Lattice-strain engineering has demonstrated its capability to influence the electronic structure and catalytic performance of electrocatalysts.Herein,we present a facile method for inducing thermal strain in cobalt/mo...Lattice-strain engineering has demonstrated its capability to influence the electronic structure and catalytic performance of electrocatalysts.Herein,we present a facile method for inducing thermal strain in cobalt/molybdenum nitride rod-shaped structures(denoted Co/Mo_(2)N)via ammonia-assisted reduction,which effectively modulating the HER performance.The optimized Co/Mo_(2)N-500,characterized by 3%tensile lattice strain,demonstrates exceptional HER activity with lower overpotentials of140 mV and 184 mV at high current density of 1000 mA cm^(-2)in alkaline freshwater and seawater electrolytes,respectively.Co/Mo_(2)N also exhibits excellent long-term durability even at a high current density of 300 mA cm^(-2),surpassing its counterparts and benchmark Pt/C catalyst.Density functional theory calculations validate that the tensile strain optimizes the d-band states,water dissociation,and hydrogen adsorption kinetics of the strained Mo_(2)N in Co/Mo_(2)N,thereby improving its catalytic efficacy.This work provides valuable insights into controlling lattice strain to develop highly efficient electrocatalysts towards advanced electrocatalytic applications.展开更多
Economical,stable,and corrosion-resistant catalytic electrodes are still urgently needed for the oxygen evolution reaction(OER)in water and seawater.Herein,a mild electroless plating strategy is used to achieve large-...Economical,stable,and corrosion-resistant catalytic electrodes are still urgently needed for the oxygen evolution reaction(OER)in water and seawater.Herein,a mild electroless plating strategy is used to achieve large-scale preparation of the“integrated”phosphorus-based precatalyst(FeP-NiP)on nickel foam(NF),which is in situ reconstructed into a highly active and corrosion-resistant(Fe)NiOOH phase for OER.The interaction between phosphate anions(PO_(x)^(y-))and iron ions(Fe^(3+))tunes the electronic structure of the catalytic phase to further enhance OER kinetics.The integrated FeP-NiP@NF electrode exhibits low overpotentials for OER in alkaline water/seawater,requiring only 275/289,320/336,and 349/358 mV to reach 0.1,0.5,and 1.0 A cm^(−2),respectively.The in situ reconstructed PO_(x)^(y-)anion electrostatically repels Cl−in seawater electrolytes,allowing stable operation for over 7 days at 1.0 A cm^(−2) in extreme electrolytes(1.0 M KOH+seawater and 6.0 M KOH+seawater),demonstrating industrial-level stability.This study overcomes the complex synthesis limitations of P-based materials through innovative material design,opening new avenues for electrochemical energy conversion.展开更多
Employing the alkaline water electrolysis system to generate hydrogen holds great prospects but still poses significant challenges,particularly for the construction of hydrogen evolution reaction(HER)catalysts operati...Employing the alkaline water electrolysis system to generate hydrogen holds great prospects but still poses significant challenges,particularly for the construction of hydrogen evolution reaction(HER)catalysts operating at ampere-level current density.Herein,the unique Ru and RuP_(2)dual nano-islands are deliberately implanted on N-doped carbon substrate(denoted as Ru-RuP_(2)/NC),in which a built-in electric field(BEF)is spontaneously generated between Ru-RuP_(2)dual nano-islands driven by their work function difference.Experimental and theoretical results unveil that such constructed BEF could serve as the driving force for triggering fast hydrogen spillover process on bridged Ru-RuP_(2)dual nano-islands,which could invalidate the inhibitory effect of high hydrogen coverage at ampere-level current density,and synchronously speed up the water dissociation on Ru nano-islands and hydrogen adsorption/desorption on RuP_(2)nano-islands through hydrogen spillover process.As a result,the Ru-RuP_(2)/NC affords an ultra-low overpotential of 218 mV to achieve 1.0 A·cm^(−2)along with the superior stability over 1000 h,holding the great promising prospect in practical applications at ampere-level current density.More importantly,this work is the first to advance the scientific understanding of the relationship between the constructed BEF and hydrogen spillover process,which could be enlightening for the rational design of the cost-effective alkaline HER catalysts at ampere-level current density.展开更多
Alkaline hydrogen evolution reaction(HER)for scalable hydrogen production largely hinges on addressing the sluggish bubble-involved kinetics on the traditional Ni-based electrode,especially for ampere-level current de...Alkaline hydrogen evolution reaction(HER)for scalable hydrogen production largely hinges on addressing the sluggish bubble-involved kinetics on the traditional Ni-based electrode,especially for ampere-level current densities and beyond.Herein,3D-printed Ni-based sulfide(3DPNS)electrodes with varying scaffolds are designed and fabricated.In situ observations at microscopic levels demonstrate that the bubble escape velocity increases with the number of hole sides(HS)in the scaffolds.Subsequently,we conduct multiphysics field simulations to illustrate that as the hole shapes transition from square,pentagon,and hexagon to circle,where a noticeable reduction in the bubble-attached HS length and the pressure balance time around the bubbles results in a decrease in bubble size and an acceleration in the rate of bubble escape.Ultimately,the 3DPNS electrode with circular hole configura-tions exhibits the most favorable HER performance with an overpotential of 297 mV at the current density of up to 1000 mA cm^(-2) for 120 h.The present study highlights a scalable and effective electrode scaffold design that promotes low-cost and low-energy green hydrogen production through the ampere-level alkaline HER.展开更多
Addressing inadequate OH^(*)adsorption in Ru Co alloy catalysts is crucial for boosting intermediate coverage and redirecting the water-splitting pathway.Herein,the adaptive P sites were strategically incorporated to ...Addressing inadequate OH^(*)adsorption in Ru Co alloy catalysts is crucial for boosting intermediate coverage and redirecting the water-splitting pathway.Herein,the adaptive P sites were strategically incorporated to overcome the aforementioned challenge.The P sites,as potent OH^(*)adsorption centers,synergize with Co sites to promote water dissociation and enrich surrounding Ru sites with H*intermediates,thus triggering the Volmer-Tafel route for hydrogen evolution reaction(HER).Besides,during the oxygen evolution reaction(OER),the surface of P-Ru Co was reconstructed into Ru-doped Co OOH with anchored PO_(4)^(3-).These PO_(4)^(3-)not only circumvent the intrinsic OH^(*)adsorption limitations of Ru-Co OOH in the adsorbate evolution mechanism(AEM)by rerouting to a more expeditious lattice oxygen oxidation mechanism(LOM)but also improve the coverage of key oxygen-containing intermediates,significantly accelerating OER kinetics.Consequently,the P-Ru Co demonstrates exceptional bifunctional performance,with overpotentials of 29 m V for HER and 222 m V for OER at 10 m A cm^(-2).Remarkably,the mass activities of PRu Co for HER(5.48 A mg^(-1))and OER(2.13 A mg^(-1))are 6.2 and 11.2 times higher than those of its commercial counterparts(Ru/C for HER and RuO_(2)for OER),respectively.When integrated into an anionexchange-membrane electrolyzer,this catalyst achieves ampere-level current densities of 1.32 A cm^(-2)for water electrolysis and 1.23 A cm^(-2)for seawater electrolysis at 2.1 V,with a 500-h durability.展开更多
Alkaline seawater electrolysis for hydrogen production powered by clean energy is increasingly driving the development of a low-carbon economy.However,the limited proton availability in the electrolyte leads to sluggi...Alkaline seawater electrolysis for hydrogen production powered by clean energy is increasingly driving the development of a low-carbon economy.However,the limited proton availability in the electrolyte leads to sluggish cathodic reaction kinetics and elevates energy consumption,which hinders its large-scale application.Herein,low Pt loaded NiCo phosphate-coated NiCoP nanoneedle arrays on Ni foam(Pt@NCPi@NCP/NF)using a spontaneous redox strategy is developed for efficient and durable electrocatalytic hydrogen production from alkaline seawater.In situ Raman spectroscopy confirms that a large number of hydrated hydrogen ion intermediates are generated on the surface of Pt@NCPi@NCP/NF during the hydrogen evolution reaction(HER)process,which successfully constructs a localized acidic microenvironment.Concurrently,the surface Pi layer functions as a proton buffer layer,effectively regulating proton supply to enhance the utilization efficiency of active sites.As a result,the catalyst exhibits excellent HER kinetics under alkaline conditions with a Tafel slope of only 39.65 mV·dec^(-1)and a low overpotential of 136 mV to reach 1000 mA·cm^(-2).展开更多
Developing non-noble metal hydrogen evolution reaction(HER)electrocatalysts with high activity and durability at ampere-level current densities is vital for emerging anion exchange membrane(AEM)water electrolysis,but ...Developing non-noble metal hydrogen evolution reaction(HER)electrocatalysts with high activity and durability at ampere-level current densities is vital for emerging anion exchange membrane(AEM)water electrolysis,but it remains challenging.Here we present an atom-stepped nickel–cobalt bimetallic sulfide(AS-Ni_(3)S_(2)/Co_(3)S_(4))heter-ostructure that exhibits superior HER performance,with ultra-low overpotentials of 28 and 195 mV at current densities of 10 and 2000 mA cm^(-2),respectively.Experimental analyses and theoretical calculations revealed that the work-function-induced interfacial built-in electric field drives electron transfer from Ni_(3)S_(2)to Co_(3)S_(4)via Ni–S–Co interfacial bridging,which effectively accelerates water activation and optimizes hydrogen adsorption and desorption.An AEM electrolyzer using an AS-Ni_(3)S_(2)/Co_(3)S_(4)heterostructure as the cathode required cell voltages of only 1.71 and 1.79 V to reach 1.0 and 2.0 A cm^(-2),respectively,and operated stably for 1200 h without activity degradation.展开更多
基金supported by the Hunan Joint International Laboratory of Advanced Materials and Technology for Clean Energy(2020CB1007)Fundamental Research Funds for the Central Universities and Guangxi Key Laboratory of Information Materials and Guilin University of Electronic Technology,China(231002-K)+4 种基金Natural Science Foundation of Guangxi Zhuang Autonomous Region(2022GXNSFAA035467)Guangxi Science and Technology Program(Guike AD21220067)National Natural Science Foundation of China(22369002)Nationally Funded Postdoctoral Researcher Program(GZC20230756)China Postdoctoral Science Foundation(2024M750858)。
文摘Lattice-strain engineering has demonstrated its capability to influence the electronic structure and catalytic performance of electrocatalysts.Herein,we present a facile method for inducing thermal strain in cobalt/molybdenum nitride rod-shaped structures(denoted Co/Mo_(2)N)via ammonia-assisted reduction,which effectively modulating the HER performance.The optimized Co/Mo_(2)N-500,characterized by 3%tensile lattice strain,demonstrates exceptional HER activity with lower overpotentials of140 mV and 184 mV at high current density of 1000 mA cm^(-2)in alkaline freshwater and seawater electrolytes,respectively.Co/Mo_(2)N also exhibits excellent long-term durability even at a high current density of 300 mA cm^(-2),surpassing its counterparts and benchmark Pt/C catalyst.Density functional theory calculations validate that the tensile strain optimizes the d-band states,water dissociation,and hydrogen adsorption kinetics of the strained Mo_(2)N in Co/Mo_(2)N,thereby improving its catalytic efficacy.This work provides valuable insights into controlling lattice strain to develop highly efficient electrocatalysts towards advanced electrocatalytic applications.
基金funding support from Natural Science Foundation of Shanghai(Grant No.23ZR1443900)the National Natural Science Foundation of China(Grant Nos.22178309,22476131 and 22176127)。
文摘Economical,stable,and corrosion-resistant catalytic electrodes are still urgently needed for the oxygen evolution reaction(OER)in water and seawater.Herein,a mild electroless plating strategy is used to achieve large-scale preparation of the“integrated”phosphorus-based precatalyst(FeP-NiP)on nickel foam(NF),which is in situ reconstructed into a highly active and corrosion-resistant(Fe)NiOOH phase for OER.The interaction between phosphate anions(PO_(x)^(y-))and iron ions(Fe^(3+))tunes the electronic structure of the catalytic phase to further enhance OER kinetics.The integrated FeP-NiP@NF electrode exhibits low overpotentials for OER in alkaline water/seawater,requiring only 275/289,320/336,and 349/358 mV to reach 0.1,0.5,and 1.0 A cm^(−2),respectively.The in situ reconstructed PO_(x)^(y-)anion electrostatically repels Cl−in seawater electrolytes,allowing stable operation for over 7 days at 1.0 A cm^(−2) in extreme electrolytes(1.0 M KOH+seawater and 6.0 M KOH+seawater),demonstrating industrial-level stability.This study overcomes the complex synthesis limitations of P-based materials through innovative material design,opening new avenues for electrochemical energy conversion.
基金the National Natural Science Foundation of China(Nos.22279124 and 52261145700)Shandong Province Natural Science Foundation(No.ZR2022ZD30)National Research Foundation of Korea(NRF)grant funded by the Korea government(MSIT)(Nos.NRF-2020R1A2C3004146 and RS-2023-00235596).
文摘Employing the alkaline water electrolysis system to generate hydrogen holds great prospects but still poses significant challenges,particularly for the construction of hydrogen evolution reaction(HER)catalysts operating at ampere-level current density.Herein,the unique Ru and RuP_(2)dual nano-islands are deliberately implanted on N-doped carbon substrate(denoted as Ru-RuP_(2)/NC),in which a built-in electric field(BEF)is spontaneously generated between Ru-RuP_(2)dual nano-islands driven by their work function difference.Experimental and theoretical results unveil that such constructed BEF could serve as the driving force for triggering fast hydrogen spillover process on bridged Ru-RuP_(2)dual nano-islands,which could invalidate the inhibitory effect of high hydrogen coverage at ampere-level current density,and synchronously speed up the water dissociation on Ru nano-islands and hydrogen adsorption/desorption on RuP_(2)nano-islands through hydrogen spillover process.As a result,the Ru-RuP_(2)/NC affords an ultra-low overpotential of 218 mV to achieve 1.0 A·cm^(−2)along with the superior stability over 1000 h,holding the great promising prospect in practical applications at ampere-level current density.More importantly,this work is the first to advance the scientific understanding of the relationship between the constructed BEF and hydrogen spillover process,which could be enlightening for the rational design of the cost-effective alkaline HER catalysts at ampere-level current density.
基金Natural Science Foundation of Hainan Province,Grant/Award Number:623MS068Fundamental Research Funds for the Central Universities,Grant/Award Number:40120631+2 种基金Natural Science Foundation of Hubei Province,Grant/Award Number:2022CFB388National Natural Science Foundation of China,Grant/Award Number:52202291Singapore MOE,Grant/Award Number:Tier 1,A-8000186-01-00。
文摘Alkaline hydrogen evolution reaction(HER)for scalable hydrogen production largely hinges on addressing the sluggish bubble-involved kinetics on the traditional Ni-based electrode,especially for ampere-level current densities and beyond.Herein,3D-printed Ni-based sulfide(3DPNS)electrodes with varying scaffolds are designed and fabricated.In situ observations at microscopic levels demonstrate that the bubble escape velocity increases with the number of hole sides(HS)in the scaffolds.Subsequently,we conduct multiphysics field simulations to illustrate that as the hole shapes transition from square,pentagon,and hexagon to circle,where a noticeable reduction in the bubble-attached HS length and the pressure balance time around the bubbles results in a decrease in bubble size and an acceleration in the rate of bubble escape.Ultimately,the 3DPNS electrode with circular hole configura-tions exhibits the most favorable HER performance with an overpotential of 297 mV at the current density of up to 1000 mA cm^(-2) for 120 h.The present study highlights a scalable and effective electrode scaffold design that promotes low-cost and low-energy green hydrogen production through the ampere-level alkaline HER.
基金supported by the National Natural Science Foundation of China(Nos.52301279 and 51901115)the Shandong Provincial Natural Science Foundation,China(ZR2023MB122 and ZR2019PEM001)+1 种基金the Outstanding Youth Innovation Team of Universities in Shandong Province(2024KJH067)the Innovation fund project for graduate student of China University of Petroleum(East China)supported by the Fundamental Research Funds for the Central Universities(No.23CX04010A)。
文摘Addressing inadequate OH^(*)adsorption in Ru Co alloy catalysts is crucial for boosting intermediate coverage and redirecting the water-splitting pathway.Herein,the adaptive P sites were strategically incorporated to overcome the aforementioned challenge.The P sites,as potent OH^(*)adsorption centers,synergize with Co sites to promote water dissociation and enrich surrounding Ru sites with H*intermediates,thus triggering the Volmer-Tafel route for hydrogen evolution reaction(HER).Besides,during the oxygen evolution reaction(OER),the surface of P-Ru Co was reconstructed into Ru-doped Co OOH with anchored PO_(4)^(3-).These PO_(4)^(3-)not only circumvent the intrinsic OH^(*)adsorption limitations of Ru-Co OOH in the adsorbate evolution mechanism(AEM)by rerouting to a more expeditious lattice oxygen oxidation mechanism(LOM)but also improve the coverage of key oxygen-containing intermediates,significantly accelerating OER kinetics.Consequently,the P-Ru Co demonstrates exceptional bifunctional performance,with overpotentials of 29 m V for HER and 222 m V for OER at 10 m A cm^(-2).Remarkably,the mass activities of PRu Co for HER(5.48 A mg^(-1))and OER(2.13 A mg^(-1))are 6.2 and 11.2 times higher than those of its commercial counterparts(Ru/C for HER and RuO_(2)for OER),respectively.When integrated into an anionexchange-membrane electrolyzer,this catalyst achieves ampere-level current densities of 1.32 A cm^(-2)for water electrolysis and 1.23 A cm^(-2)for seawater electrolysis at 2.1 V,with a 500-h durability.
文摘Alkaline seawater electrolysis for hydrogen production powered by clean energy is increasingly driving the development of a low-carbon economy.However,the limited proton availability in the electrolyte leads to sluggish cathodic reaction kinetics and elevates energy consumption,which hinders its large-scale application.Herein,low Pt loaded NiCo phosphate-coated NiCoP nanoneedle arrays on Ni foam(Pt@NCPi@NCP/NF)using a spontaneous redox strategy is developed for efficient and durable electrocatalytic hydrogen production from alkaline seawater.In situ Raman spectroscopy confirms that a large number of hydrated hydrogen ion intermediates are generated on the surface of Pt@NCPi@NCP/NF during the hydrogen evolution reaction(HER)process,which successfully constructs a localized acidic microenvironment.Concurrently,the surface Pi layer functions as a proton buffer layer,effectively regulating proton supply to enhance the utilization efficiency of active sites.As a result,the catalyst exhibits excellent HER kinetics under alkaline conditions with a Tafel slope of only 39.65 mV·dec^(-1)and a low overpotential of 136 mV to reach 1000 mA·cm^(-2).
基金supported by the National Natural Science Foundation of China(U2002213,22369025)Yunnan Applied Basic Research Projects(202201AT070095,202401AT070438)+1 种基金the Double-First Class University Plan(C176220100042)Graduate Research Innovation Project of Yunnan University(KC-23234063),and the Yunnan Revitalization Talent Support Program.
文摘Developing non-noble metal hydrogen evolution reaction(HER)electrocatalysts with high activity and durability at ampere-level current densities is vital for emerging anion exchange membrane(AEM)water electrolysis,but it remains challenging.Here we present an atom-stepped nickel–cobalt bimetallic sulfide(AS-Ni_(3)S_(2)/Co_(3)S_(4))heter-ostructure that exhibits superior HER performance,with ultra-low overpotentials of 28 and 195 mV at current densities of 10 and 2000 mA cm^(-2),respectively.Experimental analyses and theoretical calculations revealed that the work-function-induced interfacial built-in electric field drives electron transfer from Ni_(3)S_(2)to Co_(3)S_(4)via Ni–S–Co interfacial bridging,which effectively accelerates water activation and optimizes hydrogen adsorption and desorption.An AEM electrolyzer using an AS-Ni_(3)S_(2)/Co_(3)S_(4)heterostructure as the cathode required cell voltages of only 1.71 and 1.79 V to reach 1.0 and 2.0 A cm^(-2),respectively,and operated stably for 1200 h without activity degradation.
