Transition metal phosphides(TMPs)are recognized as such promising supercapacitor materials for the practical application,due to their superior electrical conductivity and excellent redox activity.Here,self-supported t...Transition metal phosphides(TMPs)are recognized as such promising supercapacitor materials for the practical application,due to their superior electrical conductivity and excellent redox activity.Here,self-supported three-dimensional NiCoP nanoparticles embedded in NiCoO2 nano wires(NiCoO2/NiCoP)electrode consisting of nickel cobalt phosphides(NiCoP)with high activity and nickel cobalt oxides(NiCoO2)with good stability were fabricated by a hydrothermal and phosphorization method.The electrode integrates the advantages of nanowire arrays for fast ion transport and foam Ni for effective charge transport and flexibility.Benefitting the proper composition control of the nanohybrid and unique structure design,the optimized NiCoO2/NiCoP-20 exhibits a high specific capacitance of 3204 F·g-1 at 1 A·g-1 in 3 mol·L-1 KOH aqueous electrolyte in a three-electrode system.Moreover,the asymmetric supercapacitor assembled with the prepared NiCoO2/NiCoP-20 and activated carbon achieves a specific capacitance of 116 F·g-1 with a high energy density of 40.32 Wh·kg-1 at the power density of 800.18 W·kg-1.The practical application is further demonstrated with all-solid-state winding supercapacitor devices,with decent flexibility,in series to light the Central South University(CSU)logo consisting of 21 red LED indicators.展开更多
The ternary cobalt-nickel-iron phosphide nanocubes (P-Co0.9Ni0.9Fe1.2 NCs) with high intrinsic activity, conductivity, defect concentration and optimized ratio have been realized through a facile phosphorization treat...The ternary cobalt-nickel-iron phosphide nanocubes (P-Co0.9Ni0.9Fe1.2 NCs) with high intrinsic activity, conductivity, defect concentration and optimized ratio have been realized through a facile phosphorization treatment using ternary cobalt-nickel-iron nanocubes of Prussian blue analogs (PBA) as a precursor. The scanning electron microscopy and transmission electron microscopy results show that the P-Co0.9Ni0.9Fe1.2 NCs maintain a cubic structure with a rough surface, implying the rich surface defects as exposed active sites. The thermal phosphorization of the ternary PBA precursor not only provids carbon doping but also leads to the in situ construction of surface defects on the NCs. The carbon doping from the PBA precursor lowers the charge transfer resistance and optimizes the electronic transformation. The synergistic effect among the ternary metal ions and rich defects contributes to the enhanced electrocatalytic performance . The P-Co0.9Ni0.9Fe1.2NCs achieve low overpotentials of -200.7 and 273.1 mV at a current density of 10 mA cm^-2 for the hydrogen evolution reaction and the oxygen evolution reaction, respectively. The potential of overall water splitting reaches 1.52 V at a current density of 10 mA cm^-2. The longterm stability of the electrocatalysts was also evaluated. This work provides a facile method to design efficient transitionmetal- based bifunctional electrocatalysts for overall water splitting.展开更多
Sodium-ion batteries have received remarkable attention as next-generation high-performance electrochemical energy storage devices because of their cost effectiveness and the broad geographical distribution of sodium....Sodium-ion batteries have received remarkable attention as next-generation high-performance electrochemical energy storage devices because of their cost effectiveness and the broad geographical distribution of sodium. As a critical component of sodium-ion batteries, anode materials, especially nanostructured anodes, have a significant effect on the electrochemical performance of sodium-ion batteries. Recent research indicates that phosphorus and metal phosphides show great promise as anode candidates for sodium-ion batteries because of their low cost and relatively high theoretical gravimetric and volumetric specific capacities. In this review, we systematically summarize recent research progress on state-of-the-art nanostructured phosphorus and phosphides, including the synthetic strategies, Na-storage mechanisms, and the relationship between the nanostructure and electrochemical performance. Moreover, we present an overview of future challenges and opportunities based on current developments.展开更多
Sodium-ion batteries(SIBs)have been extensively studied as the potential alter-native to lithium-ion batteries(LIBs)due to the abundant natural reserves and low price of sodium resources.Nevertheless,Na+ions possess a...Sodium-ion batteries(SIBs)have been extensively studied as the potential alter-native to lithium-ion batteries(LIBs)due to the abundant natural reserves and low price of sodium resources.Nevertheless,Na+ions possess a larger radius than Li+,resulting in slow diffusion dynamics in electrode materials,and thus seeking appropriate anode materials to meet high performance standards has become a trend in the field of SIBs.In this context,owing to the advantages of high theoretical capacity and proper redox potential,metal phosphides(MPs)are considered to be the promising materials to make up for the gap of SIBs anode materials.In this review,the recent development of MPs anode materials for SIBs is reviewed and analyzed comprehensively and deeply,including the synthesis method,advanced modification strategy,electrochemical performance,and Na storage mechanism.In addition,to promote the wide application of the emerg-ing MPs anodes for SIBs,several research emphases in the future are pointed out to overcome challenges toward the commercial application.展开更多
Developing low-cost and earth-abundant electrocatalysts with high performance for electrochemical water splitting is a challenging issue. Herein, we report a facile and effective way to fabricate three-dimension(3D) o...Developing low-cost and earth-abundant electrocatalysts with high performance for electrochemical water splitting is a challenging issue. Herein, we report a facile and effective way to fabricate three-dimension(3D) ordered mesoporous Co1-xFexP(x=0, 0.25, 0.5, 0.75) electrocatalyst.Benefiting from 3D ordered mesoporous pore channels and composition optimization, the Co0.75Fe0.25 P exhibits excellent electrocatalytic activities with low overpotentials of 270 and 209 mV at 10 mA cm^-2 for oxygen evolution reaction(OER)and hydrogen evolution reaction(HER), respectively, in the alkaline electrolyte along with a durable electrochemical stability. In addition, as both the cathode and anode, the Co0.75Fe0.25P also exhibits superior electrolysis water splitting performance with only an applied voltage of 1.63 V to attain a current density of 10 m A cm^-2 without obvious decay for 18 h,indicating that the Co0.75Fe0.25P is an efficient electrocatalyst for overall water splitting.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
It is a great challenge to develop highly active oxygen evolution reaction(OER)electrocatalysts with superior durability.In this study,a NiFe layered double hydroxidedecorated phosphide(NiFe LDH@CoP/NiP_(3))was constr...It is a great challenge to develop highly active oxygen evolution reaction(OER)electrocatalysts with superior durability.In this study,a NiFe layered double hydroxidedecorated phosphide(NiFe LDH@CoP/NiP_(3))was constructed to display satisfactory OER activity and good stability for water splitting in alkaline media.At an overpotential of 300 mV,NiFe LDH@CoP/NiP_(3) achieved a current density of 82 mA cm^(-2) for the OER,which was 9.1 and 2.3 times that of CoP/NiP_(3) and NiFe LDH,respectively.Moreover,the reconstruction behavior,during which oxyhydroxides formed,was studied by a combination of X-ray photoelectron spectroscopy,Raman spectroscopy,and scanning electron microscopy.A synergistic effect between NiFe LDH and CoP/NiP_(3) was also observed for the hydrogen evolution reaction.Furthermore,when NiFe LDH@CoP/NiP_(3) acted as both the cathode and anode for overall water splitting,a high current density of 100 mA cm^(-2) was maintained for more than 275 h.In addition,under Xe light irradiation,a solar-to-hydrogen efficiency of 9.89% was achieved for solar-driven water splitting.This work presents the coupling of different active compositions,and can provide a reference for designing bifunctional electrocatalysts.展开更多
Among the sustainable energy sources,hydrogen is the one most promising for alleviating the pollution issues related to the usage of conventional fuels,as it can be produced in an efficient and eco-friendly way via el...Among the sustainable energy sources,hydrogen is the one most promising for alleviating the pollution issues related to the usage of conventional fuels,as it can be produced in an efficient and eco-friendly way via electrocatalytic water splitting.The hydrogen evolution reaction(HER,a half-reaction of water splitting)plays a pivotal role in decreasing the price and increasing the catalytic efficiency of hydrogen production and is efficiently promoted by metal phosphides in different electrolytes.Herein,we summarize the recent advances in the development of metal phosphides as HER electrocatalysts,focus on their synthesis(post-treatment,in situ generation,and electrodeposition methods)and the enhancement of their electrocatalytic activity(via elemental doping,interface and vacancy engineering,construction of specific supports and nanostructures,and the design of bior polymetallic phosphides),and highlight the crucial issues and challenges of future development.展开更多
A highly active bi-functional electrocatalyst towards both hydrogen and oxygen evolution reactions is critical for the water splitting. Herein, a self-supported electrode composed of 3D network nanostructured NiCoP na...A highly active bi-functional electrocatalyst towards both hydrogen and oxygen evolution reactions is critical for the water splitting. Herein, a self-supported electrode composed of 3D network nanostructured NiCoP nanosheets grown on N-doped carbon coated Ni foam （NiCoP/NF@NC） has been synthesized by a hydrothermal route and a subsequent phosphorization process. As a bifunctional electrocatalyst, the NiCoP/NF@NC electrode needs overpotentials of 31.8 mV for hydrogen evolution reaction and 308.2 mV for oxygen evolution reaction to achieve the current density of 10 mA·cm^-2 in 1 mol·L^-1 KOH electrolyte. This is much better than the correspond- ing monometal catalysts of CoP/NF@NC and NiP/ NF@NC owing to the synergistic effect. NiCoP/NF@NC also exhibits low Tafel slope, and excellent long-term stability, which are comparable to the commercial noble catalysts of Pt/C and RuO2.展开更多
Rational design of efficient bifunctional electrocatalysts is highly imperative but still a challenge for overall water splitting.Herein,we construct novel freestanding Mo-doped NiCoP nanosheet arrays by the hydrother...Rational design of efficient bifunctional electrocatalysts is highly imperative but still a challenge for overall water splitting.Herein,we construct novel freestanding Mo-doped NiCoP nanosheet arrays by the hydrothermal and phosphation processes,serving as bifunctional electrocatalysts for overall water splitting.Notably,Mo doping could effectively modulate the electronic structure of NiCoP,leading to the increased electroactive site and improved intrinsic activity of each site.Furthermore,an electrochemical activation strategy is proposed to form Mo-doped(Ni,Co)OOH to fully boost the electrocatalytic activities for oxygen evolution reaction.Benefiting from the unique freestanding structure and Mo doping,Mo-doped NiCoP and(Ni,Co)OOH show the remarkable electrochemical performances,which are competitive among current researches.In addition,an overall water splitting device assembled by both electrodes only requires a cell voltage of 1.61 V to reach a current density of 10 mA cm?2.Therefore,this work opens up new avenues for designing nonprecious bifunctional electrocatalysts by Mo doping and in situ electrochemical activation.展开更多
The construction of highly active catalysts for methanol oxidation reaction(MOR)is central to direct methanol fuel cells.Tremendous progress has been made in transition metal phosphides(TMPs)based catalysts.However,TM...The construction of highly active catalysts for methanol oxidation reaction(MOR)is central to direct methanol fuel cells.Tremendous progress has been made in transition metal phosphides(TMPs)based catalysts.However,TMPs would be partially damaged and transformed into new substances(e.g.,Pt-M-P composite,where M represents a second transition metal)during Pt deposition process.This would pose a large obstacle to the cognition of the real promoting effects of TMPs in MOR.Herein,Co_(2)P co-catalysts(Pt-P/Co_(2)P@NPC,where NPC stands for N and P co-doped carbon)and Pt-Co-P composite catalysts(Pt-CoP/NPC)were controllably synthesized.Electrocatalysis tests show that the Pt-Co-P/NPC exhibits superior MOR activity as high as 1016 m A/mg_(Pt),significantly exceeding that of Pt-P/Co_(2)P@NPC(345 m A/mg_(Pt)).This result indicates that the promoting effect is ascribed primarily to the resultant Pt-Co-P composite,in sharply contrast to previous viewpoint that Co_(2)P itself improves the activity.Further mechanistic studies reveal that Pt-Co-P/NPC exhibits much stronger electron interaction and thus manifesting a remarkably weaker CO absorption than Pt-P/Co_(2)P@NPC and Pt/C.Moreover,Pt-Co-P is also more capable of producing oxygen-containing adsorbate and thus accelerating the removal of surface-bonded CO^(*),ultimately boosting the MOR performance.展开更多
The hydrogen evolution reaction(HER)via water electrolysis has gained immense research attention.Seawater electrolysis provides great opportunities for sustainable energy production,but is extremely challenging.Transi...The hydrogen evolution reaction(HER)via water electrolysis has gained immense research attention.Seawater electrolysis provides great opportunities for sustainable energy production,but is extremely challenging.Transition metal phosphides are promising candidate electrocatalysts.Herein,we prepared a novel Fe-Co_(2)P bundle of nanorods(BNRs)for catalyzing the HER in seawater electrolysis and over the entire p H range.Cobalt phosphides with different crystal phases and morphologies were obtained by varying the Fe doping amount.The Co:Fe molar ratio of 1:0.5 was found to be optimum.The Fe doping improved the HER performance of Co_(2)P over the entire p H range by providing favorable electronic properties and morphology,lattice distortion,and special coordination environment.The Fe-Co_(2)P BNRs showed higher catalytic activity than 20%Pt/C in seawater at high potentials.The density functional theory calculations revealed that the Fe doping reduced the hydrogen binding strength of Co_(2)P to efficiently accelerate the HER kinetics and produce a favorable charge density.This study provides valuable insights into the design and development of high-efficiency HER catalysts for large-scale seawater electrolysis.展开更多
Controllable designing of well-defined heterojunction nanostructures provides an insightful strategy for accelerating the kinetics of the hydrogen and oxygen evolution reactions(HER/OER),but such task is still challen...Controllable designing of well-defined heterojunction nanostructures provides an insightful strategy for accelerating the kinetics of the hydrogen and oxygen evolution reactions(HER/OER),but such task is still challenging.Herein,we proposed a protocol of heterojunction interface editing(HIE)strategy by oxygen atoms decoration for synergistic boosting electrocatalytic HER and OER performances.A novel Co/NiCoP nanospheres(NSs)heterojunction was synthesized by crystal seed template transformation method with Ni_(5)P_(4) microspheres as seeds.The effective oxygen atoms interface editing increased the oxidation state of Co atoms and prolonged the Co-P bond length of Co/NiCoP NSs heterojunction,thus the electron localization on P sites was enhanced,leading to the dramatically elevated HER and OER performances simultaneously.The as-constructed O-Co/NiCoP NSs show excellent electrocatalytic activity with 361 and 430 mV vs.reversible hydrogen electrode(RHE)to arrive high current density of 300 mA·cm^(-2)for HER and OER in 1 M KOH as well as good stability.The proposed HIE concept could provide a new perspective on the catalyst design for energy conversion systems.展开更多
The exploitation of electrocatalysts with high activity and durability for HER is desirable for future energy systems,but it is still a challenge.NMPs have attracted increasing attentions,but the preparation process o...The exploitation of electrocatalysts with high activity and durability for HER is desirable for future energy systems,but it is still a challenge.NMPs have attracted increasing attentions,but the preparation process often needs toxic regents or dangerous reaction conditions.Herein,we develop a general green method to fabricate metal-rich NMPs anchored on NPG through pyrolyzing DNA cross-linked complexes.The obtained Ru_(2) P-NPG exhibits an ultrasmall overpotential of 7 mV at 10 mA cm^(2) and ultralow Tafel slope of 33 mV dec^(-1) in 1.0 mol L?1 KOH,even better than that of commercial Pt/C.In addition,Ru 2 P-NPG also shows low overpotentials of 29 and 78 mV in 0.5 mol L^(-1) H_(2)SO_(4) and 1.0 mol L^(-1) PBS,respectively.The superior activity can be attributed to the ultrafine dispersion of Ru 2 P nanoparticles for more accessible sites,more defects formed for abundant active sites,the two-dimensional plane structure for accelerated electron transfer and mass transport,as well as the regulation of electron distribution of the catalyst.Moreover,the synthetic method can also be applied to prepare other metal-rich noble metal phosphides(Pd_(3)P-NPG and Rh_(2)P-NPG),which also exhibits high activity for HER.This work provides an effective strategy for designing NMP-based electrocatalysts.展开更多
Li-S batteries have been considered as one of advanced next-generation energy storage systems owing to their remarkable theoretical capacity(1672 m Ah g^(-1))and high energy density(2600 Wh kg^(-1)).However,critical i...Li-S batteries have been considered as one of advanced next-generation energy storage systems owing to their remarkable theoretical capacity(1672 m Ah g^(-1))and high energy density(2600 Wh kg^(-1)).However,critical issues,mainly pertaining to lithium polysulfide shuttle and slow sulfur reaction kinetics,have posed a fatal threat to the electrochemical performances of Li-S batteries.The situation is even worse for high sulfur-loaded and flexible cathodes,which are the essential components for practical Li-S batteries.In response,the use of metal compounds as electrocatalysts in Li-S systems have been confirmed as an effective strategy to date.Particularly,recent years have witnessed many progresses in phosphidesoptimized Li-S chemistry.This has been motivated by the superior electron conductivity and high electrocatalytic activity of phosphides.In this tutorial review,we offer a systematic summary of active metal phosphides as promoters for Li-S chemistry,aiming at helping to understanding the working mechanism of phosphide electrocatalysts and guiding the construction of advanced Li-S batteries.展开更多
The development of MXene-based heterostructures for electrocatalysis has garnered significant attention owing to their potential as high-performance catalysts that play a pivotal role in hydrogen energy.Herein,we pres...The development of MXene-based heterostructures for electrocatalysis has garnered significant attention owing to their potential as high-performance catalysts that play a pivotal role in hydrogen energy.Herein,we present a multistep strategy for the synthesis of a Ti_(3)C_(2) MXene ribbon/NiFePx@graphitic N-doped carbon(NC)heterostructure that enables the formation of three-dimensional(3D)Ti_(3)C_(2) MXene ribbon networks and bimetallic phosphide nanoarrays.With the assistance of HF etching and KOH shearing,the MXene sheets were successfully transformed into 3D MXene networks with interlaced MXene ribbons.Notably,a hydrothermal method,ion exchange route,and phosphorization process were used to anchor NiFeP_(x)@NC nanocubes derived from Ni(OH)_(2)/NiFe-based Prussian blue(NiFe-PB)onto the MXene ribbon network.The resulting MXene ribbon/NiFeP_(x)@NC heterostructure demonstrated enhanced oxygen evolution reaction(OER)activity,characterized by a low overpotential(164 mV at a current density of 10 mA cm^(-2))and a low Tafel slope(45 mV dec^(-1)).At the same time,the MXene ribbons/NiFeP_(x)@NC heterostructure exhibited outstanding long-term stability,with a 12 mV potential decay after 5000 cyclic voltammetry(CV)cycles.This study provides a robust pathway for the design of efficient MXene-based heterostructured electrocatalysts for water splitting.展开更多
Amorphous high-entropy materials with abundant defects,coordinatively unsaturated sites,and loosely bonded atoms could exhibit excellent electrocatalytic performance.However,how to fabricate such ma-terials with nanos...Amorphous high-entropy materials with abundant defects,coordinatively unsaturated sites,and loosely bonded atoms could exhibit excellent electrocatalytic performance.However,how to fabricate such ma-terials with nanostructure as well as amorphous structure is still full of challenges.In this work,high-entropy metal organic framework(HE-MOF)is employed as the self-sacrificial template to fabricate FeCoNiCuMnP x high-entropy phosphide/carbon(HEP/C)composites.The obtained composite shows a het-erostructured fusiform morphology,in which the HEP is encapsulated by a carbon layer,revealing high electron conductivity as well as rich catalytic active sites for oxygen evolution reaction(OER).Beside,it is found that there is a short-range ordered crystal structure in the amorphous phase,which is bene-ficial for revealing high OER catalytic activity as well as good stability.As a result,the optimum HEP/C composite shows an overpotential 239 mV@10 mA cm^(−2)with a small Tafel slope of 72.5 mV dec^(−1) for catalyzing OER in alkaline solution.展开更多
Nitrate(NO_(3)^(−))electroreduction reaction(NO_(3)^(−)RR)provides an attractive and sustainable route for NO_(3)^(−)pollution mitigation or energy-saved ammonia(NH3)synthesis.In this work,high-quality B and Fe co-dop...Nitrate(NO_(3)^(−))electroreduction reaction(NO_(3)^(−)RR)provides an attractive and sustainable route for NO_(3)^(−)pollution mitigation or energy-saved ammonia(NH3)synthesis.In this work,high-quality B and Fe co-doped Co_(2) P hollow nanocubes(B/Fe-Co_(2) P HNCs)are successfully synthesized though simultaneous boronation-phosphorization treatment,which reveal outstanding selectivity,activity,stability for the NO_(3)^(−)to NH_(3) conversion in neutral electrolyte because of big surface area,fast mass transport,superhydrophilic surface,and optimized electronic structure.B/Fe-Co_(2) P HNCs can achieve the high NH3 yield rate(22.67 mg h^(−1) mg_(cat)^(−1))as well as Faradaic efficiency(97.54%)for NO_(3)^(−)RR,greatly outperforming most of non-precious metal based NO_(3)^(−)RR electrocatalysts.展开更多
基金financially supported by the National Key Research and Development Program of China(No.2018YFB0104200)。
文摘Transition metal phosphides(TMPs)are recognized as such promising supercapacitor materials for the practical application,due to their superior electrical conductivity and excellent redox activity.Here,self-supported three-dimensional NiCoP nanoparticles embedded in NiCoO2 nano wires(NiCoO2/NiCoP)electrode consisting of nickel cobalt phosphides(NiCoP)with high activity and nickel cobalt oxides(NiCoO2)with good stability were fabricated by a hydrothermal and phosphorization method.The electrode integrates the advantages of nanowire arrays for fast ion transport and foam Ni for effective charge transport and flexibility.Benefitting the proper composition control of the nanohybrid and unique structure design,the optimized NiCoO2/NiCoP-20 exhibits a high specific capacitance of 3204 F·g-1 at 1 A·g-1 in 3 mol·L-1 KOH aqueous electrolyte in a three-electrode system.Moreover,the asymmetric supercapacitor assembled with the prepared NiCoO2/NiCoP-20 and activated carbon achieves a specific capacitance of 116 F·g-1 with a high energy density of 40.32 Wh·kg-1 at the power density of 800.18 W·kg-1.The practical application is further demonstrated with all-solid-state winding supercapacitor devices,with decent flexibility,in series to light the Central South University(CSU)logo consisting of 21 red LED indicators.
基金supported by the Natural Science Foundation of Shandong Province(ZR2017MB059)the Major Program of Shandong Province Natural Science Foundation(ZR2018ZC0639)+2 种基金the National Natural Science Foundation of China(21776314)the Fundamental Research Funds for the Central Universities(18CX05016A)the Postgraduate Innovation Project of China University of Petroleum(YCX2018074)
文摘The ternary cobalt-nickel-iron phosphide nanocubes (P-Co0.9Ni0.9Fe1.2 NCs) with high intrinsic activity, conductivity, defect concentration and optimized ratio have been realized through a facile phosphorization treatment using ternary cobalt-nickel-iron nanocubes of Prussian blue analogs (PBA) as a precursor. The scanning electron microscopy and transmission electron microscopy results show that the P-Co0.9Ni0.9Fe1.2 NCs maintain a cubic structure with a rough surface, implying the rich surface defects as exposed active sites. The thermal phosphorization of the ternary PBA precursor not only provids carbon doping but also leads to the in situ construction of surface defects on the NCs. The carbon doping from the PBA precursor lowers the charge transfer resistance and optimizes the electronic transformation. The synergistic effect among the ternary metal ions and rich defects contributes to the enhanced electrocatalytic performance . The P-Co0.9Ni0.9Fe1.2NCs achieve low overpotentials of -200.7 and 273.1 mV at a current density of 10 mA cm^-2 for the hydrogen evolution reaction and the oxygen evolution reaction, respectively. The potential of overall water splitting reaches 1.52 V at a current density of 10 mA cm^-2. The longterm stability of the electrocatalysts was also evaluated. This work provides a facile method to design efficient transitionmetal- based bifunctional electrocatalysts for overall water splitting.
文摘Sodium-ion batteries have received remarkable attention as next-generation high-performance electrochemical energy storage devices because of their cost effectiveness and the broad geographical distribution of sodium. As a critical component of sodium-ion batteries, anode materials, especially nanostructured anodes, have a significant effect on the electrochemical performance of sodium-ion batteries. Recent research indicates that phosphorus and metal phosphides show great promise as anode candidates for sodium-ion batteries because of their low cost and relatively high theoretical gravimetric and volumetric specific capacities. In this review, we systematically summarize recent research progress on state-of-the-art nanostructured phosphorus and phosphides, including the synthetic strategies, Na-storage mechanisms, and the relationship between the nanostructure and electrochemical performance. Moreover, we present an overview of future challenges and opportunities based on current developments.
基金National Natural Science Founda-tion of China,Grant/Award Numbers:51925207,U1910210,51872277,51972067,51802044,51902062,51802043Funda-mental Research Funds for the Central Universities,Grant/Award Number:WK2060140026+2 种基金the DNL cooperation Fund,CAS,Grant/Award Number:DNL180310National Synchrotron Radi-ation Laboratory,Grant/Award Num-ber:KY2060000173Guangdong Nat-ural Science Funds for Distinguished Young Scholar,Grant/Award Number:2019B151502039。
文摘Sodium-ion batteries(SIBs)have been extensively studied as the potential alter-native to lithium-ion batteries(LIBs)due to the abundant natural reserves and low price of sodium resources.Nevertheless,Na+ions possess a larger radius than Li+,resulting in slow diffusion dynamics in electrode materials,and thus seeking appropriate anode materials to meet high performance standards has become a trend in the field of SIBs.In this context,owing to the advantages of high theoretical capacity and proper redox potential,metal phosphides(MPs)are considered to be the promising materials to make up for the gap of SIBs anode materials.In this review,the recent development of MPs anode materials for SIBs is reviewed and analyzed comprehensively and deeply,including the synthesis method,advanced modification strategy,electrochemical performance,and Na storage mechanism.In addition,to promote the wide application of the emerg-ing MPs anodes for SIBs,several research emphases in the future are pointed out to overcome challenges toward the commercial application.
基金supported by the National Natural Science Foundation of China (51571072 and 51871078)Heilongjiang Science Foundation (E2018028)
文摘Developing low-cost and earth-abundant electrocatalysts with high performance for electrochemical water splitting is a challenging issue. Herein, we report a facile and effective way to fabricate three-dimension(3D) ordered mesoporous Co1-xFexP(x=0, 0.25, 0.5, 0.75) electrocatalyst.Benefiting from 3D ordered mesoporous pore channels and composition optimization, the Co0.75Fe0.25 P exhibits excellent electrocatalytic activities with low overpotentials of 270 and 209 mV at 10 mA cm^-2 for oxygen evolution reaction(OER)and hydrogen evolution reaction(HER), respectively, in the alkaline electrolyte along with a durable electrochemical stability. In addition, as both the cathode and anode, the Co0.75Fe0.25P also exhibits superior electrolysis water splitting performance with only an applied voltage of 1.63 V to attain a current density of 10 m A cm^-2 without obvious decay for 18 h,indicating that the Co0.75Fe0.25P is an efficient electrocatalyst for overall water splitting.
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financially supported by Hunan Provincial Science and Technology Plan Project(2017TP1001 and2020JJ4710)the National Key R&D Program of China(2018YFB0704100)the State Key Laboratory Fund。
文摘It is a great challenge to develop highly active oxygen evolution reaction(OER)electrocatalysts with superior durability.In this study,a NiFe layered double hydroxidedecorated phosphide(NiFe LDH@CoP/NiP_(3))was constructed to display satisfactory OER activity and good stability for water splitting in alkaline media.At an overpotential of 300 mV,NiFe LDH@CoP/NiP_(3) achieved a current density of 82 mA cm^(-2) for the OER,which was 9.1 and 2.3 times that of CoP/NiP_(3) and NiFe LDH,respectively.Moreover,the reconstruction behavior,during which oxyhydroxides formed,was studied by a combination of X-ray photoelectron spectroscopy,Raman spectroscopy,and scanning electron microscopy.A synergistic effect between NiFe LDH and CoP/NiP_(3) was also observed for the hydrogen evolution reaction.Furthermore,when NiFe LDH@CoP/NiP_(3) acted as both the cathode and anode for overall water splitting,a high current density of 100 mA cm^(-2) was maintained for more than 275 h.In addition,under Xe light irradiation,a solar-to-hydrogen efficiency of 9.89% was achieved for solar-driven water splitting.This work presents the coupling of different active compositions,and can provide a reference for designing bifunctional electrocatalysts.
文摘Among the sustainable energy sources,hydrogen is the one most promising for alleviating the pollution issues related to the usage of conventional fuels,as it can be produced in an efficient and eco-friendly way via electrocatalytic water splitting.The hydrogen evolution reaction(HER,a half-reaction of water splitting)plays a pivotal role in decreasing the price and increasing the catalytic efficiency of hydrogen production and is efficiently promoted by metal phosphides in different electrolytes.Herein,we summarize the recent advances in the development of metal phosphides as HER electrocatalysts,focus on their synthesis(post-treatment,in situ generation,and electrodeposition methods)and the enhancement of their electrocatalytic activity(via elemental doping,interface and vacancy engineering,construction of specific supports and nanostructures,and the design of bior polymetallic phosphides),and highlight the crucial issues and challenges of future development.
文摘A highly active bi-functional electrocatalyst towards both hydrogen and oxygen evolution reactions is critical for the water splitting. Herein, a self-supported electrode composed of 3D network nanostructured NiCoP nanosheets grown on N-doped carbon coated Ni foam （NiCoP/NF@NC） has been synthesized by a hydrothermal route and a subsequent phosphorization process. As a bifunctional electrocatalyst, the NiCoP/NF@NC electrode needs overpotentials of 31.8 mV for hydrogen evolution reaction and 308.2 mV for oxygen evolution reaction to achieve the current density of 10 mA·cm^-2 in 1 mol·L^-1 KOH electrolyte. This is much better than the correspond- ing monometal catalysts of CoP/NF@NC and NiP/ NF@NC owing to the synergistic effect. NiCoP/NF@NC also exhibits low Tafel slope, and excellent long-term stability, which are comparable to the commercial noble catalysts of Pt/C and RuO2.
基金support from the National Natural Science Foundation of China(Nos.51575135,51622503,U1537206,and 51621091)is highly appreciated.
文摘Rational design of efficient bifunctional electrocatalysts is highly imperative but still a challenge for overall water splitting.Herein,we construct novel freestanding Mo-doped NiCoP nanosheet arrays by the hydrothermal and phosphation processes,serving as bifunctional electrocatalysts for overall water splitting.Notably,Mo doping could effectively modulate the electronic structure of NiCoP,leading to the increased electroactive site and improved intrinsic activity of each site.Furthermore,an electrochemical activation strategy is proposed to form Mo-doped(Ni,Co)OOH to fully boost the electrocatalytic activities for oxygen evolution reaction.Benefiting from the unique freestanding structure and Mo doping,Mo-doped NiCoP and(Ni,Co)OOH show the remarkable electrochemical performances,which are competitive among current researches.In addition,an overall water splitting device assembled by both electrodes only requires a cell voltage of 1.61 V to reach a current density of 10 mA cm?2.Therefore,this work opens up new avenues for designing nonprecious bifunctional electrocatalysts by Mo doping and in situ electrochemical activation.
基金financially supported from the National Natural Science Foundation of China(Nos.12074048 and 12147102)the Project for Fundamental and Frontier Research in Chongqing(No.cstc2020jcyj-msxm X0796)the Fundamental Research Funds for the Central Universities(No.2022CDJXY-002)。
文摘The construction of highly active catalysts for methanol oxidation reaction(MOR)is central to direct methanol fuel cells.Tremendous progress has been made in transition metal phosphides(TMPs)based catalysts.However,TMPs would be partially damaged and transformed into new substances(e.g.,Pt-M-P composite,where M represents a second transition metal)during Pt deposition process.This would pose a large obstacle to the cognition of the real promoting effects of TMPs in MOR.Herein,Co_(2)P co-catalysts(Pt-P/Co_(2)P@NPC,where NPC stands for N and P co-doped carbon)and Pt-Co-P composite catalysts(Pt-CoP/NPC)were controllably synthesized.Electrocatalysis tests show that the Pt-Co-P/NPC exhibits superior MOR activity as high as 1016 m A/mg_(Pt),significantly exceeding that of Pt-P/Co_(2)P@NPC(345 m A/mg_(Pt)).This result indicates that the promoting effect is ascribed primarily to the resultant Pt-Co-P composite,in sharply contrast to previous viewpoint that Co_(2)P itself improves the activity.Further mechanistic studies reveal that Pt-Co-P/NPC exhibits much stronger electron interaction and thus manifesting a remarkably weaker CO absorption than Pt-P/Co_(2)P@NPC and Pt/C.Moreover,Pt-Co-P is also more capable of producing oxygen-containing adsorbate and thus accelerating the removal of surface-bonded CO^(*),ultimately boosting the MOR performance.
基金the support by the Fundamental Research Funds for the Central Universities(No.19CX02008A)the China Postdoctoral Science Foundation(No.2018M642726)+1 种基金the Petro China Innovation Foundation(No.2019D-5007-0401)the Taishan Scholars Program of Shandong Province。
文摘The hydrogen evolution reaction(HER)via water electrolysis has gained immense research attention.Seawater electrolysis provides great opportunities for sustainable energy production,but is extremely challenging.Transition metal phosphides are promising candidate electrocatalysts.Herein,we prepared a novel Fe-Co_(2)P bundle of nanorods(BNRs)for catalyzing the HER in seawater electrolysis and over the entire p H range.Cobalt phosphides with different crystal phases and morphologies were obtained by varying the Fe doping amount.The Co:Fe molar ratio of 1:0.5 was found to be optimum.The Fe doping improved the HER performance of Co_(2)P over the entire p H range by providing favorable electronic properties and morphology,lattice distortion,and special coordination environment.The Fe-Co_(2)P BNRs showed higher catalytic activity than 20%Pt/C in seawater at high potentials.The density functional theory calculations revealed that the Fe doping reduced the hydrogen binding strength of Co_(2)P to efficiently accelerate the HER kinetics and produce a favorable charge density.This study provides valuable insights into the design and development of high-efficiency HER catalysts for large-scale seawater electrolysis.
基金This work was financially supported by the National Natural Science Foundation of China(Nos.22109090 and 22108306)the Taishan Scholars Program of Shandong Province(No.tsqn201909065)+2 种基金Shandong Provincial Natural Science Foundation(Nos.ZR2021YQ15 and ZR2020QB174)Hefei National Research Center for Physical Sciences at the Microscale(No.KF2021107)the Fundamental Research Funds for the Central Universities(No.22CX07009A)。
文摘Controllable designing of well-defined heterojunction nanostructures provides an insightful strategy for accelerating the kinetics of the hydrogen and oxygen evolution reactions(HER/OER),but such task is still challenging.Herein,we proposed a protocol of heterojunction interface editing(HIE)strategy by oxygen atoms decoration for synergistic boosting electrocatalytic HER and OER performances.A novel Co/NiCoP nanospheres(NSs)heterojunction was synthesized by crystal seed template transformation method with Ni_(5)P_(4) microspheres as seeds.The effective oxygen atoms interface editing increased the oxidation state of Co atoms and prolonged the Co-P bond length of Co/NiCoP NSs heterojunction,thus the electron localization on P sites was enhanced,leading to the dramatically elevated HER and OER performances simultaneously.The as-constructed O-Co/NiCoP NSs show excellent electrocatalytic activity with 361 and 430 mV vs.reversible hydrogen electrode(RHE)to arrive high current density of 300 mA·cm^(-2)for HER and OER in 1 M KOH as well as good stability.The proposed HIE concept could provide a new perspective on the catalyst design for energy conversion systems.
基金This work was supported by the Fundamental Research Funds for the Central Universities(No.2022XJHH02)the National Key Research and Development Program of China(No.2019YFC1907602).
文摘The exploitation of electrocatalysts with high activity and durability for HER is desirable for future energy systems,but it is still a challenge.NMPs have attracted increasing attentions,but the preparation process often needs toxic regents or dangerous reaction conditions.Herein,we develop a general green method to fabricate metal-rich NMPs anchored on NPG through pyrolyzing DNA cross-linked complexes.The obtained Ru_(2) P-NPG exhibits an ultrasmall overpotential of 7 mV at 10 mA cm^(2) and ultralow Tafel slope of 33 mV dec^(-1) in 1.0 mol L?1 KOH,even better than that of commercial Pt/C.In addition,Ru 2 P-NPG also shows low overpotentials of 29 and 78 mV in 0.5 mol L^(-1) H_(2)SO_(4) and 1.0 mol L^(-1) PBS,respectively.The superior activity can be attributed to the ultrafine dispersion of Ru 2 P nanoparticles for more accessible sites,more defects formed for abundant active sites,the two-dimensional plane structure for accelerated electron transfer and mass transport,as well as the regulation of electron distribution of the catalyst.Moreover,the synthetic method can also be applied to prepare other metal-rich noble metal phosphides(Pd_(3)P-NPG and Rh_(2)P-NPG),which also exhibits high activity for HER.This work provides an effective strategy for designing NMP-based electrocatalysts.
基金supported by the Project of State Key Laboratory of Environment-Friendly Energy Materials(SWUST,China,Grant Nos.19FKSY16 and 18ZD320304)。
文摘Li-S batteries have been considered as one of advanced next-generation energy storage systems owing to their remarkable theoretical capacity(1672 m Ah g^(-1))and high energy density(2600 Wh kg^(-1)).However,critical issues,mainly pertaining to lithium polysulfide shuttle and slow sulfur reaction kinetics,have posed a fatal threat to the electrochemical performances of Li-S batteries.The situation is even worse for high sulfur-loaded and flexible cathodes,which are the essential components for practical Li-S batteries.In response,the use of metal compounds as electrocatalysts in Li-S systems have been confirmed as an effective strategy to date.Particularly,recent years have witnessed many progresses in phosphidesoptimized Li-S chemistry.This has been motivated by the superior electron conductivity and high electrocatalytic activity of phosphides.In this tutorial review,we offer a systematic summary of active metal phosphides as promoters for Li-S chemistry,aiming at helping to understanding the working mechanism of phosphide electrocatalysts and guiding the construction of advanced Li-S batteries.
基金supported by the National Natural Science Foun-dation of China(No.22269010)the Jiangxi Provincial Natural Science Foundation(No.20224BAB214021)+1 种基金the Training Program for Academic and Technical Leaders of Major Disciplines in Jiangxi Province(No.20212BCJ23020)the Science and Technology Project of the Jiangxi Provincial Department of Education(No.GJJ211305).
文摘The development of MXene-based heterostructures for electrocatalysis has garnered significant attention owing to their potential as high-performance catalysts that play a pivotal role in hydrogen energy.Herein,we present a multistep strategy for the synthesis of a Ti_(3)C_(2) MXene ribbon/NiFePx@graphitic N-doped carbon(NC)heterostructure that enables the formation of three-dimensional(3D)Ti_(3)C_(2) MXene ribbon networks and bimetallic phosphide nanoarrays.With the assistance of HF etching and KOH shearing,the MXene sheets were successfully transformed into 3D MXene networks with interlaced MXene ribbons.Notably,a hydrothermal method,ion exchange route,and phosphorization process were used to anchor NiFeP_(x)@NC nanocubes derived from Ni(OH)_(2)/NiFe-based Prussian blue(NiFe-PB)onto the MXene ribbon network.The resulting MXene ribbon/NiFeP_(x)@NC heterostructure demonstrated enhanced oxygen evolution reaction(OER)activity,characterized by a low overpotential(164 mV at a current density of 10 mA cm^(-2))and a low Tafel slope(45 mV dec^(-1)).At the same time,the MXene ribbons/NiFeP_(x)@NC heterostructure exhibited outstanding long-term stability,with a 12 mV potential decay after 5000 cyclic voltammetry(CV)cycles.This study provides a robust pathway for the design of efficient MXene-based heterostructured electrocatalysts for water splitting.
基金supported by the Natural Science Foundation of Henan Province(No.202300410433)the College Students’Innovative Entrepreneurial Training(No.2022cxcy029),ChinaHirosaki University,Japan,are appreciated.
文摘Amorphous high-entropy materials with abundant defects,coordinatively unsaturated sites,and loosely bonded atoms could exhibit excellent electrocatalytic performance.However,how to fabricate such ma-terials with nanostructure as well as amorphous structure is still full of challenges.In this work,high-entropy metal organic framework(HE-MOF)is employed as the self-sacrificial template to fabricate FeCoNiCuMnP x high-entropy phosphide/carbon(HEP/C)composites.The obtained composite shows a het-erostructured fusiform morphology,in which the HEP is encapsulated by a carbon layer,revealing high electron conductivity as well as rich catalytic active sites for oxygen evolution reaction(OER).Beside,it is found that there is a short-range ordered crystal structure in the amorphous phase,which is bene-ficial for revealing high OER catalytic activity as well as good stability.As a result,the optimum HEP/C composite shows an overpotential 239 mV@10 mA cm^(−2)with a small Tafel slope of 72.5 mV dec^(−1) for catalyzing OER in alkaline solution.
基金supported by Natural Science Foundation of Shanxi Province(No.202203021222213)Taiyuan University of Science and Technology Scientific Research Initial Funding(No.20222091)+2 种基金National Natural Science Foundation of China(No.22073061)Science and Technology Innovation Team of Shaanxi Province(No.2023-CX-TD-27)Fundamental Research Funds for the Central Universities(No.GK202202001).
文摘Nitrate(NO_(3)^(−))electroreduction reaction(NO_(3)^(−)RR)provides an attractive and sustainable route for NO_(3)^(−)pollution mitigation or energy-saved ammonia(NH3)synthesis.In this work,high-quality B and Fe co-doped Co_(2) P hollow nanocubes(B/Fe-Co_(2) P HNCs)are successfully synthesized though simultaneous boronation-phosphorization treatment,which reveal outstanding selectivity,activity,stability for the NO_(3)^(−)to NH_(3) conversion in neutral electrolyte because of big surface area,fast mass transport,superhydrophilic surface,and optimized electronic structure.B/Fe-Co_(2) P HNCs can achieve the high NH3 yield rate(22.67 mg h^(−1) mg_(cat)^(−1))as well as Faradaic efficiency(97.54%)for NO_(3)^(−)RR,greatly outperforming most of non-precious metal based NO_(3)^(−)RR electrocatalysts.
