CZTS(Cu_(2)ZnSnS_(4))is a quaternary semiconductor that is environmentally friendly,less expensive.In this paper,we report on the optimization and fabrication of CZTS-based heterojunction nanodevices for bifunctional ...CZTS(Cu_(2)ZnSnS_(4))is a quaternary semiconductor that is environmentally friendly,less expensive.In this paper,we report on the optimization and fabrication of CZTS-based heterojunction nanodevices for bifunctional applications such as solar cells and photodetectors.CZTS thin films were deposited on top of(Molybdenum)Mo-coated glass substrates via RF sputtering at 100 and 200 W.Rapid thermal processing(RTP)was used at 300,400,and 500℃temperatures.Cd S(cadmium sulphide)was deposited on CZTS using a chemical bath deposition system with 3-and 5-min deposition times.Zn O(zinc oxide)and AZO(aluminium doped zinc oxide)layers were deposited using RF(radio frequency)sputtering to create the solar device.XRD confirms the formation of a tetragonal structure with increased crystallinity due to the use of RTP.Raman reveals the characteristic Raman shift peak associated with CZTS at 336 and 335 cm^(-1).The FESEM shows a relationship with RTP temperature.Surface features,including grain size,vary with RTP temperature.The ideality factor is nearly 2,indicating imperfection in the Mo/CZTS interface.Schottky barrier height estimates range from 0.6 to 0.7 e V.Absorbance and transmittance show a predictable fluctuation with RTP temperature.Photovoltaic device was built using the higher crystalline feature of CZTS in conjunction with Cd S deposited at 3 and 5 min.The efficiency of Cd S deposited after 3 and 5 min was 1.15 and 0.97 percent,respectively.Fabricated devices were used for wavelength-dependent photodetection.This work demonstrated self-powered photodetection.展开更多
Designing a heterogeneous interface to improve the kinetics of electrocatalysts represents an effective yet challenging approach for enhancing the oxygen reduction reaction(ORR)and oxygen evolution reaction(OER).Herei...Designing a heterogeneous interface to improve the kinetics of electrocatalysts represents an effective yet challenging approach for enhancing the oxygen reduction reaction(ORR)and oxygen evolution reaction(OER).Herein,a simple MOF-assisted etching-pyrolysis strategy is proposed to fabricate an advanced Mott-Schottky(M–S)electrocatalyst composed of Co/CeO_(2)hetero-nanoparticles embedded within N-doped hollow carbon nanoboxes(H-Co/CeO_(2)@NCBs).Notably,the interfacial Co–O–Ce bond bridging productively facilitates the electron transfer and modulates the charge distribution of the active center,thereby contributing to the ORR/OER kinetics.As expected,the optimal M–S H-Co/CeO_(2)@NCBs catalyst exhibits promising bifunctional electrocatalytic activity with a small potential discrepancy of 0.65 V.Theoretical calculations reveal that the built-in electric field in the M–S heterojunction promotes electron transfer in oxygen electrocatalysis and the interfacial bridge-induced electron redistribution optimizes the adsorption/desorption of the oxygen intermediates,leading to reduced activation energy for the bifunctional ORR/OER reactions.Importantly,H-Co/CeO_(2)@NCBs-assembled Zn-air battery(ZAB)delivers high power density(179.8 mW cm^(−2))and long-term stability(400 h).Furthermore,the assembled flexible solid-state ZAB with H-Co/CeO_(2)@NCBs cathode also exhibits excellent charge–discharge reversibility and flexibility at various bending angles.This work provides a novel perspective on developing efficient and stable M–S bifunctional oxygen electrocatalysts.展开更多
High-entropy alloy(HEA)nanoparticles(NPs)have attracted great attention in electrocatalysis due to their tailorable complex compositions and unique properties.Herein,we introduce Fe,Co,Ni,Cr and Mn into the metal-poly...High-entropy alloy(HEA)nanoparticles(NPs)have attracted great attention in electrocatalysis due to their tailorable complex compositions and unique properties.Herein,we introduce Fe,Co,Ni,Cr and Mn into the metal-polyphenol coordination system to prepare HEA NPs enclosed in N-doped carbon(FeCoNiCrMn)with great potential for catalyzing oxygen reduction reaction(ORR)and oxygen evolution reaction(OER).The unique high-entropy structural characteristics in FeCoNiCrMn facilitate effective interplay between metal species,leading to improved ORR(E_(1/2)=0.89 V)and OER(η=330 mV,j=10 mA·cm^(−2))activity.Additionally,FeCoNiCrMn exhibits excellent open-circuit voltage(1.523 V),power density(110 mW·cm^(−2))and long-term durability,outperforming Pt/C+IrO_(2) electrodes as a cathode catalyst in Zn-air batteries(ZABs).Such polyphenol-assisted alloying method broadens and simplifies the development of HEA electrocatalysts for high-performance ZABs.展开更多
Water often presents significant challenges in catalysts by deactivating active sites,poisoning the reaction,and even degrading composite structure.These challenges are amplified when the water participates as a react...Water often presents significant challenges in catalysts by deactivating active sites,poisoning the reaction,and even degrading composite structure.These challenges are amplified when the water participates as a reactant and is fed as a liquid phase,such as trickle bed-type reactors in a hydrogen-water isotope exchange(HIE)reaction.The key balance in such multiphase reactions is the precise control of catalyst design to repel bulk liquid water while diffusing water vapor.Herein,a platinum-incorporated metal-organic framework(MIL-101)based bifunctional hydrophobic catalyst functionalized with long alkyl chains(C_(12),dodecylamine)and further manufactured with poly(vinylidene fluoride),Pt@MIL-101-12/PVDF,has been developed which can show dramatically improved catalytic activity under multi-phase reactions involving hydrogen gas and liquid water.Pt@MIL-101-12/PVDF demonstrates enhanced macroscopic water-blocking properties,with a notable reduction of over 65%in water adsorption capacity and newly introduced liquid water repellency.while exhibiting a negligible increase in mass transfer resistance,i.e.,bifunctional hydrophobicity.Excellent catalytic activity,evaluated via HIE reaction,and its durability underscore the impact of bifunctional hydrophobicity.In situ DRIFTS analysis elucidates water adsorption/desorption dynamics within the catalyst composite,highlighting reinforced water diffusion at the microscopic level,affirming the catalyst's bifunctionality in different length scales.With demonstrated radiation resistance,Pt@MIL-101-12/PVDF emerges as a promising candidate for isotope exchange reactions.展开更多
The continuous depletion of fossil fuels and the effects of climate change have encouraged prompt action to attain carbon neutrality.Technologies that transform and store renewable energy are crucial for creating a su...The continuous depletion of fossil fuels and the effects of climate change have encouraged prompt action to attain carbon neutrality.Technologies that transform and store renewable energy are crucial for creating a sustainable society,which is independent of fossil fuels.In this regard,electrochemical water splitting based on the oxygen evolution reaction(OER)and hydrogen evolution reaction(HER)is an attractive technique for producing carbon-free hydrogen fuels.Additionally,rechargeable metal–air batteries(MABs)are another intriguing way for renewable energy storage through reversible oxygen reactions(OER and the oxygen reduction reaction,ORR).Herein,we comprehensively review bifunctional electrocatalysts for water splitting(HER and OER)and MABs(OER and ORR),particularly 2D carbon material-derived heterostructures.The synthesis and properties of 2D carbon materials and their energy conversion and storage mechanisms are discussed to highlight the bifunc-tionality of the heterostructures.Recent studies on bifunctional electrocatalysts based on 2D carbon-derived heterostructures are also reviewed.Finally,perspectives for future studies and multifunctional catalysts are presented.展开更多
Regulating lithium(Li)plating/stripping behavior in three-dimensional(3D)conductive scaffolds is critical to stabilizing Li metal batteries(LMBs).Surface protrusions and roughness in these scaffolds can induce uneven ...Regulating lithium(Li)plating/stripping behavior in three-dimensional(3D)conductive scaffolds is critical to stabilizing Li metal batteries(LMBs).Surface protrusions and roughness in these scaffolds can induce uneven distributions of the electric fields and ionic concentrations,forming“hot spots.”Hot spots may cause uncontrollable Li dendrites growth,presenting significant challenges to the cycle stability and safety of LMBs.To address these issues,we construct a Li ionic conductive-dielectric gradient bifunctional interlayer(ICDL)onto a 3D Li-injected graphene/carbon nanotube scaffold(LGCF)via in situ reaction of exfoliated hexagonal boron nitride(fhBN)and molten Li.Microscopic and spectroscopic analyses reveal that ICDL consists of fhBN-rich outer layer and inner layer enriched with Li_(3)N and Li-boron composites(Li-B).The outer layer utilizes dielectric properties to effectively homogenize the electric field,while the inner layer ensures high Li ion conductivity.Moreover,DFT calculations indicate that ICDL can effectively adsorb Li and decrease the Li diffusion barrier,promoting enhanced Li ion transport.The modulation of Li kinetics by ICDL increases the critical length of the Li nucleus,enabling suppression of Li dendrite growth.Attributing to these advantages,the ICDL-coated LGCF(ICDL@LGCF)demonstrates impressive long-term cycle performances in both symmetric cells and full cells.展开更多
Fully conjugated covalent organic frameworks(COFs)are widely used in electrocatalysis.The COF with-ph-NH_(2)edge poly(1,4-phenyldiazo porphyrin cobalt)(A-PpazoPorCo)is synthesized by adjusting the molar ratio of the r...Fully conjugated covalent organic frameworks(COFs)are widely used in electrocatalysis.The COF with-ph-NH_(2)edge poly(1,4-phenyldiazo porphyrin cobalt)(A-PpazoPorCo)is synthesized by adjusting the molar ratio of the reaction material,and exhibits high delocalization energy to significantly enhance thermal stability.The nitrogen in the azo bond improves the adsorption capacity for ORR and OER catalytic intermediates,while the-ph-NH_(2)group further increases the electron cloud density at the Co-N_(4)center in A-PpazoPorCo.Density functional theory(DFT)calculations reveal that the strong electron-donating-ph-NH_(2)groups and the electron-donating azo bonds form an electron donor-π-electron acceptor(D-π-A)structure,which further enhances the electron cloud density.The strongπ-πinteraction between A-PpazoPorCo and three-dimensional graphene(3D-G)significantly boosts the oxygen catalytic performance of the A-PpazoPorCo/3D-G.The catalytic ORR half-wave potential(E_(1/2))of A-PpazoPorCo/3D-G can reach 0.880 V vs.RHE.The total overpotential(ΔE=E_(j=10)-E_(1/2))is 0.617 V,demonstrating excellent bifunctional oxygen catalytic performance.The efficient oxygen catalytic performance indicates that A-PpazoPorCo/3D-G has the potential for application in fuel cells cathodes and overall water splitting anodes.展开更多
Exploring efficient and nonprecious metal electrocatalysts of oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)is crucial for developing rechargeable zinc-air batteries(ZABs).Herein,an alloying-degree c...Exploring efficient and nonprecious metal electrocatalysts of oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)is crucial for developing rechargeable zinc-air batteries(ZABs).Herein,an alloying-degree control strategy was employed to fabricate nitrogen-doped carbon sphere(NCS)decorated with dual-phase Co/Co_(7)Fe_(3)heterojunctions(CoFe@NCS).The phase composition of materials has been adjusted by controlling the alloying degree.The optimal CoFe_(0.08)@NCS electrocatalyst displays a half-wave potential of 0.80 V for ORR and an overpotential of 283 mV at 10 mA·cm^(-2)for OER in an alkaline electrolyte.The intriguing bifunctional electrocatalytic activity and durability is attributed to the hierarchically porous structure and interfacial electron coupling of highly-active Co_(7)Fe_(3)alloy and metallic Co species.When the CoFe_(0.08)@NCS material is used as air-cathode catalyst of rechargeable liquid-state zinc-air battery(ZAB),the device shows a high peak power-density(157 mW·cm^(-2))and maintains a stable voltage gap over 150 h,outperforming those of the benchmark(Pt/C+RuO_(2))-based device.In particular,the as-fabricated solid-state flexible ZAB delivers a reliable compatibility under different bending conditions.Our work provides a promising strategy to develop metal/alloy-based electrocatalysts for the application in renewable energy conversion technologies.展开更多
Herein,a luminescent europium-based metal-organic framework(Eu-MOF,[Eu_(3)(L)(HL)(NO_(3))_(2)(DMF)_(2)]·4DMF·5H_(2)O,H_(4)L=5,5′-(pyrazine-2,6-diyl)diisophthalic acid,DMF=N,N-dimethylformamide)was developed...Herein,a luminescent europium-based metal-organic framework(Eu-MOF,[Eu_(3)(L)(HL)(NO_(3))_(2)(DMF)_(2)]·4DMF·5H_(2)O,H_(4)L=5,5′-(pyrazine-2,6-diyl)diisophthalic acid,DMF=N,N-dimethylformamide)was developed for the dual-functional detection of environmental pollutants.This fluorescence-quenching-based sensor exhibited excep-tional sensitivity for both 2,4,6-trinitrophenol(TNP)and tetracycline(TC),achieving remarkably low detection lim-its of 1.96×10^(-6)and 1.71×10^(-7)mol·L^(-1),respectively.Notably,the system exhibited 99%fluorescence quenching ef-ficiency for TC,indicating ultra-efficient analyte recognition.The detection performance surpasses most reported lu-minescent MOF sensors,attributed to synergistic mechanisms of fluorescence resonance energy transfer(FRET)and photoinduced electron transfer(PET).CCDC:2446483.展开更多
The tert-butyl nitrite as a bifunctional reagent mediated radical alkene difunctionalization has emerged as a powerful strategy for synthesis of structurally diverse oxime-containing compounds.However,the phosphorus-c...The tert-butyl nitrite as a bifunctional reagent mediated radical alkene difunctionalization has emerged as a powerful strategy for synthesis of structurally diverse oxime-containing compounds.However,the phosphorus-centered radical initiated transformations remain largely elusive.Herein,a visible-lightinduced radical phosphinoyloximation of alkenes with secondary phosphine oxides and tert-butyl nitrite has been developed under photocatalyst-and metal-free conditions.This protocol features mild conditions,broad substrate scope,good functional tolerance,and operational simplicity,yielding a diverse array ofα-phosphinoyl oximes in moderate to good yields with high stereoselectivities.The photomediated homolytic cleavage of O–NO bond of tert-butyl nitrite generates the reactive tert-butoxyl radical and persistent NO radical to act as both HAT reagent and the source of oximes.展开更多
Rechargeable metal-air batteries have gained significant interest due to their high energy density and environmental benignity.However,these batteries face significant challenges,particularly related to the air-breath...Rechargeable metal-air batteries have gained significant interest due to their high energy density and environmental benignity.However,these batteries face significant challenges,particularly related to the air-breathing electrode,resulting in poor cycle life,low efficiency,and catalyst degradation.Developing a robust bifunctional electrocatalyst remains difficult,as oxygen electrocatalysis involves sluggish kinetics and follows different reaction pathways,often requiring distinct active sites.Consequently,the poorly understood mechanisms and irreversible surface reconstruction in the catalyst’s microenvironment,such as atomic modulation,nano-/microscale,and surface interfaces,lead to accelerated degradation during charge and discharge cycles.Overcoming these barriers requires advancements in the development and understanding of bifunctional electrocatalysts.In this review,the critical components of metal-air batteries,the associated challenges,and the current engineering approaches to address these issues are discussed.Additionally,the mechanisms of oxygen electrocatalysis on the air electrodes are examined,along with insights into how chemical characteristics of materials influence these mechanisms.Furthermore,recent advances in bifunctional electrocatalysts are highlighted,with an emphasis on the synthesis strategies,microenvironmental modulations,and stabilized systems demonstrating efficient performance,particularly zinc-and lithium-air batteries.Finally,perspectives and future research directions are provided for designing efficient and durable bifunctional electrocatalysts for metal-air batteries.展开更多
Herein,we report the dynamic kinetic resolution asymmetric acylation ofγ-hydroxy-γ-perfluoroalkyl butenolides/phthalides catalyzed by amino acid-derived bifunctional organocatalysts,and a series of ketals were obtai...Herein,we report the dynamic kinetic resolution asymmetric acylation ofγ-hydroxy-γ-perfluoroalkyl butenolides/phthalides catalyzed by amino acid-derived bifunctional organocatalysts,and a series of ketals were obtained in high yields(up to 95%)and excellent enantioselectivities(up to 99%).In terms of synthetic utility,the reaction can be performed on a gram scale,and the product can be converted into potential biological nucleoside analog.展开更多
Direct seawater electrolysis is a promising way for hydrogen energy production.However,developing efficient and cost-effective electrocatalysts remains a significant challenge for seawater electrolysis with industrial...Direct seawater electrolysis is a promising way for hydrogen energy production.However,developing efficient and cost-effective electrocatalysts remains a significant challenge for seawater electrolysis with industrial-level current density due to high concentration of salts and compete reaction of chlorine evolution.Herein,a 1D NiFe_(2)O_(4)/NiMoO_(4) heterostructure as a bifunctional electrocatalyst for overall seawater splitting is constructed by combining NiMoO_(4) nanowires with NiFe_(2)O_(4)nanoparticles on carbon felt(CF)by a simple hydrothermal,impregnation and calcination method.The electrocatalyst exhibits low overpotential of 237 and 292 mV for oxygen evolution reaction and hydrogen evolution reaction at 400 m A/cm^(2)in the alkaline seawater(1 mol/L KOH+0.5 mol/L NaCl)due to the plentiful interfaces of NiFe_(2)O_(4)/NiMoO_4 which exposes more active sites and expands the active surface area,thereby enhancing its intrinsic activity and promoting the reaction kinetics.Notably,it displays low voltages of 1.95 V to drive current density of 400 m A/cm^(2)in alkaline seawater with its excellent stability of 200 h at above 100 m A/cm^(2),exhibiting outstanding performance and good corrosion resistance.This work provides an effective strategy for constructing efficient and cost-effective electrocatalysts for industrial seawater electrolysis,underscoring its potential for sustainable energy applications.展开更多
In response to the urgent global need to address climate change,reduce emissions,and ensure energy security,hydrogen plays a crucial role in the global energy transitio n.However,traditional hydrogen production method...In response to the urgent global need to address climate change,reduce emissions,and ensure energy security,hydrogen plays a crucial role in the global energy transitio n.However,traditional hydrogen production methods,such as fossil fuel-based steam reforming and water electrolysis,face significant environmental and economic challenges.As an abundant renewable resource,biomass has attracted much attention for hydrogen production technology,particularly sorption-enhanced steam reforming(SESR).This technology combines the principles of chemical equilibrium and sorption to capture CO_(2) using solid sorbents,thereby enhancing the efficiency and purity of hydrogen production from biomass-derived syngas.It offers advantages such as reduced costs,lower energy consumption,decreased emissions,and cu stomization for specific applications.Although SESR technology has demonstrated excellent hydrogen production performance,existing reviews mainly focus on model compounds and still lack critical analysis of its performance in real biomass application scenarios.This review provides a critical summary of the research progress of biomass feedstocks and model compounds SESR for hydrogen production,detailing the effects of feedstock characteristics,temperature,steam ratio,CO_(2) sorbent(CaO,alkali metal ceramics,and hydrotalcite),and catalysts on gas yield.In addition,it further emphasizes the research progress of advanced sorption-catalysis bifunctional composite materials and discusses the coupling application of SESR technology with other processes.The review concludes by highlighting the outstanding challenges of SESR technology and focusing on future research directions,aiming to provide theoretical support and insights for the further development of sorption-enhanced biomass hydrogen production technology.展开更多
The advancement of high-performance zinc-air battery systems necessitates the development of highly effective non-precious metal-based bifunctional electrocatalysts capable of synergistically enhancing both oxygen red...The advancement of high-performance zinc-air battery systems necessitates the development of highly effective non-precious metal-based bifunctional electrocatalysts capable of synergistically enhancing both oxygen reduction reaction(ORR)and oxygen evolution reaction(OER).To address the critical limitations of conventional non-precious catalysts in balancing multiple active sites and structural stability,we introduce an innovative in situ synthesis approach for constructing Fe_(2)P/FeNi bimetallic heterogeneous nanoparticles encapsulated within nitrogen-phosphorus dual-doped carbon matrices featuring interconnected leaf-like nanostructures(Fe_(2)P/FeNi@NPC).This architecturally optimized configuration not only mitigates transition metal degradation through protective carbon confinement but also facilitates rapid charge transfer kinetics and efficient mass diffusion pathways,substantially improving both catalytic efficiency and operational durability.Through comprehensive characterizations combining insitu monitoring and ex-situ analysis,the dynamic evolution of active sites during electrochemical operations is systematically tracked,and the genuine catalytic centers and spin state are identified.The optimized Fe_(2)P/FeNi@NPC composite exhibited remarkable electrochemical performance in alkaline media,achieving a superior ORR half-wave potential of 0.83 V and requiring only 1.62 V to achieve a current density of 10 mA cm^(-2)for OER.Notably,the assembled rechargeable zinc-air batteries(ZABs)exhibited a high specific capacity of 755.08 mAh g^(-1),a low charge-discharge voltage difference of 0.79 V,and exceptional cycling stability of over 1400 h.Furthermore,the flexible ZAB maintains excellent cycling performance even when subjected to various bending conditions.This work provides valuable insights into atomic-and electronic-scale dual-regulation strategy,offering a promising pathway to overcome current limitations in non-precious metal-based electrocatalysts for practical applications in metal-air battery systems.展开更多
Retaining satisfactory electrocatalytic performance under high current density plays a crucial role in industrial water splitting but is still limited to the enormous energy loss because of insufficient exposure of ac...Retaining satisfactory electrocatalytic performance under high current density plays a crucial role in industrial water splitting but is still limited to the enormous energy loss because of insufficient exposure of active sites caused by the blocked mass/charge transportation at this condition.Herein,we present a freestanding lamellar nanoporous Ni-Co-Mn alloy electrode(Lnp-NCM)designed by a refined variant of the“dealloying-coarsening-dealloying”protocol for highly efficient bifunctional electrocatalyst,where large porous channels distribute on the surface and small porous channels at the interlayer.With its 3D lamellar architecture regulating,the electrocatalytic properties of the electrodes with different distances between lamellas are compared,and faster energy conversion kinetics is achieved with efficient bubble transport channels and abundant electroactive sites.Note that the optimized sample(Lnp-NCM4)is expected to be a potential bifunctional electrocatalyst with low overpotentials of 258 and 439 mV at high current densities of 1000 and 900 mA·cm^(-2)for hydrogen and oxygen evolution reactions(HER and OER),respectively.During overall water splitting in a two-electrode cell with Lnp-NCM4 as cathode and anode,it only needs an ultralow cell voltage of 1.75 V to produce 100 mA·cm^(-2)with remarkable long-term stability over 50 h.This study on lamellar nanoporous electrode design approaches industrial water splitting requirements and paves a way for developing other catalytic systems.展开更多
The simplification of the process of electrolytic water catalyst preparation and the exploitation of highly active catalysts represent a meaningful but challenging task.Meanwhile,bifunctional electrolytic water cataly...The simplification of the process of electrolytic water catalyst preparation and the exploitation of highly active catalysts represent a meaningful but challenging task.Meanwhile,bifunctional electrolytic water catalysts are of great significance in improving electrolysis efficiency and simplifying catalyst preparation processes.In this study,we introduce Ru and V into CoTe,which exhibits intrinsic oxygenophilic properties,and couple it with hydrophilic and well-conducting MXene to overcome the sluggish alkaline kinetics of hydrogen evolution reaction(HER)and oxygen evolution reaction(OER).The synthesized Ru,V co-doped CoTe@MXene(RVCTM)catalysts exhibited HER overpotentials of 34 and 116 mV and OER overpotentials of 249 and 320 mV at 10 and 100 mA cm^(-2) current densities,respectively.Moreover,the catalysts demonstrated remarkable stability.Theoretical calculations demonstrated that the incorporation of Ru and V had a profound impact on the local electronic environments of Co and Te.In addition,the coupling with MXene resulted in charge redistribution at the heterogeneous interface.The combined effect of doping and heterostructure construction effectively optimizes the d-band center of the catalyst and reduces the adsorption energy barrier of reaction intermediates.This approach offers deep insights into the development of multifunctional catalysts.展开更多
The radical difunctionalization of alkenes with sulfonyl bifunctional represents a powerful and straightforward approach to access functionalized alkane derivatives.However,both the mechanistic activation mode and the...The radical difunctionalization of alkenes with sulfonyl bifunctional represents a powerful and straightforward approach to access functionalized alkane derivatives.However,both the mechanistic activation mode and the substrate scopes of this type of radical difunctionalizations are still limited.We demonstrate herein a modular photoredox strategy for the difunctionalization of alkenes,employing arylsulfonyl acetate as the bifunctional reagent.This approach involves a radical addition/Smiles rearrangement cascade process,offering a robust alternative for the synthesis of valuableγ,γ-diaryl andγ-aryl esters.A complementary oxidative bifunctional reagents activation mode is identified to govern the radical cascade reactions,facilitating the simultaneous incorporation of aryl and carboxylate-bearing alkyl groups into the alkenes with excellent diastereoselectivity.Noteworthy features of this method include mild reaction conditions,organophotocatalysis,high atom-and step-economy,excellent functional group compatibility and great structural diversity.展开更多
Exploring earth-abundant,highly active bifunctional electrocatalysts for efficient hydrogen and oxygen evolution is crucial for water splitting.However,due to their distinct free energies and conducting behaviors(elec...Exploring earth-abundant,highly active bifunctional electrocatalysts for efficient hydrogen and oxygen evolution is crucial for water splitting.However,due to their distinct free energies and conducting behaviors(electron/hole),balancing the catalytic efficiency between hydrogen and oxygen evolution remains challenging for achieving bifunctional electrocatalysts.Here,we report a locally-doped MoS_(2)monolayer with an in-plane heterostructure acting as a bifunctional electrocatalyst and apply it to the overall water splitting.In this heterostructure,the core region contains Mo/S vacancies,while the ring region was doped by Fe atoms(in two substitution configurations:1FeMo and 3FeMo-VS clusters)with a p-type conductive characteristic.Our micro-cell measurements,combined with density functional theory(DFT)calculations,reveal that the vacancies-rich core region presents remarkable hydrogen evolution reaction(HER)activity while the Fe-doped ring gives an excellent oxygen evolution reaction(OER)activity,thus forming an in-plane bifunctional electrocatalyst.Finally,as a proof-of-concept for overall water splitting,we constructed a full-cell configuration based on a locally-doped MoS_(2)monolayer,which achieved a cell voltage of 1.87 V at 10 mA·cm^(-2),demonstrating outstanding performance in strong acid electrolytes.Our work provides insight into the hetero-integration of bifunctional electrocatalysts at the atomic level,paving the way for designing transition metal dichalcogenide catalysts with activity-manipulated regions capable of multiple reactions.展开更多
Developing nonprecious electrocatalysts with bifunctional performances for oxygen reduction(ORR)and evolution reactions(OER)remains a crucial challenge in rechargeable Zn-air batteries(RZABs).In this study,we report t...Developing nonprecious electrocatalysts with bifunctional performances for oxygen reduction(ORR)and evolution reactions(OER)remains a crucial challenge in rechargeable Zn-air batteries(RZABs).In this study,we report the synthesis of a three-dimensional(3D)porous N,P-doped carbon-wrapped cobalt phosphide composite(Co2P@3DNPC)via direct calcination of a novel organic/inorganic porous coordi-nation polymer by an in-situ phosphating strategy.DFT calculations demonstrate the intricate interac-tions occurring during the PEI-directed grinding self-assembly process among Co^(2+),phytic acid(PA),and polyethylenimine(PEI).Specifically,Co^(2+)ions initially adsorb onto PEI molecules before integrating with PA to form a 3D coordination polymer matrix.As-fabricated Co2P@3DNPC composite exhibits impressive ORR/OER bifunctional performances,with a half-wave potential of 0.78 V and an overpotential of 1.71 V,respectively.Its bifunctional activities enable a power density of 148.5 mW cm^(-2)in rechargeable ZABs,with remarkable stability(>480 h)during a discharge-charge cycle.The interconnected porous structure and embedded Co2P nanoparticles optimize the electrode-electrolyte interfacial contact,boosting energy density and cycle life of as-assembled ZABs.This innovative approach paves the way for efficient,cost-effective production of bifunctional electrocatalysts for RZABs.展开更多
文摘CZTS(Cu_(2)ZnSnS_(4))is a quaternary semiconductor that is environmentally friendly,less expensive.In this paper,we report on the optimization and fabrication of CZTS-based heterojunction nanodevices for bifunctional applications such as solar cells and photodetectors.CZTS thin films were deposited on top of(Molybdenum)Mo-coated glass substrates via RF sputtering at 100 and 200 W.Rapid thermal processing(RTP)was used at 300,400,and 500℃temperatures.Cd S(cadmium sulphide)was deposited on CZTS using a chemical bath deposition system with 3-and 5-min deposition times.Zn O(zinc oxide)and AZO(aluminium doped zinc oxide)layers were deposited using RF(radio frequency)sputtering to create the solar device.XRD confirms the formation of a tetragonal structure with increased crystallinity due to the use of RTP.Raman reveals the characteristic Raman shift peak associated with CZTS at 336 and 335 cm^(-1).The FESEM shows a relationship with RTP temperature.Surface features,including grain size,vary with RTP temperature.The ideality factor is nearly 2,indicating imperfection in the Mo/CZTS interface.Schottky barrier height estimates range from 0.6 to 0.7 e V.Absorbance and transmittance show a predictable fluctuation with RTP temperature.Photovoltaic device was built using the higher crystalline feature of CZTS in conjunction with Cd S deposited at 3 and 5 min.The efficiency of Cd S deposited after 3 and 5 min was 1.15 and 0.97 percent,respectively.Fabricated devices were used for wavelength-dependent photodetection.This work demonstrated self-powered photodetection.
基金supported by the National Natural Science Foundation of China(U24A20550,52273264 and 52470073)the Key Project of the Heilongjiang Provincial Natural Science Foundation(ZD2024B001)Outstanding Youth Fund of Heilongjiang Province(JQ2022E005).
文摘Designing a heterogeneous interface to improve the kinetics of electrocatalysts represents an effective yet challenging approach for enhancing the oxygen reduction reaction(ORR)and oxygen evolution reaction(OER).Herein,a simple MOF-assisted etching-pyrolysis strategy is proposed to fabricate an advanced Mott-Schottky(M–S)electrocatalyst composed of Co/CeO_(2)hetero-nanoparticles embedded within N-doped hollow carbon nanoboxes(H-Co/CeO_(2)@NCBs).Notably,the interfacial Co–O–Ce bond bridging productively facilitates the electron transfer and modulates the charge distribution of the active center,thereby contributing to the ORR/OER kinetics.As expected,the optimal M–S H-Co/CeO_(2)@NCBs catalyst exhibits promising bifunctional electrocatalytic activity with a small potential discrepancy of 0.65 V.Theoretical calculations reveal that the built-in electric field in the M–S heterojunction promotes electron transfer in oxygen electrocatalysis and the interfacial bridge-induced electron redistribution optimizes the adsorption/desorption of the oxygen intermediates,leading to reduced activation energy for the bifunctional ORR/OER reactions.Importantly,H-Co/CeO_(2)@NCBs-assembled Zn-air battery(ZAB)delivers high power density(179.8 mW cm^(−2))and long-term stability(400 h).Furthermore,the assembled flexible solid-state ZAB with H-Co/CeO_(2)@NCBs cathode also exhibits excellent charge–discharge reversibility and flexibility at various bending angles.This work provides a novel perspective on developing efficient and stable M–S bifunctional oxygen electrocatalysts.
基金supported by the Fundamental Research Funds for the Central Universities(No.22120230104).
文摘High-entropy alloy(HEA)nanoparticles(NPs)have attracted great attention in electrocatalysis due to their tailorable complex compositions and unique properties.Herein,we introduce Fe,Co,Ni,Cr and Mn into the metal-polyphenol coordination system to prepare HEA NPs enclosed in N-doped carbon(FeCoNiCrMn)with great potential for catalyzing oxygen reduction reaction(ORR)and oxygen evolution reaction(OER).The unique high-entropy structural characteristics in FeCoNiCrMn facilitate effective interplay between metal species,leading to improved ORR(E_(1/2)=0.89 V)and OER(η=330 mV,j=10 mA·cm^(−2))activity.Additionally,FeCoNiCrMn exhibits excellent open-circuit voltage(1.523 V),power density(110 mW·cm^(−2))and long-term durability,outperforming Pt/C+IrO_(2) electrodes as a cathode catalyst in Zn-air batteries(ZABs).Such polyphenol-assisted alloying method broadens and simplifies the development of HEA electrocatalysts for high-performance ZABs.
基金supported by grants from the National Research Foundation of Korea(NRF)under grant No.RS-2022-00155422 and No.2021R1C1C102014。
文摘Water often presents significant challenges in catalysts by deactivating active sites,poisoning the reaction,and even degrading composite structure.These challenges are amplified when the water participates as a reactant and is fed as a liquid phase,such as trickle bed-type reactors in a hydrogen-water isotope exchange(HIE)reaction.The key balance in such multiphase reactions is the precise control of catalyst design to repel bulk liquid water while diffusing water vapor.Herein,a platinum-incorporated metal-organic framework(MIL-101)based bifunctional hydrophobic catalyst functionalized with long alkyl chains(C_(12),dodecylamine)and further manufactured with poly(vinylidene fluoride),Pt@MIL-101-12/PVDF,has been developed which can show dramatically improved catalytic activity under multi-phase reactions involving hydrogen gas and liquid water.Pt@MIL-101-12/PVDF demonstrates enhanced macroscopic water-blocking properties,with a notable reduction of over 65%in water adsorption capacity and newly introduced liquid water repellency.while exhibiting a negligible increase in mass transfer resistance,i.e.,bifunctional hydrophobicity.Excellent catalytic activity,evaluated via HIE reaction,and its durability underscore the impact of bifunctional hydrophobicity.In situ DRIFTS analysis elucidates water adsorption/desorption dynamics within the catalyst composite,highlighting reinforced water diffusion at the microscopic level,affirming the catalyst's bifunctionality in different length scales.With demonstrated radiation resistance,Pt@MIL-101-12/PVDF emerges as a promising candidate for isotope exchange reactions.
基金supported by National R&D Program through the National Research Foundation of Korea(NRF)funded by Ministry of Science and ICT(Nos.2022R1F1A1072420 and NRF-2020R1A3B2079803).
文摘The continuous depletion of fossil fuels and the effects of climate change have encouraged prompt action to attain carbon neutrality.Technologies that transform and store renewable energy are crucial for creating a sustainable society,which is independent of fossil fuels.In this regard,electrochemical water splitting based on the oxygen evolution reaction(OER)and hydrogen evolution reaction(HER)is an attractive technique for producing carbon-free hydrogen fuels.Additionally,rechargeable metal–air batteries(MABs)are another intriguing way for renewable energy storage through reversible oxygen reactions(OER and the oxygen reduction reaction,ORR).Herein,we comprehensively review bifunctional electrocatalysts for water splitting(HER and OER)and MABs(OER and ORR),particularly 2D carbon material-derived heterostructures.The synthesis and properties of 2D carbon materials and their energy conversion and storage mechanisms are discussed to highlight the bifunc-tionality of the heterostructures.Recent studies on bifunctional electrocatalysts based on 2D carbon-derived heterostructures are also reviewed.Finally,perspectives for future studies and multifunctional catalysts are presented.
基金the financial support from the Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education (NRF-2023R1A2C2007699 and 2022R1A6A1A0306303912)the Nano Material Technology Development Program through the NRF funded by the Ministry of Science and ICT (NRF-2015M3A7B6027970)the Technology Innovation Program by the Ministry of Trade, Industry & Energy (RS-202300236794)
文摘Regulating lithium(Li)plating/stripping behavior in three-dimensional(3D)conductive scaffolds is critical to stabilizing Li metal batteries(LMBs).Surface protrusions and roughness in these scaffolds can induce uneven distributions of the electric fields and ionic concentrations,forming“hot spots.”Hot spots may cause uncontrollable Li dendrites growth,presenting significant challenges to the cycle stability and safety of LMBs.To address these issues,we construct a Li ionic conductive-dielectric gradient bifunctional interlayer(ICDL)onto a 3D Li-injected graphene/carbon nanotube scaffold(LGCF)via in situ reaction of exfoliated hexagonal boron nitride(fhBN)and molten Li.Microscopic and spectroscopic analyses reveal that ICDL consists of fhBN-rich outer layer and inner layer enriched with Li_(3)N and Li-boron composites(Li-B).The outer layer utilizes dielectric properties to effectively homogenize the electric field,while the inner layer ensures high Li ion conductivity.Moreover,DFT calculations indicate that ICDL can effectively adsorb Li and decrease the Li diffusion barrier,promoting enhanced Li ion transport.The modulation of Li kinetics by ICDL increases the critical length of the Li nucleus,enabling suppression of Li dendrite growth.Attributing to these advantages,the ICDL-coated LGCF(ICDL@LGCF)demonstrates impressive long-term cycle performances in both symmetric cells and full cells.
基金financially supported by the National Natural Science Foundation of China(Grant Nos.22172093 and 21776167)the Natural Science Foundation of Shandong Province,China(Grant No.ZR2023MB061)。
文摘Fully conjugated covalent organic frameworks(COFs)are widely used in electrocatalysis.The COF with-ph-NH_(2)edge poly(1,4-phenyldiazo porphyrin cobalt)(A-PpazoPorCo)is synthesized by adjusting the molar ratio of the reaction material,and exhibits high delocalization energy to significantly enhance thermal stability.The nitrogen in the azo bond improves the adsorption capacity for ORR and OER catalytic intermediates,while the-ph-NH_(2)group further increases the electron cloud density at the Co-N_(4)center in A-PpazoPorCo.Density functional theory(DFT)calculations reveal that the strong electron-donating-ph-NH_(2)groups and the electron-donating azo bonds form an electron donor-π-electron acceptor(D-π-A)structure,which further enhances the electron cloud density.The strongπ-πinteraction between A-PpazoPorCo and three-dimensional graphene(3D-G)significantly boosts the oxygen catalytic performance of the A-PpazoPorCo/3D-G.The catalytic ORR half-wave potential(E_(1/2))of A-PpazoPorCo/3D-G can reach 0.880 V vs.RHE.The total overpotential(ΔE=E_(j=10)-E_(1/2))is 0.617 V,demonstrating excellent bifunctional oxygen catalytic performance.The efficient oxygen catalytic performance indicates that A-PpazoPorCo/3D-G has the potential for application in fuel cells cathodes and overall water splitting anodes.
基金financially supported by the National Natural Science Foundation of China(No.22279047)the Instrumental Analysis Center of Jiangsu University of Science and Technology。
文摘Exploring efficient and nonprecious metal electrocatalysts of oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)is crucial for developing rechargeable zinc-air batteries(ZABs).Herein,an alloying-degree control strategy was employed to fabricate nitrogen-doped carbon sphere(NCS)decorated with dual-phase Co/Co_(7)Fe_(3)heterojunctions(CoFe@NCS).The phase composition of materials has been adjusted by controlling the alloying degree.The optimal CoFe_(0.08)@NCS electrocatalyst displays a half-wave potential of 0.80 V for ORR and an overpotential of 283 mV at 10 mA·cm^(-2)for OER in an alkaline electrolyte.The intriguing bifunctional electrocatalytic activity and durability is attributed to the hierarchically porous structure and interfacial electron coupling of highly-active Co_(7)Fe_(3)alloy and metallic Co species.When the CoFe_(0.08)@NCS material is used as air-cathode catalyst of rechargeable liquid-state zinc-air battery(ZAB),the device shows a high peak power-density(157 mW·cm^(-2))and maintains a stable voltage gap over 150 h,outperforming those of the benchmark(Pt/C+RuO_(2))-based device.In particular,the as-fabricated solid-state flexible ZAB delivers a reliable compatibility under different bending conditions.Our work provides a promising strategy to develop metal/alloy-based electrocatalysts for the application in renewable energy conversion technologies.
文摘Herein,a luminescent europium-based metal-organic framework(Eu-MOF,[Eu_(3)(L)(HL)(NO_(3))_(2)(DMF)_(2)]·4DMF·5H_(2)O,H_(4)L=5,5′-(pyrazine-2,6-diyl)diisophthalic acid,DMF=N,N-dimethylformamide)was developed for the dual-functional detection of environmental pollutants.This fluorescence-quenching-based sensor exhibited excep-tional sensitivity for both 2,4,6-trinitrophenol(TNP)and tetracycline(TC),achieving remarkably low detection lim-its of 1.96×10^(-6)and 1.71×10^(-7)mol·L^(-1),respectively.Notably,the system exhibited 99%fluorescence quenching ef-ficiency for TC,indicating ultra-efficient analyte recognition.The detection performance surpasses most reported lu-minescent MOF sensors,attributed to synergistic mechanisms of fluorescence resonance energy transfer(FRET)and photoinduced electron transfer(PET).CCDC:2446483.
基金the financial support from the National Natural Science Foundation of China(Nos.22201265,22201264)the China Postdoctoral Science Foundation(Nos.2022M710133,2022TQ0287)。
文摘The tert-butyl nitrite as a bifunctional reagent mediated radical alkene difunctionalization has emerged as a powerful strategy for synthesis of structurally diverse oxime-containing compounds.However,the phosphorus-centered radical initiated transformations remain largely elusive.Herein,a visible-lightinduced radical phosphinoyloximation of alkenes with secondary phosphine oxides and tert-butyl nitrite has been developed under photocatalyst-and metal-free conditions.This protocol features mild conditions,broad substrate scope,good functional tolerance,and operational simplicity,yielding a diverse array ofα-phosphinoyl oximes in moderate to good yields with high stereoselectivities.The photomediated homolytic cleavage of O–NO bond of tert-butyl nitrite generates the reactive tert-butoxyl radical and persistent NO radical to act as both HAT reagent and the source of oximes.
基金the National Key Research and Development Program of China(no.2021YFA1600800 and 2021YFA1501000)the Fundamental Research Funds for the Central Universities(YCJJ20242227)+3 种基金the Research Plan of International Collaboration Fund for Creative Research Teams(ICFCRT)of NSFC(No.W2441008)the open research fund of Suzhou Laboratory(No.SZLAB-1308-2024-ZD010)the Innovation and Talent Recruitment Base of New Energy Chemistry and Devices(B21003)supported by the European Union’s Horizon 2020 research and innovation program under the Marie Skłodowska-Curie grant agreement(Grant No.101102946 and Grant No.945422).
文摘Rechargeable metal-air batteries have gained significant interest due to their high energy density and environmental benignity.However,these batteries face significant challenges,particularly related to the air-breathing electrode,resulting in poor cycle life,low efficiency,and catalyst degradation.Developing a robust bifunctional electrocatalyst remains difficult,as oxygen electrocatalysis involves sluggish kinetics and follows different reaction pathways,often requiring distinct active sites.Consequently,the poorly understood mechanisms and irreversible surface reconstruction in the catalyst’s microenvironment,such as atomic modulation,nano-/microscale,and surface interfaces,lead to accelerated degradation during charge and discharge cycles.Overcoming these barriers requires advancements in the development and understanding of bifunctional electrocatalysts.In this review,the critical components of metal-air batteries,the associated challenges,and the current engineering approaches to address these issues are discussed.Additionally,the mechanisms of oxygen electrocatalysis on the air electrodes are examined,along with insights into how chemical characteristics of materials influence these mechanisms.Furthermore,recent advances in bifunctional electrocatalysts are highlighted,with an emphasis on the synthesis strategies,microenvironmental modulations,and stabilized systems demonstrating efficient performance,particularly zinc-and lithium-air batteries.Finally,perspectives and future research directions are provided for designing efficient and durable bifunctional electrocatalysts for metal-air batteries.
基金supported by the National Natural Science Foundation of China(Nos.82130103,82151525 and 81903465)the Central Plains Scholars and Scientists Studio Fund(2018002)+1 种基金the Natural Science Foundation of Henan Province(No.212300410051)the Science and Technology Major Project of Henan Province(No.221100310300)。
文摘Herein,we report the dynamic kinetic resolution asymmetric acylation ofγ-hydroxy-γ-perfluoroalkyl butenolides/phthalides catalyzed by amino acid-derived bifunctional organocatalysts,and a series of ketals were obtained in high yields(up to 95%)and excellent enantioselectivities(up to 99%).In terms of synthetic utility,the reaction can be performed on a gram scale,and the product can be converted into potential biological nucleoside analog.
基金supported by the National Natural Science Foundation of China(No.51908408)the Science&Technology Development Fund of Tianjin Education Commission for Higher Education(No.2019KJ008)Basic Research Program of Jiangsu Province(No.BK20241845)。
文摘Direct seawater electrolysis is a promising way for hydrogen energy production.However,developing efficient and cost-effective electrocatalysts remains a significant challenge for seawater electrolysis with industrial-level current density due to high concentration of salts and compete reaction of chlorine evolution.Herein,a 1D NiFe_(2)O_(4)/NiMoO_(4) heterostructure as a bifunctional electrocatalyst for overall seawater splitting is constructed by combining NiMoO_(4) nanowires with NiFe_(2)O_(4)nanoparticles on carbon felt(CF)by a simple hydrothermal,impregnation and calcination method.The electrocatalyst exhibits low overpotential of 237 and 292 mV for oxygen evolution reaction and hydrogen evolution reaction at 400 m A/cm^(2)in the alkaline seawater(1 mol/L KOH+0.5 mol/L NaCl)due to the plentiful interfaces of NiFe_(2)O_(4)/NiMoO_4 which exposes more active sites and expands the active surface area,thereby enhancing its intrinsic activity and promoting the reaction kinetics.Notably,it displays low voltages of 1.95 V to drive current density of 400 m A/cm^(2)in alkaline seawater with its excellent stability of 200 h at above 100 m A/cm^(2),exhibiting outstanding performance and good corrosion resistance.This work provides an effective strategy for constructing efficient and cost-effective electrocatalysts for industrial seawater electrolysis,underscoring its potential for sustainable energy applications.
基金supported by the National Natural Science Foundation of China(No.52276193)。
文摘In response to the urgent global need to address climate change,reduce emissions,and ensure energy security,hydrogen plays a crucial role in the global energy transitio n.However,traditional hydrogen production methods,such as fossil fuel-based steam reforming and water electrolysis,face significant environmental and economic challenges.As an abundant renewable resource,biomass has attracted much attention for hydrogen production technology,particularly sorption-enhanced steam reforming(SESR).This technology combines the principles of chemical equilibrium and sorption to capture CO_(2) using solid sorbents,thereby enhancing the efficiency and purity of hydrogen production from biomass-derived syngas.It offers advantages such as reduced costs,lower energy consumption,decreased emissions,and cu stomization for specific applications.Although SESR technology has demonstrated excellent hydrogen production performance,existing reviews mainly focus on model compounds and still lack critical analysis of its performance in real biomass application scenarios.This review provides a critical summary of the research progress of biomass feedstocks and model compounds SESR for hydrogen production,detailing the effects of feedstock characteristics,temperature,steam ratio,CO_(2) sorbent(CaO,alkali metal ceramics,and hydrotalcite),and catalysts on gas yield.In addition,it further emphasizes the research progress of advanced sorption-catalysis bifunctional composite materials and discusses the coupling application of SESR technology with other processes.The review concludes by highlighting the outstanding challenges of SESR technology and focusing on future research directions,aiming to provide theoretical support and insights for the further development of sorption-enhanced biomass hydrogen production technology.
基金supported by the National Natural Science Foundation of China(Nos.22008058,No 22279135)the Natural Science Foundation of Hubei Province(No.2023AFB1010)+1 种基金the Key Project of Scientific Plan of Education Department of Hubei Province(No.D20232501)the CAS Strategic Leading Science&Technology Program(B)(XDB1040203)。
文摘The advancement of high-performance zinc-air battery systems necessitates the development of highly effective non-precious metal-based bifunctional electrocatalysts capable of synergistically enhancing both oxygen reduction reaction(ORR)and oxygen evolution reaction(OER).To address the critical limitations of conventional non-precious catalysts in balancing multiple active sites and structural stability,we introduce an innovative in situ synthesis approach for constructing Fe_(2)P/FeNi bimetallic heterogeneous nanoparticles encapsulated within nitrogen-phosphorus dual-doped carbon matrices featuring interconnected leaf-like nanostructures(Fe_(2)P/FeNi@NPC).This architecturally optimized configuration not only mitigates transition metal degradation through protective carbon confinement but also facilitates rapid charge transfer kinetics and efficient mass diffusion pathways,substantially improving both catalytic efficiency and operational durability.Through comprehensive characterizations combining insitu monitoring and ex-situ analysis,the dynamic evolution of active sites during electrochemical operations is systematically tracked,and the genuine catalytic centers and spin state are identified.The optimized Fe_(2)P/FeNi@NPC composite exhibited remarkable electrochemical performance in alkaline media,achieving a superior ORR half-wave potential of 0.83 V and requiring only 1.62 V to achieve a current density of 10 mA cm^(-2)for OER.Notably,the assembled rechargeable zinc-air batteries(ZABs)exhibited a high specific capacity of 755.08 mAh g^(-1),a low charge-discharge voltage difference of 0.79 V,and exceptional cycling stability of over 1400 h.Furthermore,the flexible ZAB maintains excellent cycling performance even when subjected to various bending conditions.This work provides valuable insights into atomic-and electronic-scale dual-regulation strategy,offering a promising pathway to overcome current limitations in non-precious metal-based electrocatalysts for practical applications in metal-air battery systems.
基金supported by the National Natural Science Foundation of China(No.52101251)the Science Research Project of Hebei Education Department(No.BJK2023058)the Natural Science Foundation of Hebei Province(Nos.E2020208069 and B2020208083).
文摘Retaining satisfactory electrocatalytic performance under high current density plays a crucial role in industrial water splitting but is still limited to the enormous energy loss because of insufficient exposure of active sites caused by the blocked mass/charge transportation at this condition.Herein,we present a freestanding lamellar nanoporous Ni-Co-Mn alloy electrode(Lnp-NCM)designed by a refined variant of the“dealloying-coarsening-dealloying”protocol for highly efficient bifunctional electrocatalyst,where large porous channels distribute on the surface and small porous channels at the interlayer.With its 3D lamellar architecture regulating,the electrocatalytic properties of the electrodes with different distances between lamellas are compared,and faster energy conversion kinetics is achieved with efficient bubble transport channels and abundant electroactive sites.Note that the optimized sample(Lnp-NCM4)is expected to be a potential bifunctional electrocatalyst with low overpotentials of 258 and 439 mV at high current densities of 1000 and 900 mA·cm^(-2)for hydrogen and oxygen evolution reactions(HER and OER),respectively.During overall water splitting in a two-electrode cell with Lnp-NCM4 as cathode and anode,it only needs an ultralow cell voltage of 1.75 V to produce 100 mA·cm^(-2)with remarkable long-term stability over 50 h.This study on lamellar nanoporous electrode design approaches industrial water splitting requirements and paves a way for developing other catalytic systems.
基金the National Natural Science Foundation of China(No.52222408)the China Baowu Low Carbon Metallurgy Innovation Foundation(No.BWLCF202302)for their financial support.
文摘The simplification of the process of electrolytic water catalyst preparation and the exploitation of highly active catalysts represent a meaningful but challenging task.Meanwhile,bifunctional electrolytic water catalysts are of great significance in improving electrolysis efficiency and simplifying catalyst preparation processes.In this study,we introduce Ru and V into CoTe,which exhibits intrinsic oxygenophilic properties,and couple it with hydrophilic and well-conducting MXene to overcome the sluggish alkaline kinetics of hydrogen evolution reaction(HER)and oxygen evolution reaction(OER).The synthesized Ru,V co-doped CoTe@MXene(RVCTM)catalysts exhibited HER overpotentials of 34 and 116 mV and OER overpotentials of 249 and 320 mV at 10 and 100 mA cm^(-2) current densities,respectively.Moreover,the catalysts demonstrated remarkable stability.Theoretical calculations demonstrated that the incorporation of Ru and V had a profound impact on the local electronic environments of Co and Te.In addition,the coupling with MXene resulted in charge redistribution at the heterogeneous interface.The combined effect of doping and heterostructure construction effectively optimizes the d-band center of the catalyst and reduces the adsorption energy barrier of reaction intermediates.This approach offers deep insights into the development of multifunctional catalysts.
基金the National Natural Science Foundation of China(No.21901199)National Training Program of Innovation and Entrepreneurship for Undergraduates(No.S202310698011)Xi’an Jiaotong University(No.7121192002)for financial support.
文摘The radical difunctionalization of alkenes with sulfonyl bifunctional represents a powerful and straightforward approach to access functionalized alkane derivatives.However,both the mechanistic activation mode and the substrate scopes of this type of radical difunctionalizations are still limited.We demonstrate herein a modular photoredox strategy for the difunctionalization of alkenes,employing arylsulfonyl acetate as the bifunctional reagent.This approach involves a radical addition/Smiles rearrangement cascade process,offering a robust alternative for the synthesis of valuableγ,γ-diaryl andγ-aryl esters.A complementary oxidative bifunctional reagents activation mode is identified to govern the radical cascade reactions,facilitating the simultaneous incorporation of aryl and carboxylate-bearing alkyl groups into the alkenes with excellent diastereoselectivity.Noteworthy features of this method include mild reaction conditions,organophotocatalysis,high atom-and step-economy,excellent functional group compatibility and great structural diversity.
基金supported by the National Natural Science Foundation of China(Nos.22175060 and 22376062)JSPS Grant-in-Aid for Scientific Research(Nos.JP21H05235,JP22H05478 and JP22F22358)+1 种基金China Postdoctoral Science Foundation(No.2022M722867)the Key Research Project of Higher Education Institutions in Henan Province(No.23A530001).
文摘Exploring earth-abundant,highly active bifunctional electrocatalysts for efficient hydrogen and oxygen evolution is crucial for water splitting.However,due to their distinct free energies and conducting behaviors(electron/hole),balancing the catalytic efficiency between hydrogen and oxygen evolution remains challenging for achieving bifunctional electrocatalysts.Here,we report a locally-doped MoS_(2)monolayer with an in-plane heterostructure acting as a bifunctional electrocatalyst and apply it to the overall water splitting.In this heterostructure,the core region contains Mo/S vacancies,while the ring region was doped by Fe atoms(in two substitution configurations:1FeMo and 3FeMo-VS clusters)with a p-type conductive characteristic.Our micro-cell measurements,combined with density functional theory(DFT)calculations,reveal that the vacancies-rich core region presents remarkable hydrogen evolution reaction(HER)activity while the Fe-doped ring gives an excellent oxygen evolution reaction(OER)activity,thus forming an in-plane bifunctional electrocatalyst.Finally,as a proof-of-concept for overall water splitting,we constructed a full-cell configuration based on a locally-doped MoS_(2)monolayer,which achieved a cell voltage of 1.87 V at 10 mA·cm^(-2),demonstrating outstanding performance in strong acid electrolytes.Our work provides insight into the hetero-integration of bifunctional electrocatalysts at the atomic level,paving the way for designing transition metal dichalcogenide catalysts with activity-manipulated regions capable of multiple reactions.
基金supported by the Research Project of the Hubei Provincial Department of Education(Grant No.Q20232503)the Hubei Provincial Natural Science Foundation and Huangshi of China(No.2022CFD039)+8 种基金the National Natural Science Foundation of China(Nos.22075072 and 52301272)the Program for Innovative Teams of Outstanding Young and Middle-aged Researchers in the Higher Education Institutions of Hubei Province(No.T2021010)the Natural Science Foundation of Hubei Province(No.2023AFB1010)the Natural Science Foundation of Zhejiang Province(No.LQ23E020002)the Wenzhou Key Scientific and Technological Innovation Research Project(No.ZG2023053)the Wenzhou Natural Science Foundation(No.G20220019)the Cooperation between industry and education project of Ministry of Education(No.220601318235513)the Wenzhou Science and Technology Association Serves Scientific and Technological Innovation Projects(KJFW0201)The State Key Laboratory funding of Disaster Prevention&Mitigation of Explosion&Impact(No.LGD-SKL-202203).
文摘Developing nonprecious electrocatalysts with bifunctional performances for oxygen reduction(ORR)and evolution reactions(OER)remains a crucial challenge in rechargeable Zn-air batteries(RZABs).In this study,we report the synthesis of a three-dimensional(3D)porous N,P-doped carbon-wrapped cobalt phosphide composite(Co2P@3DNPC)via direct calcination of a novel organic/inorganic porous coordi-nation polymer by an in-situ phosphating strategy.DFT calculations demonstrate the intricate interac-tions occurring during the PEI-directed grinding self-assembly process among Co^(2+),phytic acid(PA),and polyethylenimine(PEI).Specifically,Co^(2+)ions initially adsorb onto PEI molecules before integrating with PA to form a 3D coordination polymer matrix.As-fabricated Co2P@3DNPC composite exhibits impressive ORR/OER bifunctional performances,with a half-wave potential of 0.78 V and an overpotential of 1.71 V,respectively.Its bifunctional activities enable a power density of 148.5 mW cm^(-2)in rechargeable ZABs,with remarkable stability(>480 h)during a discharge-charge cycle.The interconnected porous structure and embedded Co2P nanoparticles optimize the electrode-electrolyte interfacial contact,boosting energy density and cycle life of as-assembled ZABs.This innovative approach paves the way for efficient,cost-effective production of bifunctional electrocatalysts for RZABs.
