Herein,we demonstrate the synthesis of bifunctional nickel cobalt selenide@nickel telluride(Ni_(x)Co_(12-x)Se@NiTe)core-shell heterostructures via an electrodeposition approach for overall urea electrolysis and superc...Herein,we demonstrate the synthesis of bifunctional nickel cobalt selenide@nickel telluride(Ni_(x)Co_(12-x)Se@NiTe)core-shell heterostructures via an electrodeposition approach for overall urea electrolysis and supercapacitors.The 3D vertically orientated NiTe dendritic frameworks induce the homogeneous nucleation of 2D Ni_(x)Co_(12-x)Se nanosheet arrays along similar crystal directions and bring a strong interfacial binding between the integrated active components.In particular,the optimized Ni_(6)Co_(6)Se@NiTe with an interface coupling effect works in concert to tune the intrinsic activity.It only needs a low overpotential of 1.33 V to yield a current density of 10 mA cm^(-2)for alkaline urea electrolysis.Meanwhile,the full urea catalysis driven only by Ni_(6)Co_(6)Se@NiTe achieves 10 mA cm^(-2)at a potential of 1.38 V and can approach a constant level of the current response for 40 h.Besides,the integrated Ni_(6)Co_(6)Se@NiTe electrode delivers an enhanced specific capacity(223 mA h g^(-1)at 1 A g^(-1))with a high cycling stability.Consequently,a hybrid asymmetric supercapacitor(HASC)device based on Ni_(6)Co_(6)Se@NiTe exhibits a favorable rate capability and reaches a high energy density of 67.7 Wh kg^(-1)and a power density of 724.8 W kg^(-1)with an exceptional capacity retention of 92.4%after sequential 12000 cycles at 5 A g^(-1).展开更多
化学气相沉积(CVD)法能够有效调节生长材料的结晶度,进而影响其各项物化性能.以泡沫镍(NF)作为基底,通过调控保温时长成功制备了不同形貌及结晶度的Ni_(x)S_(y)/C_(3)N_(4)纳米阵列材料.借助扫描电子显微镜(SEM)、X射线衍射仪(XRD)等表...化学气相沉积(CVD)法能够有效调节生长材料的结晶度,进而影响其各项物化性能.以泡沫镍(NF)作为基底,通过调控保温时长成功制备了不同形貌及结晶度的Ni_(x)S_(y)/C_(3)N_(4)纳米阵列材料.借助扫描电子显微镜(SEM)、X射线衍射仪(XRD)等表征手段,研究不同保温时长对Ni_(x)S_(y)/C_(3)N_(4)的晶体结构、形貌、比表面积及其电催化尿素氧化反应(UOR)性能的影响.研究结果显示,当保温时长为120 min时,所得Ni_(x)S_(y)/C_(3)N_(4)@120在碱性环境下表现出最优异的UOR性能.当电流密度为10 m A/cm2时,过电位为132 m V,达到100 m A/cm2的电流密度仅需要349 m V的过电位,并能保持良好的工作稳定性.机制研究表明,优化样品性能提高主要源于其电化学比表面积(ECSA)的增加,进而为UOR过程提供更多的反应活性位点.本工作为CVD方法调控材料晶体结构和形貌,进而调控其电催化性能,阐述电催化能源转换过程中催化剂的构效关系提供有意义的结果.展开更多
Levering the local electron density allows for varying the adsorption and/or desorption feature of catalysts,enabling to boost the reaction kinetics.Mott-Schottky barrier,in which it processes different Fermi levels,f...Levering the local electron density allows for varying the adsorption and/or desorption feature of catalysts,enabling to boost the reaction kinetics.Mott-Schottky barrier,in which it processes different Fermi levels,favors the electron transport at the interface.Here,a Mo-doped CoN is coupled with NiFe-LDH for constructing a Mott-Schottky heterojunction,addressing enhanced hydrogen evolution reaction(HER),oxygen evolution reaction(OER),and urea oxidation reaction(UOR)compared with the individual counterparts.The incorporation of high-valence Mo species and the formation of heterostructures significantly improve the corrosion resistance and electrocatalytic performance of Mo-CoN@NiFeLDH,requiring only 76 mV overpotential for HER and 257 mV for OER to achieve a high current density of 100 mA cm^(-2)in 1 M KOH.The advanced nature of our as-prepared Mott-Schottky heterojunction could be further evidenced by its robust nature of a configured alkaline electrolyzer for stable working over666 h at 200 mA cm^(-2).Impressively,only 1.692 V of cell voltage is required to yield a current density of 300 mA cm^(-2)over the as-prepared urea electrolyzer.This strategy for va rying the local electron density via construction of Mott-Schottky barrier could be regarded as a promising routine to achieve low-energy consumption green hydrogen generation.展开更多
As a desirable alternative for oxygen evolution reaction(OER),urea oxidation reaction(UOR)with the effectively reduced overpotential has attracted considerable attention in pollutant degradation and rechargeable Zn-ai...As a desirable alternative for oxygen evolution reaction(OER),urea oxidation reaction(UOR)with the effectively reduced overpotential has attracted considerable attention in pollutant degradation and rechargeable Zn-air battery(ZAB).Herein,a bifunctional electrocatalyst with CoNi alloy and Co-N dual active sites encapsulated by nitrogen-doped carbon nanotubes have been rationally designed and successfully prepared.The as-obtained catalyst CoNi/Co-NCNT displays excellent catalytic activity for oxygen reduction(ORR)and UOR with a narrow potential difference of 0.56 V.The urea-assisted rechargeable ZABs based on CoNi/Co-NCNT provide higher energy conversion efficiency(61%),15%higher than that of conventional ZABs.In addition to verify the UOR pathway on the CoNi/Co-NCNT,DFT calculations reveal that CoNi alloy and Co-N in CoNi/Co-NCNT synergistically function as the main active sites for ORR and UOR.The excellent ORR catalytic performance and the superior energy conversion efficiency of CoNi/Co-NCNT based urea-assisted rechargeable ZAB is expected to accelerate the practical application of ZAB technology.This work paved a new way for the development of bifunctional catalysts for higher efficiency ZABs,and also provides a potential scheme for disposing urea rich wastewater.展开更多
Untreated urea-rich wastewater exerts severeadverse impacts on both the environment and human health,prompting extensive attention towards the urea oxidationreaction(UOR)as a sustainable technology to generate cleanen...Untreated urea-rich wastewater exerts severeadverse impacts on both the environment and human health,prompting extensive attention towards the urea oxidationreaction(UOR)as a sustainable technology to generate cleanenergy in recent years.UOR has a thermodynamic advantageover oxygen evolution reaction(OER)(1.23 V vs reversiblehydrogen electrode,RHE)and only requires 0.37 V(vs RHE),which is considered as an effective alternative to H_(2)production by water electrolysis.However,the inevitable kineticslowness and complex adsorption/desorption during the processhinder its practical application.Most traditional catalystsutilized for the UOR are comprised of precious metals,resulting in limited economic viability.Inspired by natural ureases,Ni-based catalysts have emerged as promisingalternatives owing to their rich deposits,low cost,and theregulated d orbitals of transition metal Ni,demonstratingconsiderable potential for UOR.Currently,numerous studieshave explored Ni-based hydroxides,oxides,chalcogenides,andphosphides in alkaline solutions.In this review,we will explorethe UOR reaction mechanism and summarize the catalystdesign strategies of various Ni-based catalysts recently,especially Ni-MOF,which has been rarely discussed before.Then,the broad prospects of UOR in practical applications aresummarized.Finally,based on the design strategies and performance comparisons discussed above,the challenges andprospects facing the future development of Ni-based electrocatalysts for the UOR will be presented.展开更多
The development of advanced electrocatalysts for electro-oxidation reactions has attracted much attention because of the critical role of such electrocatalysts in improving the overall efficiency of coupled hydrogen p...The development of advanced electrocatalysts for electro-oxidation reactions has attracted much attention because of the critical role of such electrocatalysts in improving the overall efficiency of coupled hydrogen production.We have developed an efficient lanthanum-dopedα-Ni(OH)_(2) bifunctional catalyst with a 1D-2D-3D hierarchical nanostructure.It shows superior activity and stability in the anodic oxygen evolution reaction(OER)and urea oxidation reaction(UOR).Enrichment of the edge sites and conducting La doping inα-Ni(OH)_(2) phase enable formation and stabilization of abundant local Ni^(3+)ions.This guarantees ultralow onset potentials in electro-oxidation reactions.The 1D-2D-3D hierarchical nanostructure significantly boosts the in situ generation of high-valence active species,which results in efficient and stable OER and UOR performances,and the synergistic merit of doping-induced facile reaction kinetics.Because of the structural benefits of a large surface area,charge-transfer promotion,good structural stability,and bifunctionality,a 1%La-dopedα-Ni(OH)_(2) hierarchical nanostructure gives superior OER and UOR performances with low overpotentials,large catalytic current densities,and excellent operational stability.It is therefore a promising catalyst for use in simultaneous alkaline wastewater treatment and hydrogen production.展开更多
Deliberate modulation of the electronic structure via interface engineering is one of promising perspectives to build advanced catalysts for urea oxidation reaction(UOR)at high current densities.However,it still remai...Deliberate modulation of the electronic structure via interface engineering is one of promising perspectives to build advanced catalysts for urea oxidation reaction(UOR)at high current densities.However,it still remains some challenges originating from the intrinsically sluggish UOR dynamics and the high energy barrier for urea adsorption.In response,we report the coupled NiSe_(2)nanowrinkles with Ni_(5)P_(4)nanorods heterogeneous structure onto Ni foam(denoted as NiSe_(2)@Ni_(5)P_(4)/NF)through successive phosphorization and selenization strategy,in which the produced closely contacted interface could provide high-flux electron transfer pathways.Theoretical findings decipher that the fast charge transfer takes place at the interfacial region from Ni_(5)P_(4)to NiSe_(2),which is conducive to optimizing adsorption energy of urea molecules.As expected,the well-designed NiSe_(2)@Ni_(5)P_(4)/NF only requires the low potential of 1.402 V at the current density of 500 mA·cm^(-2).More importantly,a small Tafel slope of 27.6 mV·dec^(-1),a high turnover frequency(TOF)value of 1.037 s^(-1)as well as the prolonged stability of 950 h at the current density of 100 mA·cm^(-2)are also achieved.This study enriches the understanding on the electronic structure modulation via interface engineering and offers bright prospect to design advanced UOR catalysts.展开更多
The phase transformation of catalysts has been extensively observed in heterogeneous catalytic reactions that hinder the long cycling catalysis,and it remains a big challenge to precisely control the active phase duri...The phase transformation of catalysts has been extensively observed in heterogeneous catalytic reactions that hinder the long cycling catalysis,and it remains a big challenge to precisely control the active phase during the complex conditions in electrochemical catalysis.Here,we theoretically predict that carbon-based support could achieve the phase engineering regulation of catalysts by suppressing specific phase transformation.Taken single-walled carbon nanotube(SWCNT)as typical support,combined with calculated E-pH(Pourbaix)diagram and advanced synchrotron-based characterizations technologies prove there are two different active phases source from cobalt selenide which demonstrate that the feasibility of using support effect regulating the potential advantageous catalysts.Moreover,it is worth noting that the phase engineering derived Co_(3)O_(4)-SWCNT exhibits a low overpotential of 201 mV for delivering the current density of 10 mA/cm^(2)in electrocatalytic oxygen evolution reaction(OER).Also,it reaches a record current density of 529 mA/cm^(2)at 1.63 V(vs.RHE)in the electrocatalytic urea oxidation reaction(UOR),overwhelming most previously reported catalysts.展开更多
基金supported by the open fund of the National Defense Key Discipline Laboratory of New Micro/Nano Devices and System Technology,Zhejiang Provincial Natural Science Foundation of China,under Grant No.LY19E020014NSFC(Grant Nos 21303162 and 11604295)
文摘Herein,we demonstrate the synthesis of bifunctional nickel cobalt selenide@nickel telluride(Ni_(x)Co_(12-x)Se@NiTe)core-shell heterostructures via an electrodeposition approach for overall urea electrolysis and supercapacitors.The 3D vertically orientated NiTe dendritic frameworks induce the homogeneous nucleation of 2D Ni_(x)Co_(12-x)Se nanosheet arrays along similar crystal directions and bring a strong interfacial binding between the integrated active components.In particular,the optimized Ni_(6)Co_(6)Se@NiTe with an interface coupling effect works in concert to tune the intrinsic activity.It only needs a low overpotential of 1.33 V to yield a current density of 10 mA cm^(-2)for alkaline urea electrolysis.Meanwhile,the full urea catalysis driven only by Ni_(6)Co_(6)Se@NiTe achieves 10 mA cm^(-2)at a potential of 1.38 V and can approach a constant level of the current response for 40 h.Besides,the integrated Ni_(6)Co_(6)Se@NiTe electrode delivers an enhanced specific capacity(223 mA h g^(-1)at 1 A g^(-1))with a high cycling stability.Consequently,a hybrid asymmetric supercapacitor(HASC)device based on Ni_(6)Co_(6)Se@NiTe exhibits a favorable rate capability and reaches a high energy density of 67.7 Wh kg^(-1)and a power density of 724.8 W kg^(-1)with an exceptional capacity retention of 92.4%after sequential 12000 cycles at 5 A g^(-1).
文摘化学气相沉积(CVD)法能够有效调节生长材料的结晶度,进而影响其各项物化性能.以泡沫镍(NF)作为基底,通过调控保温时长成功制备了不同形貌及结晶度的Ni_(x)S_(y)/C_(3)N_(4)纳米阵列材料.借助扫描电子显微镜(SEM)、X射线衍射仪(XRD)等表征手段,研究不同保温时长对Ni_(x)S_(y)/C_(3)N_(4)的晶体结构、形貌、比表面积及其电催化尿素氧化反应(UOR)性能的影响.研究结果显示,当保温时长为120 min时,所得Ni_(x)S_(y)/C_(3)N_(4)@120在碱性环境下表现出最优异的UOR性能.当电流密度为10 m A/cm2时,过电位为132 m V,达到100 m A/cm2的电流密度仅需要349 m V的过电位,并能保持良好的工作稳定性.机制研究表明,优化样品性能提高主要源于其电化学比表面积(ECSA)的增加,进而为UOR过程提供更多的反应活性位点.本工作为CVD方法调控材料晶体结构和形貌,进而调控其电催化性能,阐述电催化能源转换过程中催化剂的构效关系提供有意义的结果.
基金financially supported by the National Key Research and Development Program of China(Grant No.2022YFB3807201)the National Natural Science Foundation of China(Grants Nos.52462035+6 种基金52272202W242102712464010)the Bituan Science and Technology Program(Grants No.2022DB009)project supported by the Jiangxi Provincial Natural Science Foundation(Grants No.20242BAB21002)the Project of Science and Technology Innovation and Entrepreneurship Fund of China Coal Technology&Engineering Group Co.,Ltd.(2022-MS0022023-TDMS007)。
文摘Levering the local electron density allows for varying the adsorption and/or desorption feature of catalysts,enabling to boost the reaction kinetics.Mott-Schottky barrier,in which it processes different Fermi levels,favors the electron transport at the interface.Here,a Mo-doped CoN is coupled with NiFe-LDH for constructing a Mott-Schottky heterojunction,addressing enhanced hydrogen evolution reaction(HER),oxygen evolution reaction(OER),and urea oxidation reaction(UOR)compared with the individual counterparts.The incorporation of high-valence Mo species and the formation of heterostructures significantly improve the corrosion resistance and electrocatalytic performance of Mo-CoN@NiFeLDH,requiring only 76 mV overpotential for HER and 257 mV for OER to achieve a high current density of 100 mA cm^(-2)in 1 M KOH.The advanced nature of our as-prepared Mott-Schottky heterojunction could be further evidenced by its robust nature of a configured alkaline electrolyzer for stable working over666 h at 200 mA cm^(-2).Impressively,only 1.692 V of cell voltage is required to yield a current density of 300 mA cm^(-2)over the as-prepared urea electrolyzer.This strategy for va rying the local electron density via construction of Mott-Schottky barrier could be regarded as a promising routine to achieve low-energy consumption green hydrogen generation.
基金supported by the National Natural Science Foundation of China(22171166,22235001 and 52371229)。
文摘As a desirable alternative for oxygen evolution reaction(OER),urea oxidation reaction(UOR)with the effectively reduced overpotential has attracted considerable attention in pollutant degradation and rechargeable Zn-air battery(ZAB).Herein,a bifunctional electrocatalyst with CoNi alloy and Co-N dual active sites encapsulated by nitrogen-doped carbon nanotubes have been rationally designed and successfully prepared.The as-obtained catalyst CoNi/Co-NCNT displays excellent catalytic activity for oxygen reduction(ORR)and UOR with a narrow potential difference of 0.56 V.The urea-assisted rechargeable ZABs based on CoNi/Co-NCNT provide higher energy conversion efficiency(61%),15%higher than that of conventional ZABs.In addition to verify the UOR pathway on the CoNi/Co-NCNT,DFT calculations reveal that CoNi alloy and Co-N in CoNi/Co-NCNT synergistically function as the main active sites for ORR and UOR.The excellent ORR catalytic performance and the superior energy conversion efficiency of CoNi/Co-NCNT based urea-assisted rechargeable ZAB is expected to accelerate the practical application of ZAB technology.This work paved a new way for the development of bifunctional catalysts for higher efficiency ZABs,and also provides a potential scheme for disposing urea rich wastewater.
基金supported by the National Natural Science Foundation of China (52371240)Natural Science Foundation of Jiangsu Province (BK20230566)+3 种基金the Priority Academic Program Development of Jiangsu Higher Education InstitutionsNatural Science Research Project of Guangling College, Yangzhou University (ZKZD23005)the Universities’ Philosophy and Social Science Researches in Jiangsu Province (2023SJYB2088)the technical support we received at the Testing Center of Yangzhou University。
文摘Untreated urea-rich wastewater exerts severeadverse impacts on both the environment and human health,prompting extensive attention towards the urea oxidationreaction(UOR)as a sustainable technology to generate cleanenergy in recent years.UOR has a thermodynamic advantageover oxygen evolution reaction(OER)(1.23 V vs reversiblehydrogen electrode,RHE)and only requires 0.37 V(vs RHE),which is considered as an effective alternative to H_(2)production by water electrolysis.However,the inevitable kineticslowness and complex adsorption/desorption during the processhinder its practical application.Most traditional catalystsutilized for the UOR are comprised of precious metals,resulting in limited economic viability.Inspired by natural ureases,Ni-based catalysts have emerged as promisingalternatives owing to their rich deposits,low cost,and theregulated d orbitals of transition metal Ni,demonstratingconsiderable potential for UOR.Currently,numerous studieshave explored Ni-based hydroxides,oxides,chalcogenides,andphosphides in alkaline solutions.In this review,we will explorethe UOR reaction mechanism and summarize the catalystdesign strategies of various Ni-based catalysts recently,especially Ni-MOF,which has been rarely discussed before.Then,the broad prospects of UOR in practical applications aresummarized.Finally,based on the design strategies and performance comparisons discussed above,the challenges andprospects facing the future development of Ni-based electrocatalysts for the UOR will be presented.
基金This work was supported by the Key Research and Development Program of Shandong Province(grant No.2019GGX103051)the Natural Science Foundation of Shandong Province(grant No.ZR2018JL009)the National Natural Science Foundation of China(grant No.21927811).
文摘The development of advanced electrocatalysts for electro-oxidation reactions has attracted much attention because of the critical role of such electrocatalysts in improving the overall efficiency of coupled hydrogen production.We have developed an efficient lanthanum-dopedα-Ni(OH)_(2) bifunctional catalyst with a 1D-2D-3D hierarchical nanostructure.It shows superior activity and stability in the anodic oxygen evolution reaction(OER)and urea oxidation reaction(UOR).Enrichment of the edge sites and conducting La doping inα-Ni(OH)_(2) phase enable formation and stabilization of abundant local Ni^(3+)ions.This guarantees ultralow onset potentials in electro-oxidation reactions.The 1D-2D-3D hierarchical nanostructure significantly boosts the in situ generation of high-valence active species,which results in efficient and stable OER and UOR performances,and the synergistic merit of doping-induced facile reaction kinetics.Because of the structural benefits of a large surface area,charge-transfer promotion,good structural stability,and bifunctionality,a 1%La-dopedα-Ni(OH)_(2) hierarchical nanostructure gives superior OER and UOR performances with low overpotentials,large catalytic current densities,and excellent operational stability.It is therefore a promising catalyst for use in simultaneous alkaline wastewater treatment and hydrogen production.
基金The authors extend their appreciation to the Deanship of Scientific Research at Imam Mohammad Ibn Saud Islamic University(IMSIU)for funding and supporting this work through Research Partnership Program(No.RP-21-09-75).
文摘Deliberate modulation of the electronic structure via interface engineering is one of promising perspectives to build advanced catalysts for urea oxidation reaction(UOR)at high current densities.However,it still remains some challenges originating from the intrinsically sluggish UOR dynamics and the high energy barrier for urea adsorption.In response,we report the coupled NiSe_(2)nanowrinkles with Ni_(5)P_(4)nanorods heterogeneous structure onto Ni foam(denoted as NiSe_(2)@Ni_(5)P_(4)/NF)through successive phosphorization and selenization strategy,in which the produced closely contacted interface could provide high-flux electron transfer pathways.Theoretical findings decipher that the fast charge transfer takes place at the interfacial region from Ni_(5)P_(4)to NiSe_(2),which is conducive to optimizing adsorption energy of urea molecules.As expected,the well-designed NiSe_(2)@Ni_(5)P_(4)/NF only requires the low potential of 1.402 V at the current density of 500 mA·cm^(-2).More importantly,a small Tafel slope of 27.6 mV·dec^(-1),a high turnover frequency(TOF)value of 1.037 s^(-1)as well as the prolonged stability of 950 h at the current density of 100 mA·cm^(-2)are also achieved.This study enriches the understanding on the electronic structure modulation via interface engineering and offers bright prospect to design advanced UOR catalysts.
基金the National Key R&D Program of China(Nos.2020YFA0405800 and 2017YFA0303500)the National Natural Science Foundation of China(NSFC)(Nos.U1932201,U2032113,and 22075264)+3 种基金CAS Collaborative Innovation Program of Hefei Science Center(Nos.2019HSC-CIP002 and 2020HSC-CIP002)USTC Research Funds of the Double First-Class Initiative(No.YD2310002003)Institute of Energy,Hefei Comprehensive Nation Science Center,University Synergy Innovation Program of Anhui Province(GXXT-2020-002)CAS Iterdisciplinary Innovation Team.L.S.acknowledges the support from Key Laboratory of Advanced Energy Materials Chemistry(Ministry of Education),Nankai University(111 project,B12015)。
文摘The phase transformation of catalysts has been extensively observed in heterogeneous catalytic reactions that hinder the long cycling catalysis,and it remains a big challenge to precisely control the active phase during the complex conditions in electrochemical catalysis.Here,we theoretically predict that carbon-based support could achieve the phase engineering regulation of catalysts by suppressing specific phase transformation.Taken single-walled carbon nanotube(SWCNT)as typical support,combined with calculated E-pH(Pourbaix)diagram and advanced synchrotron-based characterizations technologies prove there are two different active phases source from cobalt selenide which demonstrate that the feasibility of using support effect regulating the potential advantageous catalysts.Moreover,it is worth noting that the phase engineering derived Co_(3)O_(4)-SWCNT exhibits a low overpotential of 201 mV for delivering the current density of 10 mA/cm^(2)in electrocatalytic oxygen evolution reaction(OER).Also,it reaches a record current density of 529 mA/cm^(2)at 1.63 V(vs.RHE)in the electrocatalytic urea oxidation reaction(UOR),overwhelming most previously reported catalysts.
