The Zn-Al spinel oxide stands out as one of the most active catalysts for high-temperature methanol synthesis from CO_(2)hydrogenation.However,the structure–activity relationship of the reaction remains poorly unders...The Zn-Al spinel oxide stands out as one of the most active catalysts for high-temperature methanol synthesis from CO_(2)hydrogenation.However,the structure–activity relationship of the reaction remains poorly understood due to challenges in atomic-level structural characterizations and analysis of reaction intermediates.In this study,we prepared two Zn-Al spinel oxide catalysts via coprecipitation(ZnAl-C)and hydrothermal(ZnAl-H)methods,and conducted a comparative investigation in the CO_(2)hydrogenation reaction.Surprisingly,under similar conditions,ZnAl-C exhibited significantly higher selectivity towards methanol and DME compared to ZnAl-H.Comprehensive characterizations using X-ray diffraction(XRD),Raman spectroscopy and electron paramagnetic resonance(EPR)unveiled that ZnAl-C catalyst had abundant ZnO species on its surface,and the interaction between the ZnO species and its ZnAl spinel oxide matrix led to the formation of oxygen vacancies,which are crucial for CO_(2)adsorption and activation.Additionally,state-of-the-art solid-state nuclear magnetic resonance(NMR)techniques,including ex-situ and in-situ NMR analyses,confirmed that the surface ZnO facilitates the formation of unique highly reactive interfacial formate species,which was readily hydrogenated to methanol and DME.These insights elucidate the promotion effects of ZnO on the ZnAl spinel oxide in regulating active sites and reactive intermediates for CO_(2)-to-methanol hydrogenation reaction,which is further evidenced by the significant enhancement in methanol and DME selectivity observed upon loading ZnO onto the ZnAl-H catalyst.These molecular-level mechanism understandings reinforce the idea of optimizing the ZnO-ZnAl interface through tailored synthesis methods to achieve activity-selectivity balance.展开更多
CO_(2)hydrogenation to value-added light olefins(C_(2-4)=)is crucial for the utilization and cycling of global carbon resource.Moderate CO_(2)activation and carbon chain growth ability are key factors for iron-based c...CO_(2)hydrogenation to value-added light olefins(C_(2-4)=)is crucial for the utilization and cycling of global carbon resource.Moderate CO_(2)activation and carbon chain growth ability are key factors for iron-based catalysts for efficient CO_(2)conversion to target C_(2-4)=products.The electronic interaction and confinement effect of electron-deficient graphene inner surface on the active phase are effective to improve surface chemical properties and enhance the catalytic performance.Here,we report a core-shell FeCo alloy catalyst with graphene layers confinement prepared by a simple sol-gel method.The electron transfer from Fe species to curved graphene inner surface modifies the surface electronic structure of the active phaseχ-(Fe_(x)Co_(1-x))_(5)C_(2)and improves CO_(2)adsorption capacity,enhancing the efficient conversion of CO_(2)and moderate C-C coupling.Therefore,the catalyst FeCoK@C exhibits C_(2-4)=selectivity of 33.0%while maintaining high CO_(2)conversion of 52.0%.The high stability without obvious deactivation for over 100 h and unprecedented C_(2-4)=space time yield(STY)up to 52.9 mmolCO_(2)·g^(-1)·h^(-1)demonstrate its potential for practical application.This work provides an efficient strategy for the development of high-performance CO_(2)hydrogenation catalysts.展开更多
As one of the most important industrially viable methods for carbon dioxide(CO_(2))utilization,methanol synthesis serves as a platform for production of green fuels and commodity chemicals.For sustainable methanol syn...As one of the most important industrially viable methods for carbon dioxide(CO_(2))utilization,methanol synthesis serves as a platform for production of green fuels and commodity chemicals.For sustainable methanol synthesis,In_(2)O_(3)is an ideal catalyst and has garnered significant attention.Herein,cubic In_(2)O_(3)nanoparticles were prepared via the precipitation method and evaluated for CO_(2)hydrogenation to produce methanol.During the initial 10 h of reaction,CO_(2)conversion gradually increased,accompanied by a slow decrease of methanol selectivity,and the reaction reached equilibrium after 10-20 h on stream.This activation and induction stage may be attributed to the sintering of In_(2)O_(3)nanoparticles and the creation of more oxygen vacancies on In_(2)O_(3)surfaces.Further experimental studies demonstrate that hydrogen induction created additional oxygen vacancies during the catalyst activation stage,enhancing the performance of In_(2)O_(3)catalyst for CO_(2)hydrogenation.Density functional theory calculations and microkinetic simulations further demonstrated that surfaces with higher oxygen vacancy coverages or hydroxylated surfaces formed during this induction period can enhance the reaction rate and increase the CO_(2)conversion.However,they predominantly promote the formation of CO instead of methanol,leading to reduced methanol selectivity.These predictions align well with the above-mentioned experimental observations.Our work thus provides an in-depth analysis of the induction stage of the CO_(2)hydrogenation process on In_(2)O_(3)nano-catalyst,and offers valuable insights for significantly improving the CO_(2)reactivity of In_(2)O_(3)-based catalysts while maintaining long-term stability.展开更多
The pursuit of alternative fuel generation technologies has gained momentum due to the diminishing reserves of fossil fuels and global warming from increased CO_(2)emission.Among the proposed methods,the hydrogenation...The pursuit of alternative fuel generation technologies has gained momentum due to the diminishing reserves of fossil fuels and global warming from increased CO_(2)emission.Among the proposed methods,the hydrogenation of CO_(2)to produce marketable carbon-based products like methanol and ethanol is a practical approach that offers great potential to reduce CO_(2)emissions.Although significant volumes of methanol are currently produced from CO_(2),developing highly efficient and stable catalysts is crucial for further enhancing conversion and selectivity,thereby reducing process costs.An in-depth examination of the differences and similarities in the reaction pathways for methanol and ethanol production highlights the key factors that drive C-C coupling.Identifying these factors guides us toward developing more effective catalysts for ethanol synthesis.In this paper,we explore how different catalysts,through the production of various intermediates,can initiate the synthesis of methanol or ethanol.The catalytic mechanisms proposed by spectroscopic techniques and theoretical calculations,including operando X-ray methods,FTIR analysis,and DFT calculations,are summarized and presented.The following discussion explores the structural properties and composition of catalysts that influence C-C coupling and optimize the conversion rate of CO_(2)into ethanol.Lastly,the review examines recent catalysts employed for selective methanol and ethanol production,focusing on single-atom catalysts.展开更多
Cu/ZnO-based catalysts are widely employed for methanol synthesis via CO_(2) hydrogenation.The preparation procedure is sensitive to the particle size and interfacial structure,which are considered as potential active...Cu/ZnO-based catalysts are widely employed for methanol synthesis via CO_(2) hydrogenation.The preparation procedure is sensitive to the particle size and interfacial structure,which are considered as potential active centers influencing the rate of both methanol and CO formation.The particle size and the interaction between Cu and the support materials are influenced by the coprecipitation conditions,let alone that the mechanistic divergence remains unclear.In this work,a series of Cu/ZnO/ZrO_(2) catalysts were prepared via co-precipitation at different pH value and systematically characterized.The structure has been correlated with kinetic results to establish the structure-performance relationship.Kinetic analysis demonstrates that methanol synthesis follows a single-site Langmuir-Hinshelwood(L-H)mechanism,i.e.,Cu serves as the active site where CO_(2) and H_(2) competitively adsorb and react to form methanol.In contrast,CO formation proceeds via a dual-site L-H mechanism,where CO_(2) adsorbs onto ZnO and H_(2) onto Cu,with the reaction occurring at the Cu/ZnO interface.Therefore,for the direct formation of methanol,solely reducing the particle size of Cu would not be beneficial.展开更多
Heterogeneous solid frustrated-Lewis-pair(FLP)catalyst is of great promise in practical hydrogenation applications.It has been found that all-solid FLPs can be created on ceria via surface oxygen vacancy regulation.Co...Heterogeneous solid frustrated-Lewis-pair(FLP)catalyst is of great promise in practical hydrogenation applications.It has been found that all-solid FLPs can be created on ceria via surface oxygen vacancy regulation.Consequently,it is desired to investigate the mechanisms of the FLP-catalyzed hydrogenation of C=C and C=O and provide insight into the modification of CeO_(2)catalysts for the selective hydrogenation.In this work,the reaction mechanism of the hydrogenation of CH_(2)=CH_(2)and CH_(3)CH=O at the FLP sites constructed on CeO_(2)(110)surface was investigated by density functional theory(DFT),with the classical Lewis acid-base pairs(CLP)site as the reference.The results illustrate that at the CLP site,the dissociated hydride(H^(δ−))forms a stable H−O bond with the surface O atom,while at the FLP site,H^(δ−)is stabilized by Ce,displaying higher activity on the one hand.On the other hand,the electron cloud density of the Ce atom at the FLP site is higher,which can transfer more electrons to the adsorbed C_(C=C)and O_(C=O)atoms,leading to a higher degree of activation for C=C and C=O bonds,as indicated by the Bader charge analysis.Therefore,compared to the CLP site,the FLP site exhibits higher hydrogenation activity for CH_(2)=CH_(2)and CH_(3)CH=O.Furthermore,at the FLP sites,it demonstrates high efficiency in catalyzing the hydrogenation of CH_(2)=CH_(2)with the rate-determining barrier of 1.04 eV,but it shows limited activity for the hydrogenation of CH_(3)CH=O with the rate-determining barrier of 1.94 eV.It means that the selective hydrogenation of C=C can be effectively achieved at the FLP sites concerning selective hydrogenation catalysis.The insights shown in this work help to clarify the reaction mechanism of the hydrogenation of C=C and C=O at FLP site on CeO_(2)(110)and reveal the relationship between the catalytic performance and the nature of the active site,which is of great benefit to development of rational design of heterogeneous FLP catalysts.展开更多
The structure-performance relationship of Cu/Al_(2)O_(3) catalysts in the hydrogenation of diethyl oxalate(DEO)for the synthesis of alcohol ether esters has been investigated by various characterization techniques inc...The structure-performance relationship of Cu/Al_(2)O_(3) catalysts in the hydrogenation of diethyl oxalate(DEO)for the synthesis of alcohol ether esters has been investigated by various characterization techniques including XRD,XPS,N2O titration,and 27Al MAS-NMR.The results showed that when the crystal configurations of Al_(2)O_(3) were the same,increasing the specific surface area could effectively refine the size of copper nanoparticles(Cu NPs),and ultimately improve the conversion of DEO.Meanwhile,the smaller size ofγ-Al_(2)O_(3)(HSAl and SBAl)loaded Cu NPs promotes the reaction towards the deep hydrogenation to produce ethanol(EtOH)and ethylene glycol(EG).Besides,the larger size of Cu NPs on the surface of amorphous Al_(2)O_(3)(HTAl and SolAl)resulted in a lower conversion rate,where ethyl glycolate(Egly)is the main product.Despite there are differences in Al^(3+)ionic coordination in Al_(2)O_(3) with different crystal structures,the experimental data showed that the differences in Al^(3+)ionic coordination did not significantly affect the catalytic performance in the hydrogenation reaction.The formation of alcohol-ether ester chemicals is critically dependent on the interactions between Cu sites and acidic sites.Among them,EG and EtOH were dehydrated to form 2-ethoxyethanol via the SN2 mechanism,while Egly and EtOH were reacted to form ethyl ethoxyacetate(EEA)via the SN2 mechanism.This study provides a theoretical basis for the optimization of the coal-based glycol processes to achieve a diversified product portfolio.展开更多
On the surfaces of celestial bodies with no or thin atmospheres,such as the Moon and Mars,the solar wind irradiation process leads to the formation of hydrogen and helium enriched regions in the extraterrestrial soil ...On the surfaces of celestial bodies with no or thin atmospheres,such as the Moon and Mars,the solar wind irradiation process leads to the formation of hydrogen and helium enriched regions in the extraterrestrial soil particles.However,soil particles on the Earth with the similar composition lack such structures and properties.This discrepancy raises a key question whether there is a direct relationship between solar wind irradiation and the alterations in the structure and chemical performance of extraterrestrial materials.To address this question,this work investigates the effects of proton irradiation,simulating solar wind radiation,on the structure and photothermal catalytic properties of the classic catalyst In_(2)O_(3).It reveals that proton irradiation induces structural features in In_(2)O_(3) analogous to those characteristics of solar wind weathering observed in extraterrestrial materials.Furthermore,after proton beam irradiation with an energy of 30 keV and a dose of 3×10^(17) protons·cm^(-2),the methanol production yield of the In_(2)O_(3) catalyst increased to 2.6 times of its preirradiation level,and the methanol selectivity improved to 2.1 times of the original value.This work provides both theoretical and experimental support for the development of high-efficiency,radiation-resistant photothermal catalysts.展开更多
The production of renewable methanol(CH_(3)OH)via the photocatalytic hydrogenation of CO_(2) is an ideal method to ameliorate energy shortages and mitigate CO_(2) emissions:however,the highly selective synthesis of me...The production of renewable methanol(CH_(3)OH)via the photocatalytic hydrogenation of CO_(2) is an ideal method to ameliorate energy shortages and mitigate CO_(2) emissions:however,the highly selective synthesis of methanol at atmospheric pressure remains challenging owing to the competing reverse water-gas shift(RWGS)reaction.Herein,we present a novel approach for the synthesis of CH_(3)OH via photocatalytic CO_(2) hydrogenation using a catalyst featuring highly dispersed Au nanoparticles loaded on oxygen vacancy(OV)-rich molybdenum dioxide(MoO_(2)),resulting in a remarkable selectivity of 43.78%.The active sites in the Au/MoO_(2) catalyst are high-density Au-oxygen vacancies,which synergistically promote the tandem methanol synthesis via an initial RWGS reaction and subsequent CO hydrogenation.This work provides comprehensive insights into the design of metal-vacancy synergistic sites for the highly selective photocatalytic hydrogenation of CO_(2) to CH_(3)OH.展开更多
Metal-organic frameworks(MOFs)serve as highly effective hosts for ultrasmall metal species,creating advanced nanocatalysts with superior catalytic performance,stability,and selective activity.The synergistic interplay...Metal-organic frameworks(MOFs)serve as highly effective hosts for ultrasmall metal species,creating advanced nanocatalysts with superior catalytic performance,stability,and selective activity.The synergistic interplay between metal species confined within MOF nanopores and their active sites enhances catalytic efficiency in CO_(2)hydrogenation reactions.Herein,recent advancements in synthesizing metal-confined MOFs are discussed,along with their applications in catalyzing CO_(2)conversion through various methods such as photocatalysis,thermal catalysis,and photothermal catalysis.Additionally,we further emphasize the fundamental principles and factors that influence various types of catalytic CO_(2)hydrogenation reactions,while offering insights into future research directions in this dynamic field.展开更多
In the field of catalytic hydro-genation,two primary mecha-nistic pathways,namely the Ho-riuti-Polanyi(HP)mechanism and the non-HP mechanism,have been extensively investi-gated.Current understandings suggested that th...In the field of catalytic hydro-genation,two primary mecha-nistic pathways,namely the Ho-riuti-Polanyi(HP)mechanism and the non-HP mechanism,have been extensively investi-gated.Current understandings suggested that the non-HP mechanism preferred to occur on the coinage metal surfaces,such as copper,silver,and gold,which exhibited low activity towards H_(2) dissociation.Herein,we offered a detailed theoretical investigation into the mechanisms of CO_(2)hydrogenation to formic acid on M_(1)-In_(2)O_(3)(111)surfaces,using density functional theory calculations.Our calculations provided novel in-sights into the preference of the non-HP mechanism on reduced single-atom noble metal cata-lysts,such as r-Rh_(1)-In_(2)O_(3)(111)and r-Ir_(1)-In_(2)O_(3)(111).In these cases,molecularly adsorbed H_(2) would be polarized into H^(δ−)-H^(δ+),thus facilitating the electrophilic attack to the O in CO_(2).Conversely,the H^(δ+)species,derived from heterolytically dissociated H_(2),exhibited a strong affinity on the adjacent oxygen site at the M-O-In interface.This strong adsorption resulted in a higher energy barrier for CO_(2)hydrogenation,thereby rendering the HP mechanism less viable than the non-HP one.Our results were anticipated to provide a deeper understanding of hydrogenation reactions on oxide-supported noble single-atom catalysts and theoretical guidance for the development of novel high-performance catalysts for catalytic hydrogena-tion reactions.展开更多
Fe-based catalysts are widely used for CO_(2)hydrogenation to light olefins(C_(2–4)=);however,precise regulation of active phases and the balance between intermediate reactions remain significant challenges.Herein,we...Fe-based catalysts are widely used for CO_(2)hydrogenation to light olefins(C_(2–4)=);however,precise regulation of active phases and the balance between intermediate reactions remain significant challenges.Herein,we find that the addition of moderate amounts of Ti forms a strong interaction with Fe compositions,modulating the Fe_(3)O_(4)and Fe_(5)C_(2)contents.Enhanced interaction leads to an increased Fe_(5)C_(2)/Fe_(3)O_(4)ratio,which in turn enhances the adsorption of reactants and intermediates,promoting CO hydrogenation to unsaturated alkyl groups and facilitating C–C coupling.Furthermore,the strong Fe-Ti interaction induces the preferential growth of Fe_(5)C_(2)into prismatic structures that expose the(020),(–112),and(311)facets,forming compact active interfacial sites with Fe_(3)O_(4)nanoparticles.These facet and interfacial effects significantly promote the synergistic coupling of the reverse water gas shift and Fischer-Tropsch reactions.The optimized 3K/FeTi catalyst with the highest Fe_(5)C_(2)/Fe_(3)O_(4)ratio of 3.6 achieves a 52.2%CO_(2)conversion rate,with 44.5%selectivity for C2–4=and 9.5%for CO,and the highest space-time yield of 412.0 mg gcat^(–1)h^(–1)for C_(2–4)=.展开更多
CO_(2) hydrogenation to CH3OH is of great significance for achieving carbon neutrality.Here,we show a urea-assisted grinding strategy for synthesizing Cu-Zn-Ce ternary catalysts(CZC-G)with optimized interfacial synerg...CO_(2) hydrogenation to CH3OH is of great significance for achieving carbon neutrality.Here,we show a urea-assisted grinding strategy for synthesizing Cu-Zn-Ce ternary catalysts(CZC-G)with optimized interfacial synergy,achieving superior performance in CO_(2) hydrogenation to methanol.The CZC-G catalyst demonstrated exceptional methanol selectivity(96.8%)and a space-time yield of 73.6 gMeOH·kgcat^(–1)·h^(–1) under optimized conditions.Long-term stability tests confirmed no obvious deactivation over 100 h of continuous operation.Structural and mechanistic analyses revealed that the urea-assisted grinding method promotes the formation of Cu/Zn-O_(v)-Ce ternary interfaces and inhibits the reduction of ZnO,enabling synergistic interactions for efficient CO_(2) activation and selective stabilization of formate intermediates(HCOO^(*)),which are critical for methanol synthesis.In-situ diffuse reflectance infrared Fourier transform spectra and X-ray absorption spectroscopy studies elucidated the reaction pathway dominated by the formate mechanism,while suppressing the reverse water-gas shift reaction.This work underscores the critical role of synthetic methodologies in engineering interfacial structures,offering a strategy for designing high-performance catalysts for sustainable CO_(2) resource utilization.展开更多
Against the backdrop of global energy and environmental crises,the technology of CO_(2)hydrogenation to produce methanol is garnering widespread attention as an innovative carbon capture and utilization solution.Bimet...Against the backdrop of global energy and environmental crises,the technology of CO_(2)hydrogenation to produce methanol is garnering widespread attention as an innovative carbon capture and utilization solution.Bimetallic oxide catalysts have emerged as the most promising research subject in the field due to their exceptional catalytic performance and stability.The performance of bimetallic oxide catalysts is influenced by multiple factors,including the selection of carrier materials,the addition of promoters,and the synthesis process.Different types of bimetallic oxide catalysts exhibit significant differences in microstructure,surface active sites,and electronic structure,which directly determine the yield and selectivity of methanol.Although bimetallic oxide catalysts offer significant advantages over traditional copper-based catalysts,they still encounter challenges related to activity and cost.In order to enhance catalyst performance,future investigations must delve into microstructure control,surface modification,and reaction kinetics.展开更多
Selective synthesis of value-added xylenes and para-xylene(PX)by CO_(2)hydrogenation reduces the dependence on fossil resource and relieves the environment burden derived from the greenhouse gas CO_(2).Herein,modified...Selective synthesis of value-added xylenes and para-xylene(PX)by CO_(2)hydrogenation reduces the dependence on fossil resource and relieves the environment burden derived from the greenhouse gas CO_(2).Herein,modified MCM-22 zeolite combined with ZnCeZrOx solid solution is reported to catalyze the tandem CO_(2)hydrogenation and toluene methylation reaction at a relatively low temperature(<603 K),showing xylene selectivity of 92.4%and PX selectivity of 62%(PX/X,67%)in total aromatics at a CO_(2)conversion of 7.7%,toluene conversion of 23.6%and low CO selectivity of 11.6%,as well as giving high STY of xylene(302.0 mg·h^(–1)·gcat^(–1))and PX(201.6 mg·h^(–1)·gcat^(–1)).The outstanding catalytic performances are closely related to decreased pore sizes and eliminated external surface acid sites in modified MCM-22,which promoted zeolite shape-selectivity and suppressed secondary reactions.展开更多
Direct hydrogenation of CO_(2) to ethanol is a promising approach for utilizing CO_(2).However,it still faces challenges such as lower selectivity and unclear C-C couplingmechanisms.In this work,we prepared Co_(3)O_(4...Direct hydrogenation of CO_(2) to ethanol is a promising approach for utilizing CO_(2).However,it still faces challenges such as lower selectivity and unclear C-C couplingmechanisms.In this work,we prepared Co_(3)O_(4) catalysts and Pt-loaded Co_(3)O_(4) catalysts(Pt-Co_(3)O_(4))to investigate the influence of Pt on the properties of Co_(3)O_(4) catalysts and the CO_(2) hydrogenation process.At 240℃ and 3.2MPa,the reduced 1wt.%Pt-Co_(3)O_(4) catalyst showed 0.265 mmol/(g·h)ethanol yield,while the ethanol yield of the reduced Co_(3)O_(4) catalystwas negligible.The characterization results revealed that the presence of Pt facilitated the regeneration of oxygen vacancies on the catalyst surface,leading to enhanced cycling performance.The in-situ DRIFTS results demonstrated that the ^(*)OCH_(3) generated on the Pt-Ov site underwent couplingwith the ^(*)CH_(3) generated on the Co site,leading to ethanol production.展开更多
Manipulating catalyst structures to control product selectivity while maintaining high activity presents a considerable challenge in CO_(2)hydrogenation.Combining density functional theory calculations and microkineti...Manipulating catalyst structures to control product selectivity while maintaining high activity presents a considerable challenge in CO_(2)hydrogenation.Combining density functional theory calculations and microkinetic analysis,we proposed that graphene-supported isolated Pt atoms(Pt1/graphene)and Pt_(2)dimers(Pt_(2)/graphene)exhibited distinct selectivity in CO_(2)hydrogenation.Pt_(1)/graphene facilitated the conversion of CO_(2)into formic acid,whereas Pt_(2)/graphene favored methanol generation.The variation in product selectivity arose from the synergistic interaction of Pt_(2)dimers,which facilitated the migration of H atoms between two Pt atoms and promoted the transformation from*COOH intermediates to*C(OH)_(2)intermediates,altering the reaction pathways compared to isolated Pt atoms.Additionally,an analysis of the catalytic activities of three Pt_(1)/graphene and three Pt_(2)/graphene structures revealed that the turnover frequencies for formic acid generation on Pt_(1ii)/graphene and methanol generation on Pt_(2i)/graphene were as high as 744.48 h-1and 789.48 h^(-1),respectively.These values rivaled or even surpassed those previously reported in the literature under identical conditions.This study provides valuable insights into optimizing catalyst structures to achieve desired products in CO_(2)hydrogenation.展开更多
The catalytic hydrogenation of carbon dioxide(CO_(2))to methanol(CH_(3)OH)represents a promising strategy for mitigating carbon emissions and closing the carbon cycle.This study demonstrates that the incorporation of ...The catalytic hydrogenation of carbon dioxide(CO_(2))to methanol(CH_(3)OH)represents a promising strategy for mitigating carbon emissions and closing the carbon cycle.This study demonstrates that the incorporation of Cu into MoS_(2)catalysts significantly enhances methanol selectivity and productivity.Through a combination of transmission electron microscope,X-ray diffraction,Raman,electron paramagnetic resonance,X-ray photoelectron spectrosco py,diffu se reflectance Infrared Fourier trans form spectroscopy,Xray absorption spectroscopy,temperature-programmed desorption,and kinetic analysis,we reveal that Cu modifies edge sulfur vacancies,thereby suppressing methane formation and promoting methanol synthesis.At 220℃and 5 MPa,the 2%Cu/MoS_(2)catalyst achieves 85.5%selectivity toward CH_(3)OH,and the methanol formation rate reaches 7.88 mmol gcat^(-1)h^(-1)(0.256 mmol mMoS_(2)-2 h^(-1)),representing the highest performance among MoS_(2)-based catalysts under comparable conditions.This work provides an efficient and potentially scalable approach for designing advanced MoS_(2)-based catalysts for CO_(2)hydrogenation.展开更多
Carbon dioxide hydrogenation to gasoline can effectively alleviate the energy crisis and benefit the global environment.Owing to its orthogonally connected nanosheet configuration,large pore volume,and appropriate thi...Carbon dioxide hydrogenation to gasoline can effectively alleviate the energy crisis and benefit the global environment.Owing to its orthogonally connected nanosheet configuration,large pore volume,and appropriate thickness of single nanosheet,self-pillared pentasil(SPP)nanosheet zeolite is integrated with In_(2)O_(3)-ZrO_(2)as a tandem catalyst for CO_(2)hydrogenation to C_(5+)hydrocarbons.By substituting Al in the SPP framework with Ga,the acid strength of SPP is reduced,and acid density is increased,which favors the generation of C_(5+)hydrocarbons and enhances the cracking resistance of long-chain hydrocarbons.A maximum C_(5+)hydrocarbon selectivity of 82%was obtained on In_(2)O_(3)-ZrO_(2)/Ga-SPP(Si/Ga=100),which shows no deactivation after 200 h reaction time.Furthermore,introducing Pd into the In_(2)O_(3)-ZrO_(2)not only boosts CO_(2)conversion to 11%but also suppresses methane selectivity to below 1%.This study offers valuable insights into the design of highly active CO_(2)-to-gasoline catalysts by leveraging the distinctive structure and acidity of zeolites within the tandem catalyst systems.展开更多
CO2 hydrogenation to formate is an effective strategy for promoting the sustainable carbon cycle.However,formate yields are significantly influenced by the amount of noble metal(e.g.,Pd)used.Here,we present Pd-Ni syne...CO2 hydrogenation to formate is an effective strategy for promoting the sustainable carbon cycle.However,formate yields are significantly influenced by the amount of noble metal(e.g.,Pd)used.Here,we present Pd-Ni synergistic catalysis on the hollow NiCo2O4 spinel arrays(PdxNiy/NCO@CC)for enhanced formate production under mild conditions.The Pd-Ni dual-site structure effectively enhances electron accumulation on Pd via charge polarization and the synergistic interaction between Pd and Ni,leading to significantly improved formate yields with a reduced usage of noble metal catalyst.The optimized Pd5Ni5/NCO@CC catalyst achieved a remarkable formate yield of 282.5 molformate molPd^(-1)h^(-1)at 333 K and demonstrated high stability.This strategy of synergistically enhancing catalytic activity via bimetallic sites highlights its advantages in other catalytic fields and practical applications.展开更多
基金financially National Key R&D Program of China(No.2022YFA1504800)National Natural Science Foundation of China(Grant No.22325405,22372160,22321002)+1 种基金Liaoning Revitalization Talents Program(XLYC1807207)DICP I202104。
文摘The Zn-Al spinel oxide stands out as one of the most active catalysts for high-temperature methanol synthesis from CO_(2)hydrogenation.However,the structure–activity relationship of the reaction remains poorly understood due to challenges in atomic-level structural characterizations and analysis of reaction intermediates.In this study,we prepared two Zn-Al spinel oxide catalysts via coprecipitation(ZnAl-C)and hydrothermal(ZnAl-H)methods,and conducted a comparative investigation in the CO_(2)hydrogenation reaction.Surprisingly,under similar conditions,ZnAl-C exhibited significantly higher selectivity towards methanol and DME compared to ZnAl-H.Comprehensive characterizations using X-ray diffraction(XRD),Raman spectroscopy and electron paramagnetic resonance(EPR)unveiled that ZnAl-C catalyst had abundant ZnO species on its surface,and the interaction between the ZnO species and its ZnAl spinel oxide matrix led to the formation of oxygen vacancies,which are crucial for CO_(2)adsorption and activation.Additionally,state-of-the-art solid-state nuclear magnetic resonance(NMR)techniques,including ex-situ and in-situ NMR analyses,confirmed that the surface ZnO facilitates the formation of unique highly reactive interfacial formate species,which was readily hydrogenated to methanol and DME.These insights elucidate the promotion effects of ZnO on the ZnAl spinel oxide in regulating active sites and reactive intermediates for CO_(2)-to-methanol hydrogenation reaction,which is further evidenced by the significant enhancement in methanol and DME selectivity observed upon loading ZnO onto the ZnAl-H catalyst.These molecular-level mechanism understandings reinforce the idea of optimizing the ZnO-ZnAl interface through tailored synthesis methods to achieve activity-selectivity balance.
文摘CO_(2)hydrogenation to value-added light olefins(C_(2-4)=)is crucial for the utilization and cycling of global carbon resource.Moderate CO_(2)activation and carbon chain growth ability are key factors for iron-based catalysts for efficient CO_(2)conversion to target C_(2-4)=products.The electronic interaction and confinement effect of electron-deficient graphene inner surface on the active phase are effective to improve surface chemical properties and enhance the catalytic performance.Here,we report a core-shell FeCo alloy catalyst with graphene layers confinement prepared by a simple sol-gel method.The electron transfer from Fe species to curved graphene inner surface modifies the surface electronic structure of the active phaseχ-(Fe_(x)Co_(1-x))_(5)C_(2)and improves CO_(2)adsorption capacity,enhancing the efficient conversion of CO_(2)and moderate C-C coupling.Therefore,the catalyst FeCoK@C exhibits C_(2-4)=selectivity of 33.0%while maintaining high CO_(2)conversion of 52.0%.The high stability without obvious deactivation for over 100 h and unprecedented C_(2-4)=space time yield(STY)up to 52.9 mmolCO_(2)·g^(-1)·h^(-1)demonstrate its potential for practical application.This work provides an efficient strategy for the development of high-performance CO_(2)hydrogenation catalysts.
文摘As one of the most important industrially viable methods for carbon dioxide(CO_(2))utilization,methanol synthesis serves as a platform for production of green fuels and commodity chemicals.For sustainable methanol synthesis,In_(2)O_(3)is an ideal catalyst and has garnered significant attention.Herein,cubic In_(2)O_(3)nanoparticles were prepared via the precipitation method and evaluated for CO_(2)hydrogenation to produce methanol.During the initial 10 h of reaction,CO_(2)conversion gradually increased,accompanied by a slow decrease of methanol selectivity,and the reaction reached equilibrium after 10-20 h on stream.This activation and induction stage may be attributed to the sintering of In_(2)O_(3)nanoparticles and the creation of more oxygen vacancies on In_(2)O_(3)surfaces.Further experimental studies demonstrate that hydrogen induction created additional oxygen vacancies during the catalyst activation stage,enhancing the performance of In_(2)O_(3)catalyst for CO_(2)hydrogenation.Density functional theory calculations and microkinetic simulations further demonstrated that surfaces with higher oxygen vacancy coverages or hydroxylated surfaces formed during this induction period can enhance the reaction rate and increase the CO_(2)conversion.However,they predominantly promote the formation of CO instead of methanol,leading to reduced methanol selectivity.These predictions align well with the above-mentioned experimental observations.Our work thus provides an in-depth analysis of the induction stage of the CO_(2)hydrogenation process on In_(2)O_(3)nano-catalyst,and offers valuable insights for significantly improving the CO_(2)reactivity of In_(2)O_(3)-based catalysts while maintaining long-term stability.
基金the Canadian NRCan OERD Energy Innovation Programthe Natural Sciences and Engineering Research Council of Canada,and the Carbon Solution Program for their financial support.
文摘The pursuit of alternative fuel generation technologies has gained momentum due to the diminishing reserves of fossil fuels and global warming from increased CO_(2)emission.Among the proposed methods,the hydrogenation of CO_(2)to produce marketable carbon-based products like methanol and ethanol is a practical approach that offers great potential to reduce CO_(2)emissions.Although significant volumes of methanol are currently produced from CO_(2),developing highly efficient and stable catalysts is crucial for further enhancing conversion and selectivity,thereby reducing process costs.An in-depth examination of the differences and similarities in the reaction pathways for methanol and ethanol production highlights the key factors that drive C-C coupling.Identifying these factors guides us toward developing more effective catalysts for ethanol synthesis.In this paper,we explore how different catalysts,through the production of various intermediates,can initiate the synthesis of methanol or ethanol.The catalytic mechanisms proposed by spectroscopic techniques and theoretical calculations,including operando X-ray methods,FTIR analysis,and DFT calculations,are summarized and presented.The following discussion explores the structural properties and composition of catalysts that influence C-C coupling and optimize the conversion rate of CO_(2)into ethanol.Lastly,the review examines recent catalysts employed for selective methanol and ethanol production,focusing on single-atom catalysts.
基金supported by Research Grant from China Petroleum and Chemical Corp。
文摘Cu/ZnO-based catalysts are widely employed for methanol synthesis via CO_(2) hydrogenation.The preparation procedure is sensitive to the particle size and interfacial structure,which are considered as potential active centers influencing the rate of both methanol and CO formation.The particle size and the interaction between Cu and the support materials are influenced by the coprecipitation conditions,let alone that the mechanistic divergence remains unclear.In this work,a series of Cu/ZnO/ZrO_(2) catalysts were prepared via co-precipitation at different pH value and systematically characterized.The structure has been correlated with kinetic results to establish the structure-performance relationship.Kinetic analysis demonstrates that methanol synthesis follows a single-site Langmuir-Hinshelwood(L-H)mechanism,i.e.,Cu serves as the active site where CO_(2) and H_(2) competitively adsorb and react to form methanol.In contrast,CO formation proceeds via a dual-site L-H mechanism,where CO_(2) adsorbs onto ZnO and H_(2) onto Cu,with the reaction occurring at the Cu/ZnO interface.Therefore,for the direct formation of methanol,solely reducing the particle size of Cu would not be beneficial.
基金supported by the National Natural Science Foundation of China(22302115,22072079)the Fundamental Research Program of Shanxi Province(202303021221056).
文摘Heterogeneous solid frustrated-Lewis-pair(FLP)catalyst is of great promise in practical hydrogenation applications.It has been found that all-solid FLPs can be created on ceria via surface oxygen vacancy regulation.Consequently,it is desired to investigate the mechanisms of the FLP-catalyzed hydrogenation of C=C and C=O and provide insight into the modification of CeO_(2)catalysts for the selective hydrogenation.In this work,the reaction mechanism of the hydrogenation of CH_(2)=CH_(2)and CH_(3)CH=O at the FLP sites constructed on CeO_(2)(110)surface was investigated by density functional theory(DFT),with the classical Lewis acid-base pairs(CLP)site as the reference.The results illustrate that at the CLP site,the dissociated hydride(H^(δ−))forms a stable H−O bond with the surface O atom,while at the FLP site,H^(δ−)is stabilized by Ce,displaying higher activity on the one hand.On the other hand,the electron cloud density of the Ce atom at the FLP site is higher,which can transfer more electrons to the adsorbed C_(C=C)and O_(C=O)atoms,leading to a higher degree of activation for C=C and C=O bonds,as indicated by the Bader charge analysis.Therefore,compared to the CLP site,the FLP site exhibits higher hydrogenation activity for CH_(2)=CH_(2)and CH_(3)CH=O.Furthermore,at the FLP sites,it demonstrates high efficiency in catalyzing the hydrogenation of CH_(2)=CH_(2)with the rate-determining barrier of 1.04 eV,but it shows limited activity for the hydrogenation of CH_(3)CH=O with the rate-determining barrier of 1.94 eV.It means that the selective hydrogenation of C=C can be effectively achieved at the FLP sites concerning selective hydrogenation catalysis.The insights shown in this work help to clarify the reaction mechanism of the hydrogenation of C=C and C=O at FLP site on CeO_(2)(110)and reveal the relationship between the catalytic performance and the nature of the active site,which is of great benefit to development of rational design of heterogeneous FLP catalysts.
文摘The structure-performance relationship of Cu/Al_(2)O_(3) catalysts in the hydrogenation of diethyl oxalate(DEO)for the synthesis of alcohol ether esters has been investigated by various characterization techniques including XRD,XPS,N2O titration,and 27Al MAS-NMR.The results showed that when the crystal configurations of Al_(2)O_(3) were the same,increasing the specific surface area could effectively refine the size of copper nanoparticles(Cu NPs),and ultimately improve the conversion of DEO.Meanwhile,the smaller size ofγ-Al_(2)O_(3)(HSAl and SBAl)loaded Cu NPs promotes the reaction towards the deep hydrogenation to produce ethanol(EtOH)and ethylene glycol(EG).Besides,the larger size of Cu NPs on the surface of amorphous Al_(2)O_(3)(HTAl and SolAl)resulted in a lower conversion rate,where ethyl glycolate(Egly)is the main product.Despite there are differences in Al^(3+)ionic coordination in Al_(2)O_(3) with different crystal structures,the experimental data showed that the differences in Al^(3+)ionic coordination did not significantly affect the catalytic performance in the hydrogenation reaction.The formation of alcohol-ether ester chemicals is critically dependent on the interactions between Cu sites and acidic sites.Among them,EG and EtOH were dehydrated to form 2-ethoxyethanol via the SN2 mechanism,while Egly and EtOH were reacted to form ethyl ethoxyacetate(EEA)via the SN2 mechanism.This study provides a theoretical basis for the optimization of the coal-based glycol processes to achieve a diversified product portfolio.
基金National Key Research and Development Program of China(2020YFA0710302)The Major Research Plan of the National Natural Science Foundation of China(91963206)+2 种基金The National Natural Science Foundation of China(52072169,51972164,51972167,22279053)The Fundamental Research Funds for the Central Universities(14380193)The Program for Guangdong Introducing Innovative and Entrepreneurial Teams(2019ZT08L101).
文摘On the surfaces of celestial bodies with no or thin atmospheres,such as the Moon and Mars,the solar wind irradiation process leads to the formation of hydrogen and helium enriched regions in the extraterrestrial soil particles.However,soil particles on the Earth with the similar composition lack such structures and properties.This discrepancy raises a key question whether there is a direct relationship between solar wind irradiation and the alterations in the structure and chemical performance of extraterrestrial materials.To address this question,this work investigates the effects of proton irradiation,simulating solar wind radiation,on the structure and photothermal catalytic properties of the classic catalyst In_(2)O_(3).It reveals that proton irradiation induces structural features in In_(2)O_(3) analogous to those characteristics of solar wind weathering observed in extraterrestrial materials.Furthermore,after proton beam irradiation with an energy of 30 keV and a dose of 3×10^(17) protons·cm^(-2),the methanol production yield of the In_(2)O_(3) catalyst increased to 2.6 times of its preirradiation level,and the methanol selectivity improved to 2.1 times of the original value.This work provides both theoretical and experimental support for the development of high-efficiency,radiation-resistant photothermal catalysts.
文摘The production of renewable methanol(CH_(3)OH)via the photocatalytic hydrogenation of CO_(2) is an ideal method to ameliorate energy shortages and mitigate CO_(2) emissions:however,the highly selective synthesis of methanol at atmospheric pressure remains challenging owing to the competing reverse water-gas shift(RWGS)reaction.Herein,we present a novel approach for the synthesis of CH_(3)OH via photocatalytic CO_(2) hydrogenation using a catalyst featuring highly dispersed Au nanoparticles loaded on oxygen vacancy(OV)-rich molybdenum dioxide(MoO_(2)),resulting in a remarkable selectivity of 43.78%.The active sites in the Au/MoO_(2) catalyst are high-density Au-oxygen vacancies,which synergistically promote the tandem methanol synthesis via an initial RWGS reaction and subsequent CO hydrogenation.This work provides comprehensive insights into the design of metal-vacancy synergistic sites for the highly selective photocatalytic hydrogenation of CO_(2) to CH_(3)OH.
文摘Metal-organic frameworks(MOFs)serve as highly effective hosts for ultrasmall metal species,creating advanced nanocatalysts with superior catalytic performance,stability,and selective activity.The synergistic interplay between metal species confined within MOF nanopores and their active sites enhances catalytic efficiency in CO_(2)hydrogenation reactions.Herein,recent advancements in synthesizing metal-confined MOFs are discussed,along with their applications in catalyzing CO_(2)conversion through various methods such as photocatalysis,thermal catalysis,and photothermal catalysis.Additionally,we further emphasize the fundamental principles and factors that influence various types of catalytic CO_(2)hydrogenation reactions,while offering insights into future research directions in this dynamic field.
基金supported by the National Key Research and Development Program of Ministry of Sci-ence and Technology of China(No.2022YFA1504601)the National Natural Science Foundation of China(Nos.92045303,22132004,22121001,22072116,22072117,and 21773192).
文摘In the field of catalytic hydro-genation,two primary mecha-nistic pathways,namely the Ho-riuti-Polanyi(HP)mechanism and the non-HP mechanism,have been extensively investi-gated.Current understandings suggested that the non-HP mechanism preferred to occur on the coinage metal surfaces,such as copper,silver,and gold,which exhibited low activity towards H_(2) dissociation.Herein,we offered a detailed theoretical investigation into the mechanisms of CO_(2)hydrogenation to formic acid on M_(1)-In_(2)O_(3)(111)surfaces,using density functional theory calculations.Our calculations provided novel in-sights into the preference of the non-HP mechanism on reduced single-atom noble metal cata-lysts,such as r-Rh_(1)-In_(2)O_(3)(111)and r-Ir_(1)-In_(2)O_(3)(111).In these cases,molecularly adsorbed H_(2) would be polarized into H^(δ−)-H^(δ+),thus facilitating the electrophilic attack to the O in CO_(2).Conversely,the H^(δ+)species,derived from heterolytically dissociated H_(2),exhibited a strong affinity on the adjacent oxygen site at the M-O-In interface.This strong adsorption resulted in a higher energy barrier for CO_(2)hydrogenation,thereby rendering the HP mechanism less viable than the non-HP one.Our results were anticipated to provide a deeper understanding of hydrogenation reactions on oxide-supported noble single-atom catalysts and theoretical guidance for the development of novel high-performance catalysts for catalytic hydrogena-tion reactions.
文摘Fe-based catalysts are widely used for CO_(2)hydrogenation to light olefins(C_(2–4)=);however,precise regulation of active phases and the balance between intermediate reactions remain significant challenges.Herein,we find that the addition of moderate amounts of Ti forms a strong interaction with Fe compositions,modulating the Fe_(3)O_(4)and Fe_(5)C_(2)contents.Enhanced interaction leads to an increased Fe_(5)C_(2)/Fe_(3)O_(4)ratio,which in turn enhances the adsorption of reactants and intermediates,promoting CO hydrogenation to unsaturated alkyl groups and facilitating C–C coupling.Furthermore,the strong Fe-Ti interaction induces the preferential growth of Fe_(5)C_(2)into prismatic structures that expose the(020),(–112),and(311)facets,forming compact active interfacial sites with Fe_(3)O_(4)nanoparticles.These facet and interfacial effects significantly promote the synergistic coupling of the reverse water gas shift and Fischer-Tropsch reactions.The optimized 3K/FeTi catalyst with the highest Fe_(5)C_(2)/Fe_(3)O_(4)ratio of 3.6 achieves a 52.2%CO_(2)conversion rate,with 44.5%selectivity for C2–4=and 9.5%for CO,and the highest space-time yield of 412.0 mg gcat^(–1)h^(–1)for C_(2–4)=.
文摘CO_(2) hydrogenation to CH3OH is of great significance for achieving carbon neutrality.Here,we show a urea-assisted grinding strategy for synthesizing Cu-Zn-Ce ternary catalysts(CZC-G)with optimized interfacial synergy,achieving superior performance in CO_(2) hydrogenation to methanol.The CZC-G catalyst demonstrated exceptional methanol selectivity(96.8%)and a space-time yield of 73.6 gMeOH·kgcat^(–1)·h^(–1) under optimized conditions.Long-term stability tests confirmed no obvious deactivation over 100 h of continuous operation.Structural and mechanistic analyses revealed that the urea-assisted grinding method promotes the formation of Cu/Zn-O_(v)-Ce ternary interfaces and inhibits the reduction of ZnO,enabling synergistic interactions for efficient CO_(2) activation and selective stabilization of formate intermediates(HCOO^(*)),which are critical for methanol synthesis.In-situ diffuse reflectance infrared Fourier transform spectra and X-ray absorption spectroscopy studies elucidated the reaction pathway dominated by the formate mechanism,while suppressing the reverse water-gas shift reaction.This work underscores the critical role of synthetic methodologies in engineering interfacial structures,offering a strategy for designing high-performance catalysts for sustainable CO_(2) resource utilization.
文摘Against the backdrop of global energy and environmental crises,the technology of CO_(2)hydrogenation to produce methanol is garnering widespread attention as an innovative carbon capture and utilization solution.Bimetallic oxide catalysts have emerged as the most promising research subject in the field due to their exceptional catalytic performance and stability.The performance of bimetallic oxide catalysts is influenced by multiple factors,including the selection of carrier materials,the addition of promoters,and the synthesis process.Different types of bimetallic oxide catalysts exhibit significant differences in microstructure,surface active sites,and electronic structure,which directly determine the yield and selectivity of methanol.Although bimetallic oxide catalysts offer significant advantages over traditional copper-based catalysts,they still encounter challenges related to activity and cost.In order to enhance catalyst performance,future investigations must delve into microstructure control,surface modification,and reaction kinetics.
文摘Selective synthesis of value-added xylenes and para-xylene(PX)by CO_(2)hydrogenation reduces the dependence on fossil resource and relieves the environment burden derived from the greenhouse gas CO_(2).Herein,modified MCM-22 zeolite combined with ZnCeZrOx solid solution is reported to catalyze the tandem CO_(2)hydrogenation and toluene methylation reaction at a relatively low temperature(<603 K),showing xylene selectivity of 92.4%and PX selectivity of 62%(PX/X,67%)in total aromatics at a CO_(2)conversion of 7.7%,toluene conversion of 23.6%and low CO selectivity of 11.6%,as well as giving high STY of xylene(302.0 mg·h^(–1)·gcat^(–1))and PX(201.6 mg·h^(–1)·gcat^(–1)).The outstanding catalytic performances are closely related to decreased pore sizes and eliminated external surface acid sites in modified MCM-22,which promoted zeolite shape-selectivity and suppressed secondary reactions.
基金supported by the National Natural Science Foundation of China(Nos.22378203 and 22478193)the Natural Science Foundation of Jiangsu Province(No.BK20240188)+1 种基金Suzhou Science and Technology Plan Project(No.ST202202)the Top-notch Academic Programs Project of Jiangsu Higher Education Institutions.
文摘Direct hydrogenation of CO_(2) to ethanol is a promising approach for utilizing CO_(2).However,it still faces challenges such as lower selectivity and unclear C-C couplingmechanisms.In this work,we prepared Co_(3)O_(4) catalysts and Pt-loaded Co_(3)O_(4) catalysts(Pt-Co_(3)O_(4))to investigate the influence of Pt on the properties of Co_(3)O_(4) catalysts and the CO_(2) hydrogenation process.At 240℃ and 3.2MPa,the reduced 1wt.%Pt-Co_(3)O_(4) catalyst showed 0.265 mmol/(g·h)ethanol yield,while the ethanol yield of the reduced Co_(3)O_(4) catalystwas negligible.The characterization results revealed that the presence of Pt facilitated the regeneration of oxygen vacancies on the catalyst surface,leading to enhanced cycling performance.The in-situ DRIFTS results demonstrated that the ^(*)OCH_(3) generated on the Pt-Ov site underwent couplingwith the ^(*)CH_(3) generated on the Co site,leading to ethanol production.
基金supported by the National Key Research and Development Program(No.2022YFA1505800)the National Natural Science Foundation of China(No.22373092)+5 种基金CAS Project for Young Scientists in Basic Research(No.YSBR-051)China Association for Science and Technology(No.YESS20200031)the Start-up Funding of Central South University(No.502045005)Industry-University-Research Cooperation Projects with Zhejiang NHU Co.,Ltd.Ningbo Fengcheng Advanced Energy Materials Research Institutesupported by USTC Tang Scholarship。
文摘Manipulating catalyst structures to control product selectivity while maintaining high activity presents a considerable challenge in CO_(2)hydrogenation.Combining density functional theory calculations and microkinetic analysis,we proposed that graphene-supported isolated Pt atoms(Pt1/graphene)and Pt_(2)dimers(Pt_(2)/graphene)exhibited distinct selectivity in CO_(2)hydrogenation.Pt_(1)/graphene facilitated the conversion of CO_(2)into formic acid,whereas Pt_(2)/graphene favored methanol generation.The variation in product selectivity arose from the synergistic interaction of Pt_(2)dimers,which facilitated the migration of H atoms between two Pt atoms and promoted the transformation from*COOH intermediates to*C(OH)_(2)intermediates,altering the reaction pathways compared to isolated Pt atoms.Additionally,an analysis of the catalytic activities of three Pt_(1)/graphene and three Pt_(2)/graphene structures revealed that the turnover frequencies for formic acid generation on Pt_(1ii)/graphene and methanol generation on Pt_(2i)/graphene were as high as 744.48 h-1and 789.48 h^(-1),respectively.These values rivaled or even surpassed those previously reported in the literature under identical conditions.This study provides valuable insights into optimizing catalyst structures to achieve desired products in CO_(2)hydrogenation.
基金financially supported by the National Natural Science Foundation of China(22172013 and 22372022)Special Project for Key Research and Development Program of Xinjiang Autonomous Region(2022B01033-3)+3 种基金the Liaoning Revitalization Talent Program(XLYC2203126)the Fundamental Research Funds for the Central Universities(DUT22LAB602)the CUHK Research Startup Fund(No.#4930981)the Excellence Co-innovation Program International Exchange Fund Project(Grant number:DUTIO-ZG-202505)。
文摘The catalytic hydrogenation of carbon dioxide(CO_(2))to methanol(CH_(3)OH)represents a promising strategy for mitigating carbon emissions and closing the carbon cycle.This study demonstrates that the incorporation of Cu into MoS_(2)catalysts significantly enhances methanol selectivity and productivity.Through a combination of transmission electron microscope,X-ray diffraction,Raman,electron paramagnetic resonance,X-ray photoelectron spectrosco py,diffu se reflectance Infrared Fourier trans form spectroscopy,Xray absorption spectroscopy,temperature-programmed desorption,and kinetic analysis,we reveal that Cu modifies edge sulfur vacancies,thereby suppressing methane formation and promoting methanol synthesis.At 220℃and 5 MPa,the 2%Cu/MoS_(2)catalyst achieves 85.5%selectivity toward CH_(3)OH,and the methanol formation rate reaches 7.88 mmol gcat^(-1)h^(-1)(0.256 mmol mMoS_(2)-2 h^(-1)),representing the highest performance among MoS_(2)-based catalysts under comparable conditions.This work provides an efficient and potentially scalable approach for designing advanced MoS_(2)-based catalysts for CO_(2)hydrogenation.
基金financially supported by the National Key Research and Development Program of China(2024YFB4105401)the National Natural Science Foundation of China(22472017)+1 种基金the Liaoning Binhai Laboratory(LBLG-2024-06)the Fundamental Research Funds for the Central Universities(DUT22LAB602and DUT24RC(3)071)。
文摘Carbon dioxide hydrogenation to gasoline can effectively alleviate the energy crisis and benefit the global environment.Owing to its orthogonally connected nanosheet configuration,large pore volume,and appropriate thickness of single nanosheet,self-pillared pentasil(SPP)nanosheet zeolite is integrated with In_(2)O_(3)-ZrO_(2)as a tandem catalyst for CO_(2)hydrogenation to C_(5+)hydrocarbons.By substituting Al in the SPP framework with Ga,the acid strength of SPP is reduced,and acid density is increased,which favors the generation of C_(5+)hydrocarbons and enhances the cracking resistance of long-chain hydrocarbons.A maximum C_(5+)hydrocarbon selectivity of 82%was obtained on In_(2)O_(3)-ZrO_(2)/Ga-SPP(Si/Ga=100),which shows no deactivation after 200 h reaction time.Furthermore,introducing Pd into the In_(2)O_(3)-ZrO_(2)not only boosts CO_(2)conversion to 11%but also suppresses methane selectivity to below 1%.This study offers valuable insights into the design of highly active CO_(2)-to-gasoline catalysts by leveraging the distinctive structure and acidity of zeolites within the tandem catalyst systems.
基金support by the Natural Science Foundation of Jiangsu Province(BK20210867,BK20231342)the China Postdoctoral Science Foundation(2024M752349)+1 种基金National Natural Science Foundation of China(U1604121)the Doctor Project of Mass Entrepreneurship and Innovation in Jiangsu Province.
文摘CO2 hydrogenation to formate is an effective strategy for promoting the sustainable carbon cycle.However,formate yields are significantly influenced by the amount of noble metal(e.g.,Pd)used.Here,we present Pd-Ni synergistic catalysis on the hollow NiCo2O4 spinel arrays(PdxNiy/NCO@CC)for enhanced formate production under mild conditions.The Pd-Ni dual-site structure effectively enhances electron accumulation on Pd via charge polarization and the synergistic interaction between Pd and Ni,leading to significantly improved formate yields with a reduced usage of noble metal catalyst.The optimized Pd5Ni5/NCO@CC catalyst achieved a remarkable formate yield of 282.5 molformate molPd^(-1)h^(-1)at 333 K and demonstrated high stability.This strategy of synergistically enhancing catalytic activity via bimetallic sites highlights its advantages in other catalytic fields and practical applications.
