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
Designing highly active,durable,and nonprecious metal-based bifunctional electrocatalysts for overall water electrolysis is of urgent scientific importance to realize the sustainable hydrogen production,which remains ...Designing highly active,durable,and nonprecious metal-based bifunctional electrocatalysts for overall water electrolysis is of urgent scientific importance to realize the sustainable hydrogen production,which remains a grand challenge.Herein,an innovative approach is demonstrated to synthesize flower-like 3D homogenous trimetallic Mn,Ni,Co phosphide catalysts directly on nickel foam via electrodeposition followed by plasma phosphidation.The electrochemical activity of the catalysts with varying Mn:Ni:Co ratios is assessed to identify the optimal composition,demonstrating that the equimolar trimetallic phosphide yields an outstanding HER catalytic performance with a current density of 10 mA cm^(-2) at an ultra-low overpotential of~14 mV,outperforming the best reported electrocatalysts.This is asserted by the DFT calculations,revealing strong interaction of the metals and the P atom,resulting in enhanced water activation and optimized G_(H)^(*)values for the HER process.Moreover,this optimal composition appreciably catalyzes the OER by exposing more intrinsic active species in-situ formed on the catalyst surface during the OER.Therefore,the Mn_(1)-Ni_(1)-Co_(1)-P-(O)/NF catalyst exhibits a decreased overpotential of~289 mV at 10 mA cm^(-2).More importantly,the electrocatalyst sustains perfect durability up to 48 h at a current density of 10 mA cm^(-2) and continued 5000 cycling stability for both HER and OER.Meanwhile,the assembled MNC-P/NF||MNC-P/NF full water electrolyzer system attains an extremely low cell voltage of 1.48 V at 10 mA cm^(-2).Significantly,the robust stability of the overall system results in a remarkable current retention of~96%after a continuous 50-h run.Therefore,this study provides a facile design and a scalable construction of superb bifunctional ternary MNC-phosphide electrocatalysts for efficient electrochemical energy production systems.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
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
Boron phosphide(BP)has gained significant research attention due to its unique photoelectric and mechanical properties.In this work,we investigated the stability of BP under high pressure using x-ray diffraction and s...Boron phosphide(BP)has gained significant research attention due to its unique photoelectric and mechanical properties.In this work,we investigated the stability of BP under high pressure using x-ray diffraction and scanning electron microscope.The phase diagram of BP was explored in both B-rich and P-rich environments,revealing crucial insight into its behavior at 5.0 GPa.Additionally,we measured the melting curve of BP from 8.0 GPa to 15.0 GPa.Our findings indicate that the stability of BP under high pressure is improved within B-rich and P-rich environments.Furthermore,we report a remarkable observation of melting curve frustration at 10.0 GPa.This study will enhance our understanding of stability of BP under high pressure,shedding light on its potential application in semiconductor,thermal,and light-transmitting devices.展开更多
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.
文摘Designing highly active,durable,and nonprecious metal-based bifunctional electrocatalysts for overall water electrolysis is of urgent scientific importance to realize the sustainable hydrogen production,which remains a grand challenge.Herein,an innovative approach is demonstrated to synthesize flower-like 3D homogenous trimetallic Mn,Ni,Co phosphide catalysts directly on nickel foam via electrodeposition followed by plasma phosphidation.The electrochemical activity of the catalysts with varying Mn:Ni:Co ratios is assessed to identify the optimal composition,demonstrating that the equimolar trimetallic phosphide yields an outstanding HER catalytic performance with a current density of 10 mA cm^(-2) at an ultra-low overpotential of~14 mV,outperforming the best reported electrocatalysts.This is asserted by the DFT calculations,revealing strong interaction of the metals and the P atom,resulting in enhanced water activation and optimized G_(H)^(*)values for the HER process.Moreover,this optimal composition appreciably catalyzes the OER by exposing more intrinsic active species in-situ formed on the catalyst surface during the OER.Therefore,the Mn_(1)-Ni_(1)-Co_(1)-P-(O)/NF catalyst exhibits a decreased overpotential of~289 mV at 10 mA cm^(-2).More importantly,the electrocatalyst sustains perfect durability up to 48 h at a current density of 10 mA cm^(-2) and continued 5000 cycling stability for both HER and OER.Meanwhile,the assembled MNC-P/NF||MNC-P/NF full water electrolyzer system attains an extremely low cell voltage of 1.48 V at 10 mA cm^(-2).Significantly,the robust stability of the overall system results in a remarkable current retention of~96%after a continuous 50-h run.Therefore,this study provides a facile design and a scalable construction of superb bifunctional ternary MNC-phosphide electrocatalysts for efficient electrochemical energy production systems.
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.
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Project supported by the National Natural Science Foundation of China (Grant No.12074273)the Sichuan Science and Technology Program (Grant No.2022NSFSC1810)。
文摘Boron phosphide(BP)has gained significant research attention due to its unique photoelectric and mechanical properties.In this work,we investigated the stability of BP under high pressure using x-ray diffraction and scanning electron microscope.The phase diagram of BP was explored in both B-rich and P-rich environments,revealing crucial insight into its behavior at 5.0 GPa.Additionally,we measured the melting curve of BP from 8.0 GPa to 15.0 GPa.Our findings indicate that the stability of BP under high pressure is improved within B-rich and P-rich environments.Furthermore,we report a remarkable observation of melting curve frustration at 10.0 GPa.This study will enhance our understanding of stability of BP under high pressure,shedding light on its potential application in semiconductor,thermal,and light-transmitting devices.
