Catalyst design relies heavily on electronic metal‐support interactions,but the metal‐support interface with an uncontrollable electronic or coordination environment makes it challenging.Herein,we outline a promisin...Catalyst design relies heavily on electronic metal‐support interactions,but the metal‐support interface with an uncontrollable electronic or coordination environment makes it challenging.Herein,we outline a promising approach for the rational design of catalysts involving heteroatoms as anchors for Pd nanoparticles for ethanol oxidation reaction(EOR)catalysis.The doped B and N atoms from dimethylamine borane(DB)occupy the position of the Ti_(3)C_(2) lattice to anchor the supported Pd nanoparticles.The electrons transfer from the support to B atoms,and then to the metal Pd to form a stable electronic center.A strong electronic interaction can be produced and the d‐band center can be shifted down,driving Pd into the dominant metallic state and making Pd nanoparticles deposit uniformly on the support.As‐obtained Pd/DB–Ti_(3)C_(2) exhibits superior durability to its counterpart(∼14.6% retention)with 91.1% retention after 2000 cycles,placing it among the top single metal anodic catalysts.Further,in situ Raman and density functional theory computations confirm that Pd/DB–Ti_(3)C_(2) is capable of dehydrogenating ethanol at low reaction energies.展开更多
Bimetallic CuCo catalysts with different Cu to Co ratios on N-doped porous carbon materials(N-C)were achieved using impregnation method and applied in the hydrogenation of furfural(FAL)to furfuryl alcohol(FOL).The hig...Bimetallic CuCo catalysts with different Cu to Co ratios on N-doped porous carbon materials(N-C)were achieved using impregnation method and applied in the hydrogenation of furfural(FAL)to furfuryl alcohol(FOL).The high hydrogenation activity of FAL over Cu_(1)Co_(1)/N-C was originated from the synergistic interactions of Cu and Co species,where Co^(0)and Cu^(0)simultaneously adsorb and activate H_(2),and Cu^(+) served as Lewis acid sites to activate C]O.Meanwhile,electrons transfer from Cu to Co promoted the formation of Cu^(+).In situ Fourier transform infrared spectroscopy analysis indicated that Cu_(1)Co_(1)/N-C adsorbed FAL with a tilted η^(1)-(O)configuration.The superior Cu_(1)Co_(1)/N-C showed excellent adsorbed ability towards H_(2) and FAL,but weak adsorption for FOL.Therefore,Cu_(1)Co_(1)/N-C possessed 93.1%FAL conversion and 99.0% FOL selectivity after 5 h reaction,which also exhibited satisfactory reusability in FAL hydrogenation for five cycles.展开更多
The efficiency of electrochemical water splitting is extremely hampered by the sluggish oxygen evolution reaction(OER)occurred at the anode.Therefore,developing high-performance OER electrocatalysts is crucial for rea...The efficiency of electrochemical water splitting is extremely hampered by the sluggish oxygen evolution reaction(OER)occurred at the anode.Therefore,developing high-performance OER electrocatalysts is crucial for realizing the industrialized application of water splitting.Herein,a high-efficiency electrocatalyst of ruthenium-decorated nickel-iron hydroxide(10 Ru-NiFe LDH)supported on Ni foam is successfully synthesized for OER.Modifying NiFe LDH with ruthenium can optimize the electronic density to form high valences of metal sites,which is beneficial to promote its OER performance.Consequently,the 10 Ru-NiFe LDH only needs a low overpotential of 222 mV to achieve a current density of50 mA,cm^(-2),which exhibits fast OER kinetics with a small Tafel slope of 58 mV.dec^(-1).Moreover,this electrocatalyst shows high stability over 20 h at a high current density of 100 mA·cm^(-2)without obvious decay.The decent OER performances can be ascribed to the increased active sites and the synergistic electronic interactions among Ni,Fe and Ru.This work provides an effective approach for designing desirable electrocatalysts for OER.展开更多
Lithium-sulfur battery is strongly considered as the most promising next-generation energy storage system because of the high theoretical specific capacity.The serious"shuttle effect"and sluggish reaction ki...Lithium-sulfur battery is strongly considered as the most promising next-generation energy storage system because of the high theoretical specific capacity.The serious"shuttle effect"and sluggish reaction kinetic limited the commercial application of lithium-sulfur battery.Many hetero structure s were applied to accelerate polysulfides conversion and suppress their migration in lithium-sulfur batteries.Nevertheless,the effect of the interface in heterostructure was not clear.Here,the Co_(2)B@MXene heterostructure is synthesized through chemical reactions at room temperature and employed as the interlayer material for Li-S batteries.The theoretical calculations and experimental results indicate that the interfacial electronic interaction of Co_(2)B@MXene induce the transfer of electrons from Co_(2)B to MXene,enhancing the catalytic ability and favoring fast redox kinetics of the polysulfides,and the theoretical calculations also reveal the underlying mechanisms for the electron transfer is that the two materials have different Fermi energy levels.The cell with Co_(2)B@MXene exhibits a high initial capacity of1577 mAh/g at 0.1 C and an ultralow capacity decay of 0.0088%per cycle over 2000 cycles at 2 C.Even at5.1 mg/cm^(2) of sulfur loading,the cell with Co_(2)B@MXene delivers 5.2 mAh/cm^(2) at 0.2 C.展开更多
For CO catalytic oxidation,Cu and Ce species are of great importance,between which the synergistic effect is worth investigating.In this work,CeO_(2)/Cu_(2)O with Cu_(2)O{111}and{100}planes were comparatively explored...For CO catalytic oxidation,Cu and Ce species are of great importance,between which the synergistic effect is worth investigating.In this work,CeO_(2)/Cu_(2)O with Cu_(2)O{111}and{100}planes were comparatively explored on CO catalytic oxidation to reveal the effects of interfacial electronic interactions and oxygen defects.The activity result demonstrates that CeO_(2)/o-Cu_(2)O{111}has superior performance compared with CeO_(2)/c-Cu_(2)O{100}.Credit to the coordination unsaturated copper atoms(Cu_(CUS))on oCu_(2)O{111}surface,the interfacial electronic interactions on CeO_(2)/o-Cu_(2)O{111}are more obvious than those on CeO_(2)/c-Cu_(2)O{100},leading to richer oxygen defect generation,better redox and activation abilities of CO and O_(2)reactants.Furthermore,the reaction mechanism of CeO_(2)/o-Cu_(2)O{111}on CO oxidation is revealed,i.e.,CO and O_(2)are adsorbed on the Cucus on Cu_(2)O{111}and oxygen defect of CeO_(2),respectively,and then synergistically promote the CO oxidation to CO_(2).The work sheds light on the designing optimized ceria and copper-based catalysts and the mechanism of CO oxidation.展开更多
The electronic metal-support interaction(EMSI)is one of most intriguing phenomena in heterogeneous catalysis.In this work,this subtle effect is clearly demonstrated by density functional theory(DFT)calculations of sin...The electronic metal-support interaction(EMSI)is one of most intriguing phenomena in heterogeneous catalysis.In this work,this subtle effect is clearly demonstrated by density functional theory(DFT)calculations of single Pt atom supported on vacancies in a boron nitride nanosheet.Moreover,the relation between the EMSI and the performance of Pt in propane direct dehydrogenation(PDH)is investigated in detail.The charge state and partial density of states of single Pt atom show distinct features at different anchoring positions,such as boron and nitrogen vacancies(Bvac and Nvac,respectively).Single Pt atom become positively and negatively charged on Bvac and Nvac,respectively.Therefore,the electronic structure of Pt can be adjusted by rational deposition on the support.Moreover,Pt atoms in different charge states have been shown to have different catalytic abilities in PDH.The DFT calculations reveal that Pt atoms on Bvac(Pt-Bvac)have much higher reactivity towards reactant/product adsorption and C–H bond activation than Pt supported on Nvac(Pt-Nvac),with larger adsorption energy and lower barrier along the reaction pathway.However,the high reactivity of Pt-Bvac also hinders propene desorption,which could lead to unwanted deep dehydrogenation.Therefore,the results obtained herein suggest that a balanced reactivity for C–H activation in propane and propene desorption is required to achieve optimum yields.Based on this descriptor,a single Pt atom on a nitrogen vacancy is considered an effective catalyst for PDH.Furthermore,the deep dehydrogenation of the formed propene is significantly suppressed,owing to the large barrier on Pt-Nvac.The current work demonstrates that the catalytic properties of supported single Pt atoms can be tuned by rationally depositing them on a boron nitride nanosheet and highlights the great potential of single-atom catalysis in the PDH reaction.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
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
Nickle-based catalysts are commonly used for CO_(2)methanation.However,there is still potential to improve their catalytic performanc under mild conditions.In this study,we synthesized a series of Ru-Ni-Al catalysts f...Nickle-based catalysts are commonly used for CO_(2)methanation.However,there is still potential to improve their catalytic performanc under mild conditions.In this study,we synthesized a series of Ru-Ni-Al catalysts from Ru-doped NiAl-hydrotalcite using a hydrotherma method.The Ru-Ni-Al catalyst demonstrated much higher activity for CO_(2)methanation than the Ni-Al catalyst that did not have Ru doping Both experimental results and theoretical calculations indicate that the enhanced performance of the Ru-Ni-Al catalyst is related to electroni interactions between nickel(Ni)and ruthenium(Ru).The Ru sites transfer electrons to the Ni sites,increasing the local electron density of Ni which enhances the adsorption and activation of H_(2).Furthermore,the Ru-Ni metal interface sites improve the adsorption and activation of CO_(2)In situ Diffuse Reflectance Infrared Fourier Transform Spectroscopy(DRIFTS)analysis indicates that adjusting the electronic structure of N sites can accelerate the production of intermediates HCOO^(*),while Ru-Ni intermetallic interface sites can directly dissociate CO_(2)into CO^(*).In addition,CO_(2)methanation on the Ru-Ni-Al catalyst follows HCOO^(*)-and CO^(*)-mediated pathways.This study underscores the potential fo enhancing CO_(2)methanation performance by modulating the electronic structure of Ni sites.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
To achieve a complete industrial chain of hydrogen energy,the development of efficient electrocatalysts for hydrogen evolution reaction(HER)is of great concerns.Herein,a nickel nitride supported platinum(Pt)catalyst w...To achieve a complete industrial chain of hydrogen energy,the development of efficient electrocatalysts for hydrogen evolution reaction(HER)is of great concerns.Herein,a nickel nitride supported platinum(Pt)catalyst with highly exposed Pt(110)facets(Pt_((110))-Ni_(3)N)is obtained for catalyzing HER.Combined X-ray spectra and density functional theory studies demonstrate that the interfacial electronic interaction between Pt and Ni3N support can promote the hydrogen evolution on Pt(110)facets by weakening hydrogen adsorption.As a result,the Pt_((110))-Ni_(3)N catalyst delivers an obviously higher specific activity than commercial 20 wt.%Pt/C in acidic media.This work suggests that the suitable interface modulation may play a vital role in rationally designing advanced electrocatalysts.展开更多
Tackling the problem of poor conductivity and catalytic stability of pristine metal-organic frameworks(MOFs) is crucial to improve their oxygen evolution reaction(OER) performance.Herein,we introduce a novel strategy ...Tackling the problem of poor conductivity and catalytic stability of pristine metal-organic frameworks(MOFs) is crucial to improve their oxygen evolution reaction(OER) performance.Herein,we introduce a novel strategy of dysprosium(Dy) doping,using the unique 4f orbitals of this rare earth element to enhance electrocatalytic activity of MOFs.Our method involves constructing Dy-doped Ni-MOF(Dy@Ni-MOF) nanoneedles on carbon cloth via a Dy-induced valence electronic perturbation approach.Experiments and density functional theory(DFT) calculations reveal that Dy doping can effectively modify the electronic structure of the Ni active centers and foster a strong electronic interaction between Ni and Dy.The resulting benefits include a reduced work function and a closer proximity of the d-band center to the Fermi level,which is conducive to improving electrical conductivity and promoting the adsorption of oxygen-containing intermediates.Furthermore,the Dy@Ni-MOF achieves superhydrophilicity,ensuring effective electrolyte contact and thus accelerating reaction kinetics,Ex-situ and in-situ analysis results manifest Dy_(2)O_(3)/NiOOH as the actual active species.Therefore,Dy@Ni-MOF shows impressive OER performance,significantly surpassing Ni-MOF.Besides,the overall water splitting device with Dy@NiMOF as an anode delivers a low cell voltage of 1.51 V at 10 mA cm^(-2) and demonstrates long-term stability for 100 h,positioning it as a promising substitute for precious metal catalysts.展开更多
Constructing the efficacious and applicable bifunctional electrocatalysts and establishing out the mechanisms of organic electro-oxidation by replacing anodic oxygen evolution reaction(OER) are critical to the develop...Constructing the efficacious and applicable bifunctional electrocatalysts and establishing out the mechanisms of organic electro-oxidation by replacing anodic oxygen evolution reaction(OER) are critical to the development of electrochemicallydriven technologies for efficient hydrogen production and avoid CO_(2) emission. Herein, the hetero-nanocrystals between monodispersed Pt(~ 2 nm) and Ni_(3)S_(2)(~ 9.6 nm) are constructed as active electrocatalysts through interfacial electronic modulation, which exhibit superior bi-functional activities for methanol selective oxidation and H_(2) generation. The experimental and theoretical studies reveal that the asymmetrical charge distribution at Pt–Ni_(3)S_(2) could be modulated by the electronic interaction at the interface of dual-monodispersed heterojunctions, which thus promote the adsorption/desorption of the chemical intermediates at the interface. As a result, the selective conversion from CH_(3)OH to formate is accomplished at very low potentials(1.45 V) to attain 100 m A cm^(-2) with high electronic utilization rate(~ 98%) and without CO_(2) emission. Meanwhile, the Pt–Ni_(3)S_(2) can simultaneously exhibit a broad potential window with outstanding stability and large current densities for hydrogen evolution reaction(HER) at the cathode. Further, the excellent bi-functional performance is also indicated in the coupled methanol oxidation reaction(MOR)//HER reactor by only requiring a cell voltage of 1.60 V to achieve a current density of 50 m A cm^(-2) with good reusability.展开更多
We investigate the geometries and energies of seven electronic states X-1A1, A1B1, a-3B1, B-1A2,b-3A2, C1B2 and c-3B2 of CF2 carbene using internally contracted multireference configuration interaction methods includi...We investigate the geometries and energies of seven electronic states X-1A1, A1B1, a-3B1, B-1A2,b-3A2, C1B2 and c-3B2 of CF2 carbene using internally contracted multireference configuration interaction methods including Davidson correction （icMRCIq-Q） with different basis sets aug-cc-pVXZ （X=T, Q, 5）. For the first time, the potential energy curves of electronic states of CF2 related icMRCI＋Q/aug-cc-pVTZ level. The ab initio results will and dynamics of electronic states of CF2 radical. to the lowest dissociation limit are calculated at the further increase our understanding of the structures展开更多
As hydrogen energy technologies gain momentum,the role of renewable energy in facilitating sustainable hydrogen production is becoming increasingly critical.As a hydrogen production method,water electrolysis has attra...As hydrogen energy technologies gain momentum,the role of renewable energy in facilitating sustainable hydrogen production is becoming increasingly critical.As a hydrogen production method,water electrolysis has attracted much attention from researchers due to its operational simplicity,the high purity of the hydrogen generated,and its potential for achieving zero carbon emissions throughout the process.Numerous studies has been manipulated on platinum(Pt)-based catalysts,which exhibit superior performance in hydrogen evolution reactions.Within this category,Pt nanoclusters stand out due to their unique attributes,such as quantum size effects and unique coordination environments.These features enable them to outperform both Pt metal atoms and nanoparticles in hydrogen evolution reactions regarding activity and stability.Here,we primarily delve into the reaction mechanisms underlying Pt nanocluster-based hydrogen catalysts,with particular emphasis on the interactions between the metal catalysts and their associated support materials.We provide an exhaustive summary of the strategies employed in the synthesis,the structural analyses conducted,and the performance metrics observed for Pt nanocluster catalysts when paired with various supporting materials.In closing,we explore the future potential and challenges facing Pt nanocluster-based catalysts in the context of industrial water electrolysis,along with emerging avenues for their design and optimization.展开更多
Propane dehydrogenation(PDH)is a vital industrial process for producing propene,utilizing primarily Cr-based or Pt-based catalysts.These catalysts often suffer from challenges such as the toxicity of Cr,the high costs...Propane dehydrogenation(PDH)is a vital industrial process for producing propene,utilizing primarily Cr-based or Pt-based catalysts.These catalysts often suffer from challenges such as the toxicity of Cr,the high costs of noble metals like Pt,and deactivation issues due to sintering or coke formation at elevated temperatures.We introduce an exceptional Ru-based catalyst,Ru nanoparticles anchored on a nitrogendoped carbon matrix(Ru@NC),which achieves a propane conversion rate of 32.2%and a propene selectivity of 93.1%at 550°C,with minimal coke deposition and a low deactivation rate of 0.0065 h^(-1).Characterizations using techniques like TEM and XPS,along with carefully-designed controlled experiments,reveal that the notable performance of Ru@NC stems from the modified electronic state of Ru by nitrogen dopant and the microporous nature of the matrix,positioning it as a top contender among state-of-the-art PDH catalysts.展开更多
Proton exchange membrane(PEM)water electrolysis presents considerable advantages in green hydrogen production.Nevertheless,oxygen evolution reaction(OER)catalysts in PEM water electrolysis currently encounter several ...Proton exchange membrane(PEM)water electrolysis presents considerable advantages in green hydrogen production.Nevertheless,oxygen evolution reaction(OER)catalysts in PEM water electrolysis currently encounter several pressing challenges,including high noble metal loading,low mass activity,and inadequate durability,which impede their practical application and commercialization.Here we report a self-constructed layered catalyst for acidic OER by directly using an Ir–Ta-based metallic glass as the matrix,featuring a nanoporous IrO_(2) surface formed in situ on the amorphous IrTaO_(x) nanostructure during OER.This distinctive architecture significantly enhances the accessibility and utilization of Ir,achieving a high mass activity of 1.06 A mg_(Ir)^(−1) at a 300 mV overpotential,13.6 and 31.2 times greater than commercial Ir/C and IrO_(2),respectively.The catalyst also exhibits superb stability under industrial-relevant current densities in acid,indicating its potential for practical uses.Our analyses reveal that the coordinated nature of the surface-active Ir species is effectively modulated through electronic interaction between Ir and Ta,preventing them from rapidly evolving into high valence states and suppressing the lattice oxygen participation.Furthermore,the underlying IrTaO_(x) dynamically replenishes the depletion of surface-active sites through inward crystallization and selective dissolution,thereby ensuring the catalyst’s long-term durability.展开更多
CO_(2) conversion to CO via the reverse water-gas shift(RWGS)reaction is limited by a low CO_(2) conversion rate and CO selectivity.Herein,an efficient RWGS catalyst is constructed through Enteromorpha prolifera–deri...CO_(2) conversion to CO via the reverse water-gas shift(RWGS)reaction is limited by a low CO_(2) conversion rate and CO selectivity.Herein,an efficient RWGS catalyst is constructed through Enteromorpha prolifera–derived N-rich mesoporous biochar(EPBC)supported atomic-level Cu-Mo_(2)C clusters(Cu-Mo_(2)C/EPBC).Unlike traditional acti-vated carbon(AC)supported Cu-Mo_(2)C particles(Cu-Mo_(2)C/AC),the Cu-Mo_(2)C/EPBC not only presents the better graphitization degree and larger specific surface area,but also uniformly andfirmly anchors atomic-level Cu-Mo_(2)C clusters due to the existence of pyridine nitrogen.Furthermore,the pyridine N of Cu-Mo_(2)C/EPBC strengthens an unblocked electron transfer between Mo_(2)C and Cu clusters,as verified by X-ray absorption spectroscopy.As a result,the synergistic effect between pyridinic N anchoring and the clusters interaction in Cu-Mo_(2)C/EPBC facilitates an improved CO selectivity of 99.95%at 500℃ compared with traditional Cu-Mo_(2)C/AC(99.60%),as well as about 3-fold CO_(2) conversion rate.Density functional theory calculations confirm that pyr-idine N-modified carbon activates the local electronic redistribution at Cu-Mo_(2)C clusters,which contributes to the decreased energy barrier of the transition state of CO^(*)+O^(*)+2H^(*),thereby triggering the transformation of rate-limited step during the redox pathway.This biomass-derived strategy opens perspective on producing sustain-able fuels and building blocks through the RWGS reaction.展开更多
Development of efficient and stable metal catalysts for the selective aqueous phase hydrodeoxygenation(HDO)of biomass-derived oxygenates to value-added biofuels is highly desired.An innovative surface microenvironment...Development of efficient and stable metal catalysts for the selective aqueous phase hydrodeoxygenation(HDO)of biomass-derived oxygenates to value-added biofuels is highly desired.An innovative surface microenvironment modulation strategy was used to construct the nitrogen-doped hollow carbon sphere encapsulated with Pd(Pd@NHCS-X,X:600–800)nanoreactors for catalytic HDO of biomass-derived vanillin in water.The specific surface microenvironments of Pd@NHCS catalysts including the electronic property of active Pd centers and the surface wettability and porous structure of NHCS supports could be well-controlled by the calcination temperature of catalysts.Intrinsic kinetic evaluations demonstrated that the Pd@NHCS-600 catalyst presented a high turnover frequency of 337.77 h^(–1)and a low apparent activation energy of 18.63 kJ/mol.The excellent catalytic HDO performance was attributed to the unique surface microenvironment of Pd@NHCS catalyst based on structure-performance relationship analysis and DFT calculations.It revealed that pyridinic N species dominated the electronic property regulation of Pd sites through electronic metal-support interaction(EMSI)and produced numerous electron-rich active Pd centers,which not only intensified the dissociation and activation of H2 molecules,but also substantially improved the activation capability of vanillin via the enhanced adsorption of–C=O group.The fine hydrophilicity and abundant porous structure promoted the uniform dispersion of catalyst and ensured the effective access of reactants to catalytic active centers in water.Additionally,the Pd@NHCS-600 catalyst exhibited excellent catalytic stability and broad substrate applicability for the selective aqueous phase HDO of various biomass-derived carbonyl compounds.The proposed surface microenvironment modulation strategy will provide a new consideration for the rational design of high-performance nitrogen-doped carbon-supported metal catalysts for catalytic biomass transformation.展开更多
Single-atom catalysts(SACs)offer a promising approach for maximizing noble metals utilization in catalytic processes.However,their performance in CO_(2)hydrogenation is often constrained by the nature of metal-support...Single-atom catalysts(SACs)offer a promising approach for maximizing noble metals utilization in catalytic processes.However,their performance in CO_(2)hydrogenation is often constrained by the nature of metal-support interactions.In this study,we synthesized TiO_(2)supported Pt SACs(Pt1/TiO_(2)),with Pt single atoms dispersed on rutile(Pt1/R)and anatase(Pt1/A)phases of TiO_(2)for the reverse water-gas shift(RWGS)reaction.While both catalysts maintained 100%CO selectivity over time,Pt1/A achieved a CO_(2)conversion of 7.5%,significantly outperforming Pt1/R(3.6%).In situ diffuse reflectance infrared Fourier-transform spectroscopy and X-ray photoelectron spectroscopy revealed distinct reaction pathways:the COOH pathway was dominant on Pt1/A,whereas the–OH+HCO pathway was more competitive on Pt1/R.Analysis of electron metal-support interactions and energy barrier calculations indicated that Pt1/A better stabilized metallic Pt species and facilitates more favorable reaction pathways with lower energy barriers.These findings provide valuable insights for the design of more efficient SAC systems in CO_(2)hydrogenation processes.展开更多
基金Key Research and Development Program of Zhejiang,Grant/Award Number:2021C03022National Natural Science Foundation of China,Grant/Award Numbers:22002104,22272115,22202145,22202146,22102112,22202147。
文摘Catalyst design relies heavily on electronic metal‐support interactions,but the metal‐support interface with an uncontrollable electronic or coordination environment makes it challenging.Herein,we outline a promising approach for the rational design of catalysts involving heteroatoms as anchors for Pd nanoparticles for ethanol oxidation reaction(EOR)catalysis.The doped B and N atoms from dimethylamine borane(DB)occupy the position of the Ti_(3)C_(2) lattice to anchor the supported Pd nanoparticles.The electrons transfer from the support to B atoms,and then to the metal Pd to form a stable electronic center.A strong electronic interaction can be produced and the d‐band center can be shifted down,driving Pd into the dominant metallic state and making Pd nanoparticles deposit uniformly on the support.As‐obtained Pd/DB–Ti_(3)C_(2) exhibits superior durability to its counterpart(∼14.6% retention)with 91.1% retention after 2000 cycles,placing it among the top single metal anodic catalysts.Further,in situ Raman and density functional theory computations confirm that Pd/DB–Ti_(3)C_(2) is capable of dehydrogenating ethanol at low reaction energies.
基金the National Natural Science Foundation of China (22108189, 22278286)Science Foundation for Distinguished Young Scholar of Shanxi Province(202303021223001)SINOPEC 122027
文摘Bimetallic CuCo catalysts with different Cu to Co ratios on N-doped porous carbon materials(N-C)were achieved using impregnation method and applied in the hydrogenation of furfural(FAL)to furfuryl alcohol(FOL).The high hydrogenation activity of FAL over Cu_(1)Co_(1)/N-C was originated from the synergistic interactions of Cu and Co species,where Co^(0)and Cu^(0)simultaneously adsorb and activate H_(2),and Cu^(+) served as Lewis acid sites to activate C]O.Meanwhile,electrons transfer from Cu to Co promoted the formation of Cu^(+).In situ Fourier transform infrared spectroscopy analysis indicated that Cu_(1)Co_(1)/N-C adsorbed FAL with a tilted η^(1)-(O)configuration.The superior Cu_(1)Co_(1)/N-C showed excellent adsorbed ability towards H_(2) and FAL,but weak adsorption for FOL.Therefore,Cu_(1)Co_(1)/N-C possessed 93.1%FAL conversion and 99.0% FOL selectivity after 5 h reaction,which also exhibited satisfactory reusability in FAL hydrogenation for five cycles.
基金financially supported by the National Natural Science Foundation of China (Nos.12074435, 51871250 and 52001335)the Science and Technology Innovation Program of Hunan Province (No.2021RC4001)the State Key Laboratory of Advanced Technologies for Comprehensive Utilization of Platinum Metal (No.SKL-SPM-202005)
文摘The efficiency of electrochemical water splitting is extremely hampered by the sluggish oxygen evolution reaction(OER)occurred at the anode.Therefore,developing high-performance OER electrocatalysts is crucial for realizing the industrialized application of water splitting.Herein,a high-efficiency electrocatalyst of ruthenium-decorated nickel-iron hydroxide(10 Ru-NiFe LDH)supported on Ni foam is successfully synthesized for OER.Modifying NiFe LDH with ruthenium can optimize the electronic density to form high valences of metal sites,which is beneficial to promote its OER performance.Consequently,the 10 Ru-NiFe LDH only needs a low overpotential of 222 mV to achieve a current density of50 mA,cm^(-2),which exhibits fast OER kinetics with a small Tafel slope of 58 mV.dec^(-1).Moreover,this electrocatalyst shows high stability over 20 h at a high current density of 100 mA·cm^(-2)without obvious decay.The decent OER performances can be ascribed to the increased active sites and the synergistic electronic interactions among Ni,Fe and Ru.This work provides an effective approach for designing desirable electrocatalysts for OER.
基金supported by the State Key Laboratory of Urban Water Resource and Environment,Harbin Institute of Technology(No.2019DX13)。
文摘Lithium-sulfur battery is strongly considered as the most promising next-generation energy storage system because of the high theoretical specific capacity.The serious"shuttle effect"and sluggish reaction kinetic limited the commercial application of lithium-sulfur battery.Many hetero structure s were applied to accelerate polysulfides conversion and suppress their migration in lithium-sulfur batteries.Nevertheless,the effect of the interface in heterostructure was not clear.Here,the Co_(2)B@MXene heterostructure is synthesized through chemical reactions at room temperature and employed as the interlayer material for Li-S batteries.The theoretical calculations and experimental results indicate that the interfacial electronic interaction of Co_(2)B@MXene induce the transfer of electrons from Co_(2)B to MXene,enhancing the catalytic ability and favoring fast redox kinetics of the polysulfides,and the theoretical calculations also reveal the underlying mechanisms for the electron transfer is that the two materials have different Fermi energy levels.The cell with Co_(2)B@MXene exhibits a high initial capacity of1577 mAh/g at 0.1 C and an ultralow capacity decay of 0.0088%per cycle over 2000 cycles at 2 C.Even at5.1 mg/cm^(2) of sulfur loading,the cell with Co_(2)B@MXene delivers 5.2 mAh/cm^(2) at 0.2 C.
基金Project supported by the National Natural Science Foundation of China(21707066,21677069)。
文摘For CO catalytic oxidation,Cu and Ce species are of great importance,between which the synergistic effect is worth investigating.In this work,CeO_(2)/Cu_(2)O with Cu_(2)O{111}and{100}planes were comparatively explored on CO catalytic oxidation to reveal the effects of interfacial electronic interactions and oxygen defects.The activity result demonstrates that CeO_(2)/o-Cu_(2)O{111}has superior performance compared with CeO_(2)/c-Cu_(2)O{100}.Credit to the coordination unsaturated copper atoms(Cu_(CUS))on oCu_(2)O{111}surface,the interfacial electronic interactions on CeO_(2)/o-Cu_(2)O{111}are more obvious than those on CeO_(2)/c-Cu_(2)O{100},leading to richer oxygen defect generation,better redox and activation abilities of CO and O_(2)reactants.Furthermore,the reaction mechanism of CeO_(2)/o-Cu_(2)O{111}on CO oxidation is revealed,i.e.,CO and O_(2)are adsorbed on the Cucus on Cu_(2)O{111}and oxygen defect of CeO_(2),respectively,and then synergistically promote the CO oxidation to CO_(2).The work sheds light on the designing optimized ceria and copper-based catalysts and the mechanism of CO oxidation.
基金supported by the National Science Foundation of China(91545117)the Natural Science Foundation of Liaoning Province(201602676)+1 种基金the Fundamental Research Funds for Colleges and Universities in Liaoning Province(LQN201703)the Startup Foundation for Doctors of Shenyang Normal University(BS201620)~~
文摘The electronic metal-support interaction(EMSI)is one of most intriguing phenomena in heterogeneous catalysis.In this work,this subtle effect is clearly demonstrated by density functional theory(DFT)calculations of single Pt atom supported on vacancies in a boron nitride nanosheet.Moreover,the relation between the EMSI and the performance of Pt in propane direct dehydrogenation(PDH)is investigated in detail.The charge state and partial density of states of single Pt atom show distinct features at different anchoring positions,such as boron and nitrogen vacancies(Bvac and Nvac,respectively).Single Pt atom become positively and negatively charged on Bvac and Nvac,respectively.Therefore,the electronic structure of Pt can be adjusted by rational deposition on the support.Moreover,Pt atoms in different charge states have been shown to have different catalytic abilities in PDH.The DFT calculations reveal that Pt atoms on Bvac(Pt-Bvac)have much higher reactivity towards reactant/product adsorption and C–H bond activation than Pt supported on Nvac(Pt-Nvac),with larger adsorption energy and lower barrier along the reaction pathway.However,the high reactivity of Pt-Bvac also hinders propene desorption,which could lead to unwanted deep dehydrogenation.Therefore,the results obtained herein suggest that a balanced reactivity for C–H activation in propane and propene desorption is required to achieve optimum yields.Based on this descriptor,a single Pt atom on a nitrogen vacancy is considered an effective catalyst for PDH.Furthermore,the deep dehydrogenation of the formed propene is significantly suppressed,owing to the large barrier on Pt-Nvac.The current work demonstrates that the catalytic properties of supported single Pt atoms can be tuned by rationally depositing them on a boron nitride nanosheet and highlights the great potential of single-atom catalysis in the PDH reaction.
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 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support from the National Natural Science Foundation of China(22278006)Open Project Fund from Guangdong Provincial Key Laboratory of Materials and Technology for Energy Conversion,Guangdong Technion-Israel Institute of Technology(MATEC2024KF009)Open Research Fund of State Key Laboratory of Mesoscience and Engineering(MESO-23-D13)。
文摘Nickle-based catalysts are commonly used for CO_(2)methanation.However,there is still potential to improve their catalytic performanc under mild conditions.In this study,we synthesized a series of Ru-Ni-Al catalysts from Ru-doped NiAl-hydrotalcite using a hydrotherma method.The Ru-Ni-Al catalyst demonstrated much higher activity for CO_(2)methanation than the Ni-Al catalyst that did not have Ru doping Both experimental results and theoretical calculations indicate that the enhanced performance of the Ru-Ni-Al catalyst is related to electroni interactions between nickel(Ni)and ruthenium(Ru).The Ru sites transfer electrons to the Ni sites,increasing the local electron density of Ni which enhances the adsorption and activation of H_(2).Furthermore,the Ru-Ni metal interface sites improve the adsorption and activation of CO_(2)In situ Diffuse Reflectance Infrared Fourier Transform Spectroscopy(DRIFTS)analysis indicates that adjusting the electronic structure of N sites can accelerate the production of intermediates HCOO^(*),while Ru-Ni intermetallic interface sites can directly dissociate CO_(2)into CO^(*).In addition,CO_(2)methanation on the Ru-Ni-Al catalyst follows HCOO^(*)-and CO^(*)-mediated pathways.This study underscores the potential fo enhancing CO_(2)methanation performance by modulating the electronic structure of Ni sites.
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This program was financially supported by the National Key R&D Program of China(No.2020YFA0405800)the National Natural Science Foundation of China(NSFC)(Nos.U1932201,and 51902303)+2 种基金CAS International Partnership Program(No.211134KYSB20190063)China Postdoctoral Science Foundation(Nos.BX20200322,and 2020M682009)the Natural Science Foundation of Anhui Province(No.2108085QA31).
文摘To achieve a complete industrial chain of hydrogen energy,the development of efficient electrocatalysts for hydrogen evolution reaction(HER)is of great concerns.Herein,a nickel nitride supported platinum(Pt)catalyst with highly exposed Pt(110)facets(Pt_((110))-Ni_(3)N)is obtained for catalyzing HER.Combined X-ray spectra and density functional theory studies demonstrate that the interfacial electronic interaction between Pt and Ni3N support can promote the hydrogen evolution on Pt(110)facets by weakening hydrogen adsorption.As a result,the Pt_((110))-Ni_(3)N catalyst delivers an obviously higher specific activity than commercial 20 wt.%Pt/C in acidic media.This work suggests that the suitable interface modulation may play a vital role in rationally designing advanced electrocatalysts.
基金supported by the National Natural Science Foundation of China(52363028,21965005)the Natural Science Foundation of Guangxi Province(2021GXNSFAA076001)the Guangxi Technology Base and Talent Subject(GUIKE AD18126001,GUIKE AD20297039)。
文摘Tackling the problem of poor conductivity and catalytic stability of pristine metal-organic frameworks(MOFs) is crucial to improve their oxygen evolution reaction(OER) performance.Herein,we introduce a novel strategy of dysprosium(Dy) doping,using the unique 4f orbitals of this rare earth element to enhance electrocatalytic activity of MOFs.Our method involves constructing Dy-doped Ni-MOF(Dy@Ni-MOF) nanoneedles on carbon cloth via a Dy-induced valence electronic perturbation approach.Experiments and density functional theory(DFT) calculations reveal that Dy doping can effectively modify the electronic structure of the Ni active centers and foster a strong electronic interaction between Ni and Dy.The resulting benefits include a reduced work function and a closer proximity of the d-band center to the Fermi level,which is conducive to improving electrical conductivity and promoting the adsorption of oxygen-containing intermediates.Furthermore,the Dy@Ni-MOF achieves superhydrophilicity,ensuring effective electrolyte contact and thus accelerating reaction kinetics,Ex-situ and in-situ analysis results manifest Dy_(2)O_(3)/NiOOH as the actual active species.Therefore,Dy@Ni-MOF shows impressive OER performance,significantly surpassing Ni-MOF.Besides,the overall water splitting device with Dy@NiMOF as an anode delivers a low cell voltage of 1.51 V at 10 mA cm^(-2) and demonstrates long-term stability for 100 h,positioning it as a promising substitute for precious metal catalysts.
基金the financial support of Guangdong Basic and Applied Basic Research Foundation (No. 2023A1515010940)Shenzhen Natural Science Fund (the Stable Support Plan Program No. 20220809160022001)the Shenzhen Science and Technology Programs (No. ZDSYS20220527171401003, KQTD20190929173914967)。
文摘Constructing the efficacious and applicable bifunctional electrocatalysts and establishing out the mechanisms of organic electro-oxidation by replacing anodic oxygen evolution reaction(OER) are critical to the development of electrochemicallydriven technologies for efficient hydrogen production and avoid CO_(2) emission. Herein, the hetero-nanocrystals between monodispersed Pt(~ 2 nm) and Ni_(3)S_(2)(~ 9.6 nm) are constructed as active electrocatalysts through interfacial electronic modulation, which exhibit superior bi-functional activities for methanol selective oxidation and H_(2) generation. The experimental and theoretical studies reveal that the asymmetrical charge distribution at Pt–Ni_(3)S_(2) could be modulated by the electronic interaction at the interface of dual-monodispersed heterojunctions, which thus promote the adsorption/desorption of the chemical intermediates at the interface. As a result, the selective conversion from CH_(3)OH to formate is accomplished at very low potentials(1.45 V) to attain 100 m A cm^(-2) with high electronic utilization rate(~ 98%) and without CO_(2) emission. Meanwhile, the Pt–Ni_(3)S_(2) can simultaneously exhibit a broad potential window with outstanding stability and large current densities for hydrogen evolution reaction(HER) at the cathode. Further, the excellent bi-functional performance is also indicated in the coupled methanol oxidation reaction(MOR)//HER reactor by only requiring a cell voltage of 1.60 V to achieve a current density of 50 m A cm^(-2) with good reusability.
基金Supported by the 2014 Postdoctoral Sustentation Fund of Qingdao under Grant No 01020120517the Natural Science Foundation of Shandong Province under Grant No ZR2014AP001+1 种基金the National Natural Science Foundation of China under Grant No11447226the Scientific Research Foundation of Shandong University of Science and Technology for Recruited Talents under Grant No 2015RCJJ015
文摘We investigate the geometries and energies of seven electronic states X-1A1, A1B1, a-3B1, B-1A2,b-3A2, C1B2 and c-3B2 of CF2 carbene using internally contracted multireference configuration interaction methods including Davidson correction （icMRCIq-Q） with different basis sets aug-cc-pVXZ （X=T, Q, 5）. For the first time, the potential energy curves of electronic states of CF2 related icMRCI＋Q/aug-cc-pVTZ level. The ab initio results will and dynamics of electronic states of CF2 radical. to the lowest dissociation limit are calculated at the further increase our understanding of the structures
基金the National Key Research and Development Program of China(No.2022YFB4102000)the National Natural Science Foundation of China(NSFC,Nos.22102018 and 52171201)+4 种基金the Huzhou Science and Technology Bureau(No.2022GZ45)the Hefei National Research Center for Physical Sciences at the Microscale(No.KF2021005)the China Postdoctoral Science Foundation-Funded Project(No.2022M710601)the Huzhou Science and Technology Bureau(No.2023GZ02)the Natural Science Foundation of Sichuan Province(No.24NSFSC5779)。
文摘As hydrogen energy technologies gain momentum,the role of renewable energy in facilitating sustainable hydrogen production is becoming increasingly critical.As a hydrogen production method,water electrolysis has attracted much attention from researchers due to its operational simplicity,the high purity of the hydrogen generated,and its potential for achieving zero carbon emissions throughout the process.Numerous studies has been manipulated on platinum(Pt)-based catalysts,which exhibit superior performance in hydrogen evolution reactions.Within this category,Pt nanoclusters stand out due to their unique attributes,such as quantum size effects and unique coordination environments.These features enable them to outperform both Pt metal atoms and nanoparticles in hydrogen evolution reactions regarding activity and stability.Here,we primarily delve into the reaction mechanisms underlying Pt nanocluster-based hydrogen catalysts,with particular emphasis on the interactions between the metal catalysts and their associated support materials.We provide an exhaustive summary of the strategies employed in the synthesis,the structural analyses conducted,and the performance metrics observed for Pt nanocluster catalysts when paired with various supporting materials.In closing,we explore the future potential and challenges facing Pt nanocluster-based catalysts in the context of industrial water electrolysis,along with emerging avenues for their design and optimization.
基金supported by the National Key Research and Development Project of China(No.2022YFE0113800)the National Natural Science Foundation of China(No.22102013)+2 种基金Natural Science Foundation of Chongqing(No.cstc2021jcyj-msxmX0945)Venture and Innovation Support Program for Chongqing Overseas Returnees(No.cx2020107)Thousand Talents Program for Distinguished Young Scholars,Postdoctoral Fellowship Program of CPSF(No.GZB20230910)。
文摘Propane dehydrogenation(PDH)is a vital industrial process for producing propene,utilizing primarily Cr-based or Pt-based catalysts.These catalysts often suffer from challenges such as the toxicity of Cr,the high costs of noble metals like Pt,and deactivation issues due to sintering or coke formation at elevated temperatures.We introduce an exceptional Ru-based catalyst,Ru nanoparticles anchored on a nitrogendoped carbon matrix(Ru@NC),which achieves a propane conversion rate of 32.2%and a propene selectivity of 93.1%at 550°C,with minimal coke deposition and a low deactivation rate of 0.0065 h^(-1).Characterizations using techniques like TEM and XPS,along with carefully-designed controlled experiments,reveal that the notable performance of Ru@NC stems from the modified electronic state of Ru by nitrogen dopant and the microporous nature of the matrix,positioning it as a top contender among state-of-the-art PDH catalysts.
基金financially supported by the National Natural Science Foundation of China(Nos.52101202,52071024)the Funds for Creative Research Groups of China(No.51921001)+3 种基金the National Key Research and Development Program of China(No.2022YFB3707103)the Gusu Leading Talents Program(No.ZXL2021206)the Basic Research Program of Taicang(No.TC2023JC29)the Fundamental Research Fund for the Central Universities of China,GuangDong Basic and Applied Basic Research Foundation,and State Key Lab for Advanced Metals and Materials(No.2024-Z11).
文摘Proton exchange membrane(PEM)water electrolysis presents considerable advantages in green hydrogen production.Nevertheless,oxygen evolution reaction(OER)catalysts in PEM water electrolysis currently encounter several pressing challenges,including high noble metal loading,low mass activity,and inadequate durability,which impede their practical application and commercialization.Here we report a self-constructed layered catalyst for acidic OER by directly using an Ir–Ta-based metallic glass as the matrix,featuring a nanoporous IrO_(2) surface formed in situ on the amorphous IrTaO_(x) nanostructure during OER.This distinctive architecture significantly enhances the accessibility and utilization of Ir,achieving a high mass activity of 1.06 A mg_(Ir)^(−1) at a 300 mV overpotential,13.6 and 31.2 times greater than commercial Ir/C and IrO_(2),respectively.The catalyst also exhibits superb stability under industrial-relevant current densities in acid,indicating its potential for practical uses.Our analyses reveal that the coordinated nature of the surface-active Ir species is effectively modulated through electronic interaction between Ir and Ta,preventing them from rapidly evolving into high valence states and suppressing the lattice oxygen participation.Furthermore,the underlying IrTaO_(x) dynamically replenishes the depletion of surface-active sites through inward crystallization and selective dissolution,thereby ensuring the catalyst’s long-term durability.
基金support from National Natural Science Foundation of China(32101474 and 42377249)National Key Research and Development Program of China(2023YFD2201605).
文摘CO_(2) conversion to CO via the reverse water-gas shift(RWGS)reaction is limited by a low CO_(2) conversion rate and CO selectivity.Herein,an efficient RWGS catalyst is constructed through Enteromorpha prolifera–derived N-rich mesoporous biochar(EPBC)supported atomic-level Cu-Mo_(2)C clusters(Cu-Mo_(2)C/EPBC).Unlike traditional acti-vated carbon(AC)supported Cu-Mo_(2)C particles(Cu-Mo_(2)C/AC),the Cu-Mo_(2)C/EPBC not only presents the better graphitization degree and larger specific surface area,but also uniformly andfirmly anchors atomic-level Cu-Mo_(2)C clusters due to the existence of pyridine nitrogen.Furthermore,the pyridine N of Cu-Mo_(2)C/EPBC strengthens an unblocked electron transfer between Mo_(2)C and Cu clusters,as verified by X-ray absorption spectroscopy.As a result,the synergistic effect between pyridinic N anchoring and the clusters interaction in Cu-Mo_(2)C/EPBC facilitates an improved CO selectivity of 99.95%at 500℃ compared with traditional Cu-Mo_(2)C/AC(99.60%),as well as about 3-fold CO_(2) conversion rate.Density functional theory calculations confirm that pyr-idine N-modified carbon activates the local electronic redistribution at Cu-Mo_(2)C clusters,which contributes to the decreased energy barrier of the transition state of CO^(*)+O^(*)+2H^(*),thereby triggering the transformation of rate-limited step during the redox pathway.This biomass-derived strategy opens perspective on producing sustain-able fuels and building blocks through the RWGS reaction.
文摘Development of efficient and stable metal catalysts for the selective aqueous phase hydrodeoxygenation(HDO)of biomass-derived oxygenates to value-added biofuels is highly desired.An innovative surface microenvironment modulation strategy was used to construct the nitrogen-doped hollow carbon sphere encapsulated with Pd(Pd@NHCS-X,X:600–800)nanoreactors for catalytic HDO of biomass-derived vanillin in water.The specific surface microenvironments of Pd@NHCS catalysts including the electronic property of active Pd centers and the surface wettability and porous structure of NHCS supports could be well-controlled by the calcination temperature of catalysts.Intrinsic kinetic evaluations demonstrated that the Pd@NHCS-600 catalyst presented a high turnover frequency of 337.77 h^(–1)and a low apparent activation energy of 18.63 kJ/mol.The excellent catalytic HDO performance was attributed to the unique surface microenvironment of Pd@NHCS catalyst based on structure-performance relationship analysis and DFT calculations.It revealed that pyridinic N species dominated the electronic property regulation of Pd sites through electronic metal-support interaction(EMSI)and produced numerous electron-rich active Pd centers,which not only intensified the dissociation and activation of H2 molecules,but also substantially improved the activation capability of vanillin via the enhanced adsorption of–C=O group.The fine hydrophilicity and abundant porous structure promoted the uniform dispersion of catalyst and ensured the effective access of reactants to catalytic active centers in water.Additionally,the Pd@NHCS-600 catalyst exhibited excellent catalytic stability and broad substrate applicability for the selective aqueous phase HDO of various biomass-derived carbonyl compounds.The proposed surface microenvironment modulation strategy will provide a new consideration for the rational design of high-performance nitrogen-doped carbon-supported metal catalysts for catalytic biomass transformation.
文摘Single-atom catalysts(SACs)offer a promising approach for maximizing noble metals utilization in catalytic processes.However,their performance in CO_(2)hydrogenation is often constrained by the nature of metal-support interactions.In this study,we synthesized TiO_(2)supported Pt SACs(Pt1/TiO_(2)),with Pt single atoms dispersed on rutile(Pt1/R)and anatase(Pt1/A)phases of TiO_(2)for the reverse water-gas shift(RWGS)reaction.While both catalysts maintained 100%CO selectivity over time,Pt1/A achieved a CO_(2)conversion of 7.5%,significantly outperforming Pt1/R(3.6%).In situ diffuse reflectance infrared Fourier-transform spectroscopy and X-ray photoelectron spectroscopy revealed distinct reaction pathways:the COOH pathway was dominant on Pt1/A,whereas the–OH+HCO pathway was more competitive on Pt1/R.Analysis of electron metal-support interactions and energy barrier calculations indicated that Pt1/A better stabilized metallic Pt species and facilitates more favorable reaction pathways with lower energy barriers.These findings provide valuable insights for the design of more efficient SAC systems in CO_(2)hydrogenation processes.
