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
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
Supported metal oxide catalysts have garnered significantattention in oxidative dehydrogenation(ODH)due to their tunable metal-support interactions.The pentacoordinate Al^(3+)(Al_(V)^(3+))in γ-Al_(2)O_(3)supports pla...Supported metal oxide catalysts have garnered significantattention in oxidative dehydrogenation(ODH)due to their tunable metal-support interactions.The pentacoordinate Al^(3+)(Al_(V)^(3+))in γ-Al_(2)O_(3)supports plays a pivotal role in modulating metal-support interaction.This study investigates oxalic acid(OA)pretreatment as a defect engineering strategy to enhance the catalytic performance of CeO_(2)/γ-Al_(2)O_(3)in cyclohexane ODH.Through integrated characterization(XRD,27Al MAS NMR,H_(2)-TPR,TPRO,MS,XPS)and catalytic testing,we demonstrate that optimal OA treatment(1:10 ratio)eliminates 100%of surface Al_(V)^(3+)defects while enhancing CeO_(2)crystallinity and interfacial oxygen mobility.The removal of Al_(V)^(3+)species restructures metal-support interaction,accelerating interfacial oxygen mobility.In oxidation dehydrogenation of cyclohexane,the modified CeO_(2)/γ-Al_(2)O_(3)achieves 29%of cyclohexane conversion with stable selectivity of 49%cyclohexene.These findingsprovide an initial framework for designing redox-active catalysts via targeted support modificationin CeO_(2)/γ-Al_(2)O_(3)systems,emphasizing the relationship between metal-support interaction and oxygen mobility.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
Metal-support interactions and hydrogen spillover effects in heterogeneous catalysts play a crucial role in aromatic hydrogenation reactions;however,these effects are limited by the metal dispersion on the catalyst an...Metal-support interactions and hydrogen spillover effects in heterogeneous catalysts play a crucial role in aromatic hydrogenation reactions;however,these effects are limited by the metal dispersion on the catalyst and the number of acceptable H*receptors.This study prepares highly dispersed Ni nanoparticles(NPs)catalysts on a Beta substrate via precursor structure topology transformation.In contrast to traditional support materials,the coordination and electronic structure changes between the Ni NPs and the support were achieved,further optimizing the active interface sites and enhancing hydrogen activation and hydrogenation performance.Additionally,the-OH groups at the strong acid sites in zeolite effectively intensified the hydrogen spillover effect as receptors for H^(*)migration and anchoring,accelerating the hydrogenation rate of aromatic rings.Under solvent-free conditions,this catalyst was used for the hydrogenation reaction of aromatic-rich oils,directly producing a C_(8)-C_(14)branched cycloalkanes mixture with an aromatic conversion rate of>99%.The cycloalkanes mixture produced by this method features high density(0.92 g/mL)and a low freezing point(<-60℃),making it suitable for use as high-density aviation fuel or as an additive to enhance the volumetric heat value of conventional aviation fuels in practical applications.展开更多
Alkaline earth-metal titanates ATiO_(3)(A=Ca,Sr,and Ba)with a perovskite-type structure were used as supports for Ru-based catalysts to produce CO_(x)-free H_(2)via NH_(3)decomposition.The effects of alkalineearth met...Alkaline earth-metal titanates ATiO_(3)(A=Ca,Sr,and Ba)with a perovskite-type structure were used as supports for Ru-based catalysts to produce CO_(x)-free H_(2)via NH_(3)decomposition.The effects of alkalineearth metals on the physicochemical characteristics and catalytic activities of Ru/ATiO_(3)for NH_(3)decomposition were investigated using various techniques.The order of Ru/ATiO_(3)for NH_(3)conversion is Ru/BaTiO_(3)>Ru/SrTiO_(3)>Ru/CaTiO_(3)>Ru/TiO_(2)at the identical conditions,with the Ru/BaTiO_(3)catalyst demonstrating the highest NH_(3)conversion of 77.8%at 450℃and a gas hourly space velocity of 30,000 mL/gcat/h,which is 8.7,2.1,and 1.3 times of that over Ru/TiO_(2),Ru/CaTiO_(3),and Ru/SrTiO_(3),respectively.The formation of the ATiO_(3)phase can enrich the concentration of basic sites and oxygen vacancies compared with TiO_(2),which can induce the presence of strong metal-support interaction(SMSI)through the formation of Ru-O-Ti bonds.This SMSI effect increased the dispersion and electron density of Ru nano-particles on ATiO_(3)supports,and the electron-rich Ru nano-particles could weaken the chemisorptive strength of N_(2)and H_(2)on the Ru/ATiO_(3)catalysts,thereby promoting the reaction rate for NH_(3)decomposition.展开更多
This study explores the adsorption and reac-tion of methanol on the CeO_(2)(111)and Ni/CeO_(2)(111)surfaces,highlighting the es-sential role of metal-support interaction in methanol decomposition by a synergistic ap-p...This study explores the adsorption and reac-tion of methanol on the CeO_(2)(111)and Ni/CeO_(2)(111)surfaces,highlighting the es-sential role of metal-support interaction in methanol decomposition by a synergistic ap-proach encompassing synchrotron radiation photoemission spectroscopy,X-ray photo-electron spectroscopy,infrared reflection and absorption spectroscopy,and temperature-programmed desorption.Our findings reveal that Ni deposited on the CeO_(2)(111)surface,followed by annealing to 700 K,leads to the formation of Ce-O-Ni mixed oxide as the dominant phase.The Ni^(2+)species facilitate the methoxy decomposition into CO and H_(2)within 300-430 K,with a small amount of formalde-hyde also forming at the edge sites of ceria.Additionally,some methoxy adsorbed on the bare CeO_(2)surface migrates to the Ce-O-Ni mixed oxide,where they decompose into CO and H_(2)at 500-600 K,accompanied by a portion of the methoxy interacting with ceria to generate formaldehyde.Upon exposure to methanol at 500 K,the Ni^(2+)species are reduced to metallic Ni^(0),alongside the formation of coke and Ni_(3)C,ultimately resulting in catalyst deactivation.However,reintroducing O_(2)reactivates these sites by oxidizing metallic Ni^(0)and Ni_(3)C species.This study highlights the pivotal role of metal-support interaction in promoting oxygen trans-fer from ceria to Ni,thereby enhancing methoxy decomposition and significantly improving the performance of Ni-based catalysts for methanol decomposition into CO and H_(2).展开更多
Photoelectrochemical(PEC)water splitting using bismuth vanadate(BiVO_(4))as a photoanode shows promise for renewable hydrogen production.Depositing cobalt phosphate(CoPi)on the BiVO_(4)photoanode as an oxygen evolutio...Photoelectrochemical(PEC)water splitting using bismuth vanadate(BiVO_(4))as a photoanode shows promise for renewable hydrogen production.Depositing cobalt phosphate(CoPi)on the BiVO_(4)photoanode as an oxygen evolution cocatalyst(OEC)is an effective method to improve the PEC performance.However,the CoPi/BiVO_(4)photoanode still faces challenges in terms of slow interface photogenerated carrier transport.Herein,we utilize the advantage of the classical strong metal-support interaction(SMSI)between Au and BiVO_(4)to prepare a CoPi/Au/BiVO_(4)(SMSI-CoPi/Au/BiVO_(4))photoanode.Due to the formation of SMSI,the accumulated electrons at the interface of CoPi/Au induce the accelerated extraction of photogenerated holes.Meanwhile,the active electron density of CoPi is increased,leading to improved water oxidation kinetic.As a result,the SMSI-CoPi/Au/BiVO_(4)photoanode exhibits a high photocurrent density of 5.01 m A cm^(-2)at 1.23 V versus the reversible hydrogen electrode and an applied bias photon-to-current efficiency of 1.78%.This work highlights a novel approach to enhance hole transfer and water oxidation kinetics of OEC/BiVO_(4)composite photoanodes,offering the great potential of using SMSI for PEC water splitting.展开更多
Metal-supported solid oxide fuel cells(MS-SOFCs)have recently gained significant attention as an advanced SOFC technology,owing to their excellent mechanical robustness,ease of handling,and high manufacturability.The ...Metal-supported solid oxide fuel cells(MS-SOFCs)have recently gained significant attention as an advanced SOFC technology,owing to their excellent mechanical robustness,ease of handling,and high manufacturability.The use of metal substrates enables improved durability under thermal and redox cycling,and allows for thinner electrolyte layers,contributing to enhanced performance.However,their fabrication typically requires high-temperature sintering to ensure adequate material properties and adhesion,as most SOFC components are ceramic.These high-temperature processes can lead to undesirable effects,including metal support oxidation,chemical side reactions,and accelerated particle growth,which degrade cell performance.This study introduces an ultra-fast sintering approach for MS-SOFC fabrication by directly integrating stainless-steel metal supports with nickel-yttria-stabilized zirconia(Ni-YSZ)composite anode active layers.The application of flash light sintering-an innovative ultra-fast technique-effectively suppressed Ni catalyst particle growth,expanding the electrochemical reaction area while minimizing material diffusion between the metal support and anode layer.As a result,the fabricated cells achieved a stable open-circuit voltage(OCV)exceeding 1 V at 650℃ and a peak power density of 412 mW/cm^(2),representing an approximately 426.3% performance improvement over conventionally sintered cells.This research presents a transformative strategy for SOFC manufacturing,addressing the challenges of conventional long-duration heat treatments and demonstrating significant potential for advancing energy conversion technologies.展开更多
To develop efficient catalysts for ambient carbon monoxide(CO)oxidation is significant for indoor air purification and also for many industrial applications.In this work,the catalytic activity for CO oxidation were en...To develop efficient catalysts for ambient carbon monoxide(CO)oxidation is significant for indoor air purification and also for many industrial applications.In this work,the catalytic activity for CO oxidation were enhanced by tuning the metal-support interaction of Ru/CeO_(2)catalysts.A series of Ru/CeO_(2)catalysts were synthesized by an impregnation method with calcination at 100,200,400 and 600℃,respectively,to regulate the Ru-CeO_(2)interaction.We discovered that low temperature calcination(100℃)induced more Ru-O-Ce bonds and stronger Ru-CeO_(2)interaction,while high temperature calcination(≥400℃)caused the agglomeration of Ru species with more Ru-O-Ru bonds and weaker Ru-CeO_(2)interaction,resulting in the lower redox capacity of these catalysts,as well as lower catalytic activity for CO oxidation.Only calcination at moderate 200℃ can induce the moderate interaction between Ru species and CeO_(2)support,which can keep the high dispersion of RuO_(x)species with the high redox capacity,thus leading to complete elimination of 500 ppm CO at room temperature on Ru/Ce-200 catalyst.展开更多
A novel Cu-t-ZrO_(2)catalyst with enhanced electronic metal-support interaction(EMSI)is designed for efficient electrocatalytic conversion of nitrate(NO_(3^(-)))to ammonia(NH_(3)),achieving a remarkable Faradaic effic...A novel Cu-t-ZrO_(2)catalyst with enhanced electronic metal-support interaction(EMSI)is designed for efficient electrocatalytic conversion of nitrate(NO_(3^(-)))to ammonia(NH_(3)),achieving a remarkable Faradaic efficiency and yield rate of 97.54%and 33.64 mg h^(-1)mg_(cat)^(-1),respectively.Electrons are more likely to be transferred from Cu to t-ZrO_(2)at the electron-rich interface due to the lower work function,which promotes the formation of highly active Cu species and facilitates NO_(3^(-))adsorption,ensuring selective conversion into NH_(3).展开更多
The electron localization is considered as a promising approach to optimize electromagnetic waves(EMW)dissipation.However,it is still difficult to realize well-controlled electron localization and elucidate the relate...The electron localization is considered as a promising approach to optimize electromagnetic waves(EMW)dissipation.However,it is still difficult to realize well-controlled electron localization and elucidate the related EMW loss mechanisms for current researches.In this study,a novel two-dimensional MXene(Ti_(3)C_(2)T_(x))nanosheet decorated with Ni nanoclusters(Ni-NC)system to construct an effective electron localization model based on electronic orbital structure is explored.Theoretical simulations and experimental results reveal that the metal-support interaction between Ni-NC and MXene disrupts symmetric electronic environments,leading to enhanced electron localization and dipole polarization.Additionally,Ni-NC generate a strong interfacial electric field,strengthening heterointerface interactions and promoting interfacial polarization.As a result,the optimized material achieves an exceptional reflection loss(RLmin)of-54 dB and a broad effective absorption bandwidth of 6.8 GHz.This study offers critical insights into the in-depth relationship between electron localization and EMW dissipation,providing a pathway for electron localization engineering in functional materials such as semiconductors,spintronics,and catalysis.展开更多
Precious metal-support interaction plays an important role in thermal stability and catalytic performance of the automotive exhaust catalysts. The support is not only a cartier for active compotmds in catalysts but al...Precious metal-support interaction plays an important role in thermal stability and catalytic performance of the automotive exhaust catalysts. The support is not only a cartier for active compotmds in catalysts but also can improve the dispersion of precious metals and suppress the sintering of precious metals at high temperature; meanwhile, noble metals can also enhance the redox performance and oxygen storage capacity of support. The mechanism of metal-support interactions mainly includes electronic interaction, formation of alloy and inward diffusion of metal into the support or covered by support. The form and degree of precious metal-sup- port interaction depend on many factors, including the content of precious metal, the species of support and metal, and preparation methods. The research results about strong metal-support interaction （SMSI） gave a theory support for developing a kind of new cata- lyst with excellent performance. This paper reviewed the interaction phenomenon and mechanism of precious metals （Pt, Pd, Rh） and support such as A1203, CeO2, and CeO2-based oxides in automotive exhaust catalysts. The factors that affect SMSI and the catalysts developed by SMSI were also discussed.展开更多
Supported metal catalysts play a vital role in the chemical industry, and the metal-support interaction is an important property of the catalyst. However, in the traditional impregnation method, it is difficult to obt...Supported metal catalysts play a vital role in the chemical industry, and the metal-support interaction is an important property of the catalyst. However, in the traditional impregnation method, it is difficult to obtain sufficient metal-support interactions owing to the mobility of the metal precursor during evaporation drying. Here, freeze drying is applied during impregnation instead of evaporation drying for enhancing the metal-support interactions. 57 Fe ZSM-5 was chosen as a representative catalyst. A quantitative analysis was conducted based on Mossbauer spectroscopy. Compared with traditional evaporation-drying catalyst, freeze-drying catalyst has stronger metal-support interactions. In addition, more iron species are confined in the channel and smaller metal sizes and less diversity are obtained. The compositional change is also proved because of the superior performance of the freeze-drying catalyst during N2O decomposition. This method can be extended to other supported metal catalysts prepared through an impregnation method, which can be used to tune the metal-support interactions and metal sizes.展开更多
The metal-support interaction is of critical importance to enhance the catalytic activity and selectivity.However,it is still challenging to construct an appropriate interaction starting from the catalyst fabrication ...The metal-support interaction is of critical importance to enhance the catalytic activity and selectivity.However,it is still challenging to construct an appropriate interaction starting from the catalyst fabrication and/or activation.We herein established low-temperature treatment of Ni^(2+)ions impregnated on ceria in reductive atmosphere and reduction-oxidation cycles as effective approachs to regulate the metal-support interaction and raise the catalytic performance in the CO_(2)methanation.The proposed construction approach yielded Ni/Ce O_(2)that displayed highly dispersed Ni nanoparticles in contact with Ce O_(2)(111)and(100)facet,higher density of surface oxygen vacancies and larger amounts of weak basic sites relative to the reference samples,which increased the capacity for H2 and CO_(2)adsorption/activation.The interaction resulted in appreciably(2-3 fold)higher activity in the CO_(2)methanation with maintaining almost full selectivity to CH4 and high stability.Coverage of Ni surface by Ce O_(2)-x thin layer as a typical structure of strong metal-support interaction resulting from high-temperature reduction,can be alleviated via reduction-oxidation cycles.We also demonstrate the activation treatment-determined metalsupport interaction effect can generally extend to(Ti O_(2)and Zr O_(2))supported Ni catalysts.展开更多
High-efficiency electrochemical hydrogen evolution reaction(HER)offers a promising strategy to address energy and environmental crisis.Platinum is the most effective electrocatalyst for the HER.However,challenging sca...High-efficiency electrochemical hydrogen evolution reaction(HER)offers a promising strategy to address energy and environmental crisis.Platinum is the most effective electrocatalyst for the HER.However,challenging scarcity,valuableness,and poor electrochemical stability still hinder its wide application.Here,we designed an outstanding HER electrocatalyst,highly dispersed rhodium(Rh)nanoparticles with an average diameter of only 3 nm supported on boron(B)nanosheets.The HER catalytic activity is even comparable to that of commercial platinum catalysts,with an overpotential of only 66 mV in 0.5 M H_(2)SO_(4) and 101 mV in 1 M KOH to reach the current density of 10 mA cm−2.Meanwhile,the catalyst exhibited impressive electrochemical durability during long-term electrochemical processes in acidic and alkaline media,even the simu-lated seawater environment.Theoretical calculations unraveled that the structure-activity relationship between B(104)crystal plane and Rh(111)crystal plane is beneficial to the release of hydrogen,and surface O plays a vital role in the catalysis process.Our work may gain insights into the development of supported metal catalysts with robust catalytic performance through precise engineering of the strong metal-supported interaction effect.展开更多
The chemical transformation of CO_(2) produces carbon compounds that can be used as precursors for the production of chemicals and fuels.Here,we investigated the activity and selectivity of the transition metals(Fe,Co...The chemical transformation of CO_(2) produces carbon compounds that can be used as precursors for the production of chemicals and fuels.Here,we investigated the activity and selectivity of the transition metals(Fe,Co,and Ni)supported on CeO_(2) catalyst for CO_(2) hydrogenation at atmospheric pressure.We found that Ni/CeO_(2) shows the highest CO_(2)conversion compared with Fe/CeO_(2) and Co/CeO_(2).Besides,Co/CeO_(2)and Ni/CeO_(2) exhibit nearly 100%CH_(4)selectivity while Fe/CeO_(2) inclines to produce CO.The characterization results show that the metal-support interaction order is Fe/CeO_(2)>Co/CeO_(2)>Ni/CeO_(2),the weak metal-support inte raction over Ni/CeO_(2)benefits the activation of H_(2) and then promotes the activity of CO_(2) hydrogenation.Additionally,in situ DRIFTS results demonstrate that monodentate formate species rather than bidentate formate are the active intermediates.The main route of CO_(2) hydrogenation to CH_(4) is that CO_(2) is firstly transformed to m-HCOO*and then direct hydrogenation of the m-HCOO*to CH_(4).This study provides insights into the understanding of the mechanisms of CO_(2) hydrogenation on CeO_(2)based catalysts.展开更多
In this study,two Ru/TiO_(2)samples with different TiO_(2)facets were prepared to investigate their photo-thermal catalytic CO_(2)+H_(2)reaction behavior.Without UV irradiation,the Ru/TiO_(2)with 67%{001}facet(3 RT)di...In this study,two Ru/TiO_(2)samples with different TiO_(2)facets were prepared to investigate their photo-thermal catalytic CO_(2)+H_(2)reaction behavior.Without UV irradiation,the Ru/TiO_(2)with 67%{001}facet(3 RT)displayed improved thermal catalytic activity for CO_(2)methanation than that of Ru/TiO_(2)with 30%{001}facet(0 RT).After H_(2)pretreatment,both samples exhibited enhanced thermal catalytic activities,but the H_(2)-treated 3 RT(3 RT-H)exhibited superior activity to that of the H_(2)-treated 0 RT(0 RT-H).Under UV irradiation,3 RT-H exhibited apparent photo-promoted thermal catalytic activity and stability,but the enhanced catalytic activity was lower than that of 0 RT-H.Based on the characterization results,it is proposed that both the surface oxygen vacancies(Vos)(activating CO_(2))and the metallic Ru nanoparticles(activating H_(2))were mainly responsible for CO_(2)methanation.For 0 RT,H_(2)pretreatment and subsequent UV irradiation did not promote the formation of Vos,resulting in low catalytic activity.For 3 RT,on the one hand,H_(2)pretreatment promoted the formation of Vos,which were regenerated under UV irradiation;on the other hand,the photogenerated electrons from TiO_(2)transferred to Ru to maintain the metallic Ru nanoparticles.Both behaviors promoted the activation of CO_(2)and H_(2)and enhanced CO_(2)methanation.Moreover,the photogenerated holes favored the dissociated H at Ru migrating to TiO_(2),also promoting CO_(2)methanation.These behaviors occurring on 3 RT-H may be attributed to the suitable metal-support interaction between the Ru nanoparticles and TiO_(2){001},resulting in the easy activation of lattice oxygen in TiO_(2)to Vos.With reference to the analysis of intermediates,a photo-thermal reaction mechanism is proposed for the Ru/TiO_(2){001}facet sample.展开更多
The interactions between metals and oxide supports,so-called metal-support interactions(MSI),are of great importance in heterogeneous catalysis.Pd-based automotive exhaust control catalysts,especially Pd-based three-w...The interactions between metals and oxide supports,so-called metal-support interactions(MSI),are of great importance in heterogeneous catalysis.Pd-based automotive exhaust control catalysts,especially Pd-based three-way catalysts (TWCs),have received considerable research attention owing to its prominent oxidation activity of HCs/CO,as well as excellent thermal stability.For Pd-based TWCs,the dispersion,chemical state and thermal stability of Pd species,which are crucial to the catalytic performance,are closely associated with interactions between metal nanoparticles and their supporting matrix.Progress on the research about MSI and utilization of MSI in advanced Pd-based three-way catalysts are reviewed here.Along with the development of advanced synthesis approaches and engine control technology,the study on MSI would play a notable role in further development of catalysts for automobile exhaust control.展开更多
Different from traditional metal-support heterogenous catalysts,inverse heterogeneous catalysts,in which the surface of metal is decorated by metal oxide,have recently attracted increasing interests owing to the uniqu...Different from traditional metal-support heterogenous catalysts,inverse heterogeneous catalysts,in which the surface of metal is decorated by metal oxide,have recently attracted increasing interests owing to the unique interracial effect and electronic structure.However,a deep insight into the effect of metaloxide interaction on the catalytic performance still remains a great challenge.In our work,an inverse hematite/palladium(Fe_(2) O_(3)/Pd) hybrid nanostructure,i.e.,the active Fe_(2) O_(3) ultrathin oxide layers partially covering on the surface of Pd nanoparticles(NPs),exhibited superior electrocatalytic performance towards methanol oxidation reaction(MOR) as compared to the bare Pd NPs based on density functional theory calculation.The charge could transfer from Pd to Fe_(2) O_(3) driven by the built-in potential at the interface of Pd and Fe_(2) O_(3),which favors the downshift of d band center of Pd.With the assistance of interfacial hydroxyl OH*,the cleavage of O—H and C—H in CH_(3) OH could take place much easily with lower barrier ene rgy on Fe_(2) O_(3)/Pd than that on pure Pd via two electrons transferring reaction pathways.Our results highlight that the syne rgy of Pd and Fe_(2) O_(3) at the interface could facilitate the electrochemical transformation of methanol into formaldehyde assisted with interfacial hydroxyl OH*.展开更多
基金supported by the Natural Science Foundation of Shanxi Province(202203021221155)the Foundation of National Key Laboratory of High Efficiency and Low Carbon Utilization of Coal(J23-24-902)。
文摘With ongoing global warming and increasing energy demands,the CH_(4)-CO_(2)reforming reaction(dry reforming of methane,DRM)has garnered significant attention as a promising carbon capture and utilization technology.Nickel-based catalysts are renowned for their outstanding activity and selectivity in this process.The impact of metal-support interaction(MSI),on Ni-based catalyst performance has been extensively researched and debated recently.This paper reviews the recent research progress of MSI on Ni-based catalysts and their characterization and modulation strategies in catalytic reactions.From the perspective of MSI,the effects of different carriers(metal oxides,carbon materials and molecular sieves,etc.)are introduced on the dispersion and surface structure of Ni active metal particles,and the effect of MSI on the activity and stability of DRM reactions on Ni-based catalysts is discussed in detail.Future research should focus on better understanding and controlling MSI to improve the performance and durability of nickel-based catalysts in CH_(4)-CO_(2)reforming,advancing cleaner energy technologies.
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support from Zhejiang Provincial Natural Science Foundation of China(LZ23B060001).
文摘Supported metal oxide catalysts have garnered significantattention in oxidative dehydrogenation(ODH)due to their tunable metal-support interactions.The pentacoordinate Al^(3+)(Al_(V)^(3+))in γ-Al_(2)O_(3)supports plays a pivotal role in modulating metal-support interaction.This study investigates oxalic acid(OA)pretreatment as a defect engineering strategy to enhance the catalytic performance of CeO_(2)/γ-Al_(2)O_(3)in cyclohexane ODH.Through integrated characterization(XRD,27Al MAS NMR,H_(2)-TPR,TPRO,MS,XPS)and catalytic testing,we demonstrate that optimal OA treatment(1:10 ratio)eliminates 100%of surface Al_(V)^(3+)defects while enhancing CeO_(2)crystallinity and interfacial oxygen mobility.The removal of Al_(V)^(3+)species restructures metal-support interaction,accelerating interfacial oxygen mobility.In oxidation dehydrogenation of cyclohexane,the modified CeO_(2)/γ-Al_(2)O_(3)achieves 29%of cyclohexane conversion with stable selectivity of 49%cyclohexene.These findingsprovide an initial framework for designing redox-active catalysts via targeted support modificationin CeO_(2)/γ-Al_(2)O_(3)systems,emphasizing the relationship between metal-support interaction and oxygen mobility.
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financially supported by the National Natural Science Foundation of China(Grant 22278439,21776313)the Shandong Province Higher Education Youth Innovation Technology Support Program(Grant 2022KJ074)。
文摘Metal-support interactions and hydrogen spillover effects in heterogeneous catalysts play a crucial role in aromatic hydrogenation reactions;however,these effects are limited by the metal dispersion on the catalyst and the number of acceptable H*receptors.This study prepares highly dispersed Ni nanoparticles(NPs)catalysts on a Beta substrate via precursor structure topology transformation.In contrast to traditional support materials,the coordination and electronic structure changes between the Ni NPs and the support were achieved,further optimizing the active interface sites and enhancing hydrogen activation and hydrogenation performance.Additionally,the-OH groups at the strong acid sites in zeolite effectively intensified the hydrogen spillover effect as receptors for H^(*)migration and anchoring,accelerating the hydrogenation rate of aromatic rings.Under solvent-free conditions,this catalyst was used for the hydrogenation reaction of aromatic-rich oils,directly producing a C_(8)-C_(14)branched cycloalkanes mixture with an aromatic conversion rate of>99%.The cycloalkanes mixture produced by this method features high density(0.92 g/mL)and a low freezing point(<-60℃),making it suitable for use as high-density aviation fuel or as an additive to enhance the volumetric heat value of conventional aviation fuels in practical applications.
基金financially supported by the National Natural Science Foundation of China(21968028)the Xinjiang Tianchi Talent Project(CZ002732)。
文摘Alkaline earth-metal titanates ATiO_(3)(A=Ca,Sr,and Ba)with a perovskite-type structure were used as supports for Ru-based catalysts to produce CO_(x)-free H_(2)via NH_(3)decomposition.The effects of alkalineearth metals on the physicochemical characteristics and catalytic activities of Ru/ATiO_(3)for NH_(3)decomposition were investigated using various techniques.The order of Ru/ATiO_(3)for NH_(3)conversion is Ru/BaTiO_(3)>Ru/SrTiO_(3)>Ru/CaTiO_(3)>Ru/TiO_(2)at the identical conditions,with the Ru/BaTiO_(3)catalyst demonstrating the highest NH_(3)conversion of 77.8%at 450℃and a gas hourly space velocity of 30,000 mL/gcat/h,which is 8.7,2.1,and 1.3 times of that over Ru/TiO_(2),Ru/CaTiO_(3),and Ru/SrTiO_(3),respectively.The formation of the ATiO_(3)phase can enrich the concentration of basic sites and oxygen vacancies compared with TiO_(2),which can induce the presence of strong metal-support interaction(SMSI)through the formation of Ru-O-Ti bonds.This SMSI effect increased the dispersion and electron density of Ru nano-particles on ATiO_(3)supports,and the electron-rich Ru nano-particles could weaken the chemisorptive strength of N_(2)and H_(2)on the Ru/ATiO_(3)catalysts,thereby promoting the reaction rate for NH_(3)decomposition.
基金financially supported by the National Key R&D Program of China(2023YFA1509103)the National Natural Science Foundation of China(Nos.22272157,21872131,22106085,and U1932214)。
文摘This study explores the adsorption and reac-tion of methanol on the CeO_(2)(111)and Ni/CeO_(2)(111)surfaces,highlighting the es-sential role of metal-support interaction in methanol decomposition by a synergistic ap-proach encompassing synchrotron radiation photoemission spectroscopy,X-ray photo-electron spectroscopy,infrared reflection and absorption spectroscopy,and temperature-programmed desorption.Our findings reveal that Ni deposited on the CeO_(2)(111)surface,followed by annealing to 700 K,leads to the formation of Ce-O-Ni mixed oxide as the dominant phase.The Ni^(2+)species facilitate the methoxy decomposition into CO and H_(2)within 300-430 K,with a small amount of formalde-hyde also forming at the edge sites of ceria.Additionally,some methoxy adsorbed on the bare CeO_(2)surface migrates to the Ce-O-Ni mixed oxide,where they decompose into CO and H_(2)at 500-600 K,accompanied by a portion of the methoxy interacting with ceria to generate formaldehyde.Upon exposure to methanol at 500 K,the Ni^(2+)species are reduced to metallic Ni^(0),alongside the formation of coke and Ni_(3)C,ultimately resulting in catalyst deactivation.However,reintroducing O_(2)reactivates these sites by oxidizing metallic Ni^(0)and Ni_(3)C species.This study highlights the pivotal role of metal-support interaction in promoting oxygen trans-fer from ceria to Ni,thereby enhancing methoxy decomposition and significantly improving the performance of Ni-based catalysts for methanol decomposition into CO and H_(2).
基金supported by the National Natural Science Foundation of China(Nos.52472241,52403108 and 52301285)Department of Science and Technology of Hubei Province(Nos.2025AFA114 and 2024CSA076)+1 种基金Wuhan Science and Technology Bureau(Nos.2023020201010116 and 2024040801020319)Hubei Provincial Department of Education(No.Q20231703)。
文摘Photoelectrochemical(PEC)water splitting using bismuth vanadate(BiVO_(4))as a photoanode shows promise for renewable hydrogen production.Depositing cobalt phosphate(CoPi)on the BiVO_(4)photoanode as an oxygen evolution cocatalyst(OEC)is an effective method to improve the PEC performance.However,the CoPi/BiVO_(4)photoanode still faces challenges in terms of slow interface photogenerated carrier transport.Herein,we utilize the advantage of the classical strong metal-support interaction(SMSI)between Au and BiVO_(4)to prepare a CoPi/Au/BiVO_(4)(SMSI-CoPi/Au/BiVO_(4))photoanode.Due to the formation of SMSI,the accumulated electrons at the interface of CoPi/Au induce the accelerated extraction of photogenerated holes.Meanwhile,the active electron density of CoPi is increased,leading to improved water oxidation kinetic.As a result,the SMSI-CoPi/Au/BiVO_(4)photoanode exhibits a high photocurrent density of 5.01 m A cm^(-2)at 1.23 V versus the reversible hydrogen electrode and an applied bias photon-to-current efficiency of 1.78%.This work highlights a novel approach to enhance hole transfer and water oxidation kinetics of OEC/BiVO_(4)composite photoanodes,offering the great potential of using SMSI for PEC water splitting.
基金supported by the National Research Foundation of Korea(NRF)grant funded by the Korea government(MSIT)(RS-2024-00395914)the Korea Institute of Energy Technology Evaluation and Planning(KETEP)granted financial resource from the Ministry of Trade,Industry&Energy,Republic of Korea(20213030030040 and 20212020800090).
文摘Metal-supported solid oxide fuel cells(MS-SOFCs)have recently gained significant attention as an advanced SOFC technology,owing to their excellent mechanical robustness,ease of handling,and high manufacturability.The use of metal substrates enables improved durability under thermal and redox cycling,and allows for thinner electrolyte layers,contributing to enhanced performance.However,their fabrication typically requires high-temperature sintering to ensure adequate material properties and adhesion,as most SOFC components are ceramic.These high-temperature processes can lead to undesirable effects,including metal support oxidation,chemical side reactions,and accelerated particle growth,which degrade cell performance.This study introduces an ultra-fast sintering approach for MS-SOFC fabrication by directly integrating stainless-steel metal supports with nickel-yttria-stabilized zirconia(Ni-YSZ)composite anode active layers.The application of flash light sintering-an innovative ultra-fast technique-effectively suppressed Ni catalyst particle growth,expanding the electrochemical reaction area while minimizing material diffusion between the metal support and anode layer.As a result,the fabricated cells achieved a stable open-circuit voltage(OCV)exceeding 1 V at 650℃ and a peak power density of 412 mW/cm^(2),representing an approximately 426.3% performance improvement over conventionally sintered cells.This research presents a transformative strategy for SOFC manufacturing,addressing the challenges of conventional long-duration heat treatments and demonstrating significant potential for advancing energy conversion technologies.
基金supported by the National Natural Science Foundation of China(Nos.22025604 and 22276204)the National Key R&D Program of China(Nos.2023YFC3708401 and 2022YFC3800404).
文摘To develop efficient catalysts for ambient carbon monoxide(CO)oxidation is significant for indoor air purification and also for many industrial applications.In this work,the catalytic activity for CO oxidation were enhanced by tuning the metal-support interaction of Ru/CeO_(2)catalysts.A series of Ru/CeO_(2)catalysts were synthesized by an impregnation method with calcination at 100,200,400 and 600℃,respectively,to regulate the Ru-CeO_(2)interaction.We discovered that low temperature calcination(100℃)induced more Ru-O-Ce bonds and stronger Ru-CeO_(2)interaction,while high temperature calcination(≥400℃)caused the agglomeration of Ru species with more Ru-O-Ru bonds and weaker Ru-CeO_(2)interaction,resulting in the lower redox capacity of these catalysts,as well as lower catalytic activity for CO oxidation.Only calcination at moderate 200℃ can induce the moderate interaction between Ru species and CeO_(2)support,which can keep the high dispersion of RuO_(x)species with the high redox capacity,thus leading to complete elimination of 500 ppm CO at room temperature on Ru/Ce-200 catalyst.
基金supported by the Natural Scientific Foundation of China(Nos.22127803,22174110,22203050)Natural Scientific Foundation of Shandong(No.ZR2022QB002)China Postdoctoral Science Foundation(No.2020T130331)。
文摘A novel Cu-t-ZrO_(2)catalyst with enhanced electronic metal-support interaction(EMSI)is designed for efficient electrocatalytic conversion of nitrate(NO_(3^(-)))to ammonia(NH_(3)),achieving a remarkable Faradaic efficiency and yield rate of 97.54%and 33.64 mg h^(-1)mg_(cat)^(-1),respectively.Electrons are more likely to be transferred from Cu to t-ZrO_(2)at the electron-rich interface due to the lower work function,which promotes the formation of highly active Cu species and facilitates NO_(3^(-))adsorption,ensuring selective conversion into NH_(3).
基金supported by the National Key Research and Development Program of China (Grant No. 2024YFE0100600)the National Natural Science Foundation of China (No 52373303)+2 种基金the Shanghai Municipal Science and Technology Major Project (2021SHZDZX0100)the Fundamental Research Funds for the Central Universitiesthe Interdisciplinary Joint Research and Development Project of Tongji University (No 2024-4-ZD-03)
文摘The electron localization is considered as a promising approach to optimize electromagnetic waves(EMW)dissipation.However,it is still difficult to realize well-controlled electron localization and elucidate the related EMW loss mechanisms for current researches.In this study,a novel two-dimensional MXene(Ti_(3)C_(2)T_(x))nanosheet decorated with Ni nanoclusters(Ni-NC)system to construct an effective electron localization model based on electronic orbital structure is explored.Theoretical simulations and experimental results reveal that the metal-support interaction between Ni-NC and MXene disrupts symmetric electronic environments,leading to enhanced electron localization and dipole polarization.Additionally,Ni-NC generate a strong interfacial electric field,strengthening heterointerface interactions and promoting interfacial polarization.As a result,the optimized material achieves an exceptional reflection loss(RLmin)of-54 dB and a broad effective absorption bandwidth of 6.8 GHz.This study offers critical insights into the in-depth relationship between electron localization and EMW dissipation,providing a pathway for electron localization engineering in functional materials such as semiconductors,spintronics,and catalysis.
基金supported by National Science & Technology Pillar Program(2012BAE06B00)
文摘Precious metal-support interaction plays an important role in thermal stability and catalytic performance of the automotive exhaust catalysts. The support is not only a cartier for active compotmds in catalysts but also can improve the dispersion of precious metals and suppress the sintering of precious metals at high temperature; meanwhile, noble metals can also enhance the redox performance and oxygen storage capacity of support. The mechanism of metal-support interactions mainly includes electronic interaction, formation of alloy and inward diffusion of metal into the support or covered by support. The form and degree of precious metal-sup- port interaction depend on many factors, including the content of precious metal, the species of support and metal, and preparation methods. The research results about strong metal-support interaction （SMSI） gave a theory support for developing a kind of new cata- lyst with excellent performance. This paper reviewed the interaction phenomenon and mechanism of precious metals （Pt, Pd, Rh） and support such as A1203, CeO2, and CeO2-based oxides in automotive exhaust catalysts. The factors that affect SMSI and the catalysts developed by SMSI were also discussed.
基金supported by the National Key R&D Program of China(2016YFA0202900)the National Natural Science Foundation of China(21622606)+1 种基金Zhejiang Provincial Natural Science Foundation of China(LR18B060001)the Fundamental Research Funds for the Central Universities~~
文摘Supported metal catalysts play a vital role in the chemical industry, and the metal-support interaction is an important property of the catalyst. However, in the traditional impregnation method, it is difficult to obtain sufficient metal-support interactions owing to the mobility of the metal precursor during evaporation drying. Here, freeze drying is applied during impregnation instead of evaporation drying for enhancing the metal-support interactions. 57 Fe ZSM-5 was chosen as a representative catalyst. A quantitative analysis was conducted based on Mossbauer spectroscopy. Compared with traditional evaporation-drying catalyst, freeze-drying catalyst has stronger metal-support interactions. In addition, more iron species are confined in the channel and smaller metal sizes and less diversity are obtained. The compositional change is also proved because of the superior performance of the freeze-drying catalyst during N2O decomposition. This method can be extended to other supported metal catalysts prepared through an impregnation method, which can be used to tune the metal-support interactions and metal sizes.
基金financially supported by the Tianjin Key Science and Technology Project(19ZXNCGX00030)。
文摘The metal-support interaction is of critical importance to enhance the catalytic activity and selectivity.However,it is still challenging to construct an appropriate interaction starting from the catalyst fabrication and/or activation.We herein established low-temperature treatment of Ni^(2+)ions impregnated on ceria in reductive atmosphere and reduction-oxidation cycles as effective approachs to regulate the metal-support interaction and raise the catalytic performance in the CO_(2)methanation.The proposed construction approach yielded Ni/Ce O_(2)that displayed highly dispersed Ni nanoparticles in contact with Ce O_(2)(111)and(100)facet,higher density of surface oxygen vacancies and larger amounts of weak basic sites relative to the reference samples,which increased the capacity for H2 and CO_(2)adsorption/activation.The interaction resulted in appreciably(2-3 fold)higher activity in the CO_(2)methanation with maintaining almost full selectivity to CH4 and high stability.Coverage of Ni surface by Ce O_(2)-x thin layer as a typical structure of strong metal-support interaction resulting from high-temperature reduction,can be alleviated via reduction-oxidation cycles.We also demonstrate the activation treatment-determined metalsupport interaction effect can generally extend to(Ti O_(2)and Zr O_(2))supported Ni catalysts.
基金project was funded by National Natural Science Foundation of China(Nos.21901154,21671129)the Program for Changjiang Scholars and Innovative Research Team in University(No.IRT17R71)。
文摘High-efficiency electrochemical hydrogen evolution reaction(HER)offers a promising strategy to address energy and environmental crisis.Platinum is the most effective electrocatalyst for the HER.However,challenging scarcity,valuableness,and poor electrochemical stability still hinder its wide application.Here,we designed an outstanding HER electrocatalyst,highly dispersed rhodium(Rh)nanoparticles with an average diameter of only 3 nm supported on boron(B)nanosheets.The HER catalytic activity is even comparable to that of commercial platinum catalysts,with an overpotential of only 66 mV in 0.5 M H_(2)SO_(4) and 101 mV in 1 M KOH to reach the current density of 10 mA cm−2.Meanwhile,the catalyst exhibited impressive electrochemical durability during long-term electrochemical processes in acidic and alkaline media,even the simu-lated seawater environment.Theoretical calculations unraveled that the structure-activity relationship between B(104)crystal plane and Rh(111)crystal plane is beneficial to the release of hydrogen,and surface O plays a vital role in the catalysis process.Our work may gain insights into the development of supported metal catalysts with robust catalytic performance through precise engineering of the strong metal-supported interaction effect.
基金Project supported by the Yunnan Fundamental Research Projects(202101BE070001-001)the Special Project of Eco-Environmental Technology for Emission Peak&Carbon Neutralization(RCEES-TDZ-2021-4)the National Natural Science Foundation of China(22276204,21976196).
文摘The chemical transformation of CO_(2) produces carbon compounds that can be used as precursors for the production of chemicals and fuels.Here,we investigated the activity and selectivity of the transition metals(Fe,Co,and Ni)supported on CeO_(2) catalyst for CO_(2) hydrogenation at atmospheric pressure.We found that Ni/CeO_(2) shows the highest CO_(2)conversion compared with Fe/CeO_(2) and Co/CeO_(2).Besides,Co/CeO_(2)and Ni/CeO_(2) exhibit nearly 100%CH_(4)selectivity while Fe/CeO_(2) inclines to produce CO.The characterization results show that the metal-support interaction order is Fe/CeO_(2)>Co/CeO_(2)>Ni/CeO_(2),the weak metal-support inte raction over Ni/CeO_(2)benefits the activation of H_(2) and then promotes the activity of CO_(2) hydrogenation.Additionally,in situ DRIFTS results demonstrate that monodentate formate species rather than bidentate formate are the active intermediates.The main route of CO_(2) hydrogenation to CH_(4) is that CO_(2) is firstly transformed to m-HCOO*and then direct hydrogenation of the m-HCOO*to CH_(4).This study provides insights into the understanding of the mechanisms of CO_(2) hydrogenation on CeO_(2)based catalysts.
文摘In this study,two Ru/TiO_(2)samples with different TiO_(2)facets were prepared to investigate their photo-thermal catalytic CO_(2)+H_(2)reaction behavior.Without UV irradiation,the Ru/TiO_(2)with 67%{001}facet(3 RT)displayed improved thermal catalytic activity for CO_(2)methanation than that of Ru/TiO_(2)with 30%{001}facet(0 RT).After H_(2)pretreatment,both samples exhibited enhanced thermal catalytic activities,but the H_(2)-treated 3 RT(3 RT-H)exhibited superior activity to that of the H_(2)-treated 0 RT(0 RT-H).Under UV irradiation,3 RT-H exhibited apparent photo-promoted thermal catalytic activity and stability,but the enhanced catalytic activity was lower than that of 0 RT-H.Based on the characterization results,it is proposed that both the surface oxygen vacancies(Vos)(activating CO_(2))and the metallic Ru nanoparticles(activating H_(2))were mainly responsible for CO_(2)methanation.For 0 RT,H_(2)pretreatment and subsequent UV irradiation did not promote the formation of Vos,resulting in low catalytic activity.For 3 RT,on the one hand,H_(2)pretreatment promoted the formation of Vos,which were regenerated under UV irradiation;on the other hand,the photogenerated electrons from TiO_(2)transferred to Ru to maintain the metallic Ru nanoparticles.Both behaviors promoted the activation of CO_(2)and H_(2)and enhanced CO_(2)methanation.Moreover,the photogenerated holes favored the dissociated H at Ru migrating to TiO_(2),also promoting CO_(2)methanation.These behaviors occurring on 3 RT-H may be attributed to the suitable metal-support interaction between the Ru nanoparticles and TiO_(2){001},resulting in the easy activation of lattice oxygen in TiO_(2)to Vos.With reference to the analysis of intermediates,a photo-thermal reaction mechanism is proposed for the Ru/TiO_(2){001}facet sample.
基金supported by the National Key R&D Program of China (Nos.2017YFC0211102 and 2017YFC0211202)Guangdong Basic and Applied Basic Research Foundation (No.2019A1515110530)+1 种基金Shenzhen Science and Technology Program (No.JCYJ20210324140804013)Tsinghua Shenzhen International Graduate School (Nos.QD2021005N and JC_(2)021007)。
文摘The interactions between metals and oxide supports,so-called metal-support interactions(MSI),are of great importance in heterogeneous catalysis.Pd-based automotive exhaust control catalysts,especially Pd-based three-way catalysts (TWCs),have received considerable research attention owing to its prominent oxidation activity of HCs/CO,as well as excellent thermal stability.For Pd-based TWCs,the dispersion,chemical state and thermal stability of Pd species,which are crucial to the catalytic performance,are closely associated with interactions between metal nanoparticles and their supporting matrix.Progress on the research about MSI and utilization of MSI in advanced Pd-based three-way catalysts are reviewed here.Along with the development of advanced synthesis approaches and engine control technology,the study on MSI would play a notable role in further development of catalysts for automobile exhaust control.
基金financially supported by the National Natural Science Foundation of China (Nos.21805191,21866032)the Guangdong Basic and Applied Basic Research Foundation (No.2020A151501982)the China Postdoctoral Science Foundation (No.2020M672811)。
文摘Different from traditional metal-support heterogenous catalysts,inverse heterogeneous catalysts,in which the surface of metal is decorated by metal oxide,have recently attracted increasing interests owing to the unique interracial effect and electronic structure.However,a deep insight into the effect of metaloxide interaction on the catalytic performance still remains a great challenge.In our work,an inverse hematite/palladium(Fe_(2) O_(3)/Pd) hybrid nanostructure,i.e.,the active Fe_(2) O_(3) ultrathin oxide layers partially covering on the surface of Pd nanoparticles(NPs),exhibited superior electrocatalytic performance towards methanol oxidation reaction(MOR) as compared to the bare Pd NPs based on density functional theory calculation.The charge could transfer from Pd to Fe_(2) O_(3) driven by the built-in potential at the interface of Pd and Fe_(2) O_(3),which favors the downshift of d band center of Pd.With the assistance of interfacial hydroxyl OH*,the cleavage of O—H and C—H in CH_(3) OH could take place much easily with lower barrier ene rgy on Fe_(2) O_(3)/Pd than that on pure Pd via two electrons transferring reaction pathways.Our results highlight that the syne rgy of Pd and Fe_(2) O_(3) at the interface could facilitate the electrochemical transformation of methanol into formaldehyde assisted with interfacial hydroxyl OH*.
