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
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
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
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
Nickel-based cathodes in aqueous nickel-zinc batteries typically suffer from sluggish reaction kinetics and limited energy density.In situ introduction of metal phosphides and rational construction of heterostructures...Nickel-based cathodes in aqueous nickel-zinc batteries typically suffer from sluggish reaction kinetics and limited energy density.In situ introduction of metal phosphides and rational construction of heterostructures can effectively promote electron/ion transport.However,the complex evolution of phosphidation and intractable phosphidizing degree greatly affect the composition of active phase,active sites,charge transfer rate,and ion adsorption strength of cathodes.Herein,the critical bimetallic phosphide layer(CBPL)is constructed on the NiCo-layered double hydroxide(NiCo-LDH)skeleton by a controllable anion-exchange strategy,yielding a novel nanohybrid cathode(NiCo-P1.0,1.0 representing the mass ratio of Na_(2)H_(2)PO_(2)to NiCo-LDH).The high-conductivity CBPL with the inner NiCo-LDH forms extensive heterostructures,effectively regulating the electronic structure via charge transfer,thereby improving electrical conductivity.Remarkably,the CBPL exhibits unexpected electrochemical activity and synergizes with NiCo-LDH for electrode reactions,ultimately delivering extra energy.Benefiting from the bifunctional CBPL,NiCo-P1.0 delivers an optimal capacity of 286.64 mAh g^(−1)at 1C(1C=289 mAh g^(−1))and superb rate performance(a capacity retention of 72.22%at 40C).The assembled NiCo-P1.0//Zn battery achieves ultrahigh energy/power density(503.62 Wh kg^(−1)/18.62 kW kg^(−1),based on the mass loading of active material on the cathode),and the flexible quasi-solid-state pouch cell validates its practicality.This work demonstrates the superiority of bifunctional CBPL for surface modification,providing an effective and scalable compositing strategy in achieving high-performance cathodes for aqueous batteries.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
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
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
High-entropy metal phosphide(HEMP)has considerable potential as an electrocatalyst owing to its beneficial properties,including high-entropy alloy synergy as well as the controllable structure and high conductivity of...High-entropy metal phosphide(HEMP)has considerable potential as an electrocatalyst owing to its beneficial properties,including high-entropy alloy synergy as well as the controllable structure and high conductivity of phosphides.Herein,electrospinning and in situ phosphating were employed to prepare three-dimensional(3D)networks of self-supporting HEMP nanofibers with varying degrees of phosphate content.Comprehensive characterizations via X-ray diffraction and X-ray photoelectron spectroscopy,as well as density functional theory calculations,demonstrate that the introduction of phosphorus(P)atoms to HEMP carbon nanofibers mediates their electronic structure,leads to lattice expansion,which in turn enhances their catalytic performance in the hydrogen evolution reaction(HER).Moreover,the formation of metal-P bonds weakens metal-metal interaction and decreases the free energy of hydrogen adsorption,contributing to the exceptional activity observed in the HEMP catalyst.Electrochemical measurements demonstrate that the HEMP-0.75 catalyst with an ultralow loading of 1.22 wt%ruthenium(Ru)exhibits the highest HER catalytic activity and stability in a 1 M KOH electrolyte,achieving a minimal overpotential of 26 mV at a current density of 10 mA·cm^(-2)and Tafel slope of 50.9 mV·dec^(-1).展开更多
Due to high theoretical specific capacity and excellent thermal stability,transition metal phosphides(TMPs)have emerged as highly promising candidates of anode materials for advancing lithium-ion batteries.However,it ...Due to high theoretical specific capacity and excellent thermal stability,transition metal phosphides(TMPs)have emerged as highly promising candidates of anode materials for advancing lithium-ion batteries.However,it remains confronted with significant challenges,including large volume expansion,low specific surface area and limited electron conductivity,which hinder their practical application in the field of energy storage.Herein,nitrogen,phosphoric-codoped carbon nanosheets decorated with cobalt phosphide nanoparticles(CoP/N,P-C)are synthesized through a simple and environment-friendly synthesis method demonstrating their potential as anode materials for lithium-ion batteries.The element-doped carbon matrix can enhance electrical conductivity,accelerate ion transport,improve the active sites,and buffer the volume expansion of CoP nanoparticles,collectively leading to significantly improved electrochemical performance.The prepared CoP/N,P-C electrodes present outstanding electrochemical performance,delivering a discharge specific capacity of 920 mAh g^(-1)after 100 cycles at 0.1 A g^(-1)and 686mAh g^(-1)after 3,000 cycles even at 2.0 A g^(-1).The quantitative kinetic analysis result reveals that pseudo-capacitance dominates total capacity behavior(70.6%at 0.5 mV s-1).Furthermore,the galvanostatic intermittent titration technique(GITT)is applied to prove the super-fast diffusion coefficient of the electrodes.This work provides a simplified and environmentally friendly method for effective modification of the comprehensive properties of transition metal phosphates.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
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
The practical application of lithium-sulfur(Li-S)batteries is still impeded by the severe shuttle effect of lithium polysulfides(LiPSs)and sluggish reaction kinetics of active sulfur.Designing catalytic carriers with ...The practical application of lithium-sulfur(Li-S)batteries is still impeded by the severe shuttle effect of lithium polysulfides(LiPSs)and sluggish reaction kinetics of active sulfur.Designing catalytic carriers with abundant active sites and strong chemisorption capability for LiPSs,is regarded as effective strategy to address these issues.Herein,Se-doping is introduced into the nitrogen-doped carbon coated CoP composite(Se-CoP@NC)to generate structural defects,which effectively enlarges the lattice spacing of CoP and reduces the conversion reaction energy barriers of LiPSs.Meanwhile,Se-doping sites bridges the interface of CoP and nitrogen-doped carbon,accelerating the charge transfer behavior and conversion reaction kinetics of LiPSs.Benefiting from the structural advantages,the assembled Li-S batteries with S/Se-CoP@NC as cathode exhibit high reversible capacity of 779.6 mAh/g at 0.5 C after 500 cycles,and high specific capacity of 805.9 mAh/g at 2 C.Even under extreme conditions(high sulfur-loading content of 6.9 mg/cm^(2);lean electrolyte dosage of 7μL/mg),the corresponding Li-S batteries also keep high reversible areal capacity of 4.5 mAh/cm^(2) after 100 cycles at 0.1 C.This work will inspire the design of metal compounds-based catalysts from atomic level to facilitate the practicability of Li-S batteries.展开更多
Supercapacitors(SCs)are considered promising energy storge systems because of their outstanding power density,fast charge and discharge rate and long-term cycling stability.The exploitation of cheap and efficient elec...Supercapacitors(SCs)are considered promising energy storge systems because of their outstanding power density,fast charge and discharge rate and long-term cycling stability.The exploitation of cheap and efficient electrode materials is the key to improve the performance of supercapacitors.As the battery-type materials,transition metal phosphides(TMPs)possess high theoretical specific capacity,good electrical conductivity and superior structural stability,which have been extensively studied to be electrode materials for supercapacitors.In this review,we summarize the up-to-date progress on TMPs materials from diversified synthetic methods,diverse nanostructures and several prominent TMPs and their composites in application of supercapacitors.In the end,we also propose the remaining challenges toward the rational discovery and synthesis of high-performance TMP electrodes materials for energy storage.展开更多
Commercial hydrodesulfurization(HDS)cata-lysts consist of MoS_(2)-type phases supported on γ-Al2O3 and promoted by Co or Ni[1.2].More strin-gent environmental regulations mean that the activity of such catalysts must...Commercial hydrodesulfurization(HDS)cata-lysts consist of MoS_(2)-type phases supported on γ-Al2O3 and promoted by Co or Ni[1.2].More strin-gent environmental regulations mean that the activity of such catalysts must be improved.Thus,there isgrowing interest in developing alternatives,which in-clude transition metal nitrides and carbides[3,4],to the widely used sulfides.Transition metal phosphides have recently been reported as a new class of highly active hydroprocessing catalysts that have substantial promise as the next generation catalysts.They are a group of stable,sulfur-resistant metallic compounds that have exceptional hydroprocessing properties[5,6].In this paper,Ni_(2)P,MoP,NiMoP,Ni_(2)P/SiO_(2),MoP/SiO_(2) and NiMoP/SiO_(2) were prepared from an inexpensive phosphate precursor by the temperature-programmed reduction method.Dibenzothiophene(DBT)HDS activity of these phosphide catalysts was measured and compared with MoS_(2)/SiO_(2),NiS/SiO_(2) and NiMoS/SiO_(2) catalysts.展开更多
A wet etching process for backside via holes suitable for use on InP MMICs technologies is developed for indium phosphide substrate.PMMA is used to mount InP wafer onto glass carrier.Spattered Ta film is utilized as e...A wet etching process for backside via holes suitable for use on InP MMICs technologies is developed for indium phosphide substrate.PMMA is used to mount InP wafer onto glass carrier.Spattered Ta film is utilized as etch mask.HCl+H 3PO 4 solution realised a etch until a depth of 100μm.It is demonstrated that the wet etching backside process is controllable with large latitudes.展开更多
In order to investigate the effect of nickel phosphide nanoparticles’ （Ni-P NPs） crystallization on hydrogen evolution reaction （HER） catalytic performance, amorphous Ni-P NPs and crystalline Ni12P5 were synt...In order to investigate the effect of nickel phosphide nanoparticles’ （Ni-P NPs） crystallization on hydrogen evolution reaction （HER） catalytic performance, amorphous Ni-P NPs and crystalline Ni12P5 were synthesized by a simple and low-cost autocatalytic reduction method and heat treatment process. The result of electrochemical tests shows that crystalline Ni12P5 has much higher HER catalytic activity than the amorphous one. X-ray diffraction, transmission electron microscopy and X-ray photoelectron spectroscopy revealed that Ni？P bond formed during crystallization, making Ni positively charged and P negatively charged. This charged nature of Ni12P5 is similar to [NiFe] hydrogenase and its analogous, which make the removal of H2 less energy-cost.展开更多
Oxygen evolution reaction(OER),as an important half‐reaction involved in water splitting,has been intensely studied since the last century.Transition metal phosphide and sulfide‐based compounds have attracted increa...Oxygen evolution reaction(OER),as an important half‐reaction involved in water splitting,has been intensely studied since the last century.Transition metal phosphide and sulfide‐based compounds have attracted increasing attention as active OER catalysts due to their excellent physical and chemical characters,and massive efforts have been devoted to improving the phosphide and sulfide‐based materials with better activity and stability in recent years.In this review,the recent progress on phosphide and sulfide‐based OER electrocatalysts in terms of chemical properties,synthetic methodologies,catalytic performances evaluation and improvement strategy is reviewed.The most accepted reaction pathways as well as the thermodynamics and electrochemistry of the OER are firstly introduced in brief,followed by a summary of the recent research and optimization strategy of phosphide and sulfide‐based OER electrocatalysts.Finally,some mechanistic studies of the active phase of phosphide and sulfide‐based compounds are discussed to give insight into the nature of active catalytic sites.It is expected to indicate guidance for further improving the performances of phosphide and sulfide‐based OER electrocatalysts.展开更多
Two series of WP/Al2O3 catalyst precursors with WP mass loading in the range 18.5%—37.1% were prepared using the impregnation method and mixing method, respectively, and the catalysts were then obtained by temperatur...Two series of WP/Al2O3 catalyst precursors with WP mass loading in the range 18.5%—37.1% were prepared using the impregnation method and mixing method, respectively, and the catalysts were then obtained by temperature-programmed reduction of supported tungsten phosphate (precursor of WP/Al2O3 catatlysts) in H2 at 650℃ for 4h. The catalysts were characterized by XRD, BET, TG/DTA , XPS and 31P MAS-NMR. The activities of these catalysts were tested in the hydrodenitrogenation (HDN) of pyridine and hydrodesulfurization (HDS) of thiophene at 340℃ and 3.0MPa. The results showed that owing to the stronger interaction of the support with the active species, the precursor of WP/Al2O3 catalyst was more difficultly phosphided and a greater amount of W spe- cies was in a high valence state W6+ on the surface of the catalyst prepared by the impregnation method than that by the mixing method. 31P MAS-NMR results indicated that 31P shift from 85% H3PO4 of 2.55×10-4 for WP and 2.57 ×10-4 for WP/γ-Al2O3 catalysts prepared by mixing method. Such WP/Al2O3 catalysts showed higher HDN activi- ties and lower HDS activities than those prepared by the impregnation method under the same loading of WP. WP/γ-Al2O3 catalysts with weak interaction between support and active species were favorable for HDN reaction while the WP/γ-Al2O3 catalysts with strong interaction were favorable for HDS reaction.展开更多
Transition metal phosphides(TMPs)have been regarded as alternative hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)catalysts owing to their comparable activity to those of noble metal-based catalysts...Transition metal phosphides(TMPs)have been regarded as alternative hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)catalysts owing to their comparable activity to those of noble metal-based catalysts.TMPs have been produced in various morphologies,including hollow and porous nanostructures,which are features deemed desirable for electrocatalytic materials.Templated synthesis routes are often responsible for such morphologies.This paper reviews the latest advances and existing challenges in the synthesis of TMP-based OER and HER catalysts through templated methods.A comprehensive review of the structure-property-performance of TMP-based HER and OER catalysts prepared using different templates is presented.The discussion proceeds according to application,first by HER and further divided among the types of templates used-from hard templates,sacrificial templates,and soft templates to the emerging dynamic hydrogen bubble template.OER catalysts are then reviewed and grouped according to their morphology.Finally,prospective research directions for the synthesis of hollow and porous TMP-based catalysts,such as improvements on both activity and stability of TMPs,design of environmentally benign templates and processes,and analysis of the reaction mechanism through advanced material characterization techniques and theoretical calculations,are suggested.展开更多
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.
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 National Natural Science Foundation of China(No.52373249,W2433146)the Science and Technology Project of Yibin Sanjiang New Area(No.2023SJXQSXZJ003)the Fundamental Research Funds for the Central Universities(No.20822041F4045).
文摘Nickel-based cathodes in aqueous nickel-zinc batteries typically suffer from sluggish reaction kinetics and limited energy density.In situ introduction of metal phosphides and rational construction of heterostructures can effectively promote electron/ion transport.However,the complex evolution of phosphidation and intractable phosphidizing degree greatly affect the composition of active phase,active sites,charge transfer rate,and ion adsorption strength of cathodes.Herein,the critical bimetallic phosphide layer(CBPL)is constructed on the NiCo-layered double hydroxide(NiCo-LDH)skeleton by a controllable anion-exchange strategy,yielding a novel nanohybrid cathode(NiCo-P1.0,1.0 representing the mass ratio of Na_(2)H_(2)PO_(2)to NiCo-LDH).The high-conductivity CBPL with the inner NiCo-LDH forms extensive heterostructures,effectively regulating the electronic structure via charge transfer,thereby improving electrical conductivity.Remarkably,the CBPL exhibits unexpected electrochemical activity and synergizes with NiCo-LDH for electrode reactions,ultimately delivering extra energy.Benefiting from the bifunctional CBPL,NiCo-P1.0 delivers an optimal capacity of 286.64 mAh g^(−1)at 1C(1C=289 mAh g^(−1))and superb rate performance(a capacity retention of 72.22%at 40C).The assembled NiCo-P1.0//Zn battery achieves ultrahigh energy/power density(503.62 Wh kg^(−1)/18.62 kW kg^(−1),based on the mass loading of active material on the cathode),and the flexible quasi-solid-state pouch cell validates its practicality.This work demonstrates the superiority of bifunctional CBPL for surface modification,providing an effective and scalable compositing strategy in achieving high-performance cathodes for aqueous batteries.
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.
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(Nos.22103045 and 52273077)the State Key Laboratory of Bio-Fibers and Eco-Textiles,Qingdao University(Nos.ZDKT202108,RZ2000003334 and G2RC202022)support from the Australian National Fabrication Facility’s Queensland Node(No.ANFF-Q),the UQ-Yonsei International Research Project,and the JST-ERATO Yamauchi Materials Space-Tectonics Project(No.JPMJER2003).
文摘High-entropy metal phosphide(HEMP)has considerable potential as an electrocatalyst owing to its beneficial properties,including high-entropy alloy synergy as well as the controllable structure and high conductivity of phosphides.Herein,electrospinning and in situ phosphating were employed to prepare three-dimensional(3D)networks of self-supporting HEMP nanofibers with varying degrees of phosphate content.Comprehensive characterizations via X-ray diffraction and X-ray photoelectron spectroscopy,as well as density functional theory calculations,demonstrate that the introduction of phosphorus(P)atoms to HEMP carbon nanofibers mediates their electronic structure,leads to lattice expansion,which in turn enhances their catalytic performance in the hydrogen evolution reaction(HER).Moreover,the formation of metal-P bonds weakens metal-metal interaction and decreases the free energy of hydrogen adsorption,contributing to the exceptional activity observed in the HEMP catalyst.Electrochemical measurements demonstrate that the HEMP-0.75 catalyst with an ultralow loading of 1.22 wt%ruthenium(Ru)exhibits the highest HER catalytic activity and stability in a 1 M KOH electrolyte,achieving a minimal overpotential of 26 mV at a current density of 10 mA·cm^(-2)and Tafel slope of 50.9 mV·dec^(-1).
基金financially supported by the National Natural Science Foundation of China(Nos.52207249 and 52472131)the Excellent Youth Innovation Team Project for Higher Education Institutions of Shandong Province(No.2023KJ238)+2 种基金the Major basic research project of Natural Science Foundation of Shandong Province(Nos.ZR2023ZD12 and ZR2023ZD13)Yantai Basic Research Project(No.2022JCYJ04)the Science Fund of Shandong Laboratory of Advanced Materials and Green Manufacturing at Yantai(No.AMGM2024F27)
文摘Due to high theoretical specific capacity and excellent thermal stability,transition metal phosphides(TMPs)have emerged as highly promising candidates of anode materials for advancing lithium-ion batteries.However,it remains confronted with significant challenges,including large volume expansion,low specific surface area and limited electron conductivity,which hinder their practical application in the field of energy storage.Herein,nitrogen,phosphoric-codoped carbon nanosheets decorated with cobalt phosphide nanoparticles(CoP/N,P-C)are synthesized through a simple and environment-friendly synthesis method demonstrating their potential as anode materials for lithium-ion batteries.The element-doped carbon matrix can enhance electrical conductivity,accelerate ion transport,improve the active sites,and buffer the volume expansion of CoP nanoparticles,collectively leading to significantly improved electrochemical performance.The prepared CoP/N,P-C electrodes present outstanding electrochemical performance,delivering a discharge specific capacity of 920 mAh g^(-1)after 100 cycles at 0.1 A g^(-1)and 686mAh g^(-1)after 3,000 cycles even at 2.0 A g^(-1).The quantitative kinetic analysis result reveals that pseudo-capacitance dominates total capacity behavior(70.6%at 0.5 mV s-1).Furthermore,the galvanostatic intermittent titration technique(GITT)is applied to prove the super-fast diffusion coefficient of the electrodes.This work provides a simplified and environmentally friendly method for effective modification of the comprehensive properties of transition metal phosphates.
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the financial support from the National Natural Science Foundation of China(No.52101250)the S&T program of Hebei(Nos.215A4401D and 225A4404D)+5 种基金the Collaborative Innovation Center of Marine Science and Technology of Hainan University(No.XTCX2022HYC14)the Fundamental Research Funds for the Hebei University(No.2021YWF11)the Science Research Project of Hebei Education Department(No.QN2024087)the Xingtai City Natural Science Foundation(No.2023ZZ027)the Key Laboratory of Advanced Energy Materials Chemistry(Ministry of Education),College of Chemistry,Nankai Universitypartially supported by the Pico Election Microscopy Center of Hainan University。
文摘The practical application of lithium-sulfur(Li-S)batteries is still impeded by the severe shuttle effect of lithium polysulfides(LiPSs)and sluggish reaction kinetics of active sulfur.Designing catalytic carriers with abundant active sites and strong chemisorption capability for LiPSs,is regarded as effective strategy to address these issues.Herein,Se-doping is introduced into the nitrogen-doped carbon coated CoP composite(Se-CoP@NC)to generate structural defects,which effectively enlarges the lattice spacing of CoP and reduces the conversion reaction energy barriers of LiPSs.Meanwhile,Se-doping sites bridges the interface of CoP and nitrogen-doped carbon,accelerating the charge transfer behavior and conversion reaction kinetics of LiPSs.Benefiting from the structural advantages,the assembled Li-S batteries with S/Se-CoP@NC as cathode exhibit high reversible capacity of 779.6 mAh/g at 0.5 C after 500 cycles,and high specific capacity of 805.9 mAh/g at 2 C.Even under extreme conditions(high sulfur-loading content of 6.9 mg/cm^(2);lean electrolyte dosage of 7μL/mg),the corresponding Li-S batteries also keep high reversible areal capacity of 4.5 mAh/cm^(2) after 100 cycles at 0.1 C.This work will inspire the design of metal compounds-based catalysts from atomic level to facilitate the practicability of Li-S batteries.
基金supported by National Undergraduate Training Programs for Innovations[grant number 202210225259]the Outstanding Youth Project of Natural Science Foundation in Heilongjiang Province(YQ2022E040)+3 种基金the Shandong Provincial Natural Science Foundation(ZR2022ME166)the Postdoctoral Scientific Research Developmental Fund of Heilongjiang Province(LBH-Q20023)the University Nursing Program for Young Scholars with Creative Talents in Heilongjiang Province(UNPYSCT-2020197)the 111 Project(B20088).
文摘Supercapacitors(SCs)are considered promising energy storge systems because of their outstanding power density,fast charge and discharge rate and long-term cycling stability.The exploitation of cheap and efficient electrode materials is the key to improve the performance of supercapacitors.As the battery-type materials,transition metal phosphides(TMPs)possess high theoretical specific capacity,good electrical conductivity and superior structural stability,which have been extensively studied to be electrode materials for supercapacitors.In this review,we summarize the up-to-date progress on TMPs materials from diversified synthetic methods,diverse nanostructures and several prominent TMPs and their composites in application of supercapacitors.In the end,we also propose the remaining challenges toward the rational discovery and synthesis of high-performance TMP electrodes materials for energy storage.
基金Supported by the National Basic Researeh Program of China(G2000048003)the National Natural Science Foundationof China(20303018).
文摘Commercial hydrodesulfurization(HDS)cata-lysts consist of MoS_(2)-type phases supported on γ-Al2O3 and promoted by Co or Ni[1.2].More strin-gent environmental regulations mean that the activity of such catalysts must be improved.Thus,there isgrowing interest in developing alternatives,which in-clude transition metal nitrides and carbides[3,4],to the widely used sulfides.Transition metal phosphides have recently been reported as a new class of highly active hydroprocessing catalysts that have substantial promise as the next generation catalysts.They are a group of stable,sulfur-resistant metallic compounds that have exceptional hydroprocessing properties[5,6].In this paper,Ni_(2)P,MoP,NiMoP,Ni_(2)P/SiO_(2),MoP/SiO_(2) and NiMoP/SiO_(2) were prepared from an inexpensive phosphate precursor by the temperature-programmed reduction method.Dibenzothiophene(DBT)HDS activity of these phosphide catalysts was measured and compared with MoS_(2)/SiO_(2),NiS/SiO_(2) and NiMoS/SiO_(2) catalysts.
文摘A wet etching process for backside via holes suitable for use on InP MMICs technologies is developed for indium phosphide substrate.PMMA is used to mount InP wafer onto glass carrier.Spattered Ta film is utilized as etch mask.HCl+H 3PO 4 solution realised a etch until a depth of 100μm.It is demonstrated that the wet etching backside process is controllable with large latitudes.
基金Project(51125016)supported by the National Science Fund for Distinguished Young Scholars,ChinaProjects(51371119,51571151)supported by the National Natural Science Foundation of China
文摘In order to investigate the effect of nickel phosphide nanoparticles’ （Ni-P NPs） crystallization on hydrogen evolution reaction （HER） catalytic performance, amorphous Ni-P NPs and crystalline Ni12P5 were synthesized by a simple and low-cost autocatalytic reduction method and heat treatment process. The result of electrochemical tests shows that crystalline Ni12P5 has much higher HER catalytic activity than the amorphous one. X-ray diffraction, transmission electron microscopy and X-ray photoelectron spectroscopy revealed that Ni？P bond formed during crystallization, making Ni positively charged and P negatively charged. This charged nature of Ni12P5 is similar to [NiFe] hydrogenase and its analogous, which make the removal of H2 less energy-cost.
文摘Oxygen evolution reaction(OER),as an important half‐reaction involved in water splitting,has been intensely studied since the last century.Transition metal phosphide and sulfide‐based compounds have attracted increasing attention as active OER catalysts due to their excellent physical and chemical characters,and massive efforts have been devoted to improving the phosphide and sulfide‐based materials with better activity and stability in recent years.In this review,the recent progress on phosphide and sulfide‐based OER electrocatalysts in terms of chemical properties,synthetic methodologies,catalytic performances evaluation and improvement strategy is reviewed.The most accepted reaction pathways as well as the thermodynamics and electrochemistry of the OER are firstly introduced in brief,followed by a summary of the recent research and optimization strategy of phosphide and sulfide‐based OER electrocatalysts.Finally,some mechanistic studies of the active phase of phosphide and sulfide‐based compounds are discussed to give insight into the nature of active catalytic sites.It is expected to indicate guidance for further improving the performances of phosphide and sulfide‐based OER electrocatalysts.
基金Supported by the National Natural Science Foundation of China (No.200273011), the National 973 Project (No.G2000048003)and the Beijing Natural Science Foundation (No.2052009).
文摘Two series of WP/Al2O3 catalyst precursors with WP mass loading in the range 18.5%—37.1% were prepared using the impregnation method and mixing method, respectively, and the catalysts were then obtained by temperature-programmed reduction of supported tungsten phosphate (precursor of WP/Al2O3 catatlysts) in H2 at 650℃ for 4h. The catalysts were characterized by XRD, BET, TG/DTA , XPS and 31P MAS-NMR. The activities of these catalysts were tested in the hydrodenitrogenation (HDN) of pyridine and hydrodesulfurization (HDS) of thiophene at 340℃ and 3.0MPa. The results showed that owing to the stronger interaction of the support with the active species, the precursor of WP/Al2O3 catalyst was more difficultly phosphided and a greater amount of W spe- cies was in a high valence state W6+ on the surface of the catalyst prepared by the impregnation method than that by the mixing method. 31P MAS-NMR results indicated that 31P shift from 85% H3PO4 of 2.55×10-4 for WP and 2.57 ×10-4 for WP/γ-Al2O3 catalysts prepared by mixing method. Such WP/Al2O3 catalysts showed higher HDN activi- ties and lower HDS activities than those prepared by the impregnation method under the same loading of WP. WP/γ-Al2O3 catalysts with weak interaction between support and active species were favorable for HDN reaction while the WP/γ-Al2O3 catalysts with strong interaction were favorable for HDS reaction.
基金the support from the CIPHER Project(IIID 2018-008)funded by the Commission on Higher Education-Philippine California Advanced Research Institutes(CHED-PCARI)。
文摘Transition metal phosphides(TMPs)have been regarded as alternative hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)catalysts owing to their comparable activity to those of noble metal-based catalysts.TMPs have been produced in various morphologies,including hollow and porous nanostructures,which are features deemed desirable for electrocatalytic materials.Templated synthesis routes are often responsible for such morphologies.This paper reviews the latest advances and existing challenges in the synthesis of TMP-based OER and HER catalysts through templated methods.A comprehensive review of the structure-property-performance of TMP-based HER and OER catalysts prepared using different templates is presented.The discussion proceeds according to application,first by HER and further divided among the types of templates used-from hard templates,sacrificial templates,and soft templates to the emerging dynamic hydrogen bubble template.OER catalysts are then reviewed and grouped according to their morphology.Finally,prospective research directions for the synthesis of hollow and porous TMP-based catalysts,such as improvements on both activity and stability of TMPs,design of environmentally benign templates and processes,and analysis of the reaction mechanism through advanced material characterization techniques and theoretical calculations,are suggested.
