Endogenous hydrogen systems,consisting of metal–organic coordination catalysts and alcohols,have been widely applied for the transfer hydrogenation(TH)of biomass-derived carbonyl compounds in recent years.Metal-organ...Endogenous hydrogen systems,consisting of metal–organic coordination catalysts and alcohols,have been widely applied for the transfer hydrogenation(TH)of biomass-derived carbonyl compounds in recent years.Metal-organic coordination catalysts showed satisfactory ability of TH in the secondary alcohols,but most of them could not effectively employ the cheaper primary alcohols as hydrogen donors.Furthermore,they commonly contained high metal contents,which also led to low catalytic efficiency in significant measure.In this work,we constructed a novel magnesium single-atom catalyst(Mg-NC)with merely 0.37 wt%Mg by means of a combined self-assembly and pyrolysis strategy.The characterization results indicated that Mg was atomically dispersed and it was coordinated with four pyridinic-N in Mg-NC.Due to the obvious electron transfer from Mg to its coordinated pyridinic-N,Mg–N_(4)active centers displayed high Lewis acid-base strength with abundant content,which brought remarkable catalytic activity.When Mg-NC was used for the TH of 5-hydroxymethylfurfural(HMF)in ethanol(EtOH),2,5-bis(hydroxymethyl)furan(BHMF)yield was up to 96.3%with high productivity of 19.85 molBHMF mol_(Mg)^(−1)h^(−1)at 150°C for 5 h.More interestingly,the process of TH over Mg-NC in EtOH was proved to proceed via the hydrogen radical mechanism.Additionally,Mg-NC exhibited powerful catalytic universality;it could not only utilize other primary alcohols(such as n-propanol and n-butanol)as hydrogen donors,but also catalyze the TH of other carbonyl compounds(such as furfural,5-methylfurfural,benzaldehyde,cyclohexanone,and levulinic acid).Overall,this work offered some important clues and references to reinforce the hydrogen-supplying ability of primary alcohols in the TH of various biomass-derived carbonyl compounds to high-value fine chemicals.展开更多
Catalytic CO_(2)-to-methanol conversion presents a synergistic approach for concurrent greenhouse gas abatement and sustainable energy carrier synthesis.Single-atom catalysts(SACs)with maximized atomic utilization,tai...Catalytic CO_(2)-to-methanol conversion presents a synergistic approach for concurrent greenhouse gas abatement and sustainable energy carrier synthesis.Single-atom catalysts(SACs)with maximized atomic utilization,tailored electronic configurations and unique metal-support interactions,exhibit superior performance in CO_(2) activation and methanol synthesis.This review systematically compares reaction mechanisms and pathways across thermal,photocatalytic and electrocatalytic systems,emphasizing structure-activity relationships governed by active sites,coordination microenvironments and support functionalities.Through case studies of representative SACs,we elucidate how metal-support synergies dictate intermediate binding energetics and methanol selectivity.A critical analysis of reaction parameters(e.g.,temperature,pressure)reveals condition-dependent catalytic behaviors in thermal system,with fewer studies in photo/electrocatalytic systems identified as key knowledge gaps.While thermal catalysis achieves industrially viable methanol yields,the scalability is constrained by energy-intensive operation and catalyst sintering.Conversely,photo/electrocatalytic routes offer renewable energy integration but suffer from inefficient charge dynamics and mass transport limitations.To address the challenges,we propose strategic research priorities on precise design of active sites,synergy of multiple technological pathways,development of intelligent catalytic systems and diverse CO_(2) feedstock compatibility.These insights establish a framework for developing next-generation SACs,offering both theoretical foundations and technological blueprints for developing carbon-negative catalytic technologies.展开更多
In recent years,numer-ous single-atom catalysts(SACs)have been synthesized to activate persulfate(PS)by a non-radical pathway because of its high se-lectivity,and activity for the cata-lyst.Metal-nitrogen-carbon(M-N_(...In recent years,numer-ous single-atom catalysts(SACs)have been synthesized to activate persulfate(PS)by a non-radical pathway because of its high se-lectivity,and activity for the cata-lyst.Metal-nitrogen-carbon(M-N_(x)-C)has been identified as the key active site in SACs.Although methods for preparing SACs have been extensively reported,a systematic summary of the direct construction of M-N_(x)-C,espe-cially unconventional metal-nitrogen-carbon(UM-N_(x)-C,x≠4),on SACs for PS non-radical activation has still not been reported.The role of the M-N_(x)-C active sites on PS non-radical activation is discussed and methods for the formation of M-N_(x)-C and UM-N_(x)-C active sites in SACs and the effect of catalyst carriers such as carbon nitride(g-C_(3)N_(4)),MOFs,COFs,and other car-bon materials are reviewed.Direct and indirect methods,especially for UM-N_(x)-C active site formation,are also elaborated.Factors affecting the formation of a M-N_(x)-C active site on SACs are also discussed.Prospects for the use of M-N_(x)-C active sites for the non-radical activation of PS by SACs to remove organic contaminants from wastewater are evaluated.展开更多
The nitrogen-coordinated metal single-atom catalysts(M−N−C SACs)with an ultra-high metal loading synthetized by direct high-temperature pyrolysis have been widely reported.However,most of metal single atoms in these c...The nitrogen-coordinated metal single-atom catalysts(M−N−C SACs)with an ultra-high metal loading synthetized by direct high-temperature pyrolysis have been widely reported.However,most of metal single atoms in these catalysts were buried in the carbon matrix,resulting in a low metal utilization and inaccessibility for adsorption of reactants during the catalytic process.Herein,we reported a facile synthesis based on the hard-soft acid-base(HSAB)theory to fabricate Co single-atom catalysts with highly exposed metal atoms ligated to the external pyridinic-N sites of a nitrogen-doped carbon support.Benefiting from the highly accessible Co active sites,the prepared Co−N−C SAC exhibited a superior oxygen reduction reactivity comparable to that of the commercial Pt/C catalyst,showing a high turnover frequency(TOF)of 0.93 e^(−)·s^(-1)·site^(-1)at 0.85 V vs.RHE,far exceeding those of some representative SACs with a ultra-high metal content.This work provides a rational strategy to design and prepare M−N−C single-atom catalysts featured with high site-accessibility and site-density.展开更多
By simplifying catalyst-product separation and reducing phosphorus waste,heterogeneous hydroformylation offers a more sustainable alternative to homogeneous processes.However,heterogeneous hydroformylation catalysts d...By simplifying catalyst-product separation and reducing phosphorus waste,heterogeneous hydroformylation offers a more sustainable alternative to homogeneous processes.However,heterogeneous hydroformylation catalysts developed thus far still suffer from the issues of much lower activity and metal leaching,which severely hinder their practical application.Here,we demonstrate that incorporating phosphorus(P)atoms into graphitic carbon nitride(PCN)supports facilitates charge transfer from Rh to the PCN support,thus largely enhancing electronic metal-support interactions(EMSIs).In the styrene hydroformylation reaction,the activity of Rh_(1)/PCN single-atom catalysts(SACs)with varying P contents exhibited a volcano-shaped relationship with P doping,where the Rh_(1)/PCN SAC with optimal P doping showed exceptional activity,approximately 5.8-and 3.3-fold greater than that of the Rh_(1)/g-C_(3)N_(4)SAC without P doping and the industrial homogeneous catalyst HRh(CO)(PPh_(3))_(3),respectively.In addition,the optimal Rh_(1)/PCN SAC catalyst also demonstrated largely enhanced multicycle stability without any visible metal aggregation owing to the increased EMSIs,which sharply differed from the severe metal aggregation of large nanoparticles on the Rh_(1)/g-C_(3)N_(4)SAC.Mechan-istic studies revealed that the enhanced catalytic performance could be attributed to electron-deficient Rh species,which reduced CO adsorption while simultaneously promoting alkene adsorption through increased EMSIs.These findings suggest that tuning EMSIs is an effective way to achieve SACs with high activity and durability.展开更多
With the rapid advancement of portable energy devices and sensor technologies,enhancing their catalytic performance,sensing capabilities,and application reliability has become a critical challenge in the fields of mat...With the rapid advancement of portable energy devices and sensor technologies,enhancing their catalytic performance,sensing capabilities,and application reliability has become a critical challenge in the fields of materials and energy science.Single-atom catalysts(SACs),owing to their high atomic utilization,outstanding catalytic activity,and precisely engineered structures enabled by density functional theory and enhanced by artificial intelligence,have shown tremendous potential in advancing portable energy and sensing technologies.While existing reviews predominantly focus on the application of SACs in individual portable devices,systematic discussions on their overall development prospects and challenges within portable energy and sensor fields remain scarce.Therefore,this review comprehensively explores the application potential and recent advancements of SACs in portable zinc-air batteries,proton exchange membrane fuel cells,and sensor technologies.The article highlights the influence of key factors such as material design,structural optimization,and packaging integration on device performance,while also addressing the primary bottlenecks and challenges encountered in current practical applications.Furthermore,it suggests possible future development directions,aiming to offer theoretical insights and engineering guidance for the large-scale deployment of SACs in wearable electronic devices,portable energy systems,and smart sensing technologies.展开更多
The co-production of hydrogen and value-added biochemicals from lignocellulose utilizing solar energy has been regarded as one of the technologies most potentially able to alleviate the current energy crisis.Here,we d...The co-production of hydrogen and value-added biochemicals from lignocellulose utilizing solar energy has been regarded as one of the technologies most potentially able to alleviate the current energy crisis.Here,we demonstrate a cost-effective photoreforming strategy for lignocellulose valorization using a carbon nitride-supported platinum single-atom photocatalyst.An advanced H_(2) evolution rate of 6.34 mmol molPt^(-1) h^(-1) is achieved over the optimal catalyst,which is around 4.6 and 30.5 times higher compared with the nanosized Pt counterpart and pristine carbon nitride,respectively.Meanwhile,the monosaccharides are oxidized to value-added lactic acid with>99%conversion and extraordinary selectivity up to 97%.The theoretical calculations show that with Pt incorporation,the photogenerated holes are predominantly localized on the metal sites while the photogenerated electrons are concentrated on C_(3)N_(4),thus enhancing the effective separation of charge carriers.This work provides a promising avenue for the simultaneous production of green H2 and bio-based chemicals by biomass photorefinery.展开更多
Enhancing the corrosion resistance of carriers within Fenton-like systems and inhibiting the migration and aggregation of single atoms in reaction environments are essential for maintaining both high activity and stab...Enhancing the corrosion resistance of carriers within Fenton-like systems and inhibiting the migration and aggregation of single atoms in reaction environments are essential for maintaining both high activity and stability at catalytic sites,thus meeting fundamental requirements for practical application.The Fenton-like process of activating various strong oxidants by silicon-based single atom catalysts(SACs)prepared based on silicon-based materials(mesoporous silica,silicon-based minerals,and organosilicon materials)has unique advantages such as structural stability(especially important under strong oxidation conditions)and environmental protection.In this paper,the preparation strategies for the silicon-based SACs were assessed first,and the structural characteristics of various silicon-based SACs are systematically discussed,their application process and mechanism in Fenton-like process to achieve water purification are investigated,and the progress of Fenton-like process in density functional theory(DFT)of siliconbased derived single atom catalysts is summarized.In this paper,the preparation strategies and applications of silicon-based derived SACs are analyzed in depth,and their oxidation activities and pathways to different pollutants in water are reviewed.In addition,this paper also summarizes the device design and application of silicon-based derived SACs,and prospects the future development of silicon-based SACs in Fenton-like applications.展开更多
The single-atom M-N-C(M typically being Co or Fe)is a prominent material with exceptional reactivity in areas of catalysis for sustainable energy.However,the formation of metal nanoparticles in M-N-C materials is coup...The single-atom M-N-C(M typically being Co or Fe)is a prominent material with exceptional reactivity in areas of catalysis for sustainable energy.However,the formation of metal nanoparticles in M-N-C materials is coupled with hightemperature calcination conditions,limiting the density of M-Nx active sites and thus restricting the catalytic performance of such catalysts.Herein,we describe an effective decoupling strategy to construct high-density M-Nx active sites by generating polyfurfuryl alcohol in the MOF precursor,effectively preventing the formation of metal nanoparticles even with up to 6.377%cobalt loading.This catalyst showed a high H_(2) production rate of 778mLgcat^(−1) h^(−1) when used in the dehydrogenation reaction of formic acid.In addition to the high density of the active site,a curved carbon surface in the structure is also thought to be the reason for the high performance of the catalyst.展开更多
Metal-nitrogen-carbon(M-N-C)single-atom catalysts are widely utilized in various energy-related catalytic processes,offering a highly efficient and cost-effective catalytic system with significant potential.Recently,c...Metal-nitrogen-carbon(M-N-C)single-atom catalysts are widely utilized in various energy-related catalytic processes,offering a highly efficient and cost-effective catalytic system with significant potential.Recently,curvature-induced strain has been extensively demonstrated as a powerful tool for modulating the catalytic performance of M-N-C catalysts.However,identifying optimal strain patterns using density functional theory(DFT)is computationally intractable due to the high-dimensional search space.Here,we developed a graph neural network(GNN)integrated with an advanced topological data analysis tool-persistent homology-to predict the adsorption energy response of adsorbate under proposed curvature patterns,using nitric oxide electroreduction(NORR)as an example.Our machine learning model achieves high accuracy in predicting the adsorption energy response to curvature,with a mean absolute error(MAE)of 0.126 eV.Furthermore,we elucidate general trends in curvature-modulated adsorption energies of intermediates across various metals and coordination environments.We recommend several promising catalysts for NORR that exhibit significant potential for performance optimization via curvature modulation.This methodology can be readily extended to describe other non-bonded interactions,such as lattice strain and surface stress,providing a versatile approach for advanced catalyst design.展开更多
Lithium-sulfur batteries(LSBs)have become a favorable contender for next-generation electrochemical energy storage systems due to their outstanding features such as high energy density,low cost,and environmental frien...Lithium-sulfur batteries(LSBs)have become a favorable contender for next-generation electrochemical energy storage systems due to their outstanding features such as high energy density,low cost,and environmental friendliness.However,the commercialization of LSBs is still characterized by critical issues such as low sulfur utilization,short cycle life,and poor rate performance,which need to be resolved.Single-atom catalysts,with their outstanding features such as ultra-high atom utilization rate close to 100%and adjustable coordination configuration,have received extensive attention in the field of lithium-sulfur battery research.In this paper,the preparation and characterization of single-atom catalysts for Li-S batteries are briefly introduced,and the latest research progress of single-atom catalysts for Li-S batteries is reviewed from three aspects:cathode,separator and anode.Finally,the key technical problems and future research directions of single-atom catalysts for lithium-sulfur batteries are also prospected,with a view to promoting the further development of commercialized LSBs.展开更多
Single-atom catalysts(SACs),as the rising stars in the field of catalytic science,are leading catalytic technology into an un-precedented new era.However,the synthe-sis of high-performance SACs with well-de-fined acti...Single-atom catalysts(SACs),as the rising stars in the field of catalytic science,are leading catalytic technology into an un-precedented new era.However,the synthe-sis of high-performance SACs with well-de-fined active sites and high loadings under precise control has become a hotly debated topic in scientific research.Metal-organic frameworks(MOFs),with their exceptional properties such as ultrahigh specific surface areas,precisely controllable structural de-signs,and highly flexible functional cus-tomization capabilities,are regarded as one of the ideal matrices for supporting and sta-bilizing SACs.This review provides an in-sightful overview of the diverse preparation strategies for MOFs-derived SACs.It comprehen-sively analyzes the unique advantages and challenges of each method in achieving efficient synthesis of SACs,emphasizing the crucial role of optimized processes in unlocking the antici-pated performance of SACs.Furthermore,this review delves into a series of advanced charac-terization techniques,including aberration-corrected scanning transmission electron mi-croscopy(AC-STEM),electron energy loss spectroscopy(EELS),X-ray absorption spec-troscopy(XAS),and infrared absorption spectroscopy(IRAS),offering valuable insights into the atomic-scale fine structures and properties of SACs,significantly advancing the under-standing of SAC mechanisms.Moreover,this review focuses on exploring the potential appli-cations of MOFs-derived SACs in electrocatalysis frontier fields.This comprehensive exami-nation lays a solid theoretical foundation and provides a directional guidance for the rational design and controllable synthesis of high-performance MOFs-derived SACs.展开更多
Metal-sulfur electrochemistry represents a promising energy storage technology due to the natural abundance and unparalleled theoretical specific capacity of 1675 mAh g^(-1)of sulfur based on two-electron redox reacti...Metal-sulfur electrochemistry represents a promising energy storage technology due to the natural abundance and unparalleled theoretical specific capacity of 1675 mAh g^(-1)of sulfur based on two-electron redox reaction(S^(0)■S^(2-)).Commercially viable metal-sulfur batteries(MSBs)are hindered by sluggish sulfur conversion kinetics,which reduce the utilization efficiency of sulfur and lead to polysulfide shuttling.Single-atom catalysts(SACs)exhibit specific catalytic activity,a high atomic utilization ratio,and flexible selectivity,and are considered exceptional electrocatalysts for addressing the intractable challenges encountered by the MSBs.This review summarizes the recent progress in SACs for boosting the sulfur electrochemistry in MSBs,focusing on sulfur host materials,modified separators and functional interlayers,and analyzes the in-depth mechanisms of SACs.Moreover,the correlation between the coordination environments and the intrinsic activity of SACs is discussed.Finally,the main challenges and potential research directions of SACs for high-energy-density and long-life MSBs are outlined.This study provides significant guidance for constructing novel SACs that can accelerate the sulfur conversion kinetics in MSBs.展开更多
Single-atom catalysts(SACs)have demonstrated exceptional performance in electrocatalytic water splitting,owing to their maximized atomic utilization efficiency and superior reaction kinetics.The incorporation of SACs ...Single-atom catalysts(SACs)have demonstrated exceptional performance in electrocatalytic water splitting,owing to their maximized atomic utilization efficiency and superior reaction kinetics.The incorporation of SACs typically depends on robust metal-support interactions,which stabilize the single atoms on the support through various unsaturated chemical sites or spatial confinement.A critical challenge lies in precisely modulating the electronic structure and coordination environment of metal atoms.However,current research primarily focuses on single-atom metals,often neglecting the significant role of support materials in SACs.Two-dimensional(2D)atomically thin materials(ATMs)possess unique physicochemical properties and tunable reaction environments,which can modulate catalytic performance via metal-support interactions,positioning them as promising platforms for SAC loading.This paper reviews the recent advancements and the current status of SACs supported on 2D ATMs(SACs@ATMs).The structural design theory and synthesis strategies of SACs@ATMs are systematically discussed.The significance of advanced characterization techniques in elucidating the coordination environment and metal-support interactions is highlighted.Additionally,the reaction mechanisms and applications of SACs in electrocatalytic water splitting are summarized.Finally,the future challenges and opportunities for SACs@ATMs are outlined.This paper aims to provide insights and guidance for the rational design of SACs@ATMs with high-performance electrocatalytic water splitting capabilities.展开更多
Single-atom catalysts(SACs)have garnered interest in designing their ligand environments,facilitating the modification of single catalytic sites toward high activity and selectivity.Despite various synthetic approache...Single-atom catalysts(SACs)have garnered interest in designing their ligand environments,facilitating the modification of single catalytic sites toward high activity and selectivity.Despite various synthetic approaches,it remains challenging to achieve a catalytically favorable coordination structure simultaneously with the feasible formation of SACs at low temperatures.Here,a new type of coordination structure for Pt SACs is introduced to offer a highly efficient hydrogen evolution reaction(HER)catalyst,where Pt SACs are readily fabricated by atomically confining PtCl_(2)on chemically driven NO_(2)sites in two-dimensional nitrogen-doped carbon nanosheets at room temperature.The resultant Pt SACs form the NO_(2)-Pt-Cl_(2)coordination structure with an atomic dispersion,as revealed by X-ray spectroscopy and transmission electron microscopy investigations.Moreover,our first-principles density functional theory(DFT)calculations show strong interactions in the coordination by computing the binding energy and charge density difference between PtCl_(2)and NO_(2).Pt SACs,established on the NO_(2)-functionalized carbon support,demonstrate the onset potential of 25 mV,Tafel slope of 40 mV dec^(-1),and high specific activity of 1.35 A mgPt^(-1).Importantly,the Pt SACs also exhibit long-term stability up to 110 h,which is a significant advance in the field of single-atom Pt catalysts.The newly developed coordination structure of Pt SACs features a single Pt active center,providing hydrogen binding ability comparable to that of Pt(111),enhanced long-term durability due to strong metal-support interactions,and the advantage of room-temperature fabrication.展开更多
Metal oxides as support for constructing precious metal single-atom catalysts hold great promise for a wide range of industrial applications,but achieving a high-loading of thermally stable metal single atoms on such ...Metal oxides as support for constructing precious metal single-atom catalysts hold great promise for a wide range of industrial applications,but achieving a high-loading of thermally stable metal single atoms on such supports has been challenging.Herein,we report an innovative strategy for the fabrication of high-density single-atoms(Rh,Ru,Pd)catalysts on CaAl-layered double hydroxides(CaAl-LDH)via isomorphous substitution.The Rh species have occupied Ca^(2+)vacancies within CaAl-LDH laminate by ion-exchange,facilitating a substantial loading of isolated Rh single-atoms.Such catalysts displayed superior performance in the selective hydrogenation to quinoline,pivotal for liquid organic hydrogen storage,and the universality for the hydrogenation of N-heterocyclic aromatic hydrocarbons was also verified.Combining the experimental results and density functional theory calculations,the pathway of quinoline hydrogenation over Rh1CaAl-LDH was proposed.This synthetic strategy marks a significant advancement in the field of single-atom catalysts,expanding their horizons in green chemical processes.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
Hydrogen is a highly promising energy carrier because of its renewable and clean qualities.Among the different methods for H_(2) production,photoelectrocatalysis(PEC)water splitting has garnered significant interest,t...Hydrogen is a highly promising energy carrier because of its renewable and clean qualities.Among the different methods for H_(2) production,photoelectrocatalysis(PEC)water splitting has garnered significant interest,thanks to the abundant and perennial solar energy.Single-atom catalysts(SACs),which feature well-distributed atoms anchored on supports,have gained great attention in PEC water splitting for their unique advantages in overcoming the limitations of conventional PEC reactions.Herein,we comprehensively review SAC-incorporated photoelectrocatalysts for efficient PEC water splitting.We begin by highlighting the benefits of SACs in improving charge transfer,catalytic selectivity,and catalytic activity,which address the limitations of conventional PEC reactions.Next,we provide a comprehensive overview of established synthetic techniques for optimizing the properties of SACs,along with modern characterization methods to confirm their unique structures.Finally,we discuss the challenges and future directions in basic research and advancements,providing insights and guidance for this developing field.展开更多
The robustness of single-atom catalysts(SACs)is a critical concern for practical applications,especially for thermal catalysis at elevated temperatures under reductive conditions.In this study,a laser solid-phase synt...The robustness of single-atom catalysts(SACs)is a critical concern for practical applications,especially for thermal catalysis at elevated temperatures under reductive conditions.In this study,a laser solid-phase synthesis technique is reported to fabricate atom-nanoisland-sea structured SACs for the first time.The resultant catalysts are constructed by Pt single atoms on In_(2)O_(3)supported by Co3O4nanoislands uniformly dispersed in the sea of reduced graphene oxide.The laser process,with a maximum temperature of 2349 K within~100μs,produced abundant oxygen vacancies(up to 70.8%)and strong interactions between the Pt single atoms and In_(2)O_(3).The laser-synthesized catalysts exhibited a remarkable catalytic performance towards CO_(2)hydrogenation to methanol at 300°C with a CO_(2)conversion of 30.3%,methanol selectivity of 90.6%and exceptional stability over 48 h without any deactivation,outperforming most of the relevant catalysts reported in the literature.Characterization of the spent catalysts after testing for 48 h reveals that the Pt single atoms were retained and the oxygen vacancies remained almost unchanged.In situ diffuse reflectance infrared Fourier transform spectrum was conducted to establish the reaction mechanism supported by the density functional theory simulations.It is believed that this laser synthesis strategy opens a new avenue towards rapidly manufacturing highly active and robust thermal SACs.展开更多
Utilizing nitrate(NO_(3)^(-))as the nitrogen source to produce ammonia can effectively remove NO_(3)^(-)pollutant while obtaining valuable ammonia,and the understanding of the mechanisms is essential for the design of...Utilizing nitrate(NO_(3)^(-))as the nitrogen source to produce ammonia can effectively remove NO_(3)^(-)pollutant while obtaining valuable ammonia,and the understanding of the mechanisms is essential for the design of new catalysts.In this work,by using density functional theory calculations,the electroreduction mechanisms of nitrate reduction reaction(NO_(3)RR)on transition metal single atom supported on 3N-coordinated N-doped graphene(TM/N_(3)-G)are systematically investigated.It is found that the protonation of ^(*)OH acts as the potential determing steps except for the traditionally considered ^(*)NO_(3)/^(*)NO/^(*)NO_(2) protonation step and the desorption of water may play an important role for NO_(3)RR on some TM/N_(3)-G.By considering the stability of single-atom catalyst(SAC),the preferential adsorption of NO_(3)^(-)larger than H and H_(2)O,the limiting potential of whole NO_(3)RR,the selectivity toward NH3,V(Mn,Os)/pyrrolic-N_(3)-G and Mn(Ru,Ir)/pyridinic-N_(3)-G are screened out as potential SACs for NO_(3)RR.This work provides an understanding of the NO_(3)RR mechanism and highlights several promising NO_(3)RR catalysts based on the TM/N_(3)-G system.展开更多
基金financially supported by the National Natural Science Foundation of China(U22A20421)the Qinglan Project of Jiangsu Province,the 533 Talent Program of Huaian City,and the College Students’Innovative Entrepreneurial Training Plan Program of Jiangsu Province(X202510323027).
文摘Endogenous hydrogen systems,consisting of metal–organic coordination catalysts and alcohols,have been widely applied for the transfer hydrogenation(TH)of biomass-derived carbonyl compounds in recent years.Metal-organic coordination catalysts showed satisfactory ability of TH in the secondary alcohols,but most of them could not effectively employ the cheaper primary alcohols as hydrogen donors.Furthermore,they commonly contained high metal contents,which also led to low catalytic efficiency in significant measure.In this work,we constructed a novel magnesium single-atom catalyst(Mg-NC)with merely 0.37 wt%Mg by means of a combined self-assembly and pyrolysis strategy.The characterization results indicated that Mg was atomically dispersed and it was coordinated with four pyridinic-N in Mg-NC.Due to the obvious electron transfer from Mg to its coordinated pyridinic-N,Mg–N_(4)active centers displayed high Lewis acid-base strength with abundant content,which brought remarkable catalytic activity.When Mg-NC was used for the TH of 5-hydroxymethylfurfural(HMF)in ethanol(EtOH),2,5-bis(hydroxymethyl)furan(BHMF)yield was up to 96.3%with high productivity of 19.85 molBHMF mol_(Mg)^(−1)h^(−1)at 150°C for 5 h.More interestingly,the process of TH over Mg-NC in EtOH was proved to proceed via the hydrogen radical mechanism.Additionally,Mg-NC exhibited powerful catalytic universality;it could not only utilize other primary alcohols(such as n-propanol and n-butanol)as hydrogen donors,but also catalyze the TH of other carbonyl compounds(such as furfural,5-methylfurfural,benzaldehyde,cyclohexanone,and levulinic acid).Overall,this work offered some important clues and references to reinforce the hydrogen-supplying ability of primary alcohols in the TH of various biomass-derived carbonyl compounds to high-value fine chemicals.
基金supported by the National Natural Science Foundation of China(No.52300170).
文摘Catalytic CO_(2)-to-methanol conversion presents a synergistic approach for concurrent greenhouse gas abatement and sustainable energy carrier synthesis.Single-atom catalysts(SACs)with maximized atomic utilization,tailored electronic configurations and unique metal-support interactions,exhibit superior performance in CO_(2) activation and methanol synthesis.This review systematically compares reaction mechanisms and pathways across thermal,photocatalytic and electrocatalytic systems,emphasizing structure-activity relationships governed by active sites,coordination microenvironments and support functionalities.Through case studies of representative SACs,we elucidate how metal-support synergies dictate intermediate binding energetics and methanol selectivity.A critical analysis of reaction parameters(e.g.,temperature,pressure)reveals condition-dependent catalytic behaviors in thermal system,with fewer studies in photo/electrocatalytic systems identified as key knowledge gaps.While thermal catalysis achieves industrially viable methanol yields,the scalability is constrained by energy-intensive operation and catalyst sintering.Conversely,photo/electrocatalytic routes offer renewable energy integration but suffer from inefficient charge dynamics and mass transport limitations.To address the challenges,we propose strategic research priorities on precise design of active sites,synergy of multiple technological pathways,development of intelligent catalytic systems and diverse CO_(2) feedstock compatibility.These insights establish a framework for developing next-generation SACs,offering both theoretical foundations and technological blueprints for developing carbon-negative catalytic technologies.
文摘In recent years,numer-ous single-atom catalysts(SACs)have been synthesized to activate persulfate(PS)by a non-radical pathway because of its high se-lectivity,and activity for the cata-lyst.Metal-nitrogen-carbon(M-N_(x)-C)has been identified as the key active site in SACs.Although methods for preparing SACs have been extensively reported,a systematic summary of the direct construction of M-N_(x)-C,espe-cially unconventional metal-nitrogen-carbon(UM-N_(x)-C,x≠4),on SACs for PS non-radical activation has still not been reported.The role of the M-N_(x)-C active sites on PS non-radical activation is discussed and methods for the formation of M-N_(x)-C and UM-N_(x)-C active sites in SACs and the effect of catalyst carriers such as carbon nitride(g-C_(3)N_(4)),MOFs,COFs,and other car-bon materials are reviewed.Direct and indirect methods,especially for UM-N_(x)-C active site formation,are also elaborated.Factors affecting the formation of a M-N_(x)-C active site on SACs are also discussed.Prospects for the use of M-N_(x)-C active sites for the non-radical activation of PS by SACs to remove organic contaminants from wastewater are evaluated.
基金supported by Shanxi Province Science Foundation for Youths(202203021212300)Taiyuan University of Science and Technology Scientific Research Initial Funding(20212064)Outstanding Doctoral Award Fund in Shanxi Province(20222060).
文摘The nitrogen-coordinated metal single-atom catalysts(M−N−C SACs)with an ultra-high metal loading synthetized by direct high-temperature pyrolysis have been widely reported.However,most of metal single atoms in these catalysts were buried in the carbon matrix,resulting in a low metal utilization and inaccessibility for adsorption of reactants during the catalytic process.Herein,we reported a facile synthesis based on the hard-soft acid-base(HSAB)theory to fabricate Co single-atom catalysts with highly exposed metal atoms ligated to the external pyridinic-N sites of a nitrogen-doped carbon support.Benefiting from the highly accessible Co active sites,the prepared Co−N−C SAC exhibited a superior oxygen reduction reactivity comparable to that of the commercial Pt/C catalyst,showing a high turnover frequency(TOF)of 0.93 e^(−)·s^(-1)·site^(-1)at 0.85 V vs.RHE,far exceeding those of some representative SACs with a ultra-high metal content.This work provides a rational strategy to design and prepare M−N−C single-atom catalysts featured with high site-accessibility and site-density.
基金supported by the Petrochemical Research Institute Foundation(21-CB-09-01)the National Natural Science Foundation of China(22302186,22025205)+1 种基金the China Postdoctoral Science Foundation(2022M713030,2023T160618)the Fundamental Research Funds for the Central Universities(WK2060000058,WK2060000038).
文摘By simplifying catalyst-product separation and reducing phosphorus waste,heterogeneous hydroformylation offers a more sustainable alternative to homogeneous processes.However,heterogeneous hydroformylation catalysts developed thus far still suffer from the issues of much lower activity and metal leaching,which severely hinder their practical application.Here,we demonstrate that incorporating phosphorus(P)atoms into graphitic carbon nitride(PCN)supports facilitates charge transfer from Rh to the PCN support,thus largely enhancing electronic metal-support interactions(EMSIs).In the styrene hydroformylation reaction,the activity of Rh_(1)/PCN single-atom catalysts(SACs)with varying P contents exhibited a volcano-shaped relationship with P doping,where the Rh_(1)/PCN SAC with optimal P doping showed exceptional activity,approximately 5.8-and 3.3-fold greater than that of the Rh_(1)/g-C_(3)N_(4)SAC without P doping and the industrial homogeneous catalyst HRh(CO)(PPh_(3))_(3),respectively.In addition,the optimal Rh_(1)/PCN SAC catalyst also demonstrated largely enhanced multicycle stability without any visible metal aggregation owing to the increased EMSIs,which sharply differed from the severe metal aggregation of large nanoparticles on the Rh_(1)/g-C_(3)N_(4)SAC.Mechan-istic studies revealed that the enhanced catalytic performance could be attributed to electron-deficient Rh species,which reduced CO adsorption while simultaneously promoting alkene adsorption through increased EMSIs.These findings suggest that tuning EMSIs is an effective way to achieve SACs with high activity and durability.
文摘With the rapid advancement of portable energy devices and sensor technologies,enhancing their catalytic performance,sensing capabilities,and application reliability has become a critical challenge in the fields of materials and energy science.Single-atom catalysts(SACs),owing to their high atomic utilization,outstanding catalytic activity,and precisely engineered structures enabled by density functional theory and enhanced by artificial intelligence,have shown tremendous potential in advancing portable energy and sensing technologies.While existing reviews predominantly focus on the application of SACs in individual portable devices,systematic discussions on their overall development prospects and challenges within portable energy and sensor fields remain scarce.Therefore,this review comprehensively explores the application potential and recent advancements of SACs in portable zinc-air batteries,proton exchange membrane fuel cells,and sensor technologies.The article highlights the influence of key factors such as material design,structural optimization,and packaging integration on device performance,while also addressing the primary bottlenecks and challenges encountered in current practical applications.Furthermore,it suggests possible future development directions,aiming to offer theoretical insights and engineering guidance for the large-scale deployment of SACs in wearable electronic devices,portable energy systems,and smart sensing technologies.
文摘The co-production of hydrogen and value-added biochemicals from lignocellulose utilizing solar energy has been regarded as one of the technologies most potentially able to alleviate the current energy crisis.Here,we demonstrate a cost-effective photoreforming strategy for lignocellulose valorization using a carbon nitride-supported platinum single-atom photocatalyst.An advanced H_(2) evolution rate of 6.34 mmol molPt^(-1) h^(-1) is achieved over the optimal catalyst,which is around 4.6 and 30.5 times higher compared with the nanosized Pt counterpart and pristine carbon nitride,respectively.Meanwhile,the monosaccharides are oxidized to value-added lactic acid with>99%conversion and extraordinary selectivity up to 97%.The theoretical calculations show that with Pt incorporation,the photogenerated holes are predominantly localized on the metal sites while the photogenerated electrons are concentrated on C_(3)N_(4),thus enhancing the effective separation of charge carriers.This work provides a promising avenue for the simultaneous production of green H2 and bio-based chemicals by biomass photorefinery.
基金supported by National Natural Science Foundation of China(No.52170086)Natural Science Foundation of Shandong Province(No.ZR2021ME013)+1 种基金Natural science Foundation of Shaanxi province(No.2024JC-YBQN-0252)Special Scientific Research Project of Hanzhong City-Shaanxi University of Technology Co-construction State Key Laboratory(No.SXJ2106)。
文摘Enhancing the corrosion resistance of carriers within Fenton-like systems and inhibiting the migration and aggregation of single atoms in reaction environments are essential for maintaining both high activity and stability at catalytic sites,thus meeting fundamental requirements for practical application.The Fenton-like process of activating various strong oxidants by silicon-based single atom catalysts(SACs)prepared based on silicon-based materials(mesoporous silica,silicon-based minerals,and organosilicon materials)has unique advantages such as structural stability(especially important under strong oxidation conditions)and environmental protection.In this paper,the preparation strategies for the silicon-based SACs were assessed first,and the structural characteristics of various silicon-based SACs are systematically discussed,their application process and mechanism in Fenton-like process to achieve water purification are investigated,and the progress of Fenton-like process in density functional theory(DFT)of siliconbased derived single atom catalysts is summarized.In this paper,the preparation strategies and applications of silicon-based derived SACs are analyzed in depth,and their oxidation activities and pathways to different pollutants in water are reviewed.In addition,this paper also summarizes the device design and application of silicon-based derived SACs,and prospects the future development of silicon-based SACs in Fenton-like applications.
基金National Natural Science Foundation of China,Grant/Award Numbers:21603054,31671930Innovation and entrepreneurship training program for college students of Hebei Agricultural University,Grant/Award Numbers:2019085,s202010086046+2 种基金Scientific Research Development Fund project of Hebei Agricultural University,Grant/Award Number:JY2020028the Natural Science Foundation of Hebei Province,Grant/Award Numbers:B2016204131,B2016204136Young Topnotch Talents Foundation of Hebei Provincial Universities,Grant/Award Number:BJ2016027.
文摘The single-atom M-N-C(M typically being Co or Fe)is a prominent material with exceptional reactivity in areas of catalysis for sustainable energy.However,the formation of metal nanoparticles in M-N-C materials is coupled with hightemperature calcination conditions,limiting the density of M-Nx active sites and thus restricting the catalytic performance of such catalysts.Herein,we describe an effective decoupling strategy to construct high-density M-Nx active sites by generating polyfurfuryl alcohol in the MOF precursor,effectively preventing the formation of metal nanoparticles even with up to 6.377%cobalt loading.This catalyst showed a high H_(2) production rate of 778mLgcat^(−1) h^(−1) when used in the dehydrogenation reaction of formic acid.In addition to the high density of the active site,a curved carbon surface in the structure is also thought to be the reason for the high performance of the catalyst.
基金supported by the Natural Science Foundation of Xiamen,China(3502Z202472001)the National Natural Science Foundation of China(22402163,22021001,21925404,T2293692,and 22361132532)。
文摘Metal-nitrogen-carbon(M-N-C)single-atom catalysts are widely utilized in various energy-related catalytic processes,offering a highly efficient and cost-effective catalytic system with significant potential.Recently,curvature-induced strain has been extensively demonstrated as a powerful tool for modulating the catalytic performance of M-N-C catalysts.However,identifying optimal strain patterns using density functional theory(DFT)is computationally intractable due to the high-dimensional search space.Here,we developed a graph neural network(GNN)integrated with an advanced topological data analysis tool-persistent homology-to predict the adsorption energy response of adsorbate under proposed curvature patterns,using nitric oxide electroreduction(NORR)as an example.Our machine learning model achieves high accuracy in predicting the adsorption energy response to curvature,with a mean absolute error(MAE)of 0.126 eV.Furthermore,we elucidate general trends in curvature-modulated adsorption energies of intermediates across various metals and coordination environments.We recommend several promising catalysts for NORR that exhibit significant potential for performance optimization via curvature modulation.This methodology can be readily extended to describe other non-bonded interactions,such as lattice strain and surface stress,providing a versatile approach for advanced catalyst design.
基金supported by the Shenzhen Key Basic Research Project:Ionic Liquid-Assisted Synthesis of Single Catalyst and Its Applications in Lithium Sulfur Batteries(GXWD20220817125846003)Major Instrument Project of National Natural Science Foundation of China(62127807)Shenzhen Sustainable Development Special Project(KCXFZ20201221173000001).
文摘Lithium-sulfur batteries(LSBs)have become a favorable contender for next-generation electrochemical energy storage systems due to their outstanding features such as high energy density,low cost,and environmental friendliness.However,the commercialization of LSBs is still characterized by critical issues such as low sulfur utilization,short cycle life,and poor rate performance,which need to be resolved.Single-atom catalysts,with their outstanding features such as ultra-high atom utilization rate close to 100%and adjustable coordination configuration,have received extensive attention in the field of lithium-sulfur battery research.In this paper,the preparation and characterization of single-atom catalysts for Li-S batteries are briefly introduced,and the latest research progress of single-atom catalysts for Li-S batteries is reviewed from three aspects:cathode,separator and anode.Finally,the key technical problems and future research directions of single-atom catalysts for lithium-sulfur batteries are also prospected,with a view to promoting the further development of commercialized LSBs.
基金supported by Henan Province Key Research and Development and Promotion of Science and Technology Project(No.25A150001)the National Natural Science Foundation of China(Nos.22409171,22125303,92361302,and 92061203).
文摘Single-atom catalysts(SACs),as the rising stars in the field of catalytic science,are leading catalytic technology into an un-precedented new era.However,the synthe-sis of high-performance SACs with well-de-fined active sites and high loadings under precise control has become a hotly debated topic in scientific research.Metal-organic frameworks(MOFs),with their exceptional properties such as ultrahigh specific surface areas,precisely controllable structural de-signs,and highly flexible functional cus-tomization capabilities,are regarded as one of the ideal matrices for supporting and sta-bilizing SACs.This review provides an in-sightful overview of the diverse preparation strategies for MOFs-derived SACs.It comprehen-sively analyzes the unique advantages and challenges of each method in achieving efficient synthesis of SACs,emphasizing the crucial role of optimized processes in unlocking the antici-pated performance of SACs.Furthermore,this review delves into a series of advanced charac-terization techniques,including aberration-corrected scanning transmission electron mi-croscopy(AC-STEM),electron energy loss spectroscopy(EELS),X-ray absorption spec-troscopy(XAS),and infrared absorption spectroscopy(IRAS),offering valuable insights into the atomic-scale fine structures and properties of SACs,significantly advancing the under-standing of SAC mechanisms.Moreover,this review focuses on exploring the potential appli-cations of MOFs-derived SACs in electrocatalysis frontier fields.This comprehensive exami-nation lays a solid theoretical foundation and provides a directional guidance for the rational design and controllable synthesis of high-performance MOFs-derived SACs.
基金financial support from the National Natural Science Foundation of China(No.22379001 and 22309003)the Natural Science Research Project of Anhui Province Education department(No.2022AH030046)the Top Young Talents of Anhui University of Technology,the Young Scholars of the Introduction and Education of Talents in Anhui Province,and the Scientific Research Foundation of Anhui University of Technology for Talent Introduction。
文摘Metal-sulfur electrochemistry represents a promising energy storage technology due to the natural abundance and unparalleled theoretical specific capacity of 1675 mAh g^(-1)of sulfur based on two-electron redox reaction(S^(0)■S^(2-)).Commercially viable metal-sulfur batteries(MSBs)are hindered by sluggish sulfur conversion kinetics,which reduce the utilization efficiency of sulfur and lead to polysulfide shuttling.Single-atom catalysts(SACs)exhibit specific catalytic activity,a high atomic utilization ratio,and flexible selectivity,and are considered exceptional electrocatalysts for addressing the intractable challenges encountered by the MSBs.This review summarizes the recent progress in SACs for boosting the sulfur electrochemistry in MSBs,focusing on sulfur host materials,modified separators and functional interlayers,and analyzes the in-depth mechanisms of SACs.Moreover,the correlation between the coordination environments and the intrinsic activity of SACs is discussed.Finally,the main challenges and potential research directions of SACs for high-energy-density and long-life MSBs are outlined.This study provides significant guidance for constructing novel SACs that can accelerate the sulfur conversion kinetics in MSBs.
基金financially supported by the National Oversea Postdoctoral Talent Attraction Programthe Pilot Group Program of the Research Fund for International Senior Scientists(52350710795)the Youth Fund of the National Natural Science Foundation of China(52402288).
文摘Single-atom catalysts(SACs)have demonstrated exceptional performance in electrocatalytic water splitting,owing to their maximized atomic utilization efficiency and superior reaction kinetics.The incorporation of SACs typically depends on robust metal-support interactions,which stabilize the single atoms on the support through various unsaturated chemical sites or spatial confinement.A critical challenge lies in precisely modulating the electronic structure and coordination environment of metal atoms.However,current research primarily focuses on single-atom metals,often neglecting the significant role of support materials in SACs.Two-dimensional(2D)atomically thin materials(ATMs)possess unique physicochemical properties and tunable reaction environments,which can modulate catalytic performance via metal-support interactions,positioning them as promising platforms for SAC loading.This paper reviews the recent advancements and the current status of SACs supported on 2D ATMs(SACs@ATMs).The structural design theory and synthesis strategies of SACs@ATMs are systematically discussed.The significance of advanced characterization techniques in elucidating the coordination environment and metal-support interactions is highlighted.Additionally,the reaction mechanisms and applications of SACs in electrocatalytic water splitting are summarized.Finally,the future challenges and opportunities for SACs@ATMs are outlined.This paper aims to provide insights and guidance for the rational design of SACs@ATMs with high-performance electrocatalytic water splitting capabilities.
基金supported by the National Research Foundation of Korea(NRF)(NRF-2020M3H4A3106354,NRF-2021M3I3A1083946,and NRF-2021R1A6A3A01087461)the Korea Institute of Science and Technology,and the KISTI Supercomputing Center(KSC-2023-CRE-0492).
文摘Single-atom catalysts(SACs)have garnered interest in designing their ligand environments,facilitating the modification of single catalytic sites toward high activity and selectivity.Despite various synthetic approaches,it remains challenging to achieve a catalytically favorable coordination structure simultaneously with the feasible formation of SACs at low temperatures.Here,a new type of coordination structure for Pt SACs is introduced to offer a highly efficient hydrogen evolution reaction(HER)catalyst,where Pt SACs are readily fabricated by atomically confining PtCl_(2)on chemically driven NO_(2)sites in two-dimensional nitrogen-doped carbon nanosheets at room temperature.The resultant Pt SACs form the NO_(2)-Pt-Cl_(2)coordination structure with an atomic dispersion,as revealed by X-ray spectroscopy and transmission electron microscopy investigations.Moreover,our first-principles density functional theory(DFT)calculations show strong interactions in the coordination by computing the binding energy and charge density difference between PtCl_(2)and NO_(2).Pt SACs,established on the NO_(2)-functionalized carbon support,demonstrate the onset potential of 25 mV,Tafel slope of 40 mV dec^(-1),and high specific activity of 1.35 A mgPt^(-1).Importantly,the Pt SACs also exhibit long-term stability up to 110 h,which is a significant advance in the field of single-atom Pt catalysts.The newly developed coordination structure of Pt SACs features a single Pt active center,providing hydrogen binding ability comparable to that of Pt(111),enhanced long-term durability due to strong metal-support interactions,and the advantage of room-temperature fabrication.
文摘Metal oxides as support for constructing precious metal single-atom catalysts hold great promise for a wide range of industrial applications,but achieving a high-loading of thermally stable metal single atoms on such supports has been challenging.Herein,we report an innovative strategy for the fabrication of high-density single-atoms(Rh,Ru,Pd)catalysts on CaAl-layered double hydroxides(CaAl-LDH)via isomorphous substitution.The Rh species have occupied Ca^(2+)vacancies within CaAl-LDH laminate by ion-exchange,facilitating a substantial loading of isolated Rh single-atoms.Such catalysts displayed superior performance in the selective hydrogenation to quinoline,pivotal for liquid organic hydrogen storage,and the universality for the hydrogenation of N-heterocyclic aromatic hydrocarbons was also verified.Combining the experimental results and density functional theory calculations,the pathway of quinoline hydrogenation over Rh1CaAl-LDH was proposed.This synthetic strategy marks a significant advancement in the field of single-atom catalysts,expanding their horizons in green chemical processes.
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supported by the National Natural Science Foundation of China(Nos.22209186,22479149)Self-deployed Projects of Ganjiang Innovation Academy,CAS(No.E355F006)+2 种基金Natural Science Foundation of Jiangxi Province(No.20242BAB23016)Key Research and Development Program of Jiangxi Province(Nos.20223BBG74004,20232BBG70003)Youth Innovation Promotion Association,Chinese Academy of Sciences(No.2023343).
文摘Hydrogen is a highly promising energy carrier because of its renewable and clean qualities.Among the different methods for H_(2) production,photoelectrocatalysis(PEC)water splitting has garnered significant interest,thanks to the abundant and perennial solar energy.Single-atom catalysts(SACs),which feature well-distributed atoms anchored on supports,have gained great attention in PEC water splitting for their unique advantages in overcoming the limitations of conventional PEC reactions.Herein,we comprehensively review SAC-incorporated photoelectrocatalysts for efficient PEC water splitting.We begin by highlighting the benefits of SACs in improving charge transfer,catalytic selectivity,and catalytic activity,which address the limitations of conventional PEC reactions.Next,we provide a comprehensive overview of established synthetic techniques for optimizing the properties of SACs,along with modern characterization methods to confirm their unique structures.Finally,we discuss the challenges and future directions in basic research and advancements,providing insights and guidance for this developing field.
基金supported by the Ningbo Yongjiang Science and Technology Programme(2023A-161-C)。
文摘The robustness of single-atom catalysts(SACs)is a critical concern for practical applications,especially for thermal catalysis at elevated temperatures under reductive conditions.In this study,a laser solid-phase synthesis technique is reported to fabricate atom-nanoisland-sea structured SACs for the first time.The resultant catalysts are constructed by Pt single atoms on In_(2)O_(3)supported by Co3O4nanoislands uniformly dispersed in the sea of reduced graphene oxide.The laser process,with a maximum temperature of 2349 K within~100μs,produced abundant oxygen vacancies(up to 70.8%)and strong interactions between the Pt single atoms and In_(2)O_(3).The laser-synthesized catalysts exhibited a remarkable catalytic performance towards CO_(2)hydrogenation to methanol at 300°C with a CO_(2)conversion of 30.3%,methanol selectivity of 90.6%and exceptional stability over 48 h without any deactivation,outperforming most of the relevant catalysts reported in the literature.Characterization of the spent catalysts after testing for 48 h reveals that the Pt single atoms were retained and the oxygen vacancies remained almost unchanged.In situ diffuse reflectance infrared Fourier transform spectrum was conducted to establish the reaction mechanism supported by the density functional theory simulations.It is believed that this laser synthesis strategy opens a new avenue towards rapidly manufacturing highly active and robust thermal SACs.
基金partially supported by the National Natural Science Foundation of China(No.22373092,No.22288201)CAS Project for Young Scientists in Basic Research(YSBR-051)supported by USTC Tang Scholarship。
文摘Utilizing nitrate(NO_(3)^(-))as the nitrogen source to produce ammonia can effectively remove NO_(3)^(-)pollutant while obtaining valuable ammonia,and the understanding of the mechanisms is essential for the design of new catalysts.In this work,by using density functional theory calculations,the electroreduction mechanisms of nitrate reduction reaction(NO_(3)RR)on transition metal single atom supported on 3N-coordinated N-doped graphene(TM/N_(3)-G)are systematically investigated.It is found that the protonation of ^(*)OH acts as the potential determing steps except for the traditionally considered ^(*)NO_(3)/^(*)NO/^(*)NO_(2) protonation step and the desorption of water may play an important role for NO_(3)RR on some TM/N_(3)-G.By considering the stability of single-atom catalyst(SAC),the preferential adsorption of NO_(3)^(-)larger than H and H_(2)O,the limiting potential of whole NO_(3)RR,the selectivity toward NH3,V(Mn,Os)/pyrrolic-N_(3)-G and Mn(Ru,Ir)/pyridinic-N_(3)-G are screened out as potential SACs for NO_(3)RR.This work provides an understanding of the NO_(3)RR mechanism and highlights several promising NO_(3)RR catalysts based on the TM/N_(3)-G system.
