Atomically dispersed catalysts exhibit significant influence on facilitating the sluggish oxygen reduction reaction(ORR)kinetics with high atom economy,owing to remarkable attributes including nearly 100%atomic utiliz...Atomically dispersed catalysts exhibit significant influence on facilitating the sluggish oxygen reduction reaction(ORR)kinetics with high atom economy,owing to remarkable attributes including nearly 100%atomic utilization and exceptional catalytic functionality.Furthermore,accurately controlling atomic physical properties including spin,charge,orbital,and lattice degrees of atomically dispersed catalysts can realize the optimized chemical properties including maximum atom utilization efficiency,homogenous active centers,and satisfactory catalytic performance,but remains elusive.Here,through physical and chemical insight,we review and systematically summarize the strategies to optimize atomically dispersed ORR catalysts including adjusting the atomic coordination environment,adjacent electronic orbital and site density,and the choice of dual-atom sites.Then the emphasis is on the fundamental understanding of the correlation between the physical property and the catalytic behavior for atomically dispersed catalysts.Finally,an overview of the existing challenges and prospects to illustrate the current obstacles and potential opportunities for the advancement of atomically dispersed catalysts in the realm of electrocatalytic reactions is offered.展开更多
It is urgent to develop catalysts with application potential for oxidative coupling of methane(OCM)at relatively lower temperature.Herein,three-dimensional ordered macro porous(3 DOM)La_(2-x)Sr_(x)Ce_(2-y)CayO_(7-δ)(...It is urgent to develop catalysts with application potential for oxidative coupling of methane(OCM)at relatively lower temperature.Herein,three-dimensional ordered macro porous(3 DOM)La_(2-x)Sr_(x)Ce_(2-y)CayO_(7-δ)(A_(2)B_(2)O_(7)-type)catalysts with disordered defective cubic fluorite phased structure were successfully prepared by a colloidal crystal template method.3DOM structure promotes the accessibility of the gaseous reactants(O2and CH4)to the active sites.The co-doping of Ca and Sr ions in La_(2-x)Sr_(x)Ce_(2-y)CayO_(7-δ)catalysts improved the formation of oxygen vacancies,thereby leading to increased density of surface-active oxygen species(O_(2)^(-))for the activation of CH4and the formation of C2products(C2H6and C2H4).3DOM La_(2-x)Sr_(x)Ce_(2-y)CayO_(7-δ)catalysts exhibit high catalytic activity for OCM at low temperature.3DOM La1.7Sr0.3Ce1.7Ca0.3O7-δcatalyst with the highest density of O_(2)^(-)species exhibited the highest catalytic activity for low-temperature OCM,i.e.,its CH4conversion,selectivity and yield of C2products at 650℃are 32.2%,66.1%and 21.3%,respectively.The mechanism was proposed that the increase in surface oxygen vacancies induced by the co-doping of Ca and Sr ions boosts the key step of C-H bond breaking and C-C bond coupling in catalyzing low-temperature OCM.It is meaningful for the development of the low-temperature and high-efficient catalysts for OCM reaction in practical application.展开更多
Hydrogen sulfide(H_(2)S) not only presents significant environmental concerns but also induces severe corrosion in industrial equipment,even at low concentrations.Among various technologies,the selective oxidation of ...Hydrogen sulfide(H_(2)S) not only presents significant environmental concerns but also induces severe corrosion in industrial equipment,even at low concentrations.Among various technologies,the selective oxidation of hydrogen sulfide(SOH_(2)S) to elemental sulfur(S) has emerged as a sustainable and environmentally friendly solution.Due to its unique properties,iron oxide has been extensively investigated as a catalyst for SOH_(2)S;however,rapid deactivation has remained a significant drawback.The causes of iron oxide-based catalysts deactivation mechanisms in SOH_(2)S,including sulfur or sulfate deposition,the transformation of iron species,sintering and excessive oxygen vacancy formation,and active site loss,are thoroughly examined in this review.By focusing on the deactivation mechanisms,this review aims to provide valuable insights into enhancing the stability and efficiency of iron-based catalysts for SOH_(2)S.展开更多
Capturing and utilizing CO_(2)from the production process is the key to solving the excessive CO_(2)emission problem. CO_(2)hydrogenation with green hydrogen to produce olefins is an effective and promising way to uti...Capturing and utilizing CO_(2)from the production process is the key to solving the excessive CO_(2)emission problem. CO_(2)hydrogenation with green hydrogen to produce olefins is an effective and promising way to utilize CO_(2)and produce valuable chemicals. The olefins can be produced by CO_(2)hydrogenation through two routes, i.e., CO_(2)-FTS (carbon dioxide Fischer- Tropsch synthesis) and MeOH (methanol-mediated), among which CO_(2)-FTS has significant advantages over MeOH in practical applications due to its relatively high CO_(2)conversion and low energy consumption potentials. However, the CO_(2)-FTS faces challenges of difficult CO_(2)activation and low olefins selectivity. Iron-based catalysts are promising for CO_(2)-FTS due to their dual functionality of catalyzing RWGS and CO-FTS reactions. This review summarizes the recent progress on iron-based catalysts for CO_(2)hydrogenation via the FTS route and analyzes the catalyst optimization from the perspectives of additives, active sites, and reaction mechanisms. Furthermore, we also outline principles and challenges for rational design of high-performance CO_(2)-FTS catalysts.展开更多
Among challenges implicit in the transition to the post-fossil fuel energetic model,the finite amount of resources available for the technological implementation of CO_(2) revalorizing processes arises as a central is...Among challenges implicit in the transition to the post-fossil fuel energetic model,the finite amount of resources available for the technological implementation of CO_(2) revalorizing processes arises as a central issue.The development of fully renewable catalytic systems with easier metal recovery strategies would promote the viability and sustainability of synthetic natural gas production circular routes.Taking Ni and NiFe catalysts supported over g-Al_(2)O_(3) oxide as reference materials,this work evaluates the potentiality of Ni and NiFe supported biochar catalysts for CO_(2) methanation.The development of competitive biochar catalysts was found dependent on the creation of basic sites on the catalyst surface.Displaying lower Turn Over Frequencies than Ni/Al catalyst,the absence of basic sites achieved over Ni/C catalyst was related to the depleted catalyst performances.For NiFe catalysts,analogous Ni_(5)Fe_(1) alloys were constituted over both alumina and biochar supports.The highest specific activity of the catalyst series,exhibited by the NiFe/C catalyst,was related to the development of surface basic sites along with weaker NiFe-C interactions,which resulted in increased Ni0:NiO surface populations under reaction conditions.In summary,the present work establishes biochar supports as a competitive material to consider within the future low-carbon energetic panorama.展开更多
Nitrate pollution is of great importance in both the environmental and health contexts, necessitating the development of efficient mitigation strategies. This review provides a comprehensive analysis of the many catal...Nitrate pollution is of great importance in both the environmental and health contexts, necessitating the development of efficient mitigation strategies. This review provides a comprehensive analysis of the many catalysts employed in the electrochemical reduction of nitrate to ammonia, and presents a viable environmentally friendly approach to address the issue of nitrate pollution. Hence, the electrochemical transformation of nitrate to ammonia serves the dual purpose of addressing nitrate pollution in water bodies, and is a useful agricultural resource. This review examines a range of catalyst materials such as noble and non-noble metals, metal oxides, carbon-based materials, nitrogen-doped carbon species, metal complexes, and semiconductor photocatalysts. It evaluates catalytic efficiency, selectivity, stability, and overall process optimization. The performance of catalysts is influenced by various factors, including reaction conditions, catalyst structure, loading techniques, and electrode interfaces. Comparative analysis was performed to evaluate the catalytic activity, selectivity, Faradaic efficiency, current density, stability, and durability of the catalysts. This assessment offers significant perspectives on the structural, compositional, and electrochemical characteristics that affect the efficacy of these catalysts, thus informing future investigations and advancements in this domain. In addition to mitigating nitrate pollution, the electrochemical reduction of nitrate to ammonia is in line with sustainable agricultural methods, resource conservation, and the utilization of renewable energy resources. This study explores the factors that affect the catalytic efficiency, provides new opportunities to address nitrate pollution, and promotes the development of sustainable environmental solutions.展开更多
Carbon-based metal-free nanomaterials are promising alternatives to precious metals as electrocatalysts of key energy storage and conversion technologies.Of paramount significance are the establishment of design princi...Carbon-based metal-free nanomaterials are promising alternatives to precious metals as electrocatalysts of key energy storage and conversion technologies.Of paramount significance are the establishment of design principles by understanding the catalytic mechanisms and identifying the active sites.Distinct from sp2-conjugated graphene and carbon nanotube,fullerene possesses unique characteristics that are growingly being discovered and exploited by the electrocatalysis community.For instance,the well-defined atomic and molecular structures,the good electron affinity to tune the electronic structures of other substances,the intermolecular self-assembly into superlattices,and the on-demand chemical modification have endowed fullerene with incomparable advantages as electrocatalysts that are otherwise not applicable to other carbon ma-terials.As increasing studies are being reported on this intriguing topic,it is necessary to provide a state-of-the-art overview of the recent progress.This review takes such an initiative by summarizing the promises and challenges in the electrocatalytic applications of fullerene and its derivatives.The content is structured according to the composition and structure of fullerene,including intact fullerene(e.g.,fullerene composite and superlattices)and fullerene derivatives(e.g.,doped,endohedral,and disintegrated fullerene).The synthesis,characterization,catalytic mechanisms,and deficiencies of these fullerene-based materials are explicitly elaborated.We conclude it by sharing our perspectives on the key aspects that future efforts shall consider.展开更多
La_(0.8)A_(0.2)NiO_(3) (A=K,Ba,Y) catalysts supported on the microwave-absorbing ceramic heating carrier were prepared by the sol-gel method.The crystalline phase and the catalytic activity of the La_(0.8)A_(0.2)NiO_(...La_(0.8)A_(0.2)NiO_(3) (A=K,Ba,Y) catalysts supported on the microwave-absorbing ceramic heating carrier were prepared by the sol-gel method.The crystalline phase and the catalytic activity of the La_(0.8)A_(0.2)NiO_(3)catalysts were characterized by XRD and H_(2) temperature-programmed reduction (TPR).The effects of reaction temperature,oxygen concentration,and gas flow rate on the direct decomposition of nitric oxide over the synthesized catalysts were studied under microwave irradiation (2.45 GHz).The XRD results indicated that the La_(0.8)A_(0.2)NiO_(3) catalysts formed an ABO_(3) perovskite structure,and the H_(2)-TPR results revealed that the relative reducibility of the catalysts increased in the order of La_(0.8)K_(0.2)NiO_(3)>La_(0.8)Ba_(0.2)NiO_(3)>La_(0.8)Y_(0.2)Ni O_(3).Under microwave irradiation,the highest NO conversion amounted to 98.9%,which was obtained with the La_(0.8)K_(0.2)NiO_(3) catalyst at 400℃.The oxygen concentration did not inhibit the NO decomposition on the La_(0.8)A_(0.2)NiO_(3) catalysts,thus the N_(2) selectivity exceeded 99.8%under excess oxygen at 550℃.The NOconversion of the La_(0.8)A_(0.2)NiO_(3) catalysts decreased linearly with the increase in the gas flow rate.展开更多
Nitrogen(N)-doped carbon materials as metal catalyst supports have attracted signifi cant attention,but the eff ect of N dopants on catalytic performance remains unclear,especially for complex reaction processes such ...Nitrogen(N)-doped carbon materials as metal catalyst supports have attracted signifi cant attention,but the eff ect of N dopants on catalytic performance remains unclear,especially for complex reaction processes such as Fischer-Tropsch synthesis(FTS).Herein,we engineered ruthenium(Ru)FTS catalysts supported on N-doped carbon overlayers on TiO_(2)nanoparticles.By regulating the carbonization temperatures,we successfully controlled the types and contents of N dopants to identify their impacts on metal-support interactions(MSI).Our fi ndings revealed that N dopants establish a favorable surface environment for electron transfer from the support to the Ru species.Moreover,pyridinic N demonstrates the highest electron-donating ability,followed by pyrrolic N and graphitic N.In addition to realizing excellent catalytic stability,strengthening the interaction between Ru sites and N dopants increases the Ru^(0)/Ru^(δ+)ratios to enlarge the active site numbers and surface electron density of Ru species to enhance the strength of adsorbed CO.Consequently,it improves the catalyst’s overall performance,encompassing intrinsic and apparent activities,as well as its ability for carbon chain growth.Accordingly,the as-synthesized Ru/TiO_(2)@CN-700 catalyst with abundant pyridine N dopants exhibits a superhigh C_(5+)time yield of 219.4 mol CO/(mol Ru·h)and C_(5+)selectivity of 85.5%.展开更多
Engineering transition metal compounds(TMCs)catalysts with excellent adsorption-catalytic ability has been one of the most effec-tive strategies to accelerate the redox kinetics of sulfur cathodes.Herein,this review f...Engineering transition metal compounds(TMCs)catalysts with excellent adsorption-catalytic ability has been one of the most effec-tive strategies to accelerate the redox kinetics of sulfur cathodes.Herein,this review focuses on engineering TMCs catalysts by cation doping/anion doping/dual doping,bimetallic/bi-anionic TMCs,and TMCs-based heterostructure composites.It is obvious that introducing cations/anions to TMCs or constructing heterostructure can boost adsorption-catalytic capacity by regulating the electronic structure including energy band,d/p-band center,electron filling,and valence state.Moreover,the elec-tronic structure of doped/dual-ionic TMCs are adjusted by inducing ions with different electronegativity,electron filling,and ion radius,resulting in electron redistribution,bonds reconstruction,induced vacancies due to the electronic interaction and changed crystal structure such as lat-tice spacing and lattice distortion.Different from the aforementioned two strategies,heterostructures are constructed by two types of TMCs with different Fermi energy levels,which causes built-in electric field and electrons transfer through the interface,and induces electron redistribution and arranged local atoms to regulate the electronic structure.Additionally,the lacking studies of the three strategies to comprehensively regulate electronic structure for improving catalytic performance are pointed out.It is believed that this review can guide the design of advanced TMCs catalysts for boosting redox of lithium sulfur batteries.展开更多
Diatomic catalysts(DACs)with two adjacent metal atoms supported on graphene can offer diverse functionalities,overcoming the inherent limitations of single atom catalysts(SACs).In this study,density functional theory ...Diatomic catalysts(DACs)with two adjacent metal atoms supported on graphene can offer diverse functionalities,overcoming the inherent limitations of single atom catalysts(SACs).In this study,density functional theory calculations were conducted to investigate the reactivity of the carbon dioxide(CO_(2))reduction reaction(CO_(2)RR)on metal sites of both DACs and SACs,as well as their synergistic effects on activity and selectivity.Calculation of the Gibbs free energies of CO_(2)RR and associated values of the limiting potentials to generate C_(1) products showed that Cu acts as a promoter rather than an active catalytic centre in the catalytic CO_(2)conversion on heteronuclear DACs(CuN_(4)-MN_(4)),improving the catalytic activity on the other metal compared to the related SAC MN_(4).Cu enhances the initial reduction of CO_(2)by promoting orbital hybridization between the key intermediate*COOH 2p-orbitals and the metals 3d-orbitals around the Fermi level.This degree of hybridization in the DACs CuN_(4)-MN_(4) decreases from Fe to Co,Ni,and Zn.Our work demonstrates how Cu regulates the CO_(2)RR performance of heteronuclear DACs,offering an effective approach to designing practical,stable,and high-performing diatomic catalysts for CO_(2)electroreduction.展开更多
The continued increase in population and the industrial revolution have led to an increase in atmospheric carbon dioxide(CO_(2)) concentration. Consequently, developing and implementing effective solutions to reduce C...The continued increase in population and the industrial revolution have led to an increase in atmospheric carbon dioxide(CO_(2)) concentration. Consequently, developing and implementing effective solutions to reduce CO_(2) emissions is a global priority. The electrochemical CO_(2) reduction reaction(CO_(2)RR) is strongly believed to be a promising alternative to fossil fuel-based technologies for the production of value-added chemicals. So far, the implementation of CO_(2)RR is hindered by associated electrochemical reactions, such as low selectivity, hydrogen evolution reaction(HER), and additional overpotential induced in some cases. As a result, it is necessary to conduct a timely evaluation of the state-of-the-art strategies in CO_(2)RR, with a focus on the engineering of the electrocatalytic systems. Catalyst morphology is one factor that plays a critical role in overcoming these drawbacks and significantly contributes to enhancing product selectivity and Faradaic efficiency(FE). This review article summarizes the recent advances in the rational design of electrocatalysts with various morphologies and the influence of these morphologies on CO_(2)RR. To compare literature findings in a meaningful way, the article focuses on results reported under a well-defined period and considers the first three rows of the d-block metal catalysts. The discussion typically covers the design of nanostructured catalysts and the molecular-level understanding of morphology-performance relationship in terms of activity, selectivity, and stability during CO_(2) electrolysis. Among others, it would be convenient to recommend a comprehensive discussion on the morphologies of single metals and heterostructures, with a detailed emphasis on their impact on CO_(2) conversion.展开更多
The next-generation energy storage systems such as fuel cells,metal-air batteries,and alkali metal(Li,Na)-chalcogen(S,Se)batteries have received increasing attention owing to their high energy density and low cost.How...The next-generation energy storage systems such as fuel cells,metal-air batteries,and alkali metal(Li,Na)-chalcogen(S,Se)batteries have received increasing attention owing to their high energy density and low cost.However,one of the main obstacles of these systems is the poor reaction kinetics in the involved chemical reactions.Therefore,it is essential to incorporate suitable and efficient catalysts into the cell.These years,single-atom catalysts(SACs)are emerging as a frontier in catalysis due to their maximum atom efficiency and unique reaction selectivity.For SACs fabrication,metal-organic frameworks(MOFs)have been confirmed as promising templates or precursors due to their high metal loadings,structural adjustability,porosity,and tailorable catalytic site.In this review,we summarize effective strategies for fabricating SACs by MOFs with corresponding advanced characterization techniques and illustrate the key role of MOFs-based SACs in these batteries by explaining their reaction mechanisms and challenges.Finally,current applications,prospects,and opportunities for MOFs-based SACs in energy storage systems are discussed.展开更多
The electrochemical carbon dioxide reduction reaction(CO_(2)RR)for highvalue-added products is a promising strategy to tackle excessive CO_(2) emissions.However,the activity of and selectivity for catalysts for CO_(2)...The electrochemical carbon dioxide reduction reaction(CO_(2)RR)for highvalue-added products is a promising strategy to tackle excessive CO_(2) emissions.However,the activity of and selectivity for catalysts for CO_(2)RR still need to be improved because of the competing reaction(hydrogen evolution reaction).In this study,for the first time,we have demonstrated dual atomic catalytic sites for CO_(2)RR from a core-shell hybrid of the covalent-organic framework and the metal-organic framework.Due to abundant dual atomic sites(with CoN_(4)O and ZnN_(4) of 2.47 and 11.05 wt.%,respectively)on hollow carbon,the catalyst promoted catalysis of CO_(2)RR,with the highest Faradic efficiency for CO of 92.6%at-0.8 V and a turnover frequency value of 1370.24 h^(-1) at-1.0 V.More importantly,the activity and selectivity of the catalyst were well retained for 30 h.The theoretical calculation further revealed that CoN_(4)O was the main site for CO_(2)RR,and the activity of and selectivity for Zn sites were also improved because of the synergetic roles.展开更多
The design of efficient and robust non-precious metal electrocatalysts towards oxygen evolution reaction(OER)is of great value for developing green energy technologies.The in-situ formed high-valence(oxy)hydroxides sp...The design of efficient and robust non-precious metal electrocatalysts towards oxygen evolution reaction(OER)is of great value for developing green energy technologies.The in-situ formed high-valence(oxy)hydroxides species during the reconstruction process of pre-catalysts are recognized as the real contributing sites for OER.However,pre-catalysts generally undergo a slow and inadequate self-reconstruction.Herein,we reported a PO^(3-)_(4)optimized CoFe-based OER catalysts with amorphous structure,which enables a fast and deep reconstruction during the OER process.The amorphous structure induced by ligands PO^(3-)_(4)is prone to evolution and further form active species for OER.The electron interaction between metal sites can be modulated by electron-rich PO^(3-)_(4),which promotes generation of high active CoOOH.Simultaneously,the etching of PO^(3-)_(4)from the pre-catalysts during the catalytic process is in favor of accelerating the self-reconstruction.As a result,as-prepared precatalyst can generate high active CoOOH at a low potential of 1.4 V and achieve an in-depth reconstructed nanosheet structure with abundant OER active sites.Our work provides a promising design of pre-catalysts for realizing efficient catalysis of water oxidation.展开更多
The development of highly active,selective,and stable electrocatalysts can facilitate the effective implementation of electrocatalytic CO_(2)conversion into fuels or chemicals for mitigating the energy crisis and clim...The development of highly active,selective,and stable electrocatalysts can facilitate the effective implementation of electrocatalytic CO_(2)conversion into fuels or chemicals for mitigating the energy crisis and climate problems.Therefore,it is necessary to achieve the goal through reasonable material design based on the actuality of the operational active site at the molecular scale.Inspired by the stimulating synergistic effect of coupled heteronuclear metal atoms,a novel Ni-Co atomic pairs configuration(denoted as NiN_(3)?CoN_(3)-NC)active site was theoretically screened out for improving electrochemical CO_(2)reduction reaction(CO_(2)RR).The structure of NiN_(3)?CoN_(3)-NC was finely regulated by adjusting Zn content in the precursors Zn/Co/Ni-zeolite imidazolate frameworks(Zn/Co/Ni-ZIFs)and pyrolysis temperature.The structural features of NiN_(3)?CoN_(3)-NC were systematically confirmed by aberration-corrected HAADF-STEM coupled with 3D atom-overlapping Gaussian-function fitting mapping,XAFS,and XRD.The results of theoretical calculations reveal that the synergistic effect of Ni-Co atomic pairs can effectively promote the*COOH intermediate formation and thus the overall CO_(2)RR kinetic was improved,and also restrained the competitive hydrogen evolution reaction.Due to the attributes of Ni-Co atomic pairs configuration,the developed NiN_(3)?CoN_(3)-NC with superior catalytic activity,selectivity,and durability,with a high turnover frequency of 2265 h^(-1)at-1.1 V(vs.RHE)and maximum Faradaic efficiency of 97.7%for CO production.This work demonstrates the great potential of DACs as highly efficient catalysts for CO_(2)RR,provides a useful strategy to design heteronuclear DACs,exploits the synergistic effect of multiple metal sites to facilitate complex CO_(2)RR catalytic reactions,and inspires more efforts to develop the potential of DACs in various fields.展开更多
Rechargeable aqueous zinc iodine(ZnǀǀI_(2))batteries have been promising energy storage technologies due to low-cost position and constitutional safety of zinc anode,iodine cathode and aqueous electrolytes.Whereas,on ...Rechargeable aqueous zinc iodine(ZnǀǀI_(2))batteries have been promising energy storage technologies due to low-cost position and constitutional safety of zinc anode,iodine cathode and aqueous electrolytes.Whereas,on one hand,the low-fraction utilization of electrochemically inert host causes severe shuttle of soluble polyiodides,deficient iodine utilization and sluggish reaction kinetics.On the other hand,the usage of high mass polar electrocatalysts occupies mass and volume of electrode materials and sacrifices device-level energy density.Here,we propose a“confinement-catalysis”host composed of Fe single atom catalyst embedding inside ordered mesoporous carbon host,which can effectively confine and catalytically convert I_(2)/I^(−)couple and polyiodide intermediates.Consequently,the cathode enables the high capacity of 188.2 mAh g^(−1)at 0.3 A g^(−1),excellent rate capability with a capacity of 139.6 mAh g^(−1)delivered at high current density of 15 A g^(−1)and ultra-long cyclic stability over 50,000 cycles with 80.5%initial capacity retained under high iodine loading of 76.72 wt%.Furthermore,the electrocatalytic host can also accelerate the I^(+)↔I_(2)conversion.The greatly improved electrochemical performance originates from the modulation of physicochemical confinement and the decrease of energy barrier for reversible I−/I_(2)and I_(2)/I^(+)couples,and polyiodide intermediates conversions.展开更多
The electrochemical oxygen reduction reaction(ORR) and oxygen evolution reaction(OER) are fundamental processes in a range of energy conversion devices such as fuel cells and metal–air batteries. ORR and OER both hav...The electrochemical oxygen reduction reaction(ORR) and oxygen evolution reaction(OER) are fundamental processes in a range of energy conversion devices such as fuel cells and metal–air batteries. ORR and OER both have significant activation barriers, which severely limit the overall performance of energy conversion devices that utilize ORR/OER. Meanwhile, ORR is another very important electrochemical reaction involving oxygen that has been widely investigated. ORR occurs in aqueous solutions via two pathways: the direct 4-electron reduction or 2-electron reduction pathways from O_(2) to water(H_2O) or from O_(2) to hydrogen peroxide(H_2O_(2)). Noble metal electrocatalysts are often used to catalyze OER and ORR, despite the fact that noble metal electrocatalysts have certain intrinsic limitations, such as low storage. Thus, it is urgent to develop more active and stable low-cost electrocatalysts, especially for severe environments(e.g., acidic media). Theoretically, an ideal oxygen electrocatalyst should provide adequate binding to oxygen species. Transition metals not belonging to the platinum group metal-based oxides are a low-cost substance that could give a d orbital for oxygen species binding. As a result, transition metal oxides are regarded as a substitute for typical precious metal oxygen electrocatalysts. However, the development of oxide catalysts for oxygen reduction and oxygen evolution reactions still faces significant challenges, e.g., catalytic activity, stability, cost, and reaction mechanism. We discuss the fundamental principles underlying the design of oxide catalysts, including the influence of crystal structure, and electronic structure on their performance. We also discuss the challenges associated with developing oxide catalysts and the potential strategies to overcome these challenges.展开更多
Platinum group metals(PGMs),especially Pd,Pt,and Rh,have drawn great attention due to their unique features.Direct separation of Pd and Pt from highly acidic automobile catalyst leach liquors is disturbed by various f...Platinum group metals(PGMs),especially Pd,Pt,and Rh,have drawn great attention due to their unique features.Direct separation of Pd and Pt from highly acidic automobile catalyst leach liquors is disturbed by various factors.This work investigates the effect of various parameters including the acidity,extractant concentration,phase ratio A/O,and diluents on the Pd and Pt extraction and their stripping behaviors.The results show that the Pd and Pt are successfully separated from simulated leach liquor of spent automobile catalysts with monothioCyanex 272 and trioctylamine(TOA).Monothio-Cyanex 272 shows strong extractability and specific selectivity for Pd,and only one single stage is needed to recover more than 99.9% of Pd,leaving behind all the Pt,Rh,and base metals of Fe,Mg,Ce,Ni,Cu,and Co in the raffinate.The loaded Pd is efficiently stripped by acidic thiourea solutions.TOA shows strong extractability for Pt and Fe at acidity of 6 mol·L^(–1) HCl.More than 99.9% of Pt and all of the Fe are extracted into the organic phase after two stages of countercurrent extraction.Diluted HCl easily scrubs the loaded base metals(Fe,Cu,and Co).The loaded Pt is efficiently stripped by 1.0 mol·L^(–1) thiourea and 0.05–0.1 mol·L^(–1) Na OH solutions.Monothio-Cyanex 272 and TOA can realize the separation of Pd and Pt from highly acidic leach liquor of spent automobile catalysts.展开更多
Developing high performance and low-cost catalysts for oxygen reduction reaction(ORR)in challenging acid condition is vital for proton-exchange-membrane fuel cells(PEMFCs).Carbon-supported nonprecious metal single ato...Developing high performance and low-cost catalysts for oxygen reduction reaction(ORR)in challenging acid condition is vital for proton-exchange-membrane fuel cells(PEMFCs).Carbon-supported nonprecious metal single atom catalysts(SACs)have been identified as potential catalysts in the field.Great advance has been obtained in constructing diverse active sites of SACs for improving the performance and understanding the fundamental principles of regulating acid ORR performance.However,the ORR performance of SACs is still unsatisfactory.Importantly,microenvironment adjustment of SACs offers chance to promote the performance of acid ORR.In this review,acid ORR mechanism,attenuation mechanism and performance improvement strategies of SACs are presented.The strategies for promoting ORR activity of SACs include the adjustment of center metal and its microenvironment.The relationship of ORR performance and structure is discussed with the help of advanced experimental investigations and theoretical calculations,which will offer helpful direction for designing advanced SACs for ORR.展开更多
基金supported by the National Natural Science Foundation of China(22234005,21974070)the Natural Science Foundation of Jiangsu Province(BK20222015)。
文摘Atomically dispersed catalysts exhibit significant influence on facilitating the sluggish oxygen reduction reaction(ORR)kinetics with high atom economy,owing to remarkable attributes including nearly 100%atomic utilization and exceptional catalytic functionality.Furthermore,accurately controlling atomic physical properties including spin,charge,orbital,and lattice degrees of atomically dispersed catalysts can realize the optimized chemical properties including maximum atom utilization efficiency,homogenous active centers,and satisfactory catalytic performance,but remains elusive.Here,through physical and chemical insight,we review and systematically summarize the strategies to optimize atomically dispersed ORR catalysts including adjusting the atomic coordination environment,adjacent electronic orbital and site density,and the choice of dual-atom sites.Then the emphasis is on the fundamental understanding of the correlation between the physical property and the catalytic behavior for atomically dispersed catalysts.Finally,an overview of the existing challenges and prospects to illustrate the current obstacles and potential opportunities for the advancement of atomically dispersed catalysts in the realm of electrocatalytic reactions is offered.
基金supported by the National Key Research and Development Program of China(Nos.2022YFB3504100,2022YFB3506200)the National Natural Science Foundation of China(Nos.22208373,22376217)+1 种基金the Beijing Nova Program(No.20220484215)the Science Foundation of China University of Petroleum,Beijing(No.2462023YJRC030)。
文摘It is urgent to develop catalysts with application potential for oxidative coupling of methane(OCM)at relatively lower temperature.Herein,three-dimensional ordered macro porous(3 DOM)La_(2-x)Sr_(x)Ce_(2-y)CayO_(7-δ)(A_(2)B_(2)O_(7)-type)catalysts with disordered defective cubic fluorite phased structure were successfully prepared by a colloidal crystal template method.3DOM structure promotes the accessibility of the gaseous reactants(O2and CH4)to the active sites.The co-doping of Ca and Sr ions in La_(2-x)Sr_(x)Ce_(2-y)CayO_(7-δ)catalysts improved the formation of oxygen vacancies,thereby leading to increased density of surface-active oxygen species(O_(2)^(-))for the activation of CH4and the formation of C2products(C2H6and C2H4).3DOM La_(2-x)Sr_(x)Ce_(2-y)CayO_(7-δ)catalysts exhibit high catalytic activity for OCM at low temperature.3DOM La1.7Sr0.3Ce1.7Ca0.3O7-δcatalyst with the highest density of O_(2)^(-)species exhibited the highest catalytic activity for low-temperature OCM,i.e.,its CH4conversion,selectivity and yield of C2products at 650℃are 32.2%,66.1%and 21.3%,respectively.The mechanism was proposed that the increase in surface oxygen vacancies induced by the co-doping of Ca and Sr ions boosts the key step of C-H bond breaking and C-C bond coupling in catalyzing low-temperature OCM.It is meaningful for the development of the low-temperature and high-efficient catalysts for OCM reaction in practical application.
基金supported by Thailand Science Research and Innovation Fund Chulalongkorn University,Thailand(IND66210014)。
文摘Hydrogen sulfide(H_(2)S) not only presents significant environmental concerns but also induces severe corrosion in industrial equipment,even at low concentrations.Among various technologies,the selective oxidation of hydrogen sulfide(SOH_(2)S) to elemental sulfur(S) has emerged as a sustainable and environmentally friendly solution.Due to its unique properties,iron oxide has been extensively investigated as a catalyst for SOH_(2)S;however,rapid deactivation has remained a significant drawback.The causes of iron oxide-based catalysts deactivation mechanisms in SOH_(2)S,including sulfur or sulfate deposition,the transformation of iron species,sintering and excessive oxygen vacancy formation,and active site loss,are thoroughly examined in this review.By focusing on the deactivation mechanisms,this review aims to provide valuable insights into enhancing the stability and efficiency of iron-based catalysts for SOH_(2)S.
基金the National Natural Science Foundation of China-Outstanding Youth Foundation (No. 22322814)the National Natural Science Foundation of China (No. 22108144)the Natural Science Foundation of Shandong-Outstanding Youth Foundation (No. ZR2023YQ017)。
文摘Capturing and utilizing CO_(2)from the production process is the key to solving the excessive CO_(2)emission problem. CO_(2)hydrogenation with green hydrogen to produce olefins is an effective and promising way to utilize CO_(2)and produce valuable chemicals. The olefins can be produced by CO_(2)hydrogenation through two routes, i.e., CO_(2)-FTS (carbon dioxide Fischer- Tropsch synthesis) and MeOH (methanol-mediated), among which CO_(2)-FTS has significant advantages over MeOH in practical applications due to its relatively high CO_(2)conversion and low energy consumption potentials. However, the CO_(2)-FTS faces challenges of difficult CO_(2)activation and low olefins selectivity. Iron-based catalysts are promising for CO_(2)-FTS due to their dual functionality of catalyzing RWGS and CO-FTS reactions. This review summarizes the recent progress on iron-based catalysts for CO_(2)hydrogenation via the FTS route and analyzes the catalyst optimization from the perspectives of additives, active sites, and reaction mechanisms. Furthermore, we also outline principles and challenges for rational design of high-performance CO_(2)-FTS catalysts.
文摘Among challenges implicit in the transition to the post-fossil fuel energetic model,the finite amount of resources available for the technological implementation of CO_(2) revalorizing processes arises as a central issue.The development of fully renewable catalytic systems with easier metal recovery strategies would promote the viability and sustainability of synthetic natural gas production circular routes.Taking Ni and NiFe catalysts supported over g-Al_(2)O_(3) oxide as reference materials,this work evaluates the potentiality of Ni and NiFe supported biochar catalysts for CO_(2) methanation.The development of competitive biochar catalysts was found dependent on the creation of basic sites on the catalyst surface.Displaying lower Turn Over Frequencies than Ni/Al catalyst,the absence of basic sites achieved over Ni/C catalyst was related to the depleted catalyst performances.For NiFe catalysts,analogous Ni_(5)Fe_(1) alloys were constituted over both alumina and biochar supports.The highest specific activity of the catalyst series,exhibited by the NiFe/C catalyst,was related to the development of surface basic sites along with weaker NiFe-C interactions,which resulted in increased Ni0:NiO surface populations under reaction conditions.In summary,the present work establishes biochar supports as a competitive material to consider within the future low-carbon energetic panorama.
文摘Nitrate pollution is of great importance in both the environmental and health contexts, necessitating the development of efficient mitigation strategies. This review provides a comprehensive analysis of the many catalysts employed in the electrochemical reduction of nitrate to ammonia, and presents a viable environmentally friendly approach to address the issue of nitrate pollution. Hence, the electrochemical transformation of nitrate to ammonia serves the dual purpose of addressing nitrate pollution in water bodies, and is a useful agricultural resource. This review examines a range of catalyst materials such as noble and non-noble metals, metal oxides, carbon-based materials, nitrogen-doped carbon species, metal complexes, and semiconductor photocatalysts. It evaluates catalytic efficiency, selectivity, stability, and overall process optimization. The performance of catalysts is influenced by various factors, including reaction conditions, catalyst structure, loading techniques, and electrode interfaces. Comparative analysis was performed to evaluate the catalytic activity, selectivity, Faradaic efficiency, current density, stability, and durability of the catalysts. This assessment offers significant perspectives on the structural, compositional, and electrochemical characteristics that affect the efficacy of these catalysts, thus informing future investigations and advancements in this domain. In addition to mitigating nitrate pollution, the electrochemical reduction of nitrate to ammonia is in line with sustainable agricultural methods, resource conservation, and the utilization of renewable energy resources. This study explores the factors that affect the catalytic efficiency, provides new opportunities to address nitrate pollution, and promotes the development of sustainable environmental solutions.
基金This study is supported by the National Natural Science Foundation of China(21925104)the Natural Science Foun-dation of Hubei Province(2021CFA020)the start-up funding of Huazhong University of Science and Technology(3004110178).
文摘Carbon-based metal-free nanomaterials are promising alternatives to precious metals as electrocatalysts of key energy storage and conversion technologies.Of paramount significance are the establishment of design principles by understanding the catalytic mechanisms and identifying the active sites.Distinct from sp2-conjugated graphene and carbon nanotube,fullerene possesses unique characteristics that are growingly being discovered and exploited by the electrocatalysis community.For instance,the well-defined atomic and molecular structures,the good electron affinity to tune the electronic structures of other substances,the intermolecular self-assembly into superlattices,and the on-demand chemical modification have endowed fullerene with incomparable advantages as electrocatalysts that are otherwise not applicable to other carbon ma-terials.As increasing studies are being reported on this intriguing topic,it is necessary to provide a state-of-the-art overview of the recent progress.This review takes such an initiative by summarizing the promises and challenges in the electrocatalytic applications of fullerene and its derivatives.The content is structured according to the composition and structure of fullerene,including intact fullerene(e.g.,fullerene composite and superlattices)and fullerene derivatives(e.g.,doped,endohedral,and disintegrated fullerene).The synthesis,characterization,catalytic mechanisms,and deficiencies of these fullerene-based materials are explicitly elaborated.We conclude it by sharing our perspectives on the key aspects that future efforts shall consider.
文摘La_(0.8)A_(0.2)NiO_(3) (A=K,Ba,Y) catalysts supported on the microwave-absorbing ceramic heating carrier were prepared by the sol-gel method.The crystalline phase and the catalytic activity of the La_(0.8)A_(0.2)NiO_(3)catalysts were characterized by XRD and H_(2) temperature-programmed reduction (TPR).The effects of reaction temperature,oxygen concentration,and gas flow rate on the direct decomposition of nitric oxide over the synthesized catalysts were studied under microwave irradiation (2.45 GHz).The XRD results indicated that the La_(0.8)A_(0.2)NiO_(3) catalysts formed an ABO_(3) perovskite structure,and the H_(2)-TPR results revealed that the relative reducibility of the catalysts increased in the order of La_(0.8)K_(0.2)NiO_(3)>La_(0.8)Ba_(0.2)NiO_(3)>La_(0.8)Y_(0.2)Ni O_(3).Under microwave irradiation,the highest NO conversion amounted to 98.9%,which was obtained with the La_(0.8)K_(0.2)NiO_(3) catalyst at 400℃.The oxygen concentration did not inhibit the NO decomposition on the La_(0.8)A_(0.2)NiO_(3) catalysts,thus the N_(2) selectivity exceeded 99.8%under excess oxygen at 550℃.The NOconversion of the La_(0.8)A_(0.2)NiO_(3) catalysts decreased linearly with the increase in the gas flow rate.
基金the financial support from by the National Key Research and Development Program of China(No.2022YFB4101800)National Natural Science Foundation of China(No.22278298)Program for Introducing Talents of Discipline to Universities of China(No.BP0618007).
文摘Nitrogen(N)-doped carbon materials as metal catalyst supports have attracted signifi cant attention,but the eff ect of N dopants on catalytic performance remains unclear,especially for complex reaction processes such as Fischer-Tropsch synthesis(FTS).Herein,we engineered ruthenium(Ru)FTS catalysts supported on N-doped carbon overlayers on TiO_(2)nanoparticles.By regulating the carbonization temperatures,we successfully controlled the types and contents of N dopants to identify their impacts on metal-support interactions(MSI).Our fi ndings revealed that N dopants establish a favorable surface environment for electron transfer from the support to the Ru species.Moreover,pyridinic N demonstrates the highest electron-donating ability,followed by pyrrolic N and graphitic N.In addition to realizing excellent catalytic stability,strengthening the interaction between Ru sites and N dopants increases the Ru^(0)/Ru^(δ+)ratios to enlarge the active site numbers and surface electron density of Ru species to enhance the strength of adsorbed CO.Consequently,it improves the catalyst’s overall performance,encompassing intrinsic and apparent activities,as well as its ability for carbon chain growth.Accordingly,the as-synthesized Ru/TiO_(2)@CN-700 catalyst with abundant pyridine N dopants exhibits a superhigh C_(5+)time yield of 219.4 mol CO/(mol Ru·h)and C_(5+)selectivity of 85.5%.
基金The authors acknowledge funding from National Natural Science Foundation of China(52302307)Shaanxi Province(2023-ZDLGY-24,2023-JC-QN-0473)+2 种基金project funded by China Postdoctoral Science Foundation(2023MD734210)the Open Foundation of State Key Laboratory for Advanced Metals and Materials(2022-Z01)Shaanxi Provincial Department of Education industrialization project(21JC018).
文摘Engineering transition metal compounds(TMCs)catalysts with excellent adsorption-catalytic ability has been one of the most effec-tive strategies to accelerate the redox kinetics of sulfur cathodes.Herein,this review focuses on engineering TMCs catalysts by cation doping/anion doping/dual doping,bimetallic/bi-anionic TMCs,and TMCs-based heterostructure composites.It is obvious that introducing cations/anions to TMCs or constructing heterostructure can boost adsorption-catalytic capacity by regulating the electronic structure including energy band,d/p-band center,electron filling,and valence state.Moreover,the elec-tronic structure of doped/dual-ionic TMCs are adjusted by inducing ions with different electronegativity,electron filling,and ion radius,resulting in electron redistribution,bonds reconstruction,induced vacancies due to the electronic interaction and changed crystal structure such as lat-tice spacing and lattice distortion.Different from the aforementioned two strategies,heterostructures are constructed by two types of TMCs with different Fermi energy levels,which causes built-in electric field and electrons transfer through the interface,and induces electron redistribution and arranged local atoms to regulate the electronic structure.Additionally,the lacking studies of the three strategies to comprehensively regulate electronic structure for improving catalytic performance are pointed out.It is believed that this review can guide the design of advanced TMCs catalysts for boosting redox of lithium sulfur batteries.
基金the China Scholarship Council for financial supportthe funding by the Leverhulme Trust(RPG2019-122)+4 种基金the ACT program(Accelerating CCS Technologies,Horizon2020 Project No.294766),which funded the FUNMIN projectFinancial contributions were made from Department for Business,Energy&Industrial Strategy(BEIS)together with extra funding from NERC and EPSRC research councils,United Kingdom,ADEME(FR),MINECO-AEI(ES)partially funded by EPSRC(EP/P020194/1)funded by EPSRC(EP/L000202)supported by QMUL Research-IT。
文摘Diatomic catalysts(DACs)with two adjacent metal atoms supported on graphene can offer diverse functionalities,overcoming the inherent limitations of single atom catalysts(SACs).In this study,density functional theory calculations were conducted to investigate the reactivity of the carbon dioxide(CO_(2))reduction reaction(CO_(2)RR)on metal sites of both DACs and SACs,as well as their synergistic effects on activity and selectivity.Calculation of the Gibbs free energies of CO_(2)RR and associated values of the limiting potentials to generate C_(1) products showed that Cu acts as a promoter rather than an active catalytic centre in the catalytic CO_(2)conversion on heteronuclear DACs(CuN_(4)-MN_(4)),improving the catalytic activity on the other metal compared to the related SAC MN_(4).Cu enhances the initial reduction of CO_(2)by promoting orbital hybridization between the key intermediate*COOH 2p-orbitals and the metals 3d-orbitals around the Fermi level.This degree of hybridization in the DACs CuN_(4)-MN_(4) decreases from Fe to Co,Ni,and Zn.Our work demonstrates how Cu regulates the CO_(2)RR performance of heteronuclear DACs,offering an effective approach to designing practical,stable,and high-performing diatomic catalysts for CO_(2)electroreduction.
文摘The continued increase in population and the industrial revolution have led to an increase in atmospheric carbon dioxide(CO_(2)) concentration. Consequently, developing and implementing effective solutions to reduce CO_(2) emissions is a global priority. The electrochemical CO_(2) reduction reaction(CO_(2)RR) is strongly believed to be a promising alternative to fossil fuel-based technologies for the production of value-added chemicals. So far, the implementation of CO_(2)RR is hindered by associated electrochemical reactions, such as low selectivity, hydrogen evolution reaction(HER), and additional overpotential induced in some cases. As a result, it is necessary to conduct a timely evaluation of the state-of-the-art strategies in CO_(2)RR, with a focus on the engineering of the electrocatalytic systems. Catalyst morphology is one factor that plays a critical role in overcoming these drawbacks and significantly contributes to enhancing product selectivity and Faradaic efficiency(FE). This review article summarizes the recent advances in the rational design of electrocatalysts with various morphologies and the influence of these morphologies on CO_(2)RR. To compare literature findings in a meaningful way, the article focuses on results reported under a well-defined period and considers the first three rows of the d-block metal catalysts. The discussion typically covers the design of nanostructured catalysts and the molecular-level understanding of morphology-performance relationship in terms of activity, selectivity, and stability during CO_(2) electrolysis. Among others, it would be convenient to recommend a comprehensive discussion on the morphologies of single metals and heterostructures, with a detailed emphasis on their impact on CO_(2) conversion.
基金Financial support was provided by the Guangdong College Students’Innovative Project(202110580014)the Guangdong “Climbing”Program for Research Items(pdjh2021b0544)。
文摘The next-generation energy storage systems such as fuel cells,metal-air batteries,and alkali metal(Li,Na)-chalcogen(S,Se)batteries have received increasing attention owing to their high energy density and low cost.However,one of the main obstacles of these systems is the poor reaction kinetics in the involved chemical reactions.Therefore,it is essential to incorporate suitable and efficient catalysts into the cell.These years,single-atom catalysts(SACs)are emerging as a frontier in catalysis due to their maximum atom efficiency and unique reaction selectivity.For SACs fabrication,metal-organic frameworks(MOFs)have been confirmed as promising templates or precursors due to their high metal loadings,structural adjustability,porosity,and tailorable catalytic site.In this review,we summarize effective strategies for fabricating SACs by MOFs with corresponding advanced characterization techniques and illustrate the key role of MOFs-based SACs in these batteries by explaining their reaction mechanisms and challenges.Finally,current applications,prospects,and opportunities for MOFs-based SACs in energy storage systems are discussed.
基金Q.Xu acknowledges financial support from the Natural Science Foundation of Shanghai(20ZR1464000)G.Zeng is grateful for the support from the National Natural Science Foundation of China(21878322,22075309)the Science and Technology Commission of Shanghai(19ZR1479200).The authors also thank the Shanghai Synchrotron Radiation Facility for XAFS measurements at Beamline BL14w1.
文摘The electrochemical carbon dioxide reduction reaction(CO_(2)RR)for highvalue-added products is a promising strategy to tackle excessive CO_(2) emissions.However,the activity of and selectivity for catalysts for CO_(2)RR still need to be improved because of the competing reaction(hydrogen evolution reaction).In this study,for the first time,we have demonstrated dual atomic catalytic sites for CO_(2)RR from a core-shell hybrid of the covalent-organic framework and the metal-organic framework.Due to abundant dual atomic sites(with CoN_(4)O and ZnN_(4) of 2.47 and 11.05 wt.%,respectively)on hollow carbon,the catalyst promoted catalysis of CO_(2)RR,with the highest Faradic efficiency for CO of 92.6%at-0.8 V and a turnover frequency value of 1370.24 h^(-1) at-1.0 V.More importantly,the activity and selectivity of the catalyst were well retained for 30 h.The theoretical calculation further revealed that CoN_(4)O was the main site for CO_(2)RR,and the activity of and selectivity for Zn sites were also improved because of the synergetic roles.
基金financially supported by the National Natural Science Foundation of China (Grants Nos.51772338,51972349,91963210 and U1801255).
文摘The design of efficient and robust non-precious metal electrocatalysts towards oxygen evolution reaction(OER)is of great value for developing green energy technologies.The in-situ formed high-valence(oxy)hydroxides species during the reconstruction process of pre-catalysts are recognized as the real contributing sites for OER.However,pre-catalysts generally undergo a slow and inadequate self-reconstruction.Herein,we reported a PO^(3-)_(4)optimized CoFe-based OER catalysts with amorphous structure,which enables a fast and deep reconstruction during the OER process.The amorphous structure induced by ligands PO^(3-)_(4)is prone to evolution and further form active species for OER.The electron interaction between metal sites can be modulated by electron-rich PO^(3-)_(4),which promotes generation of high active CoOOH.Simultaneously,the etching of PO^(3-)_(4)from the pre-catalysts during the catalytic process is in favor of accelerating the self-reconstruction.As a result,as-prepared precatalyst can generate high active CoOOH at a low potential of 1.4 V and achieve an in-depth reconstructed nanosheet structure with abundant OER active sites.Our work provides a promising design of pre-catalysts for realizing efficient catalysis of water oxidation.
基金the support of the Sichuan Science and Technology Program(2023NSFC0098)the Science and Technology Development Fund from Macao SAR(FDCT)(0081/2019/AMJ,0154/2019/A3,006/2022/ALC,and 0111/2022/A2)+2 种基金the Shenzhen-Hong Kong-Macao Science and Technology Research Programme(Type C)(SGDX20210823103803017)the Multi-Year Research Grants(MYRG2022-00026-IAPME)from Research&Development Office at University of Macaothe Frontier Project of Chengdu Tianfu New Area Institute(SWUST,2022ZY017)。
文摘The development of highly active,selective,and stable electrocatalysts can facilitate the effective implementation of electrocatalytic CO_(2)conversion into fuels or chemicals for mitigating the energy crisis and climate problems.Therefore,it is necessary to achieve the goal through reasonable material design based on the actuality of the operational active site at the molecular scale.Inspired by the stimulating synergistic effect of coupled heteronuclear metal atoms,a novel Ni-Co atomic pairs configuration(denoted as NiN_(3)?CoN_(3)-NC)active site was theoretically screened out for improving electrochemical CO_(2)reduction reaction(CO_(2)RR).The structure of NiN_(3)?CoN_(3)-NC was finely regulated by adjusting Zn content in the precursors Zn/Co/Ni-zeolite imidazolate frameworks(Zn/Co/Ni-ZIFs)and pyrolysis temperature.The structural features of NiN_(3)?CoN_(3)-NC were systematically confirmed by aberration-corrected HAADF-STEM coupled with 3D atom-overlapping Gaussian-function fitting mapping,XAFS,and XRD.The results of theoretical calculations reveal that the synergistic effect of Ni-Co atomic pairs can effectively promote the*COOH intermediate formation and thus the overall CO_(2)RR kinetic was improved,and also restrained the competitive hydrogen evolution reaction.Due to the attributes of Ni-Co atomic pairs configuration,the developed NiN_(3)?CoN_(3)-NC with superior catalytic activity,selectivity,and durability,with a high turnover frequency of 2265 h^(-1)at-1.1 V(vs.RHE)and maximum Faradaic efficiency of 97.7%for CO production.This work demonstrates the great potential of DACs as highly efficient catalysts for CO_(2)RR,provides a useful strategy to design heteronuclear DACs,exploits the synergistic effect of multiple metal sites to facilitate complex CO_(2)RR catalytic reactions,and inspires more efforts to develop the potential of DACs in various fields.
基金supported by the National Key Research and Development Project(2020YFC1521900 and 2020YFC1521904)the Shaanxi Provincial Science Foundation(2021GXLH-01-11)+1 种基金We would also like to thank National Natural Science Foundation of China(52202299)Analytical&Testing Center of Northwestern Polytechnical University(2022T006).
文摘Rechargeable aqueous zinc iodine(ZnǀǀI_(2))batteries have been promising energy storage technologies due to low-cost position and constitutional safety of zinc anode,iodine cathode and aqueous electrolytes.Whereas,on one hand,the low-fraction utilization of electrochemically inert host causes severe shuttle of soluble polyiodides,deficient iodine utilization and sluggish reaction kinetics.On the other hand,the usage of high mass polar electrocatalysts occupies mass and volume of electrode materials and sacrifices device-level energy density.Here,we propose a“confinement-catalysis”host composed of Fe single atom catalyst embedding inside ordered mesoporous carbon host,which can effectively confine and catalytically convert I_(2)/I^(−)couple and polyiodide intermediates.Consequently,the cathode enables the high capacity of 188.2 mAh g^(−1)at 0.3 A g^(−1),excellent rate capability with a capacity of 139.6 mAh g^(−1)delivered at high current density of 15 A g^(−1)and ultra-long cyclic stability over 50,000 cycles with 80.5%initial capacity retained under high iodine loading of 76.72 wt%.Furthermore,the electrocatalytic host can also accelerate the I^(+)↔I_(2)conversion.The greatly improved electrochemical performance originates from the modulation of physicochemical confinement and the decrease of energy barrier for reversible I−/I_(2)and I_(2)/I^(+)couples,and polyiodide intermediates conversions.
基金the Natural Science Foundation of China (22005250)National Key R D Program of China (2022YFB2502000)FWO (12ZV320N)。
文摘The electrochemical oxygen reduction reaction(ORR) and oxygen evolution reaction(OER) are fundamental processes in a range of energy conversion devices such as fuel cells and metal–air batteries. ORR and OER both have significant activation barriers, which severely limit the overall performance of energy conversion devices that utilize ORR/OER. Meanwhile, ORR is another very important electrochemical reaction involving oxygen that has been widely investigated. ORR occurs in aqueous solutions via two pathways: the direct 4-electron reduction or 2-electron reduction pathways from O_(2) to water(H_2O) or from O_(2) to hydrogen peroxide(H_2O_(2)). Noble metal electrocatalysts are often used to catalyze OER and ORR, despite the fact that noble metal electrocatalysts have certain intrinsic limitations, such as low storage. Thus, it is urgent to develop more active and stable low-cost electrocatalysts, especially for severe environments(e.g., acidic media). Theoretically, an ideal oxygen electrocatalyst should provide adequate binding to oxygen species. Transition metals not belonging to the platinum group metal-based oxides are a low-cost substance that could give a d orbital for oxygen species binding. As a result, transition metal oxides are regarded as a substitute for typical precious metal oxygen electrocatalysts. However, the development of oxide catalysts for oxygen reduction and oxygen evolution reactions still faces significant challenges, e.g., catalytic activity, stability, cost, and reaction mechanism. We discuss the fundamental principles underlying the design of oxide catalysts, including the influence of crystal structure, and electronic structure on their performance. We also discuss the challenges associated with developing oxide catalysts and the potential strategies to overcome these challenges.
基金financially supported by the National Key Research and Development Program for Young Scientists,China(No.2021YFC2901100)。
文摘Platinum group metals(PGMs),especially Pd,Pt,and Rh,have drawn great attention due to their unique features.Direct separation of Pd and Pt from highly acidic automobile catalyst leach liquors is disturbed by various factors.This work investigates the effect of various parameters including the acidity,extractant concentration,phase ratio A/O,and diluents on the Pd and Pt extraction and their stripping behaviors.The results show that the Pd and Pt are successfully separated from simulated leach liquor of spent automobile catalysts with monothioCyanex 272 and trioctylamine(TOA).Monothio-Cyanex 272 shows strong extractability and specific selectivity for Pd,and only one single stage is needed to recover more than 99.9% of Pd,leaving behind all the Pt,Rh,and base metals of Fe,Mg,Ce,Ni,Cu,and Co in the raffinate.The loaded Pd is efficiently stripped by acidic thiourea solutions.TOA shows strong extractability for Pt and Fe at acidity of 6 mol·L^(–1) HCl.More than 99.9% of Pt and all of the Fe are extracted into the organic phase after two stages of countercurrent extraction.Diluted HCl easily scrubs the loaded base metals(Fe,Cu,and Co).The loaded Pt is efficiently stripped by 1.0 mol·L^(–1) thiourea and 0.05–0.1 mol·L^(–1) Na OH solutions.Monothio-Cyanex 272 and TOA can realize the separation of Pd and Pt from highly acidic leach liquor of spent automobile catalysts.
基金supported by the Joint Funds of the National Natural Science Foundation of China(U20A20280)the Postgraduate Scientific Research Innovation Project of Hunan Province(CX20210171)。
文摘Developing high performance and low-cost catalysts for oxygen reduction reaction(ORR)in challenging acid condition is vital for proton-exchange-membrane fuel cells(PEMFCs).Carbon-supported nonprecious metal single atom catalysts(SACs)have been identified as potential catalysts in the field.Great advance has been obtained in constructing diverse active sites of SACs for improving the performance and understanding the fundamental principles of regulating acid ORR performance.However,the ORR performance of SACs is still unsatisfactory.Importantly,microenvironment adjustment of SACs offers chance to promote the performance of acid ORR.In this review,acid ORR mechanism,attenuation mechanism and performance improvement strategies of SACs are presented.The strategies for promoting ORR activity of SACs include the adjustment of center metal and its microenvironment.The relationship of ORR performance and structure is discussed with the help of advanced experimental investigations and theoretical calculations,which will offer helpful direction for designing advanced SACs for ORR.
