To realize the practical application of anion exchange membrane water electrolysis(AEMWE),it is essential to develop highly active,durable,and cost-effective electrocatalyst for oxygen evolution reaction(OER).Herein,w...To realize the practical application of anion exchange membrane water electrolysis(AEMWE),it is essential to develop highly active,durable,and cost-effective electrocatalyst for oxygen evolution reaction(OER).Herein,we report a hollow-structured Ni_(x)Co_(1−x)O/Ni_(3)S_(2)/Co_(9)S_(8)heterostructure synthesized via sequential template-assisted growth,thermal oxidation,and controlled sulfidation process.The abundant bimetallic heterointerfaces not only provide additional active sites but also promote electronic modulation via charge redistribution.Additionally,the porous and hollow architecture enhances active surface area and mass transfer ability,thereby increasing the number of accessible active sites for alkaline OER.As a result,the prepared electrocatalyst achieves low overpotential of 310 mV at 10 mA cm^(−2)and small Tafel slope of 55.94 mV dec^(−1),demonstrating the exceptional electrocatalytic performance for alkaline OER.When integrated as the anode in an AEMWE cell,it delivers outstanding performance with only 1.657 V at 1.0 A cm^(−2)and reaches high current density of 5.0 A cm^(−2)at 1.989 V,surpassing those of commercial RuO_(2).The cell also shows excellent long-term durability over 100 h with minimal degradation.This study highlights the strong potential of rationally engineered oxide/sulfide heterostructures for next-generation alkaline water electrolysis.展开更多
Seawater zinc-air batteries are promising energy storage devices due to their high energy density and utilization of seawater electrolytes.However,their efficiency is hindered by the sluggish oxygen reduction reaction...Seawater zinc-air batteries are promising energy storage devices due to their high energy density and utilization of seawater electrolytes.However,their efficiency is hindered by the sluggish oxygen reduction reaction(ORR)and chlorideinduced degradation over conventional catalysts.In this study,we proposed a universal synthetic strategy to construct heteroatom axially coordinated Fe–N_(4) single-atom seawater catalyst materials(Cl–Fe–N_(4) and S–Fe–N_(4)).X-ray absorption spectroscopy confirmed their five-coordinated square pyramidal structure.Systematic evaluation of catalytic activities revealed that compared with S–Fe–N_(4),Cl–Fe–N_(4) exhibits smaller electrochemical active surface area and specific surface area,yet demonstrates higher limiting current density(5.8 mA cm^(−2)).The assembled zinc-air batteries using Cl–Fe–N_(4) showed superior power density(187.7 mW cm^(−2) at 245.1 mA cm^(−2)),indicating that Cl axial coordination more effectively enhances the intrinsic ORR activity.Moreover,Cl–Fe–N_(4) demonstrates stronger Cl−poisoning resistance in seawater environments.Chronoamperometry tests and zinc-air battery cycling performance evaluations confirmed its enhanced stability.Density functional theory calculations revealed that the introduction of heteroatoms in the axial direction regulates the electron center of Fe single atom,leading to more active reaction intermediates and increased electron density of Fe single sites,thereby enhancing the reduction in adsorbed intermediates and hence the overall ORR catalytic activity.展开更多
Ball milling is an environmentally friendly technology for the remediation of petroleumcontaminated soil(PCS),but the cleanup of organic pollutants requires a long time,and the post-remediation soil needs an economica...Ball milling is an environmentally friendly technology for the remediation of petroleumcontaminated soil(PCS),but the cleanup of organic pollutants requires a long time,and the post-remediation soil needs an economically viable disposal/reuse strategy due to its vast volume.The present paper develops a ball milling process under oxygen atmosphere to enhance PCS remediation and reuse the obtained carbonized soil(BCS-O)as wastewater treatment materials.The total petroleum hydrocarbon removal rates by ball milling under vacuum,air,and oxygen atmospheres are 39.83%,55.21%,and 93.84%,respectively.The Langmuir and pseudo second-order models satisfactorily describe the adsorption capacity and behavior of BCS-O for transition metals.The Cu^(2+),Ni^(2+),and Mn^(2+)adsorbed onto BCS-O were mainly bound to metal carbonates and metal oxides.Furthermore,BCS-O can effectively activate persulfate(PDS)oxidation to degrade aniline,while BCS-O loaded with transition metal(BCS-O-Me)shows better activation efficiency and reusability.BCS-O and BCS-O-Me activated PDS oxidation systems are dominated by^(1)O_(2)oxidation and electron transfer.The main active sites are oxygen-containing functional groups,vacancy defects,and graphitized carbon.The oxygen-containing functional groups and vacancy defects primarily activate PDS to generate^(1)O_(2)and attack aniline.Graphitized carbon promotes aniline degradation by accelerating electron transfer.The paper develops an innovative strategy to simultaneously realize efficient remediation of PCS and sequential reuse of the postremediation soil.展开更多
Singlet oxygen(^(1)O_(2)),as an electrophilic oxidant,is essential for the selective water decontamination of pollutants from water.Herein,we showcase a high-performing electrocatalytic filtration system composed of c...Singlet oxygen(^(1)O_(2)),as an electrophilic oxidant,is essential for the selective water decontamination of pollutants from water.Herein,we showcase a high-performing electrocatalytic filtration system composed of carbon nanotubes functionalized with CoFe alloy nanoparticles(CoFeCNT)to selectively facilitate the electrochemical activation of O_(2)to^(1)O_(2).Benefiting from the prominently featured bimetal active sites of CoFeCNT,nearly complete production of^(1)O_(2)is achieved by the electrocatalytic activation of O_(2).Additionally,the proposed system exhibits a consistent pollutant removal efficiency>90%in a flow-through reactor over 48 h of continuous operation without a noticeable decline in performance,highlighting the dependable stability of the system for practical applications.The flow-through configuration demonstrates a striking 8-fold enhancement in tetracycline oxidation compared to a conventional batch reactor.This work provides a molecular level understanding of the oxygen reduction reaction,showing promising potential for the selective removal of emerging organic contaminants from water.展开更多
Photocatalytic H_(2)O_(2) production still confronts the challenges of its dependence on organic electron donors or high-purity O_(2),which restricts the practical application,and there are few studies on the photo sy...Photocatalytic H_(2)O_(2) production still confronts the challenges of its dependence on organic electron donors or high-purity O_(2),which restricts the practical application,and there are few studies on the photo synthesis of H_(2)O_(2) via both oxygen reduction reaction(ORR)and water oxidation reaction(WOR).In this paper,bismuth yttrium oxyhalides Bi_(2)YO_(4)X(X=Cl,Br,or I)are demonstrated to afford sufficient driving forces to produce H_(2)O_(2) in the absence of sacrificial reagents.After modification with Pt and IrO_(2) as cocatalysts,which can selectively promote both ORR and WOR reactions on Bi_(2)YO_(4)Cl,the IrO_(2)-Pt/Bi_(2)YO_(4)Cl sample yields H_(2)O_(2) production activity of 647μmol L^(-1)h^(-1)with negligible decay in the long-term reaction using only H_(2)O and an air atmosphere as the electron donors and O_(2) source.Detailed characterizations reveal that the ORR reaction obeys a two-electron pathway.We present the first example of oxyhalides(Bi_(2)YO_(4)X)capable of efficient photocata lytic H_2O_(2) generation with record-breaking activity.展开更多
Proton exchange membrane water electrolyzers(PEMWEs)are pivotal for efficient hydrogen production due to their high energy efficiency and ability to operate at high current densities,making them ideally suited for int...Proton exchange membrane water electrolyzers(PEMWEs)are pivotal for efficient hydrogen production due to their high energy efficiency and ability to operate at high current densities,making them ideally suited for integration with renewable energy sources.Cobalt(Co)-based nanomaterials,characterized by diverse oxidation states,tunable electronic spin states,and hybrid orbitals,have emerged as promising non-noble metal alternatives to platinum group catalysts for accelerating the anodic oxygen evolution reaction(OER).Based on their inherent properties,this review provides a comprehensive overview of the latest developments in Co-based nanomaterials for acidic OER.The review begins by introducing the operational principles of PEMWEs,the underlying catalytic mechanisms,and the critical design considerations for OER catalysts.It then explores strategies to enhance the activity and stability of Co-based catalysts for acidic OER in PEMWEs,including the incorporation of corrosion-resistant metals or dispersion on acid-resistant supports to increase active surface area and stability;utilization of geometric structural engineering to improve structural integrity and active site efficiency;the optimization of reaction mechanisms to fine-tune catalytic pathways for enhanced stability and performance.The performance degradation mechanisms and metal leaching analysis for Co-based catalysts in PEMWE are also clarified.Finally,this review not only outlines the key challenges associated with Co-based catalysts for acidic OER but also proposes potential strategies to overcome these limitations,offering a roadmap for future advancements and practical implementation of PEMWE technology.展开更多
The harsh corrosive environment and sluggish oxygen evolution reaction(OER)kinetics at the anode of proton exchange membrane water electrolysis(PEMWE)cells warrant the use of excess Ir,thereby hindering large-scale in...The harsh corrosive environment and sluggish oxygen evolution reaction(OER)kinetics at the anode of proton exchange membrane water electrolysis(PEMWE)cells warrant the use of excess Ir,thereby hindering large-scale industrialization.To mitigate these issues,the present study aimed at fabricating a robust low-Ir-loading electrode via one-pot synthesis for efficient PEMWE.The pre-electrode was first prepared by alloying through the co-electrodeposition of Ir and Co,followed by the fabrication of Ir–Co oxide(Co-incorporated Ir oxide)electrodes via electrochemical dealloying.Two distinct dealloying techniques resulted in a modified valence state of Ir,and the effects of Co incorporation on the activity and stability of the OER catalysts were clarified using density functional theory(DFT)calculations,which offered theoretical insights into the reaction mechanism.While direct experimental validation of the oxygen evolution mechanism remains challenging under the current conditions,DFT-based theoretical modeling provided valuable perspectives on how Co incorporation could influence key steps in oxygen evolution catalysis.The Ir–Co oxide electrode with a selectively modulated valence state showed impressive performance with an overpotential of 258 mV at 10 mA cm^(−2),a low Tafel slope of 29.4 mV dec^(−1),and stability for 100 h at 100 mA cm^(−2)in the OER,in addition to a low overpotential of 16 mV at−10 mA cm^(−2)and high stability for 24 h in the hydrogen evolution reaction.The PEMWE cell equipped with the bifunctional Ir–Co oxide electrode as the anode and cathode exhibited outstanding performance(11.4 A cm^(−2)at 2.3 Vcell)despite having a low noble-metal content of 0.4 mgNM cm^(−2).展开更多
Currently,endeavors to scale up the production of amorphous catalysts are still impeded by intricate synthesis conditions.Here,we have prepared a series of metal-based molybdate via one-step coprecipitation method.Aft...Currently,endeavors to scale up the production of amorphous catalysts are still impeded by intricate synthesis conditions.Here,we have prepared a series of metal-based molybdate via one-step coprecipitation method.After ingredient optimization,amorphous Co_(2)CeFe_(2)-MoO_(4) was identified as exhibiting the highest intrinsic activity among its counterparts.Modulation of electron structure enables Co_(2)CeFe_(2)-MoO_(4) to balance the adsorption behavior towards reactive intermediates.Ultimately,the obtained Co_(2)CeFe_(2)-MoO_(4) molybdate demonstrated a captivating OER performance,showcasing a low overpotential of 230 mV at 10 mA cm^(-2).Moreover,the alkaline electrolyzer employing the Co_(2)CeFe_(2)-MoO_(4) anode exhibited a low cell voltage of 1.50 V for water splitting and underwent an acceptable attenuation of 4.99% after 165 h of continuous operation,demonstrating its favorable catalytic activity and durability.This work provides a facile and eco-friendly synthesis pathway for crafting cost-effective and durable earth-abundant OER electrocatalysts tailored for water splitting to produce clean hydrogen.展开更多
Proton exchange membrane water electrolysis(PEMWE)is a favorable technology for producing highpurity hydrogen under high current density using intermittent renewable energy.The performance of PEMWE is largely determin...Proton exchange membrane water electrolysis(PEMWE)is a favorable technology for producing highpurity hydrogen under high current density using intermittent renewable energy.The performance of PEMWE is largely determined by the oxygen evolution reaction(OER),a sluggish four-electron reaction with a high reaction barrier.Nowadays,iridium(Ir)-based catalysts are the catalysts of choice for OER due to their excellent activity and durability in acidic solution.However,its high price and unsatisfactory electrochemical performance severely restrict the PEMWE’s practical application.In this review,we initiate by introducing the current OER reaction mechanisms,namely adsorbate evolution mechanism and lattice oxygen mechanism,with degradation mechanisms discussed.Optimized strategies in the preparation of advanced Ir-based catalysts are further introduced,with merits and potential problems also discussed.The parameters that determine the performance of PEMWE are then introduced,with unsolved issues and related outlooks summarized in the end.展开更多
Urgent requirements of the renewable energy boost the development of stable and clean hydrogen,which could effectively displace fossil fuels in mitigating climate changes.The efficient interconversion of hydrogen and ...Urgent requirements of the renewable energy boost the development of stable and clean hydrogen,which could effectively displace fossil fuels in mitigating climate changes.The efficient interconversion of hydrogen and electronic is highly based on polymer electrolyte membrane fuel cells(PEMFCs)and water electrolysis(PEMWEs).However,the high cost continues to impede large-scale commercialization of both PEMFC and PEMWE technologies,with the expense primarily attributed to noble catalysts serving as a major bottleneck.The reduction of Pt loading in PEMFCs is essential but limited by the oxygen transport resistance in the cathode catalyst layers(CCLs),while the oxygen transport in anode catalyst layers(ACLs)in PEMWEs also being focused as the Ir/IrO_(x) catalyst reduced.The pore structure and the catalyst-ionomer agglomerates play important roles in the oxygen transport process of both PEMFCs and PEMWEs due to the similarity of membrane electrode assembly(MEA).Herein,the oxygen transport mechanism of PEMFCs in pore structure and ionomer thin films in CCLs is systematically reviewed,while state-of-the-art strategies are presented for enhancing oxygen transport and performance through materials and structural design.The deeply research opens avenues for exploring similar key scientific problems in oxygen transport process of PEMWEs and their further development.展开更多
The oxygen evolution reaction(OER)serves as a fundamental half–reaction in the electrolysis of water for hydrogen production,which is restricted by the sluggish OER reaction kinetics and unable to be practically appl...The oxygen evolution reaction(OER)serves as a fundamental half–reaction in the electrolysis of water for hydrogen production,which is restricted by the sluggish OER reaction kinetics and unable to be practically applied.The traditional lattice oxygen oxidation mechanism(LOM)offers an advantageous route by circumventing the formation of M-OOH^(*)in the adsorption evolution mechanism(AEM),thus enhancing the reaction kinetics of the OER but resulting in possible structural destabilization due to the decreased M–O bond order.Fortunately,the asymmetry of tetrahedral and octahedral sites in transition metal spinel oxides permits the existence of non-bonding oxygen,which could be activated by rational band structure design for direct O-O coupling,where the M–O bond maintains its initial bond order.Here,non-bonding oxygen was introduced into NiFe_(2)O_(4)via annealing in an oxygen-deficient atmosphere.Then,in-situ grown sulfate species on octahedral nickel sites significantly improved the reactivity of the non-bonding oxygen electrons,thereby facilitating the transformation of the redox center from metal to oxygen.LOM based on non-bonding oxygen(LOMNB)was successfully activated within NiFe_(2)O_(4),exhibiting a low overpotential of 206 mV to achieve a current density of 10 mA cm^(-2)and excellent durability of stable operation for over 150 h.Additionally,catalysts featuring varying band structures were synthesized for comparative analysis,and it was found that the reversible redox processes of non-bonding oxygen and the accumulation of non-bonding oxygen species containing 2p holes are critical prerequisites for triggering and sustaining the LOMNB pathway in transition metal spinel oxides.These findings may provide valuable insights for the future development of spinel-oxide-based LOM catalysts.展开更多
Development of robust electrocatalyst for oxygen reduction reaction(ORR)in a seawater electrolyte is the key to realize seawater electrolyte-based zinc-air batteries(SZABs).Herein,constructing a local electric field c...Development of robust electrocatalyst for oxygen reduction reaction(ORR)in a seawater electrolyte is the key to realize seawater electrolyte-based zinc-air batteries(SZABs).Herein,constructing a local electric field coupled with chloride ions(Cl-)fixation strategy in dual single-atom catalysts(DSACs)was proposed,and the resultant catalyst delivered considerable ORR performance in a seawater electrolyte,with a high half-wave potential(E_(1/2))of 0.868 V and a good maximum power density(Pmax)of 182 mW·cm^(−2)in the assembled SZABs,much higher than those of the Pt/C catalyst(E_(1/2):0.846 V;Pmax:150 mW·cm^(−2)).The in-situ characterization and theoretical calculations revealed that the Fe sites have a higher Cl^(−)adsorption affinity than the Co sites,and preferentially adsorbs Cl^(−)in a seawater electrolyte during the ORR process,and thus constructs a low-concentration Cl^(−)local microenvironment through the common-ion exclusion effect,which prevents Cl^(−)adsorption and corrosion in the Co active centers,achieving impressive catalytic stability.In addition,the directional charge movement between Fe and Co atomic pairs establishes a local electric field,optimizing the adsorption energy of Co sites for oxygen-containing intermediates,and further improving the ORR activity.展开更多
Component leaching plays a pivotal role in enhancing the activity and stability of high-entropy-based catalysts by triggering structural reconstruction during the oxygen evolution reaction(OER).In this study,we employ...Component leaching plays a pivotal role in enhancing the activity and stability of high-entropy-based catalysts by triggering structural reconstruction during the oxygen evolution reaction(OER).In this study,we employed soluble V and Mo as sacrificial components alongside a Co stabilizer to synthesize NiFeCoVMo high-entropy catalysts,aiming to simultaneously modulate the reconstruction behavior and optimize catalytic performance.The synergistic interplay between dual-component dissolution and in situ deposition/adsorption mechanisms accelerates structural evolution,ultimately yielding MoO_(4)^(2-)-modified NiFeCo oxyhydroxide(NiFeCoOOH-MoO_(4)^(2-)).Mechanistic studies reveal that the NiFeCo-based system is particularly conducive to the reconstruction process,while adsorbed MoO_(4)^(2-)function as electronic modulators that redistribute charge densities within the reconstructed layers and reduce surface energy.As a result,this reconstructed catalyst demonstrates exceptional OER activity,achieving an overpotential of 172 mV at 10 mA cm^(-2),along with remarkable long-term durability(up to500 h at 50 mA cm^(-2)).This study provides fundamental insights into the origins of the superior electrocatalytic performance of high-entropy materials,paving the way for further exploration and optimization of these advanced catalysts.展开更多
Four-electron oxygen evolving reaction is limited by proton adsorption and desorption,making its reaction kinetics sluggish,which poses a major challenge for catalyst design.Here,we present an unsaturated coordination...Four-electron oxygen evolving reaction is limited by proton adsorption and desorption,making its reaction kinetics sluggish,which poses a major challenge for catalyst design.Here,we present an unsaturated coordination interface by constructing a fast electron transfer channel between Cu_(2)V_(2)O_(7)(CVO)and BiVO4(BVO).X-ray absorption spectroscopy(XAS)and theoretical calculations results confirm that CVO and BVO between interfaces are bonded by the way of unsaturated coordination oxygen(Ouc).The Ouc optimizes the O-O coupled energy barrier at the V active site and promotes the disconnection of O-H bond,which increases the photocurrent intensity of CVO by 6 times.In addition,due to the high electronegativity of the Ouc,the bonding energies of Bi-O and Cu-O at the interface are enhanced,resulting in the long-term stability of the photoanode during the water splitting.Finally,by integrating the working electrode with a polysilicon solar cell,we assembled a device that demonstrated exceptional catalytic performance,achieving a hydrogen production rate of 100.6μmol·cm^(-2),and maintaining a hydrogen-to-oxygen volume ratio of 2:1 after continuous operation for 4 h.This discovery aids in a deeper understanding of photoanode design and offers further insights for industrial applications.展开更多
Perovskite oxides(ABO_(3))are thought to be promising electrocatalysts for oxygen evolution reaction(OER),but their specific surface area(SSA)is too low(usually<10 m^(2) g^(−1)).Developing advanced ABO_(3) electroc...Perovskite oxides(ABO_(3))are thought to be promising electrocatalysts for oxygen evolution reaction(OER),but their specific surface area(SSA)is too low(usually<10 m^(2) g^(−1)).Developing advanced ABO_(3) electrocatalysts with high SSA and optimized structure is of great significance but remains a tremendous challenge.Herein,we propose a general strategy for fabrication of mesoporous perovskite oxide nanosheets(MPONs)with controllable atomic doping via self-sacrificial template-induced nanostructure modulation.A variety of MPONs including LaFeO_(3),A-site-doped LaFeO_(3)(A-LaFeO_(3),where A is Pr,Nd,Sm,Eu,or Gd)and B-site-doped LaFeO_(3)(B-LaFeO_(3),where B is Mn,Co,Ni,Cu,or Zn)have been achieved.Interestingly,it is discovered that the catalytic activities of A-LaFeO_(3) MPONs as OER catalysts are overall higher than those of B-LaFeO_(3) ones.Especially,the screened Eu-LaFeO_(3) MPONs only require a low overpotential of 267 mV at 10 mA cm^(−2),outperforming most reported perovskite oxides.The superior catalytic activity of Eu-LaFeO_(3) MPONs is attributed to their favorable porous structure,which increases the density of active sites,and enhanced lattice oxygen participation,which improves the intrinsic activity.This study provides guidance for the design and controlled synthesis of advanced rare-earth-doped MPONs with ultrahigh SSA for enhanced electrocatalysis.展开更多
The electrolysis of alkaline seawater is critical for sustainable hydrogen production but is hindered by the sluggish oxygen evolution reaction in saline environments.Advanced electrocatalysts with tailored structures...The electrolysis of alkaline seawater is critical for sustainable hydrogen production but is hindered by the sluggish oxygen evolution reaction in saline environments.Advanced electrocatalysts with tailored structures and electronic properties are essential,and phase engineering provides a transformative approach by modulating crystallographic symmetry and electronic configurations.Two-dimensional(2D)LaMnO_(3) perovskites show promise due to their exposed active sites and tunable electronic properties.However,the conventional stable rhombohedral phase limits oxygen diffusion despite good electron transport.Unconventional metastable phases with superior symmetry enhance lattice oxygen activity in saline environments but are challenging to synthesize.Herein,we propose a microwave shock method incorporating Co atoms to rapidly produce 2D LaMnO_(3) in rhombohedral,hexagonal,and metastable cubic phases.This strategy circumvents the limitations of high-temperature synthesis,preserving the 2D morphology while enabling the formation of metastable cubic phases.The metastable cubic phase exhibits superior OER activity and stability even in alkaline seawater due to optimal symmetry,interlayer spacing,and Mn-O covalency.X-ray absorption spectroscopy and theoretical calculations further highlight its balanced oxygen adsorption and desorption.This work underscores the role of metastable phase engineering in advancing seawater electrolysis and establishes a scalable route for designing high-performance 2D electrocatalysts.展开更多
It is necessary to adopt a specific strategy to construct an efficient and low-cost transition metal-based composite to replace the precious metal-based electrocatalyst for OER catalytic processes.In this work,a beade...It is necessary to adopt a specific strategy to construct an efficient and low-cost transition metal-based composite to replace the precious metal-based electrocatalyst for OER catalytic processes.In this work,a beaded stream-like N and P-codoped carbon-coated Fe_(3)O_(4)nanocomposite(N,P-Fe_(3)O_(4)@C)is derived from MIL-88A by two-step annealing.The unique 3D nanostructure and amorphous N-doped carbon layer enlarge the number of active sites,and P doping changes the pathway from AEM to LOM.The synergistic effect of these factors results in N,P-Fe_(3)O_(4)@C presenting excellent OER catalytic activity with an overpotential of 201 mV(η10),a Tafel slope of 57.1 mV/dec and stable operation for 100 h(the current density is 10 mA/cm^(2)).Density functional theory calculations and electrochemical tests reveal that the P doping enhances the overlap of Fe 3d orbital bands and O 2p orbitals,and thus significantly increases the metaloxygen covalency,triggering the pathway transition from AEM to LOM.This work provides a new way to construct more efficient transition metal-based composite carbon materials.展开更多
A hydrogen spillover-bridged water dissociation/hydrogen formation could concurrently promote Volmer/Tafel process and improve the efficiency of hydrogen evolution reaction(HER)under alkaline conditions.However,it is ...A hydrogen spillover-bridged water dissociation/hydrogen formation could concurrently promote Volmer/Tafel process and improve the efficiency of hydrogen evolution reaction(HER)under alkaline conditions.However,it is still challenging to promote occurrence of hydrogen spillover for the large interfacial transport barriers of H_(2)O and hydrogen on active sites.Herein,the strategy of energy barrier gradient to induce hydrogen spillover was proposed by constructing Ru nanoclusters coupled with single atom onto oxygen vacancy cerium dioxide(Ru/CeO_(2)-Ov-2).Density functional theory(DFT)calculations uncover that the adsorption/desorption of H2O occurs at the Ru clusters sites and then the dissociated H*spontaneously overflows from Ru clusters with high binding energy into the adjacent Ru single atom sites with low binding energy,which facilitate the hydrogen formation.Consequently,the synthesized Ru/CeO_(2)-Ov-2 exhibits a small overpotential of 41 mV at 10 mA cm^(-2)and good stability at 500 mA cm^(-2)for 100 h in alkaline seawater,which could be ascribed to the rapid hydrogen spillover and strong coupling interaction between Ru and CeO_(2)-O_(v).This work provides a novel insight that synthesizing cooperative sites with energy barrier gradient helps to promote hydrogen spillover and accelerate the Volmer/Tafel process of HER.展开更多
The typical wastewater treatment is focused on the photocatalytic efficiency in the degradation of organic pollutants,with little attention to the involved selectivity which may correlate with toxicant residues.Herein...The typical wastewater treatment is focused on the photocatalytic efficiency in the degradation of organic pollutants,with little attention to the involved selectivity which may correlate with toxicant residues.Herein,an electron localization strategy for specific O2 adsorption/activation enabled by photothermal/pyroelectric effect and in situ constructed active centers of single-atom Co and oxygen vacancy(Co-O_(V))on the Co/BiOCl-O_(V)photocatalyst was developed for photocatalytic degradation of glyphosate(GLP)wastewater of high performance/selectivity.Under full-spectrum-light irradiation,a high GLP degradation rate of 99.8%with over 90%C-P bond-breaking selectivity was achieved within 2 h,while effectively circumventing toxicant residues such as aminomethylphosphonic acid(AMPA).X-ray absorption spectroscopy and relevant characterizations expounded the tailored anchoring of Co single atoms onto the BiOCl-O_(V)carrier and photothermal/pyroelectric effect.The oriented formation of more•O_(2)^(−)on Co/BiOCl-O_(V)could be achieved with the Co-O_(V)coupled center that had excellent O2 adsorption/activation capacity,as demonstrated by quantum calculations.The formed unique Co-O_(V)active sites could largely decrease the C-P bond-breaking energy barrier,thus greatly improving the selectivity toward the initial C-P bond scission and the activity in subsequent conversion steps in the directional photocatalytic degradation of GLP.The electron localization strategy by in situ constructing the coupled active centers provides an efficient scheme and new insights for the low-toxic photodegradation of organic pollutants containing C-X bonds.展开更多
Seawater splitting provides a sustainable approach for large-scale hydrogen production without straining freshwater resources.However,the challenge lies in achieving high catalytic activity and stability due to electr...Seawater splitting provides a sustainable approach for large-scale hydrogen production without straining freshwater resources.However,the challenge lies in achieving high catalytic activity and stability due to electrocatalyst deactivation from structural degradation,poor corrosion resistance,and surface instability in both alkaline and seawater electrolysis.To address this,we propose a novel strategy combining Fe-doping with dual-phase lattice strain engineering in nickel-molybdenum transition metal nitrides(TMNs).The Fe-doped Ni_(3)Mo_(3)N/Mo_(2)N electrocatalyst exhibits compressive lattice strains of-4.52%and-2.91%in the Ni_(3)Mo_(3)N and Mo_(2)N phases,respectively,enhancing its structural integrity and electronic properties.Consequently,Fe-Ni_(3)Mo_(3)N/Mo_(2)N achieves low overpotentials of 167 and 371 mV at current densities of 10 and 500 mA cm^(-2),respectively,in 1 M alkaline seawater,with exceptional stability over 100 h at 100 and 500 mA cm^(-2).Theoretical calculations reveal that these compressive strains optimize the adsorption of OER intermediates and improve catalytic kinetics.This work demonstrates the promise of dual-phase lattice strain engineering in TMNs for efficient,durable,and scalable electrocatalysts in seawater electrolysis,a strategy that has yet to be fully explored for OER.展开更多
基金supported by the Korea Institute for Advancement of Technology (KIAT)the Ministry of Trade,Industry&Energy (MOTIE) of the Republic of Korea (No. P0022130)by the Institute of Information&Communications Technology Planning&Evaluation(IITP)-Innovative Human Resource Development for Local Intellectualization program grant funded by the Korea government (MSIT)(IITP-2025-RS-2023-00259678)
文摘To realize the practical application of anion exchange membrane water electrolysis(AEMWE),it is essential to develop highly active,durable,and cost-effective electrocatalyst for oxygen evolution reaction(OER).Herein,we report a hollow-structured Ni_(x)Co_(1−x)O/Ni_(3)S_(2)/Co_(9)S_(8)heterostructure synthesized via sequential template-assisted growth,thermal oxidation,and controlled sulfidation process.The abundant bimetallic heterointerfaces not only provide additional active sites but also promote electronic modulation via charge redistribution.Additionally,the porous and hollow architecture enhances active surface area and mass transfer ability,thereby increasing the number of accessible active sites for alkaline OER.As a result,the prepared electrocatalyst achieves low overpotential of 310 mV at 10 mA cm^(−2)and small Tafel slope of 55.94 mV dec^(−1),demonstrating the exceptional electrocatalytic performance for alkaline OER.When integrated as the anode in an AEMWE cell,it delivers outstanding performance with only 1.657 V at 1.0 A cm^(−2)and reaches high current density of 5.0 A cm^(−2)at 1.989 V,surpassing those of commercial RuO_(2).The cell also shows excellent long-term durability over 100 h with minimal degradation.This study highlights the strong potential of rationally engineered oxide/sulfide heterostructures for next-generation alkaline water electrolysis.
基金funded by the Innovative Research Group Project of the National Natural Science Foundation of China(52121004)the Research Development Fund(No.RDF-21-02-060)by Xi’an Jiaotong-Liverpool University+1 种基金support received from the Suzhou Industrial Park High Quality Innovation Platform of Functional Molecular Materials and Devices(YZCXPT2023105)the XJTLU Advanced Materials Research Center(AMRC).
文摘Seawater zinc-air batteries are promising energy storage devices due to their high energy density and utilization of seawater electrolytes.However,their efficiency is hindered by the sluggish oxygen reduction reaction(ORR)and chlorideinduced degradation over conventional catalysts.In this study,we proposed a universal synthetic strategy to construct heteroatom axially coordinated Fe–N_(4) single-atom seawater catalyst materials(Cl–Fe–N_(4) and S–Fe–N_(4)).X-ray absorption spectroscopy confirmed their five-coordinated square pyramidal structure.Systematic evaluation of catalytic activities revealed that compared with S–Fe–N_(4),Cl–Fe–N_(4) exhibits smaller electrochemical active surface area and specific surface area,yet demonstrates higher limiting current density(5.8 mA cm^(−2)).The assembled zinc-air batteries using Cl–Fe–N_(4) showed superior power density(187.7 mW cm^(−2) at 245.1 mA cm^(−2)),indicating that Cl axial coordination more effectively enhances the intrinsic ORR activity.Moreover,Cl–Fe–N_(4) demonstrates stronger Cl−poisoning resistance in seawater environments.Chronoamperometry tests and zinc-air battery cycling performance evaluations confirmed its enhanced stability.Density functional theory calculations revealed that the introduction of heteroatoms in the axial direction regulates the electron center of Fe single atom,leading to more active reaction intermediates and increased electron density of Fe single sites,thereby enhancing the reduction in adsorbed intermediates and hence the overall ORR catalytic activity.
基金supported by the National Natural Science Foundation of China(No.41772240)the Key Research and Development program of Jiangsu Province(No.BE2021637).
文摘Ball milling is an environmentally friendly technology for the remediation of petroleumcontaminated soil(PCS),but the cleanup of organic pollutants requires a long time,and the post-remediation soil needs an economically viable disposal/reuse strategy due to its vast volume.The present paper develops a ball milling process under oxygen atmosphere to enhance PCS remediation and reuse the obtained carbonized soil(BCS-O)as wastewater treatment materials.The total petroleum hydrocarbon removal rates by ball milling under vacuum,air,and oxygen atmospheres are 39.83%,55.21%,and 93.84%,respectively.The Langmuir and pseudo second-order models satisfactorily describe the adsorption capacity and behavior of BCS-O for transition metals.The Cu^(2+),Ni^(2+),and Mn^(2+)adsorbed onto BCS-O were mainly bound to metal carbonates and metal oxides.Furthermore,BCS-O can effectively activate persulfate(PDS)oxidation to degrade aniline,while BCS-O loaded with transition metal(BCS-O-Me)shows better activation efficiency and reusability.BCS-O and BCS-O-Me activated PDS oxidation systems are dominated by^(1)O_(2)oxidation and electron transfer.The main active sites are oxygen-containing functional groups,vacancy defects,and graphitized carbon.The oxygen-containing functional groups and vacancy defects primarily activate PDS to generate^(1)O_(2)and attack aniline.Graphitized carbon promotes aniline degradation by accelerating electron transfer.The paper develops an innovative strategy to simultaneously realize efficient remediation of PCS and sequential reuse of the postremediation soil.
基金supported by the Natural Science Foundation of Shanghai(No.23ZR1401300)the National Natural Science Foundation of China(No.52170068).
文摘Singlet oxygen(^(1)O_(2)),as an electrophilic oxidant,is essential for the selective water decontamination of pollutants from water.Herein,we showcase a high-performing electrocatalytic filtration system composed of carbon nanotubes functionalized with CoFe alloy nanoparticles(CoFeCNT)to selectively facilitate the electrochemical activation of O_(2)to^(1)O_(2).Benefiting from the prominently featured bimetal active sites of CoFeCNT,nearly complete production of^(1)O_(2)is achieved by the electrocatalytic activation of O_(2).Additionally,the proposed system exhibits a consistent pollutant removal efficiency>90%in a flow-through reactor over 48 h of continuous operation without a noticeable decline in performance,highlighting the dependable stability of the system for practical applications.The flow-through configuration demonstrates a striking 8-fold enhancement in tetracycline oxidation compared to a conventional batch reactor.This work provides a molecular level understanding of the oxygen reduction reaction,showing promising potential for the selective removal of emerging organic contaminants from water.
基金supported by the National Natural Science Foundation of China(22479040,22279138)the Natural Science Foundation of Tianjin(24JCQNJC00360)+3 种基金Government Guide the Development of Local Science and Technology Special Funds(246Z3707G)Young Scientific and Technological Talents(Level Three)in Tianjin(QN20230343)Hebei Yanzhao Golden Platform Talent Gathering Plan Backbone Talent Project(HJYB202501)the Natural Science Foundation of Liaoning Province(2022-MS023)。
文摘Photocatalytic H_(2)O_(2) production still confronts the challenges of its dependence on organic electron donors or high-purity O_(2),which restricts the practical application,and there are few studies on the photo synthesis of H_(2)O_(2) via both oxygen reduction reaction(ORR)and water oxidation reaction(WOR).In this paper,bismuth yttrium oxyhalides Bi_(2)YO_(4)X(X=Cl,Br,or I)are demonstrated to afford sufficient driving forces to produce H_(2)O_(2) in the absence of sacrificial reagents.After modification with Pt and IrO_(2) as cocatalysts,which can selectively promote both ORR and WOR reactions on Bi_(2)YO_(4)Cl,the IrO_(2)-Pt/Bi_(2)YO_(4)Cl sample yields H_(2)O_(2) production activity of 647μmol L^(-1)h^(-1)with negligible decay in the long-term reaction using only H_(2)O and an air atmosphere as the electron donors and O_(2) source.Detailed characterizations reveal that the ORR reaction obeys a two-electron pathway.We present the first example of oxyhalides(Bi_(2)YO_(4)X)capable of efficient photocata lytic H_2O_(2) generation with record-breaking activity.
基金financially supported by the National Natural Science Foundation of China(22172063)the Young Taishan Scholars Program(tsqn201812080)+2 种基金the China Scholarship Council(CSC)for scholarship support(202008130132)the Independent Cultivation Program of Innovation Team of Ji’nan City(2021GXRC052)funding from CERCA Programme/Generalitat de Catalunya。
文摘Proton exchange membrane water electrolyzers(PEMWEs)are pivotal for efficient hydrogen production due to their high energy efficiency and ability to operate at high current densities,making them ideally suited for integration with renewable energy sources.Cobalt(Co)-based nanomaterials,characterized by diverse oxidation states,tunable electronic spin states,and hybrid orbitals,have emerged as promising non-noble metal alternatives to platinum group catalysts for accelerating the anodic oxygen evolution reaction(OER).Based on their inherent properties,this review provides a comprehensive overview of the latest developments in Co-based nanomaterials for acidic OER.The review begins by introducing the operational principles of PEMWEs,the underlying catalytic mechanisms,and the critical design considerations for OER catalysts.It then explores strategies to enhance the activity and stability of Co-based catalysts for acidic OER in PEMWEs,including the incorporation of corrosion-resistant metals or dispersion on acid-resistant supports to increase active surface area and stability;utilization of geometric structural engineering to improve structural integrity and active site efficiency;the optimization of reaction mechanisms to fine-tune catalytic pathways for enhanced stability and performance.The performance degradation mechanisms and metal leaching analysis for Co-based catalysts in PEMWE are also clarified.Finally,this review not only outlines the key challenges associated with Co-based catalysts for acidic OER but also proposes potential strategies to overcome these limitations,offering a roadmap for future advancements and practical implementation of PEMWE technology.
基金supported by the National Research Foundation of Korea(NRF)grant funded by the Korean government(MSIT)(RS-2024-00340074,RS-2024-00409901,2022M3I3A1081901,and RS-2024-00413272)。
文摘The harsh corrosive environment and sluggish oxygen evolution reaction(OER)kinetics at the anode of proton exchange membrane water electrolysis(PEMWE)cells warrant the use of excess Ir,thereby hindering large-scale industrialization.To mitigate these issues,the present study aimed at fabricating a robust low-Ir-loading electrode via one-pot synthesis for efficient PEMWE.The pre-electrode was first prepared by alloying through the co-electrodeposition of Ir and Co,followed by the fabrication of Ir–Co oxide(Co-incorporated Ir oxide)electrodes via electrochemical dealloying.Two distinct dealloying techniques resulted in a modified valence state of Ir,and the effects of Co incorporation on the activity and stability of the OER catalysts were clarified using density functional theory(DFT)calculations,which offered theoretical insights into the reaction mechanism.While direct experimental validation of the oxygen evolution mechanism remains challenging under the current conditions,DFT-based theoretical modeling provided valuable perspectives on how Co incorporation could influence key steps in oxygen evolution catalysis.The Ir–Co oxide electrode with a selectively modulated valence state showed impressive performance with an overpotential of 258 mV at 10 mA cm^(−2),a low Tafel slope of 29.4 mV dec^(−1),and stability for 100 h at 100 mA cm^(−2)in the OER,in addition to a low overpotential of 16 mV at−10 mA cm^(−2)and high stability for 24 h in the hydrogen evolution reaction.The PEMWE cell equipped with the bifunctional Ir–Co oxide electrode as the anode and cathode exhibited outstanding performance(11.4 A cm^(−2)at 2.3 Vcell)despite having a low noble-metal content of 0.4 mgNM cm^(−2).
基金supported by the National Natural Science Foundation of China (No. 21872153)。
文摘Currently,endeavors to scale up the production of amorphous catalysts are still impeded by intricate synthesis conditions.Here,we have prepared a series of metal-based molybdate via one-step coprecipitation method.After ingredient optimization,amorphous Co_(2)CeFe_(2)-MoO_(4) was identified as exhibiting the highest intrinsic activity among its counterparts.Modulation of electron structure enables Co_(2)CeFe_(2)-MoO_(4) to balance the adsorption behavior towards reactive intermediates.Ultimately,the obtained Co_(2)CeFe_(2)-MoO_(4) molybdate demonstrated a captivating OER performance,showcasing a low overpotential of 230 mV at 10 mA cm^(-2).Moreover,the alkaline electrolyzer employing the Co_(2)CeFe_(2)-MoO_(4) anode exhibited a low cell voltage of 1.50 V for water splitting and underwent an acceptable attenuation of 4.99% after 165 h of continuous operation,demonstrating its favorable catalytic activity and durability.This work provides a facile and eco-friendly synthesis pathway for crafting cost-effective and durable earth-abundant OER electrocatalysts tailored for water splitting to produce clean hydrogen.
基金supported by the National Key Research and Development Program of China(No.2022YFB4004100)National Natural Science Foundation of China(Nos.U22A20396,22209168)+1 种基金Natural Science Foundation of Anhui Province(No.2208085UD04)Liaoning Binhai Laboratory(No.LBLF-2023-04),and Shandong Energy Institute(No.SEI U202307).
文摘Proton exchange membrane water electrolysis(PEMWE)is a favorable technology for producing highpurity hydrogen under high current density using intermittent renewable energy.The performance of PEMWE is largely determined by the oxygen evolution reaction(OER),a sluggish four-electron reaction with a high reaction barrier.Nowadays,iridium(Ir)-based catalysts are the catalysts of choice for OER due to their excellent activity and durability in acidic solution.However,its high price and unsatisfactory electrochemical performance severely restrict the PEMWE’s practical application.In this review,we initiate by introducing the current OER reaction mechanisms,namely adsorbate evolution mechanism and lattice oxygen mechanism,with degradation mechanisms discussed.Optimized strategies in the preparation of advanced Ir-based catalysts are further introduced,with merits and potential problems also discussed.The parameters that determine the performance of PEMWE are then introduced,with unsolved issues and related outlooks summarized in the end.
基金supported by the National Key Research and Development Program of China(No.2021YFB4001305).
文摘Urgent requirements of the renewable energy boost the development of stable and clean hydrogen,which could effectively displace fossil fuels in mitigating climate changes.The efficient interconversion of hydrogen and electronic is highly based on polymer electrolyte membrane fuel cells(PEMFCs)and water electrolysis(PEMWEs).However,the high cost continues to impede large-scale commercialization of both PEMFC and PEMWE technologies,with the expense primarily attributed to noble catalysts serving as a major bottleneck.The reduction of Pt loading in PEMFCs is essential but limited by the oxygen transport resistance in the cathode catalyst layers(CCLs),while the oxygen transport in anode catalyst layers(ACLs)in PEMWEs also being focused as the Ir/IrO_(x) catalyst reduced.The pore structure and the catalyst-ionomer agglomerates play important roles in the oxygen transport process of both PEMFCs and PEMWEs due to the similarity of membrane electrode assembly(MEA).Herein,the oxygen transport mechanism of PEMFCs in pore structure and ionomer thin films in CCLs is systematically reviewed,while state-of-the-art strategies are presented for enhancing oxygen transport and performance through materials and structural design.The deeply research opens avenues for exploring similar key scientific problems in oxygen transport process of PEMWEs and their further development.
文摘The oxygen evolution reaction(OER)serves as a fundamental half–reaction in the electrolysis of water for hydrogen production,which is restricted by the sluggish OER reaction kinetics and unable to be practically applied.The traditional lattice oxygen oxidation mechanism(LOM)offers an advantageous route by circumventing the formation of M-OOH^(*)in the adsorption evolution mechanism(AEM),thus enhancing the reaction kinetics of the OER but resulting in possible structural destabilization due to the decreased M–O bond order.Fortunately,the asymmetry of tetrahedral and octahedral sites in transition metal spinel oxides permits the existence of non-bonding oxygen,which could be activated by rational band structure design for direct O-O coupling,where the M–O bond maintains its initial bond order.Here,non-bonding oxygen was introduced into NiFe_(2)O_(4)via annealing in an oxygen-deficient atmosphere.Then,in-situ grown sulfate species on octahedral nickel sites significantly improved the reactivity of the non-bonding oxygen electrons,thereby facilitating the transformation of the redox center from metal to oxygen.LOM based on non-bonding oxygen(LOMNB)was successfully activated within NiFe_(2)O_(4),exhibiting a low overpotential of 206 mV to achieve a current density of 10 mA cm^(-2)and excellent durability of stable operation for over 150 h.Additionally,catalysts featuring varying band structures were synthesized for comparative analysis,and it was found that the reversible redox processes of non-bonding oxygen and the accumulation of non-bonding oxygen species containing 2p holes are critical prerequisites for triggering and sustaining the LOMNB pathway in transition metal spinel oxides.These findings may provide valuable insights for the future development of spinel-oxide-based LOM catalysts.
基金supported by the National Natural Science Foundation of China(52164028,52274297)the Start-up Research Foundation of Hainan University(KYQD(ZR)20008,KYQD(ZR)21125,KYQD(ZR)23169))+1 种基金Collaborative Innovation Center of Marine Science and Technology of Hainan University(XTCX2022HYC14)Innovative Research Project for Postgraduate Students in Hainan Province(Qhyb2024-95).
文摘Development of robust electrocatalyst for oxygen reduction reaction(ORR)in a seawater electrolyte is the key to realize seawater electrolyte-based zinc-air batteries(SZABs).Herein,constructing a local electric field coupled with chloride ions(Cl-)fixation strategy in dual single-atom catalysts(DSACs)was proposed,and the resultant catalyst delivered considerable ORR performance in a seawater electrolyte,with a high half-wave potential(E_(1/2))of 0.868 V and a good maximum power density(Pmax)of 182 mW·cm^(−2)in the assembled SZABs,much higher than those of the Pt/C catalyst(E_(1/2):0.846 V;Pmax:150 mW·cm^(−2)).The in-situ characterization and theoretical calculations revealed that the Fe sites have a higher Cl^(−)adsorption affinity than the Co sites,and preferentially adsorbs Cl^(−)in a seawater electrolyte during the ORR process,and thus constructs a low-concentration Cl^(−)local microenvironment through the common-ion exclusion effect,which prevents Cl^(−)adsorption and corrosion in the Co active centers,achieving impressive catalytic stability.In addition,the directional charge movement between Fe and Co atomic pairs establishes a local electric field,optimizing the adsorption energy of Co sites for oxygen-containing intermediates,and further improving the ORR activity.
基金supported by Zhejiang Provincial Natural Science Foundation of China(LD25B060003,LD25E020003)National Natural Science Foundation of China(22379020,52372235,52222103,12364021)+8 种基金Key Scientific Research Project of Hangzhou(2024SZD1B12)Science and Technology Project of Huzhou(2024GZ02)State Key Laboratory of New Textile Materials and Advanced Processing Technologies(FZ2024009)Fund Projects of Guizhou Provincial Department of Science and Technology/Department of Education(QJJ[2022]318 and QKHJC[2024]youth336/337)Zunyi R&D Base of New Optoelectronic Materials and Electronic DevicesNational Science Foundation of Sichuan Province of China(24NSFSC5819)China Postdoctoral Science Foundation Funded Project(W030241021007)Key Laboratory of Engineering Dielectrics and Its Application(Harbin University of Science and Technology)Ministry of Education(KFM202303)。
文摘Component leaching plays a pivotal role in enhancing the activity and stability of high-entropy-based catalysts by triggering structural reconstruction during the oxygen evolution reaction(OER).In this study,we employed soluble V and Mo as sacrificial components alongside a Co stabilizer to synthesize NiFeCoVMo high-entropy catalysts,aiming to simultaneously modulate the reconstruction behavior and optimize catalytic performance.The synergistic interplay between dual-component dissolution and in situ deposition/adsorption mechanisms accelerates structural evolution,ultimately yielding MoO_(4)^(2-)-modified NiFeCo oxyhydroxide(NiFeCoOOH-MoO_(4)^(2-)).Mechanistic studies reveal that the NiFeCo-based system is particularly conducive to the reconstruction process,while adsorbed MoO_(4)^(2-)function as electronic modulators that redistribute charge densities within the reconstructed layers and reduce surface energy.As a result,this reconstructed catalyst demonstrates exceptional OER activity,achieving an overpotential of 172 mV at 10 mA cm^(-2),along with remarkable long-term durability(up to500 h at 50 mA cm^(-2)).This study provides fundamental insights into the origins of the superior electrocatalytic performance of high-entropy materials,paving the way for further exploration and optimization of these advanced catalysts.
基金supported by the Natural Science Foundation of China(Nos.22278094 and 22379033)Guangdong Graduate Education Innovation Program(No.2023JGXM_102)+2 种基金the Basic and Applied Basic Research Program of Guangzhou(No.SL2024A03J00499)the University Innovation Team Scientific Research Project of Guangzhou(No.202235246)Hainan Province Graduate Innovation Research Project(No.Qhyb2023-143).
文摘Four-electron oxygen evolving reaction is limited by proton adsorption and desorption,making its reaction kinetics sluggish,which poses a major challenge for catalyst design.Here,we present an unsaturated coordination interface by constructing a fast electron transfer channel between Cu_(2)V_(2)O_(7)(CVO)and BiVO4(BVO).X-ray absorption spectroscopy(XAS)and theoretical calculations results confirm that CVO and BVO between interfaces are bonded by the way of unsaturated coordination oxygen(Ouc).The Ouc optimizes the O-O coupled energy barrier at the V active site and promotes the disconnection of O-H bond,which increases the photocurrent intensity of CVO by 6 times.In addition,due to the high electronegativity of the Ouc,the bonding energies of Bi-O and Cu-O at the interface are enhanced,resulting in the long-term stability of the photoanode during the water splitting.Finally,by integrating the working electrode with a polysilicon solar cell,we assembled a device that demonstrated exceptional catalytic performance,achieving a hydrogen production rate of 100.6μmol·cm^(-2),and maintaining a hydrogen-to-oxygen volume ratio of 2:1 after continuous operation for 4 h.This discovery aids in a deeper understanding of photoanode design and offers further insights for industrial applications.
基金financially supported by the National Key Research and Development Program(Nos.2022YFB2502104 and 2022YFA1602700)the Key Research and Development Program of Jiangsu Provincial Department of Science and Technology of China(No.BE2022332)+4 种基金the Jiangsu Carbon Peak Carbon Neutralization Science and Technology Innovation Special Fund(No.BE2022605)the National Natural Science Foundation of China(Nos.22109073,22379071)the DECRA program of Australian Research Council(No.DE230100357)the JSPS KAKENHI(No.JP23K13703)the Center for Computational Materials Science,Institute for Materials Research,Tohoku University for the use of MASAMUNE-IMR(202312-SCKXX-0203)。
文摘Perovskite oxides(ABO_(3))are thought to be promising electrocatalysts for oxygen evolution reaction(OER),but their specific surface area(SSA)is too low(usually<10 m^(2) g^(−1)).Developing advanced ABO_(3) electrocatalysts with high SSA and optimized structure is of great significance but remains a tremendous challenge.Herein,we propose a general strategy for fabrication of mesoporous perovskite oxide nanosheets(MPONs)with controllable atomic doping via self-sacrificial template-induced nanostructure modulation.A variety of MPONs including LaFeO_(3),A-site-doped LaFeO_(3)(A-LaFeO_(3),where A is Pr,Nd,Sm,Eu,or Gd)and B-site-doped LaFeO_(3)(B-LaFeO_(3),where B is Mn,Co,Ni,Cu,or Zn)have been achieved.Interestingly,it is discovered that the catalytic activities of A-LaFeO_(3) MPONs as OER catalysts are overall higher than those of B-LaFeO_(3) ones.Especially,the screened Eu-LaFeO_(3) MPONs only require a low overpotential of 267 mV at 10 mA cm^(−2),outperforming most reported perovskite oxides.The superior catalytic activity of Eu-LaFeO_(3) MPONs is attributed to their favorable porous structure,which increases the density of active sites,and enhanced lattice oxygen participation,which improves the intrinsic activity.This study provides guidance for the design and controlled synthesis of advanced rare-earth-doped MPONs with ultrahigh SSA for enhanced electrocatalysis.
文摘The electrolysis of alkaline seawater is critical for sustainable hydrogen production but is hindered by the sluggish oxygen evolution reaction in saline environments.Advanced electrocatalysts with tailored structures and electronic properties are essential,and phase engineering provides a transformative approach by modulating crystallographic symmetry and electronic configurations.Two-dimensional(2D)LaMnO_(3) perovskites show promise due to their exposed active sites and tunable electronic properties.However,the conventional stable rhombohedral phase limits oxygen diffusion despite good electron transport.Unconventional metastable phases with superior symmetry enhance lattice oxygen activity in saline environments but are challenging to synthesize.Herein,we propose a microwave shock method incorporating Co atoms to rapidly produce 2D LaMnO_(3) in rhombohedral,hexagonal,and metastable cubic phases.This strategy circumvents the limitations of high-temperature synthesis,preserving the 2D morphology while enabling the formation of metastable cubic phases.The metastable cubic phase exhibits superior OER activity and stability even in alkaline seawater due to optimal symmetry,interlayer spacing,and Mn-O covalency.X-ray absorption spectroscopy and theoretical calculations further highlight its balanced oxygen adsorption and desorption.This work underscores the role of metastable phase engineering in advancing seawater electrolysis and establishes a scalable route for designing high-performance 2D electrocatalysts.
基金the National Nature Science Foundation of China(No.22304021)National Key Research and Development Project(No.2022YFA1505300)Sichuan Department of Science and Technology Program of China(No.2022YFG0312)for financial support。
文摘It is necessary to adopt a specific strategy to construct an efficient and low-cost transition metal-based composite to replace the precious metal-based electrocatalyst for OER catalytic processes.In this work,a beaded stream-like N and P-codoped carbon-coated Fe_(3)O_(4)nanocomposite(N,P-Fe_(3)O_(4)@C)is derived from MIL-88A by two-step annealing.The unique 3D nanostructure and amorphous N-doped carbon layer enlarge the number of active sites,and P doping changes the pathway from AEM to LOM.The synergistic effect of these factors results in N,P-Fe_(3)O_(4)@C presenting excellent OER catalytic activity with an overpotential of 201 mV(η10),a Tafel slope of 57.1 mV/dec and stable operation for 100 h(the current density is 10 mA/cm^(2)).Density functional theory calculations and electrochemical tests reveal that the P doping enhances the overlap of Fe 3d orbital bands and O 2p orbitals,and thus significantly increases the metaloxygen covalency,triggering the pathway transition from AEM to LOM.This work provides a new way to construct more efficient transition metal-based composite carbon materials.
基金funding support from the National Natural Science Foundation of China(5237122722002068+8 种基金52272222,and 52072197)the Taishan Scholar Young Talent Program(tsqn201909114)the Shandong Province“Double-Hundred Talent Plan”(WST2020003)the Youth Innovation and Technology Foundation of Shandong Higher Education Institutions,China(2019KJC004)the Outstanding Youth Foundation of Shandong Province,China(ZR2019JQ14)the Major Basic Research Program of Natural Science Foundation of Shandong Province under Grant No.ZR2020ZD09the Major Scientific and Technological Innovation Project(2019JZZY020405)the University Youth Innovation Team of Shandong Province(202201010318)the Youth Innovation Team Development Program of Shandong Higher Education Institutions(2022KJ155)。
文摘A hydrogen spillover-bridged water dissociation/hydrogen formation could concurrently promote Volmer/Tafel process and improve the efficiency of hydrogen evolution reaction(HER)under alkaline conditions.However,it is still challenging to promote occurrence of hydrogen spillover for the large interfacial transport barriers of H_(2)O and hydrogen on active sites.Herein,the strategy of energy barrier gradient to induce hydrogen spillover was proposed by constructing Ru nanoclusters coupled with single atom onto oxygen vacancy cerium dioxide(Ru/CeO_(2)-Ov-2).Density functional theory(DFT)calculations uncover that the adsorption/desorption of H2O occurs at the Ru clusters sites and then the dissociated H*spontaneously overflows from Ru clusters with high binding energy into the adjacent Ru single atom sites with low binding energy,which facilitate the hydrogen formation.Consequently,the synthesized Ru/CeO_(2)-Ov-2 exhibits a small overpotential of 41 mV at 10 mA cm^(-2)and good stability at 500 mA cm^(-2)for 100 h in alkaline seawater,which could be ascribed to the rapid hydrogen spillover and strong coupling interaction between Ru and CeO_(2)-O_(v).This work provides a novel insight that synthesizing cooperative sites with energy barrier gradient helps to promote hydrogen spillover and accelerate the Volmer/Tafel process of HER.
基金supported by the National Natural Science Foundation of China(No.22368014)Guizhou Provincial S&T Project(Nos.GCC[2023]011,ZK[2022]011)Guizhou Provincial Higher Education Institution Program(No.Qianjiaoji[2023]082).
文摘The typical wastewater treatment is focused on the photocatalytic efficiency in the degradation of organic pollutants,with little attention to the involved selectivity which may correlate with toxicant residues.Herein,an electron localization strategy for specific O2 adsorption/activation enabled by photothermal/pyroelectric effect and in situ constructed active centers of single-atom Co and oxygen vacancy(Co-O_(V))on the Co/BiOCl-O_(V)photocatalyst was developed for photocatalytic degradation of glyphosate(GLP)wastewater of high performance/selectivity.Under full-spectrum-light irradiation,a high GLP degradation rate of 99.8%with over 90%C-P bond-breaking selectivity was achieved within 2 h,while effectively circumventing toxicant residues such as aminomethylphosphonic acid(AMPA).X-ray absorption spectroscopy and relevant characterizations expounded the tailored anchoring of Co single atoms onto the BiOCl-O_(V)carrier and photothermal/pyroelectric effect.The oriented formation of more•O_(2)^(−)on Co/BiOCl-O_(V)could be achieved with the Co-O_(V)coupled center that had excellent O2 adsorption/activation capacity,as demonstrated by quantum calculations.The formed unique Co-O_(V)active sites could largely decrease the C-P bond-breaking energy barrier,thus greatly improving the selectivity toward the initial C-P bond scission and the activity in subsequent conversion steps in the directional photocatalytic degradation of GLP.The electron localization strategy by in situ constructing the coupled active centers provides an efficient scheme and new insights for the low-toxic photodegradation of organic pollutants containing C-X bonds.
基金supported by the Hunan Joint International Laboratory of Advanced Materials and Technology for Clean Energy(2020CB1007)Guangxi Key Laboratory of Information Materials(Guangxi Science and Technology Program AD25069070)+1 种基金Nationally Funded Postdoctoral Researcher Program(GZC20230756)China Postdoctoral Science Foundation(2024M750858)。
文摘Seawater splitting provides a sustainable approach for large-scale hydrogen production without straining freshwater resources.However,the challenge lies in achieving high catalytic activity and stability due to electrocatalyst deactivation from structural degradation,poor corrosion resistance,and surface instability in both alkaline and seawater electrolysis.To address this,we propose a novel strategy combining Fe-doping with dual-phase lattice strain engineering in nickel-molybdenum transition metal nitrides(TMNs).The Fe-doped Ni_(3)Mo_(3)N/Mo_(2)N electrocatalyst exhibits compressive lattice strains of-4.52%and-2.91%in the Ni_(3)Mo_(3)N and Mo_(2)N phases,respectively,enhancing its structural integrity and electronic properties.Consequently,Fe-Ni_(3)Mo_(3)N/Mo_(2)N achieves low overpotentials of 167 and 371 mV at current densities of 10 and 500 mA cm^(-2),respectively,in 1 M alkaline seawater,with exceptional stability over 100 h at 100 and 500 mA cm^(-2).Theoretical calculations reveal that these compressive strains optimize the adsorption of OER intermediates and improve catalytic kinetics.This work demonstrates the promise of dual-phase lattice strain engineering in TMNs for efficient,durable,and scalable electrocatalysts in seawater electrolysis,a strategy that has yet to be fully explored for OER.
