rate of MgSO_(3) was influenced by the catalyst dosage,the reaction temperature,the solution pH,the airflow rate,and the SO_(3)^(2-) concentration.Additionally,after recycling experiments,the regenerated catalyst retained its high catalytic performance for the MgSO_(3) oxidation.The reaction mechanism for the catalytic oxidation of MgSO_(3) by Co-Bent catalyst was also proposed.The generation of active free radicals(OH·,SO_(4)^(-)·,SO_(3)^(-)·,SO_(5)^(-)·)accelerated the MgSO_(3) oxidation.These results provide theoretical support for the treatment of MgSO_(3) and the development of durable catalyst.
基金Project supported by the National Key Research and Development Program(2022YFB3504200)National Natrual Science Foundation of China(22376061,21922602,22076047,U21A20326)+1 种基金Shanghai Science and Technology Innovation Action Plan(20dz1204200)Fundamental Re search Funds for the Central Universities。
文摘Pd-based catalysts have been extensively studied in the catalytic oxidation of methane,but their longterm stability and water resistance are unsatisfactory as the active sites are susceptible to water toxicity.The addition of Pt to Pd-based catalysts is found to be the most effective and promising method.However,distinct states of existence of Pt can affect the catalytic performance to different degrees,even negatively.Therefore,the impact mechanism of Pt on Pd-based catalysts needs to be further understood.In this work,A-site defective La_(0.9)AlO_(x)perovskite was used as a support,and the state of Pt in catalysts was regulated by adjusting the introducing sequence of Pd and Pt,It is found that only when Pt is introduced preferentially,the activity and water resistance of the bimetal can be improved.Combining a series of characterization results of the fresh catalysts,reduced catalysts,and the samples after reduction and use,it is found that the higher Pt^(2+)content in the catalyst is the main reason for promoting bimetallic properties,while more Pt0has an inhibitory effect.This work provides a new understanding of the promotion effect of Pt on Pd-Pt bimetal in the catalytic oxidation reaction of methane.
基金financial support from the National Natural Science Foundation of China(Nos.22276159,J2224005)the Key research project plan for higher education institutions of Henan province(No.24ZX009)+1 种基金the Development Program for Key Young Teachers in Colleges and Universities of Henan Province(No.2020GGJS146)the Starting Research Fund of Xinxiang Medical University(No.XYBSKYZZ201911)。
文摘In this work,atomic Co catalysts are anchored on a three-dimensional(3D)interconnected g-C_(3)N_(4)(SACo-CN)through Co-N coordination,which exhibit efficient charge carrier transition and low activation energy barriers for peroxymonosulfate(PMS).The incorporation of Co atoms extends the absorption spectrum and enhances the photoelectron-hole separation efficiency of the SACo-CN samples.The 3D interconnected structure,combined with the synergistic interplay between Co-N coordination and visible light irradiation,results in SACo-CN catalysts demonstrating excellent catalytic activity and stability for PMS activation.This leads to a degradation rate of 98.8%for oxytetracycline(OTC)within 30 min under visible light.The research proposes three potential mineralization pathways with eight intermediates,leading to a significant decrease in the toxicity of the intermediates.This work provides a facile and promising approach for the preparation of metal single atom catalysts with highly efficient PMS activation performance.
