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
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
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
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
Water electrolysis poses a significant challenge for balancing catalytic activity and stability of oxygen evolution reaction(OER)electrocatalysts.In this study,we address this challenge by constructing asymmetric redo...Water electrolysis poses a significant challenge for balancing catalytic activity and stability of oxygen evolution reaction(OER)electrocatalysts.In this study,we address this challenge by constructing asymmetric redox chemistry through elaborate surface OO–Ru–OH and bulk Ru–O–Ni/Fe coordination moieties within single-atom Ru-decorated defective NiFe LDH nanosheets(Ru@d-NiFe LDH)in conjunction with strong metal-support interactions(SMSI).Rigorous spectroscopic characterization and theoretical calculations indicate that single-atom Ru can delocalize the O 2p electrons on the surface and optimize d-electron configurations of metal atoms in bulk through SMSI.The^(18)O isotope labeling experiment based on operando differential electrochemical mass spectrometry(DEMS),chemical probe experiments,and theoretical calculations confirm the encouraged surface lattice oxygen,stabilized bulk lattice oxygen,and enhanced adsorption of oxygen-containing intermediates for bulk metals in Ru@d-NiFe LDH,leading to asymmetric redox chemistry for OER.The Ru@d-NiFe LDH electrocatalyst exhibits exceptional performance with an overpotential of 230 mV to achieve 10 mA cm^(−2)and maintains high robustness under industrial current density.This approach for achieving asymmetric redox chemistry through SMSI presents a new avenue for developing high-performance electrocatalysts and instills confidence in its industrial applicability.展开更多
Tuning Strong Metal-support Interactions(SMSI)is a key strategy to obtain highly active catalysts,but conventional methods usually enable TiO_(x) encapsulation of noble metal components to minimize the exposure of nob...Tuning Strong Metal-support Interactions(SMSI)is a key strategy to obtain highly active catalysts,but conventional methods usually enable TiO_(x) encapsulation of noble metal components to minimize the exposure of noble metals.This study demonstrates a catalyst preparation method to modulate a weak encapsulation of Pt metal nanoparticles(NPs)with the supported TiO_(2),achieving the moderate suppression of SMSI effects.The introduction of silica inhibits this encapsulation,as reflected in the characterization results such as XPS and HRTEM,while the Ti^(4+) to Ti^(3+) conversion due to SMSI can still be found on the support surface.Furthermore,the hydrogenation of cinnamaldehyde(CAL)as a probe reaction revealed that once this encapsulation behavior was suppressed,the adsorption capacity of the catalyst for small molecules like H_(2) and CO was enhanced,which thereby improved the catalytic activity and facilitated the hydrogenation of CAL.Meanwhile,the introduction of SiO_(2) also changed the surface structure of the catalyst,which inhibited the occurrence of the acetal reaction and improved the conversion efficiency of C=O and C=C hydrogenation.Systematic manipulation of SMSI formation and its consequence on the performance in catalytic hydrogenation reactions are discussed.展开更多
This study aimed to explore the chemical looping gasification(CLG)reaction characteristics of the metal-supported composite phosphogypsum(PG)oxygen carriers(OCs)and the thermodynamic mechanism.The FactSage 7.1 thermod...This study aimed to explore the chemical looping gasification(CLG)reaction characteristics of the metal-supported composite phosphogypsum(PG)oxygen carriers(OCs)and the thermodynamic mechanism.The FactSage 7.1 thermodynamic simulation was used to explore the oxygen release and H_(2)S removal mechanisms.The experimental results showed that the syngas yield of CLG with PG-CuFe_(2)O_(4)was more than that with PG-Fe_(2)O_(3)20/CuO40 or PG-Fe_(2)O_(3)30/CuO30 OC at 1023 K when the water vapor content was 0.3.Furthermore,the maximum syngas yield of the CO selectivity was 70.3% and of the CO_(2)selectivity was 23.8%.The H_(2)/CO value was 0.78,and the highest carbon conversion efficiency was 91.9% in PG-CuFe_(2)O_(4)at the gasification temperature of 1073 K.The metal-supported PG composite oxygen carrier was proved not only as an oxygen carrier to participate in the preparation of syngas but also as a catalyst to catalyze coal gasification reactions.Furthermore,both the experimental results and FactSage 7.1 thermodynamic analysis revealed that the trapping mechanism of H_(2)S by composite OCs was as follows:CuO first lost lattice oxygen as an oxygen carrier to generate Cu_(2)O,which,in turn,reacted with H_(2)S to generate Cu_(2)S.This study provided efficient guidance and reference for OC design in CLG.展开更多
Monochloroacetic acid(MCAA)is identified as a highly carcinogenic disinfection by-product in chlorinated drinking water.In this study,a series of CeO_(2)-supported Pd catalysts(Pd/MCeO_(2))were synthesized through one...Monochloroacetic acid(MCAA)is identified as a highly carcinogenic disinfection by-product in chlorinated drinking water.In this study,a series of CeO_(2)-supported Pd catalysts(Pd/MCeO_(2))were synthesized through one-step calcination of Pd-loaded Ce-UiO-66-BDC(CeMOF),and the liquid-phase catalytic hydrodechlorination of MCA A was explored using these catalysts.For comparison,Pd/CeO_(2)catalysts were additionally synthesized using the conventional impregnation method.The characterization results reveal that the catalysts exhibit strong metal-support interaction,leading to high Pd dispersion and Pd^(n+)content.Additionally,the calcination temperature significantly influences catalytic performance,with the catalyst calcined at 500℃(Pd/MCeO_(2)-500)demonstrating the highest catalytic activity and achieving complete dechlorination of MCA A within 50 min.Furthermore,it is found that the catalytic MCAA hydrodechlorination using the catalysts adheres to the Langmuir-Hinshelwood model.Accordingly,low reaction pH is favorable for the catalytic hydrodechlorination of MCAA,enhancing MCAA adsorption on the catalyst surface due to the electrostatic interaction between MCAA and the catalyst surface.Theoretical results suggest that the presence of Pd^(n+)efficiently facilitates MCAA adsorption and C-Cl cleavage,thus significantly enhancing the liquid-phase catalytic hydrodechlorination.展开更多
The modulation of metal-support interfacial interaction is significant but challenging in the design of high-efficiency and high-stability supported catalysts.Here,we report a synthetic strategy to upgrade Cu-CeO_(2)i...The modulation of metal-support interfacial interaction is significant but challenging in the design of high-efficiency and high-stability supported catalysts.Here,we report a synthetic strategy to upgrade Cu-CeO_(2)interfacial interaction by the pyrolysis of mixed metal-organic framework(MOF)structure.The obtained highly dispersed Cu/CeO_(2)-MOF catalyst via this strategy was used to catalyze water-gas shift reaction(WGSR),which exhibited high activity of 40.5μmolCOgcat^(-1).s^(-1)at 300℃and high stability of about 120 h.Based on comprehensive studies of electronic structure,pyrolysis strategy has significant effect on enhancing metal-support interaction and then stabilizing interfacial Cu^(+)species under reaction conditions.Abundant Cu^(+)species and generated oxygen vacancies over Cu/CeO_(2)-MOF catalyst played a key role in CO molecule activation and H2O molecule dissociation,respectively.Both collaborated closely and then promoted WGSR catalytic performance in comparison with traditio nal supported catalysts.This study shall offer a robust approach to harvest highly dispersed catalysts with finely-tuned metal-support interactions for stabilizing the most interfacial active metal species in diverse heterogeneous catalytic reactions.展开更多
Polar surfaces are prevalent in metal oxides,the interactions between surface species with polar surfaces are different from those with non-polar surfaces,a thorough understanding of the interactions is key to regulat...Polar surfaces are prevalent in metal oxides,the interactions between surface species with polar surfaces are different from those with non-polar surfaces,a thorough understanding of the interactions is key to regulate the performance of heterogeneous catalysts.In this work,we delve into the interaction of Pt_(n)(n=1-4)with polar ZnO(0001)-Zn and ZnO(0001)-O,and the influence of the surface polarity on the electronic structures and reactivity of Pt_(n) by using density functional theory calculations.The results suggest distinct differences in electronic structures of two exposed terminations,leading to different interactions with Pt_(n).The interaction between Pt_(n) and two terminations not only stabilizes the surface and clusters through polar compensation,but also induces opposite charges on the cluster at two terminations.Remarkably,the Pearson correlation coefficient reveals the interdependency between the electronic states of Pt_(n) and its performance in terms of small molecule adsorption/activation.These observations demonstrate the crucial role of surface polarity in regulating the electronic states and catalytic performance of active sites,and offer a possible design principle for supported catalysts.展开更多
Designing high-performance and low-cost electrocatalysts for oxygen evolu-tion reaction(OER)is critical for the conversion and storage of sustainable energy technologies.Inspired by the biomineralization process,we ut...Designing high-performance and low-cost electrocatalysts for oxygen evolu-tion reaction(OER)is critical for the conversion and storage of sustainable energy technologies.Inspired by the biomineralization process,we utilized the phosphorylation sites of collagen molecules to combine with cobalt-based mononuclear precursors at the molecular level and built a three-dimensional(3D)porous hierarchical material through a bottom-up biomimetic self-assembly strategy to obtain single-atom catalysts confined on carbonized biomimetic self-assembled carriers(Co SACs/cBSC)after subsequent high-temperature annealing.In this strategy,the biomolecule improved the anchoring efficiency of the metal precursor through precise functional groups;meanwhile,the binding-then-assembling strategy also effectively suppressed the nonspecific adsorption of metal ions,ultimately preventing atomic agglomeration and achieving strong electronic metal-support interactions(EMSIs).Experimental characterizations confirm that binding forms between cobalt metal and carbonized self-assembled substrate(Co–O_(4)–P).Theoretical calculations disclose that the local environment changes significantly tailored the Co d-band center,and optimized the binding energy of oxygenated intermediates and the energy barrier of oxygen release.As a result,the obtained Co SACs/cBSC catalyst can achieve remarkable OER activity and 24 h durability in 1 M KOH(η_(10) at 288 mV;Tafel slope of 44 mV dec^(-1)),better than other transition metal-based catalysts and commercial IrO_(2).Overall,we presented a self-assembly strategy to prepare transition metal SACs with strong EMSIs,providing a new avenue for the preparation of efficient catalysts with fine atomic structures.展开更多
Inducing the classic strong metal-support interaction(SMSI)is an effective approach to enhance the performance of supported metal catalysts by encapsulating the metal nanoparticles(NPs)with supports.Conventional therm...Inducing the classic strong metal-support interaction(SMSI)is an effective approach to enhance the performance of supported metal catalysts by encapsulating the metal nanoparticles(NPs)with supports.Conventional thermal reduction method for inducing SMSI processes is often accompanied by undesirable structural evolution of metal NPs.In this study,a mild electrochemical method has been developed as a new approach to induce SMSI,using the cable structured core@shell CNT@SnO_(2) loaded Pt NPs as a proof of concept.The induced SnO_(x) encapsulation layer on the surface of Pt NPs can protect Pt NPs from the poisoned of CO impurity in hydrogen oxidation reaction(HOR),and the HOR current density could still maintain 85% for 2000 s with 10,000 ppm CO in H_(2),while the commercial Pt/C is completely inactivated.In addition,the electrons transfer from SnO_(x) to Pt NPs improved the HOR activity of the E-Pt-CNT@SnO_(2),achieving the excellent exchange current density of 1.55 A·mgPt^(-1).In situ Raman spectra and theoretical calculations show that the key to the electrochemical-method-induced SMSI is the formation of defects and the migration of SnO_(x) caused by the electrochemical redox operation,and the weakening the SneO bond strength by Pt NPs.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
基金supported by the Petrochemical Research Institute Foundation(21-CB-09-01)the National Natural Science Foundation of China(22302186,22025205)+1 种基金the China Postdoctoral Science Foundation(2022M713030,2023T160618)the Fundamental Research Funds for the Central Universities(WK2060000058,WK2060000038).
文摘By simplifying catalyst-product separation and reducing phosphorus waste,heterogeneous hydroformylation offers a more sustainable alternative to homogeneous processes.However,heterogeneous hydroformylation catalysts developed thus far still suffer from the issues of much lower activity and metal leaching,which severely hinder their practical application.Here,we demonstrate that incorporating phosphorus(P)atoms into graphitic carbon nitride(PCN)supports facilitates charge transfer from Rh to the PCN support,thus largely enhancing electronic metal-support interactions(EMSIs).In the styrene hydroformylation reaction,the activity of Rh_(1)/PCN single-atom catalysts(SACs)with varying P contents exhibited a volcano-shaped relationship with P doping,where the Rh_(1)/PCN SAC with optimal P doping showed exceptional activity,approximately 5.8-and 3.3-fold greater than that of the Rh_(1)/g-C_(3)N_(4)SAC without P doping and the industrial homogeneous catalyst HRh(CO)(PPh_(3))_(3),respectively.In addition,the optimal Rh_(1)/PCN SAC catalyst also demonstrated largely enhanced multicycle stability without any visible metal aggregation owing to the increased EMSIs,which sharply differed from the severe metal aggregation of large nanoparticles on the Rh_(1)/g-C_(3)N_(4)SAC.Mechan-istic studies revealed that the enhanced catalytic performance could be attributed to electron-deficient Rh species,which reduced CO adsorption while simultaneously promoting alkene adsorption through increased EMSIs.These findings suggest that tuning EMSIs is an effective way to achieve SACs with high activity and durability.
基金supported by the 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(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 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 the Guangdong Basic and Applied Basic Research Foundation(2021B1515120072)the Natural Science Foundation of China(22279096 and T2241003)the Fundamental Research Funds for the Central Universities(WUT:2023IVA094).
文摘Water electrolysis poses a significant challenge for balancing catalytic activity and stability of oxygen evolution reaction(OER)electrocatalysts.In this study,we address this challenge by constructing asymmetric redox chemistry through elaborate surface OO–Ru–OH and bulk Ru–O–Ni/Fe coordination moieties within single-atom Ru-decorated defective NiFe LDH nanosheets(Ru@d-NiFe LDH)in conjunction with strong metal-support interactions(SMSI).Rigorous spectroscopic characterization and theoretical calculations indicate that single-atom Ru can delocalize the O 2p electrons on the surface and optimize d-electron configurations of metal atoms in bulk through SMSI.The^(18)O isotope labeling experiment based on operando differential electrochemical mass spectrometry(DEMS),chemical probe experiments,and theoretical calculations confirm the encouraged surface lattice oxygen,stabilized bulk lattice oxygen,and enhanced adsorption of oxygen-containing intermediates for bulk metals in Ru@d-NiFe LDH,leading to asymmetric redox chemistry for OER.The Ru@d-NiFe LDH electrocatalyst exhibits exceptional performance with an overpotential of 230 mV to achieve 10 mA cm^(−2)and maintains high robustness under industrial current density.This approach for achieving asymmetric redox chemistry through SMSI presents a new avenue for developing high-performance electrocatalysts and instills confidence in its industrial applicability.
基金the National Natural Science Foundation of China(21576291,22003076)National Natural Science Foundation of China-Outstanding Youth foundation(22322814)the Fundamental Research Funds for the Central Universities(23CX03007A,22CX06012A)are gratefully acknowledge。
文摘Tuning Strong Metal-support Interactions(SMSI)is a key strategy to obtain highly active catalysts,but conventional methods usually enable TiO_(x) encapsulation of noble metal components to minimize the exposure of noble metals.This study demonstrates a catalyst preparation method to modulate a weak encapsulation of Pt metal nanoparticles(NPs)with the supported TiO_(2),achieving the moderate suppression of SMSI effects.The introduction of silica inhibits this encapsulation,as reflected in the characterization results such as XPS and HRTEM,while the Ti^(4+) to Ti^(3+) conversion due to SMSI can still be found on the support surface.Furthermore,the hydrogenation of cinnamaldehyde(CAL)as a probe reaction revealed that once this encapsulation behavior was suppressed,the adsorption capacity of the catalyst for small molecules like H_(2) and CO was enhanced,which thereby improved the catalytic activity and facilitated the hydrogenation of CAL.Meanwhile,the introduction of SiO_(2) also changed the surface structure of the catalyst,which inhibited the occurrence of the acetal reaction and improved the conversion efficiency of C=O and C=C hydrogenation.Systematic manipulation of SMSI formation and its consequence on the performance in catalytic hydrogenation reactions are discussed.
基金supported by the National Key Research and Development Program of China(No.2022YFC3203203)。
文摘This study aimed to explore the chemical looping gasification(CLG)reaction characteristics of the metal-supported composite phosphogypsum(PG)oxygen carriers(OCs)and the thermodynamic mechanism.The FactSage 7.1 thermodynamic simulation was used to explore the oxygen release and H_(2)S removal mechanisms.The experimental results showed that the syngas yield of CLG with PG-CuFe_(2)O_(4)was more than that with PG-Fe_(2)O_(3)20/CuO40 or PG-Fe_(2)O_(3)30/CuO30 OC at 1023 K when the water vapor content was 0.3.Furthermore,the maximum syngas yield of the CO selectivity was 70.3% and of the CO_(2)selectivity was 23.8%.The H_(2)/CO value was 0.78,and the highest carbon conversion efficiency was 91.9% in PG-CuFe_(2)O_(4)at the gasification temperature of 1073 K.The metal-supported PG composite oxygen carrier was proved not only as an oxygen carrier to participate in the preparation of syngas but also as a catalyst to catalyze coal gasification reactions.Furthermore,both the experimental results and FactSage 7.1 thermodynamic analysis revealed that the trapping mechanism of H_(2)S by composite OCs was as follows:CuO first lost lattice oxygen as an oxygen carrier to generate Cu_(2)O,which,in turn,reacted with H_(2)S to generate Cu_(2)S.This study provided efficient guidance and reference for OC design in CLG.
基金financially supported by the National Natural Science Foundation of China(Nos.21976086 and 22002059)。
文摘Monochloroacetic acid(MCAA)is identified as a highly carcinogenic disinfection by-product in chlorinated drinking water.In this study,a series of CeO_(2)-supported Pd catalysts(Pd/MCeO_(2))were synthesized through one-step calcination of Pd-loaded Ce-UiO-66-BDC(CeMOF),and the liquid-phase catalytic hydrodechlorination of MCA A was explored using these catalysts.For comparison,Pd/CeO_(2)catalysts were additionally synthesized using the conventional impregnation method.The characterization results reveal that the catalysts exhibit strong metal-support interaction,leading to high Pd dispersion and Pd^(n+)content.Additionally,the calcination temperature significantly influences catalytic performance,with the catalyst calcined at 500℃(Pd/MCeO_(2)-500)demonstrating the highest catalytic activity and achieving complete dechlorination of MCA A within 50 min.Furthermore,it is found that the catalytic MCAA hydrodechlorination using the catalysts adheres to the Langmuir-Hinshelwood model.Accordingly,low reaction pH is favorable for the catalytic hydrodechlorination of MCAA,enhancing MCAA adsorption on the catalyst surface due to the electrostatic interaction between MCAA and the catalyst surface.Theoretical results suggest that the presence of Pd^(n+)efficiently facilitates MCAA adsorption and C-Cl cleavage,thus significantly enhancing the liquid-phase catalytic hydrodechlorination.
基金sponsored by the National Key R&D Program of China(2021YFA1501100)the National Natural Science Foundation of China(21832001 and 22293042)the Beijing National Laboratory for Molecular Sciences(BNLMS-CXXM-202104)。
文摘The modulation of metal-support interfacial interaction is significant but challenging in the design of high-efficiency and high-stability supported catalysts.Here,we report a synthetic strategy to upgrade Cu-CeO_(2)interfacial interaction by the pyrolysis of mixed metal-organic framework(MOF)structure.The obtained highly dispersed Cu/CeO_(2)-MOF catalyst via this strategy was used to catalyze water-gas shift reaction(WGSR),which exhibited high activity of 40.5μmolCOgcat^(-1).s^(-1)at 300℃and high stability of about 120 h.Based on comprehensive studies of electronic structure,pyrolysis strategy has significant effect on enhancing metal-support interaction and then stabilizing interfacial Cu^(+)species under reaction conditions.Abundant Cu^(+)species and generated oxygen vacancies over Cu/CeO_(2)-MOF catalyst played a key role in CO molecule activation and H2O molecule dissociation,respectively.Both collaborated closely and then promoted WGSR catalytic performance in comparison with traditio nal supported catalysts.This study shall offer a robust approach to harvest highly dispersed catalysts with finely-tuned metal-support interactions for stabilizing the most interfacial active metal species in diverse heterogeneous catalytic reactions.
基金This work was financially supported by the National Natural Science Foundation of China(Nos.22303085,22102150 and 22172146)the Zhejiang Provincial Natural Science Foundation of China(LQ24B030014 andLQ21B030010).
文摘Polar surfaces are prevalent in metal oxides,the interactions between surface species with polar surfaces are different from those with non-polar surfaces,a thorough understanding of the interactions is key to regulate the performance of heterogeneous catalysts.In this work,we delve into the interaction of Pt_(n)(n=1-4)with polar ZnO(0001)-Zn and ZnO(0001)-O,and the influence of the surface polarity on the electronic structures and reactivity of Pt_(n) by using density functional theory calculations.The results suggest distinct differences in electronic structures of two exposed terminations,leading to different interactions with Pt_(n).The interaction between Pt_(n) and two terminations not only stabilizes the surface and clusters through polar compensation,but also induces opposite charges on the cluster at two terminations.Remarkably,the Pearson correlation coefficient reveals the interdependency between the electronic states of Pt_(n) and its performance in terms of small molecule adsorption/activation.These observations demonstrate the crucial role of surface polarity in regulating the electronic states and catalytic performance of active sites,and offer a possible design principle for supported catalysts.
基金The work was supported by the National Natural Science Foundation of China(52372174)Carbon Neutrality Research Institute Fund(CNIF20230204)Special Project of Strategic Cooperation between China National Petroleum Corporation and China University of Petroleum(Beijing)(ZLZX-2020-04).
文摘Designing high-performance and low-cost electrocatalysts for oxygen evolu-tion reaction(OER)is critical for the conversion and storage of sustainable energy technologies.Inspired by the biomineralization process,we utilized the phosphorylation sites of collagen molecules to combine with cobalt-based mononuclear precursors at the molecular level and built a three-dimensional(3D)porous hierarchical material through a bottom-up biomimetic self-assembly strategy to obtain single-atom catalysts confined on carbonized biomimetic self-assembled carriers(Co SACs/cBSC)after subsequent high-temperature annealing.In this strategy,the biomolecule improved the anchoring efficiency of the metal precursor through precise functional groups;meanwhile,the binding-then-assembling strategy also effectively suppressed the nonspecific adsorption of metal ions,ultimately preventing atomic agglomeration and achieving strong electronic metal-support interactions(EMSIs).Experimental characterizations confirm that binding forms between cobalt metal and carbonized self-assembled substrate(Co–O_(4)–P).Theoretical calculations disclose that the local environment changes significantly tailored the Co d-band center,and optimized the binding energy of oxygenated intermediates and the energy barrier of oxygen release.As a result,the obtained Co SACs/cBSC catalyst can achieve remarkable OER activity and 24 h durability in 1 M KOH(η_(10) at 288 mV;Tafel slope of 44 mV dec^(-1)),better than other transition metal-based catalysts and commercial IrO_(2).Overall,we presented a self-assembly strategy to prepare transition metal SACs with strong EMSIs,providing a new avenue for the preparation of efficient catalysts with fine atomic structures.
基金the“National Natural Science Foundation of China(No.22122202)”.
文摘Inducing the classic strong metal-support interaction(SMSI)is an effective approach to enhance the performance of supported metal catalysts by encapsulating the metal nanoparticles(NPs)with supports.Conventional thermal reduction method for inducing SMSI processes is often accompanied by undesirable structural evolution of metal NPs.In this study,a mild electrochemical method has been developed as a new approach to induce SMSI,using the cable structured core@shell CNT@SnO_(2) loaded Pt NPs as a proof of concept.The induced SnO_(x) encapsulation layer on the surface of Pt NPs can protect Pt NPs from the poisoned of CO impurity in hydrogen oxidation reaction(HOR),and the HOR current density could still maintain 85% for 2000 s with 10,000 ppm CO in H_(2),while the commercial Pt/C is completely inactivated.In addition,the electrons transfer from SnO_(x) to Pt NPs improved the HOR activity of the E-Pt-CNT@SnO_(2),achieving the excellent exchange current density of 1.55 A·mgPt^(-1).In situ Raman spectra and theoretical calculations show that the key to the electrochemical-method-induced SMSI is the formation of defects and the migration of SnO_(x) caused by the electrochemical redox operation,and the weakening the SneO bond strength by Pt NPs.
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.
