The continuous depletion of fossil fuels and the effects of climate change have encouraged prompt action to attain carbon neutrality.Technologies that transform and store renewable energy are crucial for creating a su...The continuous depletion of fossil fuels and the effects of climate change have encouraged prompt action to attain carbon neutrality.Technologies that transform and store renewable energy are crucial for creating a sustainable society,which is independent of fossil fuels.In this regard,electrochemical water splitting based on the oxygen evolution reaction(OER)and hydrogen evolution reaction(HER)is an attractive technique for producing carbon-free hydrogen fuels.Additionally,rechargeable metal–air batteries(MABs)are another intriguing way for renewable energy storage through reversible oxygen reactions(OER and the oxygen reduction reaction,ORR).Herein,we comprehensively review bifunctional electrocatalysts for water splitting(HER and OER)and MABs(OER and ORR),particularly 2D carbon material-derived heterostructures.The synthesis and properties of 2D carbon materials and their energy conversion and storage mechanisms are discussed to highlight the bifunc-tionality of the heterostructures.Recent studies on bifunctional electrocatalysts based on 2D carbon-derived heterostructures are also reviewed.Finally,perspectives for future studies and multifunctional catalysts are presented.展开更多
The combination of solar energy and natural hydro-thermal systems will innovate the chemistry ofCO_(2)hydrogenation;however,the approach remains challenging due to the lack of robust and cost-effective catalytic syste...The combination of solar energy and natural hydro-thermal systems will innovate the chemistry ofCO_(2)hydrogenation;however,the approach remains challenging due to the lack of robust and cost-effective catalytic system.Here,Zn which can be recycled with solar energy-induced approach was chosen as the reductant and Co as catalyst to achieve robust hydrothermalCO_(2)methanation.Nanosheets of honeycomb ZnO were grown in situ on the Co surface,resulting in a new motif(Co@ZnO catalyst)that inhibits Co deacti-vation through ZnO-assistedCoOx reduction.The stabilized Co and interaction between Co and ZnO functioned collaboratively toward the full conversion ofCO_(2)–CH_(4).In situ hydrothermal infrared spectros-copy confirmed the formation of formic acid as an intermediate,thereby avoiding CO formation and unwanted side reaction pathways.This study presents a straightforward one-step process for both highly efficientCO_(2)conversion and catalyst synthesis,paving the way for solar-drivenCO_(2)methanation.展开更多
Hydrothermal liquefaction technology is an effective method for the resource utilization and energy conversion of biomass under the dual-carbon context,facilitating the conversion of biomass into liquid fuels and high...Hydrothermal liquefaction technology is an effective method for the resource utilization and energy conversion of biomass under the dual-carbon context,facilitating the conversion of biomass into liquid fuels and high-value chemicals.This paper reviews the latest advancements in the production of liquid fuels and chemicals from biomass hydrothermal liquefaction.It briefly introduces the effects of different types of biomass,such as organic waste,lignocellulosic materials,and algae,on the conversion efficiency and product yield during hydrothermal liquefaction.The specific mechanisms of solvent and catalyst systems in the hydrothermal liquefaction process are analyzed in detail.Compared to water and organic solvents,the biphasic solvent system yields higher concentrations of furan platform compounds,and the addition of an appropriate amount of NaCl to the solvent significantly enhances product yield.Homogeneous catalysts exhibit advantages in reaction rate and selectivity but are limited by high costs and difficulties in separation and recovery.In contrast,heterogeneous catalysts possess good separability and regeneration capabilities and can operate under high-temperature conditions,but their mass transfer efficiency and deactivation issues may affect catalytic performance.The direct hydrothermal catalytic conversion of biomass is also discussed for the efficient production of chemicals and fuels such as hexanol,ethylene glycol,lactic acid,and C5/C6 liquid alkanes.Finally,the advantages and current challenges of producing liquid fuels and chemicals from biomass hydrothermal liquefaction are thoroughly analyzed,along with potential future research directions.展开更多
High density polyethylene(HDPE)pyrolysis and in-line oxidative steam reforming was carried out in a two-step reaction system consisting of a conical spouted bed reactor and a fluidized bed reactor.Continuous plastic p...High density polyethylene(HDPE)pyrolysis and in-line oxidative steam reforming was carried out in a two-step reaction system consisting of a conical spouted bed reactor and a fluidized bed reactor.Continuous plastic pyrolysis was conducted at 550℃ and the volatiles formed were fed in-line to the oxidative steam reforming step(space-time 3.12 gcat min gHDPE−1;ER=0.2 and steam/plastic=3)operating at 700℃.The influence Ni based reforming catalyst support(Al_(2)O_(3),ZrO_(2),SiO_(2))and promoter(CeO_(2),La_(2)O_(3))have on HDPE pyrolysis volatiles conversion and H_(2) production was assessed.The catalysts were prepared by the wet impregnation and they were characterized by means of N_(2) adsorption-desorption,X-ray fluorescence,temperature-programmed reduction and X-ray powder diffraction.A preliminary study on coke deposition and the deterioration of catalysts properties was carried out,by analyzing the tested catalysts through temperature programmed oxidation of coke,transmission electron microscopy,and N_(2) adsorption-desorption.Among the supports tested,ZrO_(2) showed the best performance,attaining conversion and H_(2) production values of 92.2% and 12.8 wt%,respectively.Concerning promoted catalysts,they led to similar conversion values(around 90%),but significant differences were observed in H_(2) production.Thus,higher H_(2) productions were obtained on the Ni/La_(2)O_(3)-Al_(2)O_(3) catalyst(12.1 wt%)than on CeO_(2) promoted catalysts due to La_(2)O_(3) capability for enhancing water adsorption on the catalyst surface.展开更多
The dispersibility of active components in hydrodesulfurization(HDS)catalysts significantly influences the corresponding catalytic performance.In this study,sugar-based materials(glucose,chitosan,soluble starch,and co...The dispersibility of active components in hydrodesulfurization(HDS)catalysts significantly influences the corresponding catalytic performance.In this study,sugar-based materials(glucose,chitosan,soluble starch,and corn starch)were utilized to prepare CoMo bulk HDS catalysts through a sugar foaming process.The foaming intermediates were analyzed using TG,FTIR,and Raman techniques to investigate the pyrolysis and carbonization process,revealing the presence of graphitic carbon in the 3 DPG,3 DPSS,and 3 DPCS catalysts even after calcination in an air atmosphere.The catalysts were further characterized using SEM,XRD,TEM,low-temperature N_(2) physical adsorption,and XPS.The 3 DPSS catalyst exhibited a thiophene conversion of 94.8%at 360℃ and 1 MPa,which could be ascribed to its unique three-dimensional pore structure,high dispersion of MoS_(2)(0.21),and high fraction of Mo^(4+)(83.14%).This study demonstrates the potential of using the sugar foaming technique to develop highly efficient HDS catalysts and provides new insights into the relationship between the physicochemical properties of the obtained catalysts and their catalytic performance.展开更多
The efficient conversion of lignin into mono-cycloalkanes via both C–O and C–C bonds cleavage are attractive,but challenging due to the high C–C bond dissociation energy.Previous studies have demonstrated that NbO_...The efficient conversion of lignin into mono-cycloalkanes via both C–O and C–C bonds cleavage are attractive,but challenging due to the high C–C bond dissociation energy.Previous studies have demonstrated that NbO_(x)-based catalysts exhibited exceptional capabilities for C_(Ar)–C bond cleavage and broken the limitation of lignin monomers.In this work,we presented an economical multifunctional Pt-Nb/MOR catalyst that achieved an impressive monomer yield of 147%during the depolymerization and hydrodeoxygenation of lignin into mono-cycloalkanes.Reaction pathway studies showed that unlike traditional NbO_(x)-based catalytic system,bicyclohexane was an important intermediate in this system and followed the C_(sp3)–C_(sp3)cleavage pathway after complete cyclic-hydrogenation.Deep investigations demonstrated that the doping of Nb in Pt/MOR not only enhanced the activation of hydrogen by Pt,but also increased the acidity of MOR,both of these are favor for the hydrogenolytic cleavage of C_(sp3)–C_(sp3)bonds.This work provides a low-cost catalyst to obtain high-yield monomers from lignin under relatively mild conditions and would help to design catalysts with higher activity for the valorization of lignin.展开更多
Lithium-sulfur(Li-S)batteries are promising for high-energy-density storage,but their performance is limited by sluggish lithium polysulfide(LiPS)conversion kinetics.Here,we tackle this issue by synthesizing ultrafine...Lithium-sulfur(Li-S)batteries are promising for high-energy-density storage,but their performance is limited by sluggish lithium polysulfide(LiPS)conversion kinetics.Here,we tackle this issue by synthesizing ultrafine truncated octahedral TiO_(2) nanocrystals(P-O_(v)-TiO_(2)),featuring specific{101}facets and dual defects—phosphorus doping and oxygen vacancies.Acting as an efficient electrocatalyst in the separator,P-O_(v)-TiO_(2) exhibits superior catalytic properties,where oxygen vacancies modulate the electronic structure,enhancing electron enrichment and charge transfer;phosphorus doping tailors the d-band center of the catalyst,strengthening Ti-S interactions between the{101}facets and LiPSs.As a result,Li-S coin cells modified with P-O_(v)-TiO_(2) achieve a high specific capacity of 895 mAh g^(−1) at 5 C and exhibit a minimal decay rate of 0.14%per cycle over 200 cycles.Furthermore,Li-S pouch cells deliver a high capacity of 1004 mAh g^(−1) at 0.1 C under lean electrolyte conditions.This study elucidates the mechanisms of charge states on specific crystal planes and deepens our understanding of dual-defect engineering in Li-S electrochemistry,offering a promising approach for developing efficient and cost-effective catalysts for Li-S battery applications.展开更多
Hierarchical Ni/ZSM-22-SBA-15 meso-microporous catalysts(Ni/ZS-x)with different acid properties and diffusion characteristics(acid-diffusion)properties were synthesized successfully and applied to the production of hi...Hierarchical Ni/ZSM-22-SBA-15 meso-microporous catalysts(Ni/ZS-x)with different acid properties and diffusion characteristics(acid-diffusion)properties were synthesized successfully and applied to the production of high-quality jet fuel by the efficient one-step hydrogenation(hydrodeoxygenation,isomerization,and cracking)of oleic acid.The acid-diffusion properties of the catalysts are modulated by tuning the ZSM-22 seed content,and their effects on the hydrogenation reactions were investigated.Acid properties affect the extent of isomerization and cleavage reactions,whereas diffusion properties affect the accessibility of active centers.The balanced acid-diffusion properties are conducive to efficient hydrogenation reactions of oleic acid.The optimal Ni/ZS-3 exhibits the highest jet fuel yield(56.3%,340°C)and superior iso/n-alkane ratio(i/n=3.12)because of its well-balanced acid-diffusion properties.Besides,the possible hydrogenation mechanism of oleic acid is proposed.展开更多
Integrating the CO_(2)capture process with the CO_(2)electrochemical reduction process into a single system can eliminate the need for storage and transportation following CO_(2)capture.This integrated process offers ...Integrating the CO_(2)capture process with the CO_(2)electrochemical reduction process into a single system can eliminate the need for storage and transportation following CO_(2)capture.This integrated process offers several advantages over multi-step cascade processes,including reduced costs and enhanced CO_(2)utilization.However,the integrated CO_(2)capture and electrochemical reduction(CCER)process encounters several challenges,including the low CO_(2)adsorption performance of the gas diffusion electrode(GDE)and catalyst,as well as the poor activity and selectivity of the catalyst for the electrochemical reduction of CO_(2).This review aims to systematically summarize the fundamentals of the CCER process.Based on an in-depth understanding of the CO_(2)mass transfer,adsorption,and electrochemical reduction processes,GDE design strategies based on the modulation of wettability and structure are discussed to enhance the CO_(2)capture capability at the GDE level.At the catalyst level,catalyst design strategies based on the introduction of CO_(2)capture sites and the construction of CO_(2)mass transfer channels were analyzed,and catalyst design strategies for enhanced CO_(2)capture were proposed.This review summarizes the most common catalysts for CO_(2)electrochemical reduction,such as Ni-based,Bi-based,and Cubased catalysts,and analyzes their design strategies based on reaction pathways for generating specific products.Finally,the problems and challenges of the CCER process are summarized and proposed,which provide ideas for the further application of this technology in the future.展开更多
Aiming at the problems of insufficient activity and selectivity of Cu-based catalysts in CO_(2)hydrogenation to methanol,Al_(2)O_(3),ZrO_(2)and CeO_(2)modified Cu-ZnO catalysts by the co-precipitation method were prep...Aiming at the problems of insufficient activity and selectivity of Cu-based catalysts in CO_(2)hydrogenation to methanol,Al_(2)O_(3),ZrO_(2)and CeO_(2)modified Cu-ZnO catalysts by the co-precipitation method were prepared,and the influence mechanism of additives on the structure-performance relationship of the catalysts was systematically explored.Through a variety of characterization methods such as XRD,N2 physical adsorption-desorption,TEM,H_(2)-TPR,CO_(2)-TPD and XPS,combined with catalytic performance evaluation experiments,the correlation between the microstructure of catalysts and the reaction performance of CO_(2)hydrogenation to methanol was analyzed in depth.The results show that metal additives significantly improve the performance of catalysts.After the introduction of additives,the specific surface area and pore volume of the catalysts increase,the grain size of Cu decreases,and its dispersion improves.The Ce-modified CZC catalyst exhibited the best performance,with the grain size of CuO as small as 11.41 nm,and the surface oxygen vacancy concentration(OⅡ/OⅠ=3.15)was significantly higher than that of other samples.The reaction performance test shows that under the conditions of 2.8 MPa,8000 h−1 and 280℃,the CO_(2)conversion of the CZC catalyst reached 18.83%,the methanol selectivity was 68.40%,and the methanol yield was 12.88%,all of which are superior to other catalysts.Its excellent performance can be attributed to the fact that CeO_(2)enhances the metal-support interaction,increases the surface basicity,promotes the adsorption and activation of CO_(2),and simultaneously inhibits the reverse water-gas shift side reaction.This study clarifies the structure-activity regulation mechanism of additive modification on Cu-ZnO catalysts,providing a theoretical basis and technical reference for the development of efficient catalysts for CO_(2)hydrogenation to methanol.展开更多
Photothermal catalytic methane dry reforming(DRM)technology can convert greenhouse gases(i.e.CH_(4)and CO_(2))into syngas(i.e.H_(2)and CO),providing more opportunities for reducing the greenhouse effect and achieving ...Photothermal catalytic methane dry reforming(DRM)technology can convert greenhouse gases(i.e.CH_(4)and CO_(2))into syngas(i.e.H_(2)and CO),providing more opportunities for reducing the greenhouse effect and achieving carbon neutrality.In the DRM field,Ni-based catalysts attract wide attention due to their low cost and high activity.However,the carbon deposition over Ni-based catalysts always leads to rapid deactivation,which is still a main challenge.To improve the long-term stability of Ni-based catalysts,this work proposes a carbon-atom-diffusion strategy under photothermal conditions and investigates its effect on a Zn-doped Ni-based photothermal catalyst(Ni_(3)Zn@CeO_(2)).The photothermal catalytic behavior of Ni_(3)Zn@CeO_(2)can maintain more than 70 h in DRM reaction.And the photocatalytic DRM activity of Ni_(3)Zn@CeO_(2)is 1.2 times higher than thermal catalytic activity.Density functional theory(DFT)calculation and experimental characterizations indicate that Ni_(3)Zn promotes the diffusion of carbon atoms into the Ni_(3)Zn to form the Ni_(3)ZnC0.7 phase with body-centered cubic(bcc)structure,thus inhibiting carbon deposition.Further,in-situ diffuse reflectance infrared Fourier transform(DRIFT)spectroscopy and DFT calculation prove Ni_(3)Zn@CeO_(2)benefits the CH_(4)activation and inhibits the carbon deposition during the DRM process.Through inducing carbon atoms diffusion within the Ni_(3)Zn lattice,this work provides a straightforward and feasible strategy for achieving efficient photothermal catalytic DRM and even other CH_(4)conversion implementations with long-term stability.展开更多
Electrochemical reduction of CO_(2)(CO_(2)RR)to form high-energy-density and high-value-added multicarbon products has attracted much attention.Selective reduction of CO_(2)to C^(2+)products face the problems of low r...Electrochemical reduction of CO_(2)(CO_(2)RR)to form high-energy-density and high-value-added multicarbon products has attracted much attention.Selective reduction of CO_(2)to C^(2+)products face the problems of low reaction rate,complex mechanism and low selectivity.Currently,except for a few examples,copper-based catalysts are the only option capable of achieving efficient generation of C^(2+)products.However,the continuous dynamic reconstruction of the catalyst causes great difficulty in understanding the structure-performance relationship of CO_(2)RR.In this review,we first discuss the mechanism of C^(2+)product generation.The structural factors promoting C^(2+)product generation are outlined,and the dynamic evolution of these structural factors is discussed.Furthermore,the effects of electrolyte and electrolysis conditions are reviewed in a vision of dynamic surface.Finally,further exploration of the reconstruction mechanism of Cu-based catalysts and the application of emerging robotic AI chemists are discussed.展开更多
Exploring efficient transition-metal-based electrocatalysts is critical for the wide application of electrochemical hydrogen generation technology.Although the phase displays prominent influence on their performance,i...Exploring efficient transition-metal-based electrocatalysts is critical for the wide application of electrochemical hydrogen generation technology.Although the phase displays prominent influence on their performance,it remains a major challenge to achieve phase regulation in the same synthesis method and elucidate the intrinsic relationship between the phase and activity.Herein,we developed a sulfur induced electrodeposition strategy to achieve the precise phase regulation of nickel-based materials from Ni(OH)_(2)to Ni and Ni_(3)S_(2).S atoms can be introduced into Ni and Ni(OH)_(2)due to sulfur inducement,and the S proportion is finely controlled via changing the deposition parameters.Importantly,the obtained S-Ni catalyst displays enhanced hydrogen evolution activity with an ultralow overpotential of 27 mV at 10 mA cm^(-2),which is superior to the S-Ni(OH)_(2),Ni_(3)S_(2),and even Pt/C.Density functional theory(DFT)calculations disclose the S-Ni catalyst exhibits optimal charge state and local coordination,remarkably optimizing the water adsorption and Ni-H^(*)binding energy.This work provides new insights into phase regulation in electrodeposition and an understanding of the intrinsic relationship between phase and activity.展开更多
The electrochemical nitric oxide reduction reaction(NORR)to NH_(3)represents a promising avenue for NO removal and NH_(3)synthesis.It is essential to develop catalysts with superior performance for this process.We sys...The electrochemical nitric oxide reduction reaction(NORR)to NH_(3)represents a promising avenue for NO removal and NH_(3)synthesis.It is essential to develop catalysts with superior performance for this process.We systematically studied a series of single-atom alloy catalysts(SAACs)with Pd single-atom dopants using density functional theory(DFT)calculations and machine learning(ML).Based on the energetic span model,we take G_(max)(η)as a descriptor to evaluate the reaction activity of SAACs.After comprehensively considering the stability,activity,and NH_(3)selectivity of SAACs,Cu and Pd/Cu SAAC are screened out as candidate NORR to NH_(3)catalysts.To predict the G_(max)(η)descriptor,the extreme gradient boosting regression(XGBR)ML algorithm was adopted with geometric/electronic properties of the SAACs as input features.Additionally,we proposed a mathematical formula to correlate the crucial features and the G_(max)(η)descriptor using the sure independence screening and sparsifying operator(SISSO)approach.This work provides an understanding of the complex NORR mechanisms and offers a strategy to rationally design highly efficient SAACs.展开更多
Three-dimensional(3D)covalent organic frameworks(COFs)have attracted extensive attention as photocatalysts for CO_(2)reduction reactions.Introducing metal atoms is essential for enhancing activity,but previous metal s...Three-dimensional(3D)covalent organic frameworks(COFs)have attracted extensive attention as photocatalysts for CO_(2)reduction reactions.Introducing metal atoms is essential for enhancing activity,but previous metal sites in 3D COFs predominantly exhibit symmetrical coordination,making them unsuitable for CO_(2)activation.Here,we design a 3D COF with 2,2'-pyridine linked around tetra-(4-anilyl)methane(TCM-Bpy-COF),where Co^(2+)is asymmetrically coordinated by bipyridine and acetates(TCMBpy-COF-CoAc).The TCM-Bpy-COF-CoAc exhibits outstanding photocatalytic CO_(2)reduction performance under weak visible light,achieving a CO evolution rate of 26,650μmol g^(-1)h^(-1)under 5 W of lightemitting-diode(LED)lamp and high apparent quantum efficiency.The performance far exceeds that of symmetrically coordinated bipyridine-Co-bipyridine TCM-Bpy-COF and surpasses most reported COF-based photocatalysts.In-situ spectral characterizations and theoretical calculations show that asymmetric N,O-coordination around the Co^(2+)center polarizes electron density and lowers reaction energy barriers of^(*)COOH intermediates,enhancing the conversion of CO_(2)to CO.This work inspires the design of 3D COF-based photocatalysts with highly catalytic efficiency.展开更多
Anion exchange membrane fuel cells(AEMFCs),regarded as a promising alternative to proton exchange membrane fuel cells(PEMFCs),have garnered increasing attention because of their cost-effectiveness by using the non-nob...Anion exchange membrane fuel cells(AEMFCs),regarded as a promising alternative to proton exchange membrane fuel cells(PEMFCs),have garnered increasing attention because of their cost-effectiveness by using the non-noble metal catalysts and hydrocarbon-based ionomers as membrane[1].However,despite of extensive researches on non-noble metal catalysts such as Co[2].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
A composite metal-organic frameworks(MOFs)structure,designated as Co-hmta@La-salen,was synthesized through coordination interactions between a one-dimensional lanthanum MOFs(La-salen)with high density of uncoordinated...A composite metal-organic frameworks(MOFs)structure,designated as Co-hmta@La-salen,was synthesized through coordination interactions between a one-dimensional lanthanum MOFs(La-salen)with high density of uncoordinated imine(-CH=N-)groups and a cobalt-based MOFs(Co-hmta)structure prepared using hydrogen bonding stacking with hexamethylenetetramine(hmta)as the organic ligand.Subsequently,the Co-hmta@La-salen composite was chosen as a template for the pyrolysis process to synthesize a La(OH)_(3)supported metallic Co catalyst incorporating carbon-nitrogen(Co/La(OH)_(3)-CNhmta)catalyst.The catalytic results show that Co/La(OH)_(3)-CN-hmta(54%and 46%selectivity for aniline and N-phenylbenzylamine,respectively)displays superior cascade performance compared to classic Co/La(OH)_(3)-CN-nit catalyst(69%and 31%selectivity for aniline and N-phenylbenzylamine,respectively).Moreover,the kinetic test results indicate that N-alkylation is the rate-limiting step of the overall cascade reaction.The Co/La(OH)_(3)-CN-hmta catalyst can be separated from the reaction system using a magnet,and it also exhibits good cyclic stability.All of these suggest that the“MOFs plus MOFs via coordination”templating method can be employed as an efficient strategy for the preparation of supported catalysts.展开更多
Under the backdrop of“Carbon Peak and Carbon Neutrality”(dual carbon)goal in China,the methane-carbon dioxide reforming reaction has attracted considerable attention due to its environmental benefits of converting t...Under the backdrop of“Carbon Peak and Carbon Neutrality”(dual carbon)goal in China,the methane-carbon dioxide reforming reaction has attracted considerable attention due to its environmental benefits of converting two greenhouse gases(methane and carbon dioxide)into syngas and its promising industrial applications.Nickel(Ni)-based catalysts,with high catalytic activity,low cost,and abundant resources,are considered ideal candidates for industrial applications.In this article,three reaction kinetic models were briefly introduced,namely the Power-Law(PL)model,the Eley-Rideal(ER)model,and the Langmuir-Hinshelwood-Hougen-Watson(LHHW)model.Based on the LHHW model,the reaction kinetics and mechanisms of different catalytic systems were systematically discussed,including the properties of supports,the doping of noble metals and transition metals,the role of promoters,and the influence of the geometric and electronic structures of Ni on the reaction mechanism.Furthermore,the kinetics of carbon deposition and elimination on various catalysts were analyzed.Based on the reaction rate expressions for carbon elimination,the reasons for the high activity of transition metal iron(Fe)-doped catalysts and core-shell structured catalysts in carbon elimination were explained.Based on the detailed collation and comparative analysis of the reaction mechanisms and kinetic characteristics across diverse Ni-based catalytic systems,a theoretical guidance for the designing of high-performance catalysts was provided in this work.展开更多
基金supported by National R&D Program through the National Research Foundation of Korea(NRF)funded by Ministry of Science and ICT(Nos.2022R1F1A1072420 and NRF-2020R1A3B2079803).
文摘The continuous depletion of fossil fuels and the effects of climate change have encouraged prompt action to attain carbon neutrality.Technologies that transform and store renewable energy are crucial for creating a sustainable society,which is independent of fossil fuels.In this regard,electrochemical water splitting based on the oxygen evolution reaction(OER)and hydrogen evolution reaction(HER)is an attractive technique for producing carbon-free hydrogen fuels.Additionally,rechargeable metal–air batteries(MABs)are another intriguing way for renewable energy storage through reversible oxygen reactions(OER and the oxygen reduction reaction,ORR).Herein,we comprehensively review bifunctional electrocatalysts for water splitting(HER and OER)and MABs(OER and ORR),particularly 2D carbon material-derived heterostructures.The synthesis and properties of 2D carbon materials and their energy conversion and storage mechanisms are discussed to highlight the bifunc-tionality of the heterostructures.Recent studies on bifunctional electrocatalysts based on 2D carbon-derived heterostructures are also reviewed.Finally,perspectives for future studies and multifunctional catalysts are presented.
基金the National Natural Science Foundation of China(No.22108171)the Shanghai Key Laboratory of Hydrogen Science&Center of Hydrogen Science,Shanghai Jiao Tong University,China.
文摘The combination of solar energy and natural hydro-thermal systems will innovate the chemistry ofCO_(2)hydrogenation;however,the approach remains challenging due to the lack of robust and cost-effective catalytic system.Here,Zn which can be recycled with solar energy-induced approach was chosen as the reductant and Co as catalyst to achieve robust hydrothermalCO_(2)methanation.Nanosheets of honeycomb ZnO were grown in situ on the Co surface,resulting in a new motif(Co@ZnO catalyst)that inhibits Co deacti-vation through ZnO-assistedCoOx reduction.The stabilized Co and interaction between Co and ZnO functioned collaboratively toward the full conversion ofCO_(2)–CH_(4).In situ hydrothermal infrared spectros-copy confirmed the formation of formic acid as an intermediate,thereby avoiding CO formation and unwanted side reaction pathways.This study presents a straightforward one-step process for both highly efficientCO_(2)conversion and catalyst synthesis,paving the way for solar-drivenCO_(2)methanation.
基金supported by the National Natural Science Foundation of China(Grant Nos.52306125,52176095)Natural Science Research Project of Colleges and Universities in Anhui Province(Nos.2022AH050311,KJ2020ZD29)Anhui Provincial Natural Science Foundation(No.2008085J25).
文摘Hydrothermal liquefaction technology is an effective method for the resource utilization and energy conversion of biomass under the dual-carbon context,facilitating the conversion of biomass into liquid fuels and high-value chemicals.This paper reviews the latest advancements in the production of liquid fuels and chemicals from biomass hydrothermal liquefaction.It briefly introduces the effects of different types of biomass,such as organic waste,lignocellulosic materials,and algae,on the conversion efficiency and product yield during hydrothermal liquefaction.The specific mechanisms of solvent and catalyst systems in the hydrothermal liquefaction process are analyzed in detail.Compared to water and organic solvents,the biphasic solvent system yields higher concentrations of furan platform compounds,and the addition of an appropriate amount of NaCl to the solvent significantly enhances product yield.Homogeneous catalysts exhibit advantages in reaction rate and selectivity but are limited by high costs and difficulties in separation and recovery.In contrast,heterogeneous catalysts possess good separability and regeneration capabilities and can operate under high-temperature conditions,but their mass transfer efficiency and deactivation issues may affect catalytic performance.The direct hydrothermal catalytic conversion of biomass is also discussed for the efficient production of chemicals and fuels such as hexanol,ethylene glycol,lactic acid,and C5/C6 liquid alkanes.Finally,the advantages and current challenges of producing liquid fuels and chemicals from biomass hydrothermal liquefaction are thoroughly analyzed,along with potential future research directions.
文摘High density polyethylene(HDPE)pyrolysis and in-line oxidative steam reforming was carried out in a two-step reaction system consisting of a conical spouted bed reactor and a fluidized bed reactor.Continuous plastic pyrolysis was conducted at 550℃ and the volatiles formed were fed in-line to the oxidative steam reforming step(space-time 3.12 gcat min gHDPE−1;ER=0.2 and steam/plastic=3)operating at 700℃.The influence Ni based reforming catalyst support(Al_(2)O_(3),ZrO_(2),SiO_(2))and promoter(CeO_(2),La_(2)O_(3))have on HDPE pyrolysis volatiles conversion and H_(2) production was assessed.The catalysts were prepared by the wet impregnation and they were characterized by means of N_(2) adsorption-desorption,X-ray fluorescence,temperature-programmed reduction and X-ray powder diffraction.A preliminary study on coke deposition and the deterioration of catalysts properties was carried out,by analyzing the tested catalysts through temperature programmed oxidation of coke,transmission electron microscopy,and N_(2) adsorption-desorption.Among the supports tested,ZrO_(2) showed the best performance,attaining conversion and H_(2) production values of 92.2% and 12.8 wt%,respectively.Concerning promoted catalysts,they led to similar conversion values(around 90%),but significant differences were observed in H_(2) production.Thus,higher H_(2) productions were obtained on the Ni/La_(2)O_(3)-Al_(2)O_(3) catalyst(12.1 wt%)than on CeO_(2) promoted catalysts due to La_(2)O_(3) capability for enhancing water adsorption on the catalyst surface.
基金supported by the Natural Science Foundation of Shandong Province(ZR2022MB019,ZR2021MB134)the National Natural Science Foundation of China(22008131,51974086)。
文摘The dispersibility of active components in hydrodesulfurization(HDS)catalysts significantly influences the corresponding catalytic performance.In this study,sugar-based materials(glucose,chitosan,soluble starch,and corn starch)were utilized to prepare CoMo bulk HDS catalysts through a sugar foaming process.The foaming intermediates were analyzed using TG,FTIR,and Raman techniques to investigate the pyrolysis and carbonization process,revealing the presence of graphitic carbon in the 3 DPG,3 DPSS,and 3 DPCS catalysts even after calcination in an air atmosphere.The catalysts were further characterized using SEM,XRD,TEM,low-temperature N_(2) physical adsorption,and XPS.The 3 DPSS catalyst exhibited a thiophene conversion of 94.8%at 360℃ and 1 MPa,which could be ascribed to its unique three-dimensional pore structure,high dispersion of MoS_(2)(0.21),and high fraction of Mo^(4+)(83.14%).This study demonstrates the potential of using the sugar foaming technique to develop highly efficient HDS catalysts and provides new insights into the relationship between the physicochemical properties of the obtained catalysts and their catalytic performance.
文摘The efficient conversion of lignin into mono-cycloalkanes via both C–O and C–C bonds cleavage are attractive,but challenging due to the high C–C bond dissociation energy.Previous studies have demonstrated that NbO_(x)-based catalysts exhibited exceptional capabilities for C_(Ar)–C bond cleavage and broken the limitation of lignin monomers.In this work,we presented an economical multifunctional Pt-Nb/MOR catalyst that achieved an impressive monomer yield of 147%during the depolymerization and hydrodeoxygenation of lignin into mono-cycloalkanes.Reaction pathway studies showed that unlike traditional NbO_(x)-based catalytic system,bicyclohexane was an important intermediate in this system and followed the C_(sp3)–C_(sp3)cleavage pathway after complete cyclic-hydrogenation.Deep investigations demonstrated that the doping of Nb in Pt/MOR not only enhanced the activation of hydrogen by Pt,but also increased the acidity of MOR,both of these are favor for the hydrogenolytic cleavage of C_(sp3)–C_(sp3)bonds.This work provides a low-cost catalyst to obtain high-yield monomers from lignin under relatively mild conditions and would help to design catalysts with higher activity for the valorization of lignin.
基金supported by the Hebei Province Key R&D Technology Project(23314401D)2023 Hebei Province High-level Talent Team Construction Special Project(235A4401D)+6 种基金Hebei North University Youth Fund Project(XJ2024013)School-level Cultivation Research Project of Hebei North University(XJPY2024025)First Batch of School-level Scientific Research Projects of Hebei North University in 2023(B2023405004)Hebei North University High-level Talent Research Start-up Fund(BSJJ202303,BSJJ202313,BSJJ202421)Science and Technology Research Project of Higher Education Institutions in Hebei Province(QN2023222)Central Guided Local Science and Technology Development Funding Program(236Z4401G)Natural Science Foundation of Hebei Province(B2022405005).
文摘Lithium-sulfur(Li-S)batteries are promising for high-energy-density storage,but their performance is limited by sluggish lithium polysulfide(LiPS)conversion kinetics.Here,we tackle this issue by synthesizing ultrafine truncated octahedral TiO_(2) nanocrystals(P-O_(v)-TiO_(2)),featuring specific{101}facets and dual defects—phosphorus doping and oxygen vacancies.Acting as an efficient electrocatalyst in the separator,P-O_(v)-TiO_(2) exhibits superior catalytic properties,where oxygen vacancies modulate the electronic structure,enhancing electron enrichment and charge transfer;phosphorus doping tailors the d-band center of the catalyst,strengthening Ti-S interactions between the{101}facets and LiPSs.As a result,Li-S coin cells modified with P-O_(v)-TiO_(2) achieve a high specific capacity of 895 mAh g^(−1) at 5 C and exhibit a minimal decay rate of 0.14%per cycle over 200 cycles.Furthermore,Li-S pouch cells deliver a high capacity of 1004 mAh g^(−1) at 0.1 C under lean electrolyte conditions.This study elucidates the mechanisms of charge states on specific crystal planes and deepens our understanding of dual-defect engineering in Li-S electrochemistry,offering a promising approach for developing efficient and cost-effective catalysts for Li-S battery applications.
基金sponsored by the National Natural Science Foundation of China(Grant Nos.22308381 and 22522818)Science Foundation of China University of Petroleum-Beijing(Grant Nos.2462023QNXZ002 and 2462023QNXZ005)+1 种基金Beijing Nova Program(Grant No.20220484096)the National Key R&D Program of China(Grant No.2021YFA1501201).
文摘Hierarchical Ni/ZSM-22-SBA-15 meso-microporous catalysts(Ni/ZS-x)with different acid properties and diffusion characteristics(acid-diffusion)properties were synthesized successfully and applied to the production of high-quality jet fuel by the efficient one-step hydrogenation(hydrodeoxygenation,isomerization,and cracking)of oleic acid.The acid-diffusion properties of the catalysts are modulated by tuning the ZSM-22 seed content,and their effects on the hydrogenation reactions were investigated.Acid properties affect the extent of isomerization and cleavage reactions,whereas diffusion properties affect the accessibility of active centers.The balanced acid-diffusion properties are conducive to efficient hydrogenation reactions of oleic acid.The optimal Ni/ZS-3 exhibits the highest jet fuel yield(56.3%,340°C)and superior iso/n-alkane ratio(i/n=3.12)because of its well-balanced acid-diffusion properties.Besides,the possible hydrogenation mechanism of oleic acid is proposed.
基金supported by the National Natural Science Foundation of China(U23A20573,U23A20140)the Hebei Natural Science Foundation(B202420809,B2024208088)+2 种基金S&T Program of Hebei(242Q4301Z,22373709D)Project of Basic Research at Universities in Shijiazhuang(241790977A)Huang jin tai plan project of Hebei provincial department of education(HJZD202512)。
文摘Integrating the CO_(2)capture process with the CO_(2)electrochemical reduction process into a single system can eliminate the need for storage and transportation following CO_(2)capture.This integrated process offers several advantages over multi-step cascade processes,including reduced costs and enhanced CO_(2)utilization.However,the integrated CO_(2)capture and electrochemical reduction(CCER)process encounters several challenges,including the low CO_(2)adsorption performance of the gas diffusion electrode(GDE)and catalyst,as well as the poor activity and selectivity of the catalyst for the electrochemical reduction of CO_(2).This review aims to systematically summarize the fundamentals of the CCER process.Based on an in-depth understanding of the CO_(2)mass transfer,adsorption,and electrochemical reduction processes,GDE design strategies based on the modulation of wettability and structure are discussed to enhance the CO_(2)capture capability at the GDE level.At the catalyst level,catalyst design strategies based on the introduction of CO_(2)capture sites and the construction of CO_(2)mass transfer channels were analyzed,and catalyst design strategies for enhanced CO_(2)capture were proposed.This review summarizes the most common catalysts for CO_(2)electrochemical reduction,such as Ni-based,Bi-based,and Cubased catalysts,and analyzes their design strategies based on reaction pathways for generating specific products.Finally,the problems and challenges of the CCER process are summarized and proposed,which provide ideas for the further application of this technology in the future.
基金Supported by National Key R&D Program of China(2022YFA1503400)。
文摘Aiming at the problems of insufficient activity and selectivity of Cu-based catalysts in CO_(2)hydrogenation to methanol,Al_(2)O_(3),ZrO_(2)and CeO_(2)modified Cu-ZnO catalysts by the co-precipitation method were prepared,and the influence mechanism of additives on the structure-performance relationship of the catalysts was systematically explored.Through a variety of characterization methods such as XRD,N2 physical adsorption-desorption,TEM,H_(2)-TPR,CO_(2)-TPD and XPS,combined with catalytic performance evaluation experiments,the correlation between the microstructure of catalysts and the reaction performance of CO_(2)hydrogenation to methanol was analyzed in depth.The results show that metal additives significantly improve the performance of catalysts.After the introduction of additives,the specific surface area and pore volume of the catalysts increase,the grain size of Cu decreases,and its dispersion improves.The Ce-modified CZC catalyst exhibited the best performance,with the grain size of CuO as small as 11.41 nm,and the surface oxygen vacancy concentration(OⅡ/OⅠ=3.15)was significantly higher than that of other samples.The reaction performance test shows that under the conditions of 2.8 MPa,8000 h−1 and 280℃,the CO_(2)conversion of the CZC catalyst reached 18.83%,the methanol selectivity was 68.40%,and the methanol yield was 12.88%,all of which are superior to other catalysts.Its excellent performance can be attributed to the fact that CeO_(2)enhances the metal-support interaction,increases the surface basicity,promotes the adsorption and activation of CO_(2),and simultaneously inhibits the reverse water-gas shift side reaction.This study clarifies the structure-activity regulation mechanism of additive modification on Cu-ZnO catalysts,providing a theoretical basis and technical reference for the development of efficient catalysts for CO_(2)hydrogenation to methanol.
文摘Photothermal catalytic methane dry reforming(DRM)technology can convert greenhouse gases(i.e.CH_(4)and CO_(2))into syngas(i.e.H_(2)and CO),providing more opportunities for reducing the greenhouse effect and achieving carbon neutrality.In the DRM field,Ni-based catalysts attract wide attention due to their low cost and high activity.However,the carbon deposition over Ni-based catalysts always leads to rapid deactivation,which is still a main challenge.To improve the long-term stability of Ni-based catalysts,this work proposes a carbon-atom-diffusion strategy under photothermal conditions and investigates its effect on a Zn-doped Ni-based photothermal catalyst(Ni_(3)Zn@CeO_(2)).The photothermal catalytic behavior of Ni_(3)Zn@CeO_(2)can maintain more than 70 h in DRM reaction.And the photocatalytic DRM activity of Ni_(3)Zn@CeO_(2)is 1.2 times higher than thermal catalytic activity.Density functional theory(DFT)calculation and experimental characterizations indicate that Ni_(3)Zn promotes the diffusion of carbon atoms into the Ni_(3)Zn to form the Ni_(3)ZnC0.7 phase with body-centered cubic(bcc)structure,thus inhibiting carbon deposition.Further,in-situ diffuse reflectance infrared Fourier transform(DRIFT)spectroscopy and DFT calculation prove Ni_(3)Zn@CeO_(2)benefits the CH_(4)activation and inhibits the carbon deposition during the DRM process.Through inducing carbon atoms diffusion within the Ni_(3)Zn lattice,this work provides a straightforward and feasible strategy for achieving efficient photothermal catalytic DRM and even other CH_(4)conversion implementations with long-term stability.
文摘Electrochemical reduction of CO_(2)(CO_(2)RR)to form high-energy-density and high-value-added multicarbon products has attracted much attention.Selective reduction of CO_(2)to C^(2+)products face the problems of low reaction rate,complex mechanism and low selectivity.Currently,except for a few examples,copper-based catalysts are the only option capable of achieving efficient generation of C^(2+)products.However,the continuous dynamic reconstruction of the catalyst causes great difficulty in understanding the structure-performance relationship of CO_(2)RR.In this review,we first discuss the mechanism of C^(2+)product generation.The structural factors promoting C^(2+)product generation are outlined,and the dynamic evolution of these structural factors is discussed.Furthermore,the effects of electrolyte and electrolysis conditions are reviewed in a vision of dynamic surface.Finally,further exploration of the reconstruction mechanism of Cu-based catalysts and the application of emerging robotic AI chemists are discussed.
基金supported by the National Natural Science Foundation of China(52271210,22179032,52171176)。
文摘Exploring efficient transition-metal-based electrocatalysts is critical for the wide application of electrochemical hydrogen generation technology.Although the phase displays prominent influence on their performance,it remains a major challenge to achieve phase regulation in the same synthesis method and elucidate the intrinsic relationship between the phase and activity.Herein,we developed a sulfur induced electrodeposition strategy to achieve the precise phase regulation of nickel-based materials from Ni(OH)_(2)to Ni and Ni_(3)S_(2).S atoms can be introduced into Ni and Ni(OH)_(2)due to sulfur inducement,and the S proportion is finely controlled via changing the deposition parameters.Importantly,the obtained S-Ni catalyst displays enhanced hydrogen evolution activity with an ultralow overpotential of 27 mV at 10 mA cm^(-2),which is superior to the S-Ni(OH)_(2),Ni_(3)S_(2),and even Pt/C.Density functional theory(DFT)calculations disclose the S-Ni catalyst exhibits optimal charge state and local coordination,remarkably optimizing the water adsorption and Ni-H^(*)binding energy.This work provides new insights into phase regulation in electrodeposition and an understanding of the intrinsic relationship between phase and activity.
基金support from the He Bei Natural Science Foundation(Nos.B2022205029 and B2022205013)。
文摘The electrochemical nitric oxide reduction reaction(NORR)to NH_(3)represents a promising avenue for NO removal and NH_(3)synthesis.It is essential to develop catalysts with superior performance for this process.We systematically studied a series of single-atom alloy catalysts(SAACs)with Pd single-atom dopants using density functional theory(DFT)calculations and machine learning(ML).Based on the energetic span model,we take G_(max)(η)as a descriptor to evaluate the reaction activity of SAACs.After comprehensively considering the stability,activity,and NH_(3)selectivity of SAACs,Cu and Pd/Cu SAAC are screened out as candidate NORR to NH_(3)catalysts.To predict the G_(max)(η)descriptor,the extreme gradient boosting regression(XGBR)ML algorithm was adopted with geometric/electronic properties of the SAACs as input features.Additionally,we proposed a mathematical formula to correlate the crucial features and the G_(max)(η)descriptor using the sure independence screening and sparsifying operator(SISSO)approach.This work provides an understanding of the complex NORR mechanisms and offers a strategy to rationally design highly efficient SAACs.
基金financial support from the National Natural Science Foundation of China(No.22072183)the Natural Science Foundation of Hunan Province,China(No.2022JJ30690)supported in part by the High Performance Computing Center of Central South University。
文摘Three-dimensional(3D)covalent organic frameworks(COFs)have attracted extensive attention as photocatalysts for CO_(2)reduction reactions.Introducing metal atoms is essential for enhancing activity,but previous metal sites in 3D COFs predominantly exhibit symmetrical coordination,making them unsuitable for CO_(2)activation.Here,we design a 3D COF with 2,2'-pyridine linked around tetra-(4-anilyl)methane(TCM-Bpy-COF),where Co^(2+)is asymmetrically coordinated by bipyridine and acetates(TCMBpy-COF-CoAc).The TCM-Bpy-COF-CoAc exhibits outstanding photocatalytic CO_(2)reduction performance under weak visible light,achieving a CO evolution rate of 26,650μmol g^(-1)h^(-1)under 5 W of lightemitting-diode(LED)lamp and high apparent quantum efficiency.The performance far exceeds that of symmetrically coordinated bipyridine-Co-bipyridine TCM-Bpy-COF and surpasses most reported COF-based photocatalysts.In-situ spectral characterizations and theoretical calculations show that asymmetric N,O-coordination around the Co^(2+)center polarizes electron density and lowers reaction energy barriers of^(*)COOH intermediates,enhancing the conversion of CO_(2)to CO.This work inspires the design of 3D COF-based photocatalysts with highly catalytic efficiency.
基金supported by the National Natural Science Foundation of China(Nos.22162014 and U24A2044).
文摘Anion exchange membrane fuel cells(AEMFCs),regarded as a promising alternative to proton exchange membrane fuel cells(PEMFCs),have garnered increasing attention because of their cost-effectiveness by using the non-noble metal catalysts and hydrocarbon-based ionomers as membrane[1].However,despite of extensive researches on non-noble metal catalysts such as Co[2].
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.
基金Project supported by the Natural Science Foundation of Jiangsu Province (BK20210066)Natural Science Foundation of Heilongjiang Province (ZD2022E007).
文摘A composite metal-organic frameworks(MOFs)structure,designated as Co-hmta@La-salen,was synthesized through coordination interactions between a one-dimensional lanthanum MOFs(La-salen)with high density of uncoordinated imine(-CH=N-)groups and a cobalt-based MOFs(Co-hmta)structure prepared using hydrogen bonding stacking with hexamethylenetetramine(hmta)as the organic ligand.Subsequently,the Co-hmta@La-salen composite was chosen as a template for the pyrolysis process to synthesize a La(OH)_(3)supported metallic Co catalyst incorporating carbon-nitrogen(Co/La(OH)_(3)-CNhmta)catalyst.The catalytic results show that Co/La(OH)_(3)-CN-hmta(54%and 46%selectivity for aniline and N-phenylbenzylamine,respectively)displays superior cascade performance compared to classic Co/La(OH)_(3)-CN-nit catalyst(69%and 31%selectivity for aniline and N-phenylbenzylamine,respectively).Moreover,the kinetic test results indicate that N-alkylation is the rate-limiting step of the overall cascade reaction.The Co/La(OH)_(3)-CN-hmta catalyst can be separated from the reaction system using a magnet,and it also exhibits good cyclic stability.All of these suggest that the“MOFs plus MOFs via coordination”templating method can be employed as an efficient strategy for the preparation of supported catalysts.
基金Supported by Innovation Capability Support Program of Shaanxi(2024RS-CXTD-53,2024ZC-KJXX-096)the Key R&D Program of Shaanxi Province(2022QCY-LL-69)Xi’an Science and Technology Project(24GXFW0089)。
文摘Under the backdrop of“Carbon Peak and Carbon Neutrality”(dual carbon)goal in China,the methane-carbon dioxide reforming reaction has attracted considerable attention due to its environmental benefits of converting two greenhouse gases(methane and carbon dioxide)into syngas and its promising industrial applications.Nickel(Ni)-based catalysts,with high catalytic activity,low cost,and abundant resources,are considered ideal candidates for industrial applications.In this article,three reaction kinetic models were briefly introduced,namely the Power-Law(PL)model,the Eley-Rideal(ER)model,and the Langmuir-Hinshelwood-Hougen-Watson(LHHW)model.Based on the LHHW model,the reaction kinetics and mechanisms of different catalytic systems were systematically discussed,including the properties of supports,the doping of noble metals and transition metals,the role of promoters,and the influence of the geometric and electronic structures of Ni on the reaction mechanism.Furthermore,the kinetics of carbon deposition and elimination on various catalysts were analyzed.Based on the reaction rate expressions for carbon elimination,the reasons for the high activity of transition metal iron(Fe)-doped catalysts and core-shell structured catalysts in carbon elimination were explained.Based on the detailed collation and comparative analysis of the reaction mechanisms and kinetic characteristics across diverse Ni-based catalytic systems,a theoretical guidance for the designing of high-performance catalysts was provided in this work.
