Lithium-sulfur (Li-S) batteries have gained great attention due to the high theoretical energy density and low cost,yet their further commercialization has been obstructed by the notorious shuttle effect and sluggish ...Lithium-sulfur (Li-S) batteries have gained great attention due to the high theoretical energy density and low cost,yet their further commercialization has been obstructed by the notorious shuttle effect and sluggish redox dynamics.Herein,we supply a strategy to optimize the electron structure of Ni_(2)P by concurrently introducing B-doped atoms and P vacancies in Ni_(2)P (Vp-B-Ni_(2)P),thereby enhancing the bidirectional sulfur conversion.The study indicates that the simultaneous introduction of B-doped atoms and P vacancies in Ni_(2)P causes the redistribution of electron around Ni atoms,bringing about the upward shift of d-band center of Ni atoms and effective d-p orbital hybridization between Ni atoms and sulfur species,thus strengthening the chemical anchoring for lithium polysulfides (LiPSs) as well as expediting the bidirectional conversion kinetics of sulfur species.Meanwhile,theoretical calculations reveal that the incorporation of B-doped atoms and P vacancies in Ni_(2)P selectively promotes Li2S dissolution and nucleation processes.Thus,the Li-S batteries with Vp-B-Ni_(2)P-separators present outstanding rate ability of 777 m A h g^(-1)at 5 C and high areal capacity of 8.03 mA h cm^(-2)under E/S of 5μL mg^(-1)and sulfur loading of 7.20 mg cm^(-2).This work elucidates that introducing heteroatom and vacancy in metal phosphide collaboratively regulates the electron structure to accelerate bidirectional sulfur conversion.展开更多
Seawater electrolysis is a promising approach for sustainable energy without relying on precious freshwater.However,the large-scale seawater electrolysis is hindered by low catalytic efficiency and severe anode corros...Seawater electrolysis is a promising approach for sustainable energy without relying on precious freshwater.However,the large-scale seawater electrolysis is hindered by low catalytic efficiency and severe anode corrosion caused by the harmful chlorine.In contrast to the oxygen evolution reaction (OER)and chlorin ion oxidation reaction (ClOR),glycerol oxidation reaction (GOR) is more thermodynamically and kinetically favorable alternative.Herein,a Ru doping cobalt phosphide (Ru-CoP_(2)) is proposed as a robust bifunctional electrocatalyst for seawater electrolysis and GOR,for the concurrent productions of hydrogen and value-added formate.The in situ and ex situ characterization analyses demonstrated that Ru doping featured in the dynamic reconstruction process from Ru-CoP_(2)to Ru-CoOOH,accounting for the superior GOR performance.Further coupling GOR with hydrogen evolution was realized by employing Ru-CoP_(2)as both anode and cathode,requiring only a low voltage of 1.43 V at 100 mA cm^(-2),which was 250 m V lower than that in alkaline seawater.This work guides the design of bifunctional electrocatalysts for energy-efficient seawater electrolysis coupled with biomass resource upcycling.展开更多
Although bimetallic phosphide cocatalysts have attracted considerable interest in photocatalysis research owing to their advantageous thermodynamic characteristics,superstable and efficient cocatalysts have rarely bee...Although bimetallic phosphide cocatalysts have attracted considerable interest in photocatalysis research owing to their advantageous thermodynamic characteristics,superstable and efficient cocatalysts have rarely been produced through the modulation of their structure and composition.In this study,a series of bimetallic nickel-iron phosphide(Ni_(x)Fe_(2-x)P,where 0<x<2)cocatalysts with controllable structures and overpotentials were designed by adjusting the atomic ratio of Ni/Fe onto nonmetallic elemental red phosphorus(RP)for the photocatalytic selective oxidation of benzyl alcohol(BA)coupled with hydrogen production.The catalysts exhibited an outstanding photocatalytic activity for benzaldehyde and a high H_(2)yield.The RP regulated by bimetallic phosphide cocatalysts(Ni_(x)Fe_(2-x)P)demonstrated higher photocatalytic oxidation-reduction activity than that regulated by monometallic phosphide cocatalysts(Ni_(2)P and Fe2P).In particular,the RP regulated by Ni_(1.25)Fe_(0.75)P exhibited the best photocatalytic performance.In addition,experimental and theoretical calculations further illustrated that Ni_(1.25)Fe_(0.75)P,with the optimized electronic structure,possessed good electrical conductivity and provided strong adsorption and abundant active sites,thereby accelerating electron migration and lowering the reaction energy barrier of RP.This finding offers valuable insights into the rational design of highly effective cocatalysts aimed at optimizing the photocatalytic activity of composite photocatalysts.展开更多
Preparation of highly active hydrodesulfurization catalysts is extremely meaningful for the sulfur removal from thiophene substances.In this work,commercial nano-Al_(2)O_(3)with mesoporous structure supported monometa...Preparation of highly active hydrodesulfurization catalysts is extremely meaningful for the sulfur removal from thiophene substances.In this work,commercial nano-Al_(2)O_(3)with mesoporous structure supported monometallic phosphide(NiP/Al_(2)O_(3)and MoP/Al_(2)O_(3))and bimetallic phosphide(NiMoP/Al_(2)O_(3)with various Ni/Mo molar ratio)catalysts are successfully prepared by temperature-programmed reduction.X-ray diffraction(XRD)result shows the Ni/Mo molar ratio affect the crystal phase in catalysts.Scanning electron microscopy(SEM),transmission electron microscopy(TEM)and X-ray photoelectron spectroscopy(XPS)characterizations co-confirm the interact between Ni and Mo elements in bimetallic phosphide.Catalyst evaluation in hydrodesulfurization of dibenzothiophene shows that bimetallic phosphide samples exhibit better catalytic performance than monometallic phosphide.62.1%conversion and 86.3%biphenyl selectivity with 30 h stability are achieved over NiMoP/Al_(2)O_(3)(Ni/Mo=1∶1)catalyst at 400℃under 3 MPa H_(2).All characterization results demonstrate that the improved activity of bimetallic phosphide owes to the Ni-Mo synergistic effect in NiMoP/Al_(2)O_(3)(Ni/Mo=1∶1)catalyst.This finding provides a guide to the design of bimetallic catalyst with synergistic effect.展开更多
Sodium-ion batteries(SIBs) are promising electrochemical energy storage systems as lithium-ion batteries by virtue of their similar chemical properties and natural abundance and availability.However,the ionic radius o...Sodium-ion batteries(SIBs) are promising electrochemical energy storage systems as lithium-ion batteries by virtue of their similar chemical properties and natural abundance and availability.However,the ionic radius of Na^(+)is larger than that of Li^(+),leading to challenges in its insertion/extraction at anode side.As a class of anode materials,phosphorus allotropes(PAs,red,and black) and metal phosphides(MPs) have shown great prospects because of high theoretical gravimetric/volumetric capacity,high carrier mobility,and suitable redox potential.In this review,recent developments in the studies of PAs and MPs with particular emphasis on understanding sodium storage mechanisms,developing novel synthesis strategies,and performance validations have been manifested valuable solutions to address these challenges.We begin with the introduction and classification of the macroscopic sodiation mechanisms of PAs and MPs,and the various fabrication strategies of PAs and MPs are comprehensively summarized in second section.The third section thoroughly reviews the progresses on PAs and MPs-based advanced materials for their application in SIBs.Finally,we also discuss the significant challenges and outline a roadmap for future research directions.展开更多
The reasonable design of material morphology and eco-friendly electrocatalysts are essential to highly efficient water splitting.It is proposed that a promising strategy effectively regulates the electronic structure ...The reasonable design of material morphology and eco-friendly electrocatalysts are essential to highly efficient water splitting.It is proposed that a promising strategy effectively regulates the electronic structure of the d-orbitals of CoP using cerium doping in this paper,thus significantly improving the intrinsic property and conductivity of CoP for water splitting.As a result,the as-synthesize porous Ce-doped CoP micro-polyhedron composite derived from Ce-ZIF-67 as bifunctional electrocatalytic materials exhibits excellent electrocatalytic performance in both the oxygen evolution reaction(OER)and the hydrogen evolution reaction(HER),overpotentials of about 152 mV for HER at 10 mA cm^(-2)and about 352 mV for OER at 50 mA cm^(-2),and especially it shows outstanding long-term stability.Besides,an alkaline electrolyzer,using Ce0.04Co0.96P electrocatalyst as both the anode and cathode,delivers a cell voltage value of1.55 V at the current density of 10 mA cm^(-2).The calculation results of the density functional theory(DFT)demonstrate that the introduction of an appropriate amount of Ce into CoP can enhance the conductivity,and can induce the electronic modulation to regulate the selective adsorption of reaction intermediates on catalytic surface and the formation of O*intermediates(CoOOH),which exhibits an excellent electrocatalytic performance.This study provides novel insights into the design of an extraordinary performance water-splitting of the multicomponent electrocatalysts.展开更多
Azoxy aromatics are extensively utilized in materials science,pharmaceuticals,and synthetic chemistry,but their controlled and environmentally-friendly synthesis has rarely been reported.Herein,a potential-mediated el...Azoxy aromatics are extensively utilized in materials science,pharmaceuticals,and synthetic chemistry,but their controlled and environmentally-friendly synthesis has rarely been reported.Herein,a potential-mediated electrosynthesis strategy was developed by selective reduction of 4-nitrobenzyl alcohol(4-NBA)on Mn-doped Ni_(2)P nanosheets@nickel foam(Mn-Ni_(2)P/NF),enabling efficient N−N coupling to produce Azoxy with 100%selectivity at potentials of−0.6 to−0.8 V(vs.Hg/HgO).At more cathodic potentials,the product was converted to Azo and then to amino aromatics due to facilitated nitrogen hydrogenation.Additionally,the organic energetic material,5,5′-azotetrazolate,was also synthesized by anodic N−N coupling of 5-amino-1H-tetrazole on Cu(OH)_(2)nanowires@copper foam(Cu(OH)_(2)/CF).It bypassed harsh conditions(strong oxidants,high temperature,by-products separation,etc.)for the traditional synthesis of this class of materials.As a consequence,a two-electrode electrolyzer Cu(OH)_(2)/CF||Mn-Ni_(2)P/NF was assembled,allowing paired electrochemical N−N coupling into Azoxy and 5,5′-azotetrazolate.It achieves a current density of 50 mA cm^(−2)at a voltage of only 1.19 V,880 mV lower than the competitive water splitting.This electrolyzer can be efficiently driven by a 1.2 V solar panel with excellent yield and selectivity,paving the way for green synthesis of valuable chemicals through electrochemical N−N coupling strategies.展开更多
The electrochemical conversion of toxic nitrite(NO_(2)-)is a promising approach for the simultaneous removal of nitrogen contaminants and synthesis of ammonia(NH_(3)).In this study,we present the Er-doping-induced ele...The electrochemical conversion of toxic nitrite(NO_(2)-)is a promising approach for the simultaneous removal of nitrogen contaminants and synthesis of ammonia(NH_(3)).In this study,we present the Er-doping-induced electronic modulation of CoP integrated with nitrogen-doped carbon(CN)nanosheets supported on a titanium mesh(Er-CoP@NC/TM)for the electrocatalytic NO_(2)-reduction reaction(eNO_(2)-RR)for NH_(3)synthesis.The catalyst demonstrates a high Faraday efficiency of 97.08±2.22%and a high yield of 2087.60±17.10μmol h^(-1)cm^(-2)for NH_(3)production.Characterization and theoretical calculations revealed that Er-doping facilitated the electronic modulation of CoP in Er-CoP@NC/TM,which regulated the adsorption behaviors of intermediates and was the rate-limiting step for the eNO_(2)-RR,thereby enhancing the electrocatalytic performance.Quenching experiments and electron paramagnetic resonance tests suggest that both direct electrocatalytic reduction by active hydrogen and electron transfer are critical for the eNO_(2)-RR for NH_(3)synthesis.Furthermore,Er-CoP@NC/TM exhibited high performance across a wide range of NO_(2)-concentrations(0.05-0.1 mol L^(-1))and pH values(4-13).In addition,the catalyst demonstrated strong resistance to anions and a long cycle life in simulated wastewater environments.This study offers a powerful approach for the remediation of NO_(2)-wastewater and recovery of valuable inorganic compounds.展开更多
Understanding the catalytic mechanism at real catalytically active layer is essential for the advancement of water oxidation.Nevertheless,it is difficult to explore the surface effect of active layer of catalysts on o...Understanding the catalytic mechanism at real catalytically active layer is essential for the advancement of water oxidation.Nevertheless,it is difficult to explore the surface effect of active layer of catalysts on oxygen evolution reaction(OER)independently because of the coexistence of bulk phase and surfaceactive layer.Herein,by designing ultra-thin shell amorphous CoO_(x)hollow nanospheres,we explored the effect of single catalytic active layer on OER activity,further revealing the surface catalytic mechanism for seawater oxidation.The amorphous catalytic active layer CoO_(x)contain phosphates(CoO_(x)PO_(4)),induced by completely bulk reconstruction of CoP_(x)hollow nanospheres.Compared with autologous crystalline CoO,amorphous catalytic active species CoO_(x)-PO_(4)possesses higher OER performance with ultralow overpotential of 229 mV to achieve 10 mA cm^(-2).Remarkably,self-built phosphate film could effectively block chloride anions and implement robust seawater oxidation.This work brings direct insights of the surface effect of amorphous catalytic active layer on water oxidation,which is critical for the performance optimization of water oxidation.展开更多
Cobalt phosphides are potential catalysts to assist the conversion of lithium polysulfides(LiPSs)in lithium-sulfur(Li-S)batteries.However,existing synthesis methods have difficulty precisely tuning their band valences...Cobalt phosphides are potential catalysts to assist the conversion of lithium polysulfides(LiPSs)in lithium-sulfur(Li-S)batteries.However,existing synthesis methods have difficulty precisely tuning their band valences,which is crucial to balancing intermediate products'adsorption and conversion abilities in Li-S batteries.Moreover,studies on the relationship between their band structures and electrochemical performance are limited.Herein,we report cobalt phosphides(Co_(x)P)with a heterogeneous interface of CoP/Co2P embedded in hollow carbon nanofibers(denoted as Co_(x)P@HCNF)via a one-step sequential phosphorization and carbonization strategy,which is applied as an effective interlayer for Li-S batteries.The Co band valence in CoxP was adjusted to regulate the d-p band gap.Theoretical calculations predict that Co_(x)P with a narrowed d-p band center can optimize the electron transfer kinetics and the adsorption affinity with LiPSs.Li-S full cells with a Co_(x)P@HCNF interlayer demonstrated a high specific capacity of1265 mA h g^(-1)at 0.2C and excellent cycle stability of 788 mA h g^(-1)over 400 cycles at 2.0C.A cell with a lean electrolyte(6.0μL mg^(-1))and a high sulfur loading(6.2 mg cm^(-2))delivered a high areal capacity of4.5 mA h cm^(-2)at 0.5C.This study demonstrates that bimetallic coupling-induced electronic-state modulation effectively balances the chemical adsorption and catalytic capability for developing high-performance Li-S batteries.展开更多
Green hydrogen is crucial for advancing renewable energy technologies and protecting the environment.This study introduces a controllable method for bimetallic nickel-cobalt phosphide on reduced graphene oxide on nick...Green hydrogen is crucial for advancing renewable energy technologies and protecting the environment.This study introduces a controllable method for bimetallic nickel-cobalt phosphide on reduced graphene oxide on nickel foam(NiCo_(3)P.C/NF).The material demonstrated low overpotentials of 58 and 180 mV at10 mA cm^(-2)for hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)in 1.0 M KOH.It achieved excellent electrochemical water-splitting performance with operating voltages of 1.54 and 2.6 V at 10 and 500 mA cm^(-2),respectively.The overall water-splitting performance of NiCo_(3).C/NF was extremely stable after 75 h of operation at 53 mA cm^(-2),retaining 98%efficiency,better than the sample Pt-C+RuO_(2),and outperforming previous reports.Density functional theory(DFT)results revealed a synergistic NiCo_(3)P.C interaction that yields nearly zero Gibbs free energy change(-0.100 eV)and upshift d-band center,the real active site at the Ni in HER,and the lowest overpotentials 0.26 V at the P active sites for OER.Furthermore,electronic charge distribution shows the maximum charge distribution between the NiCo_(3)P phase and graphene sheet heterojunction,enhancing the electrocatalyst conductivity.This combined approach offers an innovative strategy to design sustainable electrocatalysts for water s plitting.展开更多
The existence of multiple vacancies leads to significant changes in the local atomic structure,which can regulate the electronic structure of the surface and form unsaturated coordination geometries.However,the curren...The existence of multiple vacancies leads to significant changes in the local atomic structure,which can regulate the electronic structure of the surface and form unsaturated coordination geometries.However,the current methods employed to generate multiple vacancies in two-dimensional(2D)layered double hydroxide(LDH)materials are still difficult to achieve to some extent and are primarily limited to monolayer LDH structures.Here,we present an improved method to synthesize NiMoP/Ni_(2)P catalysts with a sponge-like porous structure.Firstly,NiO with dual defects was constructed by subjecting NiMo-LDH/Ni to air calcination.Subsequently,we performed phosphorization treatment and introduced multiple Ni vacancies and O vacancies as defect sites to tune the edge and substrate surfaces of LDH.At the same time,the electronic structure was tuned by adding P heteroatoms.The synergistic effect of porous structure,heterogeneous interfaces,vacancies,doping defects,and amorphous states can greatly enhance the electron transfer effect inside the catalysts,which significantly improves the catalytic ability of the oxygen evolution reaction(OER).Therefore,the overpotential for the oxygen evolution reaction of NiMoP/Ni_(2)P heterointerfaces reaches 270 mV at a current density of 10 mA·cm^(-2)under alkaline conditions,with the catalysts capable of sustaining high current densities even after the durability testing for 35 h.展开更多
Heteroatom doping has emerged as a powerful strategy to optimize the catalytic and adsorption abilities of electrocatalysts by regulating the electronic structure,thereby enabling the development of efficient electroc...Heteroatom doping has emerged as a powerful strategy to optimize the catalytic and adsorption abilities of electrocatalysts by regulating the electronic structure,thereby enabling the development of efficient electrocatalysts for lithium-sulfur(Li-S)batteries.However,the correlation between the properties of doped atoms and adsorptio n-catalytic ability,as well as the interconnection between adsorption strength and catalytic activity,remains underexplored.Herein,we employed halogen atoms(F,Cl,and Br)with different electronegativities to dope nickel phosphide(Ni_(2)P),aiming to modulate the adsorption properties toward lithium polysulfides(LiPSs).We systematically explored the relationship between the electronegativity of the doping atoms and the adsorption strength,followed by exploring the connection between adsorption and catalytic capabilities.Combined experimental and theoretical analyses reveal that doping halogen atoms effectively strengthens d-p orbital hybridization between Ni atoms and S atoms,thereby enhancing LiPSs anchoring and conversion.Specifically,the chemical adsorption capability is enhanced as the electronegativity of the doped atoms increases.Moreover,the catalytic activity presents a volcano-like trend with the enhancement of adsorption performance,wherein the activity initially increases and subsequently diminishes.Therefore,Cl-doped Ni_(2)P with moderate chemisorption ability exhibits optimal redox kinetics in bidirectional sulfur conversion.Consequently,the Li-S batteries with Cl-Ni_(2)P-separators deliver a high-rate capacity of 790 mAh g^(-1)at 5 C and achieve a remarkable areal capacity of 7.36 mAh cm^(-2)under practical conditions(sulfur loading:7.10 mg cm^(-2);electrolyte/sulfur(E/S)ratio:5μL mg^(-1)).This work uncovers the significance of achieving a balance between adsorption and catalytic capabilities,offering insights into designing efficient electrocatalysts for lithium-sulfur batteries.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
Transition metal phosphides(TMPs)have emerged as promising alternatives to commercial noblemetal-based electrocatalysts for the hydrogen evolution reaction(HER).However,their electrocatalytic performance is still far ...Transition metal phosphides(TMPs)have emerged as promising alternatives to commercial noblemetal-based electrocatalysts for the hydrogen evolution reaction(HER).However,their electrocatalytic performance is still far from practical application.Herein,a novel self-supported CoP-based electrode(MoZn-CoP/CC)was prepared,in which Mo and Zn co-doped CoP nanosheet arrays are tightly anchored on a carbon cloth(CC)matrix.Remarkably,the as-prepared MoZn-CoP/CC electrode exhibits outstanding HER performance with exceptional pH universality.More importantly,it only requires modest overpotentials to deliver the current densities exceeding1.0 A cm^(-2)in both alkaline and acidic media,outperforming the commercial Pt catalyst.Experimental results combined with theoretical analysis reveal that co-doping of Mo and Zn can modulate the electronic structure of CoP,thereby optimizing the adsorption energy of hydrogen and ultimately improving the HER performance.This work provides an effective strategy to tune the electronic properties of TMPs via heteroatom doping for enhancing their electrocatalytic performance.展开更多
Engineering a phosphide-based multifunctional heterostructure with high redox activity,stability,and efficient charge kinetics for both supercapacitors and water splitting remains challenging due to sluggish reaction ...Engineering a phosphide-based multifunctional heterostructure with high redox activity,stability,and efficient charge kinetics for both supercapacitors and water splitting remains challenging due to sluggish reaction kinetics and structural instability.This study overcomes these challenges by implementing a rapid,energy-efficient approach to develop a MOF-modulated MnP@Cu_(3)P heterostructure via a hydrothermal process followed by high-temperature phosphorization.The heterostructure demonstrates superior redox activity with enhanced stability and improved charge kinetics achieving a high specific capacity of 1131 C g^(-1)as supported by density functional theory findings of increased DOS near the Fermi level.The flexible supercapacitor achieves a peak energy density of 99.20 Wh kg^(-1)and power density of 15.40 kW kg^(-1).Simultaneously,it shows exceptional hydrogen evolution reaction performance with an overpotential of η_(10)=44 mV and η_(1000)=225 mV,attributed to electron transfer from Cu to Mn via P bridging,which shifts the active centers from Mn and Cu sites to the P site,confirmed by lowestΔG_(H)^(*)value of-0.16 eV.The overall water-splitting in full-cell electrocatalyzer delivers cell voltage of E_(20)=1.48 V and E_(1000)=1.88 V and setting a new standard in solar-to-hydrogen efficiency of 20.02%.The electrolyzer cell maintained prolonged stability at industrial-scale current densities of 1.0 A cm^(-2)under alkaline electrolysis achieving an estimated hydrogen production cost of INR 146.7 or US$1.67per kilogram aligning with the cost target of $2/kg by 2026 established by the Clean Hydrogen Electrolysis Program,U.S.department of energy.Furthermore,real-phase demonstration highlights the uninterrupted hydrogen production till 6-minutes via connecting this electrocatalyzer with photovoltaic-charged supercapacitors effectively addressing solar intermittency and gas fluctuations challenges in water-electrolysis.展开更多
Electrochemical water splitting is a highly promising approach for producing carbon-neutral hydrogen.The development of efficient electrocatalysts for the hydrogen evolution reaction(HER)is crucial to lowering the ene...Electrochemical water splitting is a highly promising approach for producing carbon-neutral hydrogen.The development of efficient electrocatalysts for the hydrogen evolution reaction(HER)is crucial to lowering the energy barriers and enhancing hydrogen production.This drives the search for HER electrocatalysts that are not only cost-effective and abundant but also exhibit high activity and long-term stability.In this review,we provide an in-depth analysis of recent progress in the application of ruthenium phosphides as HER electrocatalysts,offering key insights into their design and performance.Meanwhile,we explore various strategies to enhance their catalytic efficiency,such as increasing the availability of active sites and optimizing their electronic structure.Finally,we outline the key challenges and future directions for developing the next generation of ruthenium phosphide-based HER electrocatalysts.展开更多
Developing efficient electrocatalysts for oxygen evolution reaction(OER)is imperative to enhance the overall efficiency of electrolysis systems and rechargeable metal-air batteries operating in aqueous solutions.High-...Developing efficient electrocatalysts for oxygen evolution reaction(OER)is imperative to enhance the overall efficiency of electrolysis systems and rechargeable metal-air batteries operating in aqueous solutions.High-entropy materials,featured with their distinctive multi-component properties,have found extensive application as catalysts in electrochemical energy storage and conversion devices.However,synthesizing nanostructured high-entropy compounds under mild conditions poses a significant challenge due to the difficulty in overcoming the immiscibility of multiple metallic constituents.In this context,the current study focuses on the synthesis of an array of nano-sized high entropy sulfides tailored for OER via a facile precursor pyrolysis method at low temperature.The representative compound,Fe Co Ni Cu Mn Sx,demonstrates remarkable OER performance,achieving a current density of 10 m A/cm^(2) at an overpotential of merely 220 m V and excellent stability with constant electrolysis at 100 m A/cm^(2) for over 400 h.The in-situ formed metal(oxy)hydroxide has been confirmed as the real active sites and its exceptional performance can be primarily attributed to the synergistic effects arising from its multiple components.Furthermore,the synthetic methodology presented here is versatile and can be extended to the preparation of high entropy phosphides,which also present favorable OER performance.This research not only introduces promising non-noble electrocatalysts for OER but also offers a facile approach to expand the family of nano high-entropy materials,contributing significantly to the field of electrochemical energy conversion.展开更多
In recent years,the discharge of urea-containing wastewater from industrial and domestic sources has posed a continuing threat to aquatic ecosystems and human health.In this context,the urea oxidation reaction(UOR)has...In recent years,the discharge of urea-containing wastewater from industrial and domestic sources has posed a continuing threat to aquatic ecosystems and human health.In this context,the urea oxidation reaction(UOR)has attracted significant attention due to its low thermodynamic potential of 0.37 V(vs.RHE).Compared with oxygen evolution reaction(OER),this reaction can significantly reduce the energy consumption of electrolysis while realizing wastewater treatment,and has the dual functions of hydrogen energy preparation and wastewater purification.However,UOR involves complex six-electron transfer and intermediate adsorption/desorption processes,resulting in slow reaction kinetics.Therefore,the development of economical and efficient catalysts has become a research focus,among which transition metal phosphides(TMPs)stand out due to their low cost,excellent activity and adjustable electronic structure.Compared with other non-noble metal systems,TMPs have unique electronic structure and surface properties that can adsorb and activate urea molecules more efficiently.However,there is still a lack of systematic reviews on TMP catalysts at present.Therefore,this review aims to deeply and systematically elaborate the design strategies of TMP catalysts and their applications in UOR,thoroughly discuss the current progress,challenges and future directions,and provide theoretical support and design ideas for the development of a new generation of efficient and stable UOR catalysts.展开更多
Strain effects have garnered significant attention in catalytic applications due to their ability to modulate the electronic structure and surface adsorption properties of catalysts.In this study,we propose a novel ap...Strain effects have garnered significant attention in catalytic applications due to their ability to modulate the electronic structure and surface adsorption properties of catalysts.In this study,we propose a novel approach called“similar stacking”for stress modulation,achieved through the loading of Co_(2)P on Ni_(2)P(Ni_(2)P/Co_(2)P).Theoretical simulations reveal that the compressive strain induced by Co_(2)P influences orbital overlap and electron transfer with hydrogen atoms.Furthermore,the number of stacked layers can be adjusted by varying the precursor soaking time,which further modulates the strain range and hydrogen adsorption.Under a 2-h soaking condition,the strain effect proves favorable for efficient hydrogen production.Experimental characterizations using X-ray diffraction,high-angel annular dark-field scanning transmission election microscope(HAADF-STEM),and X-ray absorption near-edge structure spectroscopy successfully demonstrate lattice contraction of Co_(2)P and bond length shortening of Co-P.Remarkably,our catalyst shows an ultrahigh current density of 1 A cm^(-2) at an overpotential of only 388 mV,surpassing that of commercial Pt/C,while maintaining long-term stability.This material design strategy of similar stacking opens up new avenues of strain modulation and the deeper development of electrocatalysts.展开更多
基金Institute of Technology Research Fund Program for Young Scholars21C Innovation Laboratory Contemporary Amperex Technology Co.,Limited,Ninde, 352100, China (21C–OP-202314)。
文摘Lithium-sulfur (Li-S) batteries have gained great attention due to the high theoretical energy density and low cost,yet their further commercialization has been obstructed by the notorious shuttle effect and sluggish redox dynamics.Herein,we supply a strategy to optimize the electron structure of Ni_(2)P by concurrently introducing B-doped atoms and P vacancies in Ni_(2)P (Vp-B-Ni_(2)P),thereby enhancing the bidirectional sulfur conversion.The study indicates that the simultaneous introduction of B-doped atoms and P vacancies in Ni_(2)P causes the redistribution of electron around Ni atoms,bringing about the upward shift of d-band center of Ni atoms and effective d-p orbital hybridization between Ni atoms and sulfur species,thus strengthening the chemical anchoring for lithium polysulfides (LiPSs) as well as expediting the bidirectional conversion kinetics of sulfur species.Meanwhile,theoretical calculations reveal that the incorporation of B-doped atoms and P vacancies in Ni_(2)P selectively promotes Li2S dissolution and nucleation processes.Thus,the Li-S batteries with Vp-B-Ni_(2)P-separators present outstanding rate ability of 777 m A h g^(-1)at 5 C and high areal capacity of 8.03 mA h cm^(-2)under E/S of 5μL mg^(-1)and sulfur loading of 7.20 mg cm^(-2).This work elucidates that introducing heteroatom and vacancy in metal phosphide collaboratively regulates the electron structure to accelerate bidirectional sulfur conversion.
基金National Natural Science Foundation of China (Nos. 42276035, 22309030)Guangdong Basic and Applied Basic Research Foundation (Nos. 2023A1515012589,2020A1515110473)Key Plat Form Programs and Technology Innovation Team Project of Guangdong Provincial Department of Education (Nos. 2019GCZX002, 2020KCXTD011)。
文摘Seawater electrolysis is a promising approach for sustainable energy without relying on precious freshwater.However,the large-scale seawater electrolysis is hindered by low catalytic efficiency and severe anode corrosion caused by the harmful chlorine.In contrast to the oxygen evolution reaction (OER)and chlorin ion oxidation reaction (ClOR),glycerol oxidation reaction (GOR) is more thermodynamically and kinetically favorable alternative.Herein,a Ru doping cobalt phosphide (Ru-CoP_(2)) is proposed as a robust bifunctional electrocatalyst for seawater electrolysis and GOR,for the concurrent productions of hydrogen and value-added formate.The in situ and ex situ characterization analyses demonstrated that Ru doping featured in the dynamic reconstruction process from Ru-CoP_(2)to Ru-CoOOH,accounting for the superior GOR performance.Further coupling GOR with hydrogen evolution was realized by employing Ru-CoP_(2)as both anode and cathode,requiring only a low voltage of 1.43 V at 100 mA cm^(-2),which was 250 m V lower than that in alkaline seawater.This work guides the design of bifunctional electrocatalysts for energy-efficient seawater electrolysis coupled with biomass resource upcycling.
文摘Although bimetallic phosphide cocatalysts have attracted considerable interest in photocatalysis research owing to their advantageous thermodynamic characteristics,superstable and efficient cocatalysts have rarely been produced through the modulation of their structure and composition.In this study,a series of bimetallic nickel-iron phosphide(Ni_(x)Fe_(2-x)P,where 0<x<2)cocatalysts with controllable structures and overpotentials were designed by adjusting the atomic ratio of Ni/Fe onto nonmetallic elemental red phosphorus(RP)for the photocatalytic selective oxidation of benzyl alcohol(BA)coupled with hydrogen production.The catalysts exhibited an outstanding photocatalytic activity for benzaldehyde and a high H_(2)yield.The RP regulated by bimetallic phosphide cocatalysts(Ni_(x)Fe_(2-x)P)demonstrated higher photocatalytic oxidation-reduction activity than that regulated by monometallic phosphide cocatalysts(Ni_(2)P and Fe2P).In particular,the RP regulated by Ni_(1.25)Fe_(0.75)P exhibited the best photocatalytic performance.In addition,experimental and theoretical calculations further illustrated that Ni_(1.25)Fe_(0.75)P,with the optimized electronic structure,possessed good electrical conductivity and provided strong adsorption and abundant active sites,thereby accelerating electron migration and lowering the reaction energy barrier of RP.This finding offers valuable insights into the rational design of highly effective cocatalysts aimed at optimizing the photocatalytic activity of composite photocatalysts.
基金supported by National Natural Science Foundation of China(22202093)the Scientific and Technological Innovation Youth Talent Team of Shanxi Province(202204051001005)。
文摘Preparation of highly active hydrodesulfurization catalysts is extremely meaningful for the sulfur removal from thiophene substances.In this work,commercial nano-Al_(2)O_(3)with mesoporous structure supported monometallic phosphide(NiP/Al_(2)O_(3)and MoP/Al_(2)O_(3))and bimetallic phosphide(NiMoP/Al_(2)O_(3)with various Ni/Mo molar ratio)catalysts are successfully prepared by temperature-programmed reduction.X-ray diffraction(XRD)result shows the Ni/Mo molar ratio affect the crystal phase in catalysts.Scanning electron microscopy(SEM),transmission electron microscopy(TEM)and X-ray photoelectron spectroscopy(XPS)characterizations co-confirm the interact between Ni and Mo elements in bimetallic phosphide.Catalyst evaluation in hydrodesulfurization of dibenzothiophene shows that bimetallic phosphide samples exhibit better catalytic performance than monometallic phosphide.62.1%conversion and 86.3%biphenyl selectivity with 30 h stability are achieved over NiMoP/Al_(2)O_(3)(Ni/Mo=1∶1)catalyst at 400℃under 3 MPa H_(2).All characterization results demonstrate that the improved activity of bimetallic phosphide owes to the Ni-Mo synergistic effect in NiMoP/Al_(2)O_(3)(Ni/Mo=1∶1)catalyst.This finding provides a guide to the design of bimetallic catalyst with synergistic effect.
基金financially supported by the Natural Science Foundation of China(Nos.22208214,22005190,and 21938005)the Science&Technology Commission of Shanghai Municipality(Nos.20QB1405700,and 19DZ1205500)Zhejiang Key Research and Development Program(No.2020C01128)
文摘Sodium-ion batteries(SIBs) are promising electrochemical energy storage systems as lithium-ion batteries by virtue of their similar chemical properties and natural abundance and availability.However,the ionic radius of Na^(+)is larger than that of Li^(+),leading to challenges in its insertion/extraction at anode side.As a class of anode materials,phosphorus allotropes(PAs,red,and black) and metal phosphides(MPs) have shown great prospects because of high theoretical gravimetric/volumetric capacity,high carrier mobility,and suitable redox potential.In this review,recent developments in the studies of PAs and MPs with particular emphasis on understanding sodium storage mechanisms,developing novel synthesis strategies,and performance validations have been manifested valuable solutions to address these challenges.We begin with the introduction and classification of the macroscopic sodiation mechanisms of PAs and MPs,and the various fabrication strategies of PAs and MPs are comprehensively summarized in second section.The third section thoroughly reviews the progresses on PAs and MPs-based advanced materials for their application in SIBs.Finally,we also discuss the significant challenges and outline a roadmap for future research directions.
基金supported by the National Natural Science Foundation of China(No.12162023&52268042)Key R&D Program of Gansu Province-International Cooperation Project(No.20YF8WA064)Natural Science Foundation of Gansu Province(No.22JR5RA253).
文摘The reasonable design of material morphology and eco-friendly electrocatalysts are essential to highly efficient water splitting.It is proposed that a promising strategy effectively regulates the electronic structure of the d-orbitals of CoP using cerium doping in this paper,thus significantly improving the intrinsic property and conductivity of CoP for water splitting.As a result,the as-synthesize porous Ce-doped CoP micro-polyhedron composite derived from Ce-ZIF-67 as bifunctional electrocatalytic materials exhibits excellent electrocatalytic performance in both the oxygen evolution reaction(OER)and the hydrogen evolution reaction(HER),overpotentials of about 152 mV for HER at 10 mA cm^(-2)and about 352 mV for OER at 50 mA cm^(-2),and especially it shows outstanding long-term stability.Besides,an alkaline electrolyzer,using Ce0.04Co0.96P electrocatalyst as both the anode and cathode,delivers a cell voltage value of1.55 V at the current density of 10 mA cm^(-2).The calculation results of the density functional theory(DFT)demonstrate that the introduction of an appropriate amount of Ce into CoP can enhance the conductivity,and can induce the electronic modulation to regulate the selective adsorption of reaction intermediates on catalytic surface and the formation of O*intermediates(CoOOH),which exhibits an excellent electrocatalytic performance.This study provides novel insights into the design of an extraordinary performance water-splitting of the multicomponent electrocatalysts.
基金supported by the National Key R&D Program of China(2024YFA1211004)the National Natural Science Foundation of China(22402150,22072107)+1 种基金the Natural Science Foundation of Shanghai(23ZR1464800,24ZR1470200)the Foundation of State Key Laboratory of Pollution Control and Resource Reuse(Tongji University)。
文摘Azoxy aromatics are extensively utilized in materials science,pharmaceuticals,and synthetic chemistry,but their controlled and environmentally-friendly synthesis has rarely been reported.Herein,a potential-mediated electrosynthesis strategy was developed by selective reduction of 4-nitrobenzyl alcohol(4-NBA)on Mn-doped Ni_(2)P nanosheets@nickel foam(Mn-Ni_(2)P/NF),enabling efficient N−N coupling to produce Azoxy with 100%selectivity at potentials of−0.6 to−0.8 V(vs.Hg/HgO).At more cathodic potentials,the product was converted to Azo and then to amino aromatics due to facilitated nitrogen hydrogenation.Additionally,the organic energetic material,5,5′-azotetrazolate,was also synthesized by anodic N−N coupling of 5-amino-1H-tetrazole on Cu(OH)_(2)nanowires@copper foam(Cu(OH)_(2)/CF).It bypassed harsh conditions(strong oxidants,high temperature,by-products separation,etc.)for the traditional synthesis of this class of materials.As a consequence,a two-electrode electrolyzer Cu(OH)_(2)/CF||Mn-Ni_(2)P/NF was assembled,allowing paired electrochemical N−N coupling into Azoxy and 5,5′-azotetrazolate.It achieves a current density of 50 mA cm^(−2)at a voltage of only 1.19 V,880 mV lower than the competitive water splitting.This electrolyzer can be efficiently driven by a 1.2 V solar panel with excellent yield and selectivity,paving the way for green synthesis of valuable chemicals through electrochemical N−N coupling strategies.
文摘The electrochemical conversion of toxic nitrite(NO_(2)-)is a promising approach for the simultaneous removal of nitrogen contaminants and synthesis of ammonia(NH_(3)).In this study,we present the Er-doping-induced electronic modulation of CoP integrated with nitrogen-doped carbon(CN)nanosheets supported on a titanium mesh(Er-CoP@NC/TM)for the electrocatalytic NO_(2)-reduction reaction(eNO_(2)-RR)for NH_(3)synthesis.The catalyst demonstrates a high Faraday efficiency of 97.08±2.22%and a high yield of 2087.60±17.10μmol h^(-1)cm^(-2)for NH_(3)production.Characterization and theoretical calculations revealed that Er-doping facilitated the electronic modulation of CoP in Er-CoP@NC/TM,which regulated the adsorption behaviors of intermediates and was the rate-limiting step for the eNO_(2)-RR,thereby enhancing the electrocatalytic performance.Quenching experiments and electron paramagnetic resonance tests suggest that both direct electrocatalytic reduction by active hydrogen and electron transfer are critical for the eNO_(2)-RR for NH_(3)synthesis.Furthermore,Er-CoP@NC/TM exhibited high performance across a wide range of NO_(2)-concentrations(0.05-0.1 mol L^(-1))and pH values(4-13).In addition,the catalyst demonstrated strong resistance to anions and a long cycle life in simulated wastewater environments.This study offers a powerful approach for the remediation of NO_(2)-wastewater and recovery of valuable inorganic compounds.
基金support from the Starting Research Funds of Hebei University of Science and Technology,the National Natural Science Foundation of China(22109038)the Hebei Natural Science Foundation(D2022208001)the S&T Program of Hebei(21344601D,242G4601Z)。
文摘Understanding the catalytic mechanism at real catalytically active layer is essential for the advancement of water oxidation.Nevertheless,it is difficult to explore the surface effect of active layer of catalysts on oxygen evolution reaction(OER)independently because of the coexistence of bulk phase and surfaceactive layer.Herein,by designing ultra-thin shell amorphous CoO_(x)hollow nanospheres,we explored the effect of single catalytic active layer on OER activity,further revealing the surface catalytic mechanism for seawater oxidation.The amorphous catalytic active layer CoO_(x)contain phosphates(CoO_(x)PO_(4)),induced by completely bulk reconstruction of CoP_(x)hollow nanospheres.Compared with autologous crystalline CoO,amorphous catalytic active species CoO_(x)-PO_(4)possesses higher OER performance with ultralow overpotential of 229 mV to achieve 10 mA cm^(-2).Remarkably,self-built phosphate film could effectively block chloride anions and implement robust seawater oxidation.This work brings direct insights of the surface effect of amorphous catalytic active layer on water oxidation,which is critical for the performance optimization of water oxidation.
基金support from the National Natural Science Foundation of China(U21A20174)the Fundamental Research Program of Shanxi Province(202203021221049)+3 种基金the Science and Technology Innovation Talent Team Project of Shanxi Province(202304051001010)support from the Shenzhen Science and Technology Program(RCBS20221008093340100)support from the Australian Research Council(ARC)Discovery Early Career Researcher Award(DE230101068)support from the ARC Research Hub for Safe and Reliable Energy(IH200100035)。
文摘Cobalt phosphides are potential catalysts to assist the conversion of lithium polysulfides(LiPSs)in lithium-sulfur(Li-S)batteries.However,existing synthesis methods have difficulty precisely tuning their band valences,which is crucial to balancing intermediate products'adsorption and conversion abilities in Li-S batteries.Moreover,studies on the relationship between their band structures and electrochemical performance are limited.Herein,we report cobalt phosphides(Co_(x)P)with a heterogeneous interface of CoP/Co2P embedded in hollow carbon nanofibers(denoted as Co_(x)P@HCNF)via a one-step sequential phosphorization and carbonization strategy,which is applied as an effective interlayer for Li-S batteries.The Co band valence in CoxP was adjusted to regulate the d-p band gap.Theoretical calculations predict that Co_(x)P with a narrowed d-p band center can optimize the electron transfer kinetics and the adsorption affinity with LiPSs.Li-S full cells with a Co_(x)P@HCNF interlayer demonstrated a high specific capacity of1265 mA h g^(-1)at 0.2C and excellent cycle stability of 788 mA h g^(-1)over 400 cycles at 2.0C.A cell with a lean electrolyte(6.0μL mg^(-1))and a high sulfur loading(6.2 mg cm^(-2))delivered a high areal capacity of4.5 mA h cm^(-2)at 0.5C.This study demonstrates that bimetallic coupling-induced electronic-state modulation effectively balances the chemical adsorption and catalytic capability for developing high-performance Li-S batteries.
基金supported by the Regional Leading Research Center Program(2019R1A5A8080326)funding from the Basic Science Research Program(2021R1F1A1048758,2022R1I1A1A01053248)+1 种基金the Regional Innovation Strategy(RIS)(2023RIS-008)through the National Research Foundation of Korea(NRF),funded by the Ministry of Educationsupported by the National Supercomputing Center,which provided supercomputing resources and technical support(TS-2024-RE-0039)。
文摘Green hydrogen is crucial for advancing renewable energy technologies and protecting the environment.This study introduces a controllable method for bimetallic nickel-cobalt phosphide on reduced graphene oxide on nickel foam(NiCo_(3)P.C/NF).The material demonstrated low overpotentials of 58 and 180 mV at10 mA cm^(-2)for hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)in 1.0 M KOH.It achieved excellent electrochemical water-splitting performance with operating voltages of 1.54 and 2.6 V at 10 and 500 mA cm^(-2),respectively.The overall water-splitting performance of NiCo_(3).C/NF was extremely stable after 75 h of operation at 53 mA cm^(-2),retaining 98%efficiency,better than the sample Pt-C+RuO_(2),and outperforming previous reports.Density functional theory(DFT)results revealed a synergistic NiCo_(3)P.C interaction that yields nearly zero Gibbs free energy change(-0.100 eV)and upshift d-band center,the real active site at the Ni in HER,and the lowest overpotentials 0.26 V at the P active sites for OER.Furthermore,electronic charge distribution shows the maximum charge distribution between the NiCo_(3)P phase and graphene sheet heterojunction,enhancing the electrocatalyst conductivity.This combined approach offers an innovative strategy to design sustainable electrocatalysts for water s plitting.
基金supported by the National Natural Science Foundation of China(No.22269010)Jiangxi Provincial Natural Science Foundation(No.20224BAB214021)the Opening Project of National Engineering Research Center for Domestic&Building Ceramics(No.GXZX2302).
文摘The existence of multiple vacancies leads to significant changes in the local atomic structure,which can regulate the electronic structure of the surface and form unsaturated coordination geometries.However,the current methods employed to generate multiple vacancies in two-dimensional(2D)layered double hydroxide(LDH)materials are still difficult to achieve to some extent and are primarily limited to monolayer LDH structures.Here,we present an improved method to synthesize NiMoP/Ni_(2)P catalysts with a sponge-like porous structure.Firstly,NiO with dual defects was constructed by subjecting NiMo-LDH/Ni to air calcination.Subsequently,we performed phosphorization treatment and introduced multiple Ni vacancies and O vacancies as defect sites to tune the edge and substrate surfaces of LDH.At the same time,the electronic structure was tuned by adding P heteroatoms.The synergistic effect of porous structure,heterogeneous interfaces,vacancies,doping defects,and amorphous states can greatly enhance the electron transfer effect inside the catalysts,which significantly improves the catalytic ability of the oxygen evolution reaction(OER).Therefore,the overpotential for the oxygen evolution reaction of NiMoP/Ni_(2)P heterointerfaces reaches 270 mV at a current density of 10 mA·cm^(-2)under alkaline conditions,with the catalysts capable of sustaining high current densities even after the durability testing for 35 h.
基金supported by the Beijing Institute of Technology Research Fund Program for Young Scholars and 21C Innovation Laboratory Contemporary Amperex Technology Co.,Limited,Ninde,352100,China(21C-OP-202314)。
文摘Heteroatom doping has emerged as a powerful strategy to optimize the catalytic and adsorption abilities of electrocatalysts by regulating the electronic structure,thereby enabling the development of efficient electrocatalysts for lithium-sulfur(Li-S)batteries.However,the correlation between the properties of doped atoms and adsorptio n-catalytic ability,as well as the interconnection between adsorption strength and catalytic activity,remains underexplored.Herein,we employed halogen atoms(F,Cl,and Br)with different electronegativities to dope nickel phosphide(Ni_(2)P),aiming to modulate the adsorption properties toward lithium polysulfides(LiPSs).We systematically explored the relationship between the electronegativity of the doping atoms and the adsorption strength,followed by exploring the connection between adsorption and catalytic capabilities.Combined experimental and theoretical analyses reveal that doping halogen atoms effectively strengthens d-p orbital hybridization between Ni atoms and S atoms,thereby enhancing LiPSs anchoring and conversion.Specifically,the chemical adsorption capability is enhanced as the electronegativity of the doped atoms increases.Moreover,the catalytic activity presents a volcano-like trend with the enhancement of adsorption performance,wherein the activity initially increases and subsequently diminishes.Therefore,Cl-doped Ni_(2)P with moderate chemisorption ability exhibits optimal redox kinetics in bidirectional sulfur conversion.Consequently,the Li-S batteries with Cl-Ni_(2)P-separators deliver a high-rate capacity of 790 mAh g^(-1)at 5 C and achieve a remarkable areal capacity of 7.36 mAh cm^(-2)under practical conditions(sulfur loading:7.10 mg cm^(-2);electrolyte/sulfur(E/S)ratio:5μL mg^(-1)).This work uncovers the significance of achieving a balance between adsorption and catalytic capabilities,offering insights into designing efficient electrocatalysts for lithium-sulfur batteries.
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financially supported by the National Key Research and Development Program of China(No.2024YFE0211500)the National Natural Science Foundation of China(Nos.52332007 and 22305247)the Natural Science Foundation of Fujian Province(Nos.2022L3092 and 2022J05086)
文摘Transition metal phosphides(TMPs)have emerged as promising alternatives to commercial noblemetal-based electrocatalysts for the hydrogen evolution reaction(HER).However,their electrocatalytic performance is still far from practical application.Herein,a novel self-supported CoP-based electrode(MoZn-CoP/CC)was prepared,in which Mo and Zn co-doped CoP nanosheet arrays are tightly anchored on a carbon cloth(CC)matrix.Remarkably,the as-prepared MoZn-CoP/CC electrode exhibits outstanding HER performance with exceptional pH universality.More importantly,it only requires modest overpotentials to deliver the current densities exceeding1.0 A cm^(-2)in both alkaline and acidic media,outperforming the commercial Pt catalyst.Experimental results combined with theoretical analysis reveal that co-doping of Mo and Zn can modulate the electronic structure of CoP,thereby optimizing the adsorption energy of hydrogen and ultimately improving the HER performance.This work provides an effective strategy to tune the electronic properties of TMPs via heteroatom doping for enhancing their electrocatalytic performance.
基金supported financially by the Ministry of Textiles(Grant No-2/3/2021-NTTM(Pt.)),Govt.of India。
文摘Engineering a phosphide-based multifunctional heterostructure with high redox activity,stability,and efficient charge kinetics for both supercapacitors and water splitting remains challenging due to sluggish reaction kinetics and structural instability.This study overcomes these challenges by implementing a rapid,energy-efficient approach to develop a MOF-modulated MnP@Cu_(3)P heterostructure via a hydrothermal process followed by high-temperature phosphorization.The heterostructure demonstrates superior redox activity with enhanced stability and improved charge kinetics achieving a high specific capacity of 1131 C g^(-1)as supported by density functional theory findings of increased DOS near the Fermi level.The flexible supercapacitor achieves a peak energy density of 99.20 Wh kg^(-1)and power density of 15.40 kW kg^(-1).Simultaneously,it shows exceptional hydrogen evolution reaction performance with an overpotential of η_(10)=44 mV and η_(1000)=225 mV,attributed to electron transfer from Cu to Mn via P bridging,which shifts the active centers from Mn and Cu sites to the P site,confirmed by lowestΔG_(H)^(*)value of-0.16 eV.The overall water-splitting in full-cell electrocatalyzer delivers cell voltage of E_(20)=1.48 V and E_(1000)=1.88 V and setting a new standard in solar-to-hydrogen efficiency of 20.02%.The electrolyzer cell maintained prolonged stability at industrial-scale current densities of 1.0 A cm^(-2)under alkaline electrolysis achieving an estimated hydrogen production cost of INR 146.7 or US$1.67per kilogram aligning with the cost target of $2/kg by 2026 established by the Clean Hydrogen Electrolysis Program,U.S.department of energy.Furthermore,real-phase demonstration highlights the uninterrupted hydrogen production till 6-minutes via connecting this electrocatalyzer with photovoltaic-charged supercapacitors effectively addressing solar intermittency and gas fluctuations challenges in water-electrolysis.
基金supported by the Frontier Exploration Projects of Longmen Laboratory(No.LMQYTSKT008)the Program for Science and Technology Innovation Talents in Universities of Henan Province(Nos.22HASTIT008 and 24HASTIT006)+2 种基金the Natural Science Foundations of Henan Province(Nos.222300420502 and 242300420045)the Programs for Science and Technology Development of Henan Province(No.242102240066)the Key Scientific Research Projects of University in Henan Province(No.23B430002)。
文摘Electrochemical water splitting is a highly promising approach for producing carbon-neutral hydrogen.The development of efficient electrocatalysts for the hydrogen evolution reaction(HER)is crucial to lowering the energy barriers and enhancing hydrogen production.This drives the search for HER electrocatalysts that are not only cost-effective and abundant but also exhibit high activity and long-term stability.In this review,we provide an in-depth analysis of recent progress in the application of ruthenium phosphides as HER electrocatalysts,offering key insights into their design and performance.Meanwhile,we explore various strategies to enhance their catalytic efficiency,such as increasing the availability of active sites and optimizing their electronic structure.Finally,we outline the key challenges and future directions for developing the next generation of ruthenium phosphide-based HER electrocatalysts.
基金financially supported by the National Natural Science Foundation of China(Nos.22209183,22225902,U22A20436)the Advanced Talents of Jiangsu University,China(No.23JDG027)。
文摘Developing efficient electrocatalysts for oxygen evolution reaction(OER)is imperative to enhance the overall efficiency of electrolysis systems and rechargeable metal-air batteries operating in aqueous solutions.High-entropy materials,featured with their distinctive multi-component properties,have found extensive application as catalysts in electrochemical energy storage and conversion devices.However,synthesizing nanostructured high-entropy compounds under mild conditions poses a significant challenge due to the difficulty in overcoming the immiscibility of multiple metallic constituents.In this context,the current study focuses on the synthesis of an array of nano-sized high entropy sulfides tailored for OER via a facile precursor pyrolysis method at low temperature.The representative compound,Fe Co Ni Cu Mn Sx,demonstrates remarkable OER performance,achieving a current density of 10 m A/cm^(2) at an overpotential of merely 220 m V and excellent stability with constant electrolysis at 100 m A/cm^(2) for over 400 h.The in-situ formed metal(oxy)hydroxide has been confirmed as the real active sites and its exceptional performance can be primarily attributed to the synergistic effects arising from its multiple components.Furthermore,the synthetic methodology presented here is versatile and can be extended to the preparation of high entropy phosphides,which also present favorable OER performance.This research not only introduces promising non-noble electrocatalysts for OER but also offers a facile approach to expand the family of nano high-entropy materials,contributing significantly to the field of electrochemical energy conversion.
基金financially supported by the Natural Science Foundation of Xinjiang Uygur Autonomous Region(2022D01E38).
文摘In recent years,the discharge of urea-containing wastewater from industrial and domestic sources has posed a continuing threat to aquatic ecosystems and human health.In this context,the urea oxidation reaction(UOR)has attracted significant attention due to its low thermodynamic potential of 0.37 V(vs.RHE).Compared with oxygen evolution reaction(OER),this reaction can significantly reduce the energy consumption of electrolysis while realizing wastewater treatment,and has the dual functions of hydrogen energy preparation and wastewater purification.However,UOR involves complex six-electron transfer and intermediate adsorption/desorption processes,resulting in slow reaction kinetics.Therefore,the development of economical and efficient catalysts has become a research focus,among which transition metal phosphides(TMPs)stand out due to their low cost,excellent activity and adjustable electronic structure.Compared with other non-noble metal systems,TMPs have unique electronic structure and surface properties that can adsorb and activate urea molecules more efficiently.However,there is still a lack of systematic reviews on TMP catalysts at present.Therefore,this review aims to deeply and systematically elaborate the design strategies of TMP catalysts and their applications in UOR,thoroughly discuss the current progress,challenges and future directions,and provide theoretical support and design ideas for the development of a new generation of efficient and stable UOR catalysts.
基金Self-innovation Capability Construction of Jilin Province Development and Reform Commission,Grant/Award Number:2021C026National Natural Science Foundation of China,Grant/Award Numbers:12034002,22202080,22279044,51872116Jilin Province Science and Technology Development Program,Grant/Award Number:20210301009GX。
文摘Strain effects have garnered significant attention in catalytic applications due to their ability to modulate the electronic structure and surface adsorption properties of catalysts.In this study,we propose a novel approach called“similar stacking”for stress modulation,achieved through the loading of Co_(2)P on Ni_(2)P(Ni_(2)P/Co_(2)P).Theoretical simulations reveal that the compressive strain induced by Co_(2)P influences orbital overlap and electron transfer with hydrogen atoms.Furthermore,the number of stacked layers can be adjusted by varying the precursor soaking time,which further modulates the strain range and hydrogen adsorption.Under a 2-h soaking condition,the strain effect proves favorable for efficient hydrogen production.Experimental characterizations using X-ray diffraction,high-angel annular dark-field scanning transmission election microscope(HAADF-STEM),and X-ray absorption near-edge structure spectroscopy successfully demonstrate lattice contraction of Co_(2)P and bond length shortening of Co-P.Remarkably,our catalyst shows an ultrahigh current density of 1 A cm^(-2) at an overpotential of only 388 mV,surpassing that of commercial Pt/C,while maintaining long-term stability.This material design strategy of similar stacking opens up new avenues of strain modulation and the deeper development of electrocatalysts.
