Electrocatalytic nitrate reduction reaction(NO_(3)RR)offers a unique rationale for green NH_(3) synthesis,yet the lack of high-efficiency NO_(3)RR catalysts remains a great challenge.In this work,we show that Au nanoc...Electrocatalytic nitrate reduction reaction(NO_(3)RR)offers a unique rationale for green NH_(3) synthesis,yet the lack of high-efficiency NO_(3)RR catalysts remains a great challenge.In this work,we show that Au nanoclusters anchored on TiO_(2) nanosheets can efficiently catalyze the conversion of NO_(3)RR-to-NH_(3) under ambient conditions,achieving a maximal Faradic efficiency of 91%,a peak yield rate of 1923μg·h^(-1)·mgcat.-1,and high durability over 10 consecutive cycles,all of which are comparable to the recently reported metrics(including transition metal and noble metal-based catalysts)and exceed those of pristine TiO_(2).Moreover,a galvanic Zn-nitrate battery using the catalyst as the cathode was proposed,which shows a power density of 3.62 mW·cm^(-2) and a yield rate of 452μg·h^(-1)·mgcat.-1.Theoretical simulations further indicate that the atomically dispersed Au clusters can promote the adsorption and activation of NO_(3)-species,and reduce the NO_(3)RR-to-NH_(3) barrier,thus leading to an accelerated cathodic reaction.This work highlights the importance of metal clusters for the NH_(3) electrosynthesis and nitrate removal.展开更多
Electrocatalytic NO reduction reaction offers a sustainable route to achieving environmental protection and NH3 production targets as well.In this work,a class of dealloyed Ti_(60)Cu_(33)Mn_(7)ribbons with enough nano...Electrocatalytic NO reduction reaction offers a sustainable route to achieving environmental protection and NH3 production targets as well.In this work,a class of dealloyed Ti_(60)Cu_(33)Mn_(7)ribbons with enough nanoparticles for the high-efficient NO reduction reaction to NH_(3)is fabricated,reaching an excellent Faradaic efficiency of 93.2%at–0.5 V vs reversible hydrogen electrode and a high NH_(3) synthesis rate of 717.4μmol·h^(-1)·mg_(cat).^(-1) at–0.6 V vs reversible hydrogen electrode.The formed nanoparticles on the surface of the catalyst could facilitate the exposure of active sites and the transportation of various reactive ions and gases.Meanwhile,the Mn content in the TiCuMn ribbons modulates the chemical and physical properties of its surface,such as modifying the electronic structure of the Cu species,optimizing the adsorption energy of N^(*)atoms,decreasing the strength of the NO adsorption,and eliminating the thermodynamic energy barrier,thus improving the NO reduction reaction catalytic performance.Moreover,a Zn-NO battery was fabricated using the catalyst and Zn plates,generating an NH_(3) yield of 129.1µmol·h^(-1)·cm^(-2)while offering a peak power density of 1.45 mW·cm^(-2).展开更多
Electrochemical nitric oxide reduction reaction(NORR)to produce ammonia(NH3)under ambient conditions is a promising alternative to the energy and carbon-intensive Haber–Bosch approach,but its performance is still imp...Electrochemical nitric oxide reduction reaction(NORR)to produce ammonia(NH3)under ambient conditions is a promising alternative to the energy and carbon-intensive Haber–Bosch approach,but its performance is still improved.Herein,molybdenum carbides(MoC)nanocrystals confined by nitrogen-doped carbon nanosheets are first designed as an efficient and durable electrocatalyst for catalyzing the reduction of NO to NH3 with maximal Faradaic efficiency of 89%±2%and a yield rate of 1,350±15μg·h^(−1)·cm^(−2) at the applied potential of−0.8 V vs.reversible hydrogen electrode(RHE)as well as high stable activity with negligible current density and NH3 yield rate decays over a 30 h continue the test.Moreover,as a proof-of-concept of Zn–NO battery,it achieves a peak power density of 1.8 mW·cm^(−2) and a large NH3 yield rate of 782±10μg·h^(−1)·cm^(−2),which are comparable to the best-reported results.Theoretical calculations reveal that the MoC(111)has a strong electronic interaction with NO molecules and thus lowering the energy barrier of the potential-determining step and suppressing hydrogen evolution kinetics.This work suggests that Mo-based materials are a powerful platform providing great opportunities to explore highly selective and active catalysts for NH3 production.展开更多
Aqueous rechargeable Zn–gas batteries are regarded as promising energy storage and conversion devices due to their high safety and inherent environmental friendliness.However,the energy efficiency and power density o...Aqueous rechargeable Zn–gas batteries are regarded as promising energy storage and conversion devices due to their high safety and inherent environmental friendliness.However,the energy efficiency and power density of Zn–gas batteries are restricted by the kinetically sluggish cathode reactions,such as oxygen evolution reaction(OER)during charging and oxygen reduction reaction(ORR)/carbon dioxide reduction reaction(CO_(2)RR)/nitrogen reduction reaction(NRR)/nitric oxide reduction reaction(NORR)during discharge.In this review,battery configurations and fundamental reactions in Zn–gas batteries are first introduced,including Zn–air,Zn-CO_(2),Zn-N_(2),and Zn-NO batteries.Afterward,recent advances in active site engineering for enhancing the intrinsic catalytic activities of cathode catalysts are summarized.Subsequently,the structure and surface regulation strategies of cathode materials for optimizing the three-phase interface and improving the performance of Zn–gas batteries are discussed.Finally,some personal perspectives for the future development of Zn–gas batteries are presented.展开更多
Electrocatalytic NO reduction reaction to generate NH_(3)under ambient conditions offers an attractive alternative to the energy-extensive Haber-Bosch route;however,the challenge still lies in the development of cost-...Electrocatalytic NO reduction reaction to generate NH_(3)under ambient conditions offers an attractive alternative to the energy-extensive Haber-Bosch route;however,the challenge still lies in the development of cost-effective and high-performance electrocatalysts.Herein,nanoporous VN film is first designed as a highly selective and stable electrocatalyst for catalyzing reduction of NO to NH_(3)with a maximal Faradaic efficiency of 85%and a peak yield rate of 1.05×10^(-7)mol·cm^(-2)·s^(-1)(corresponding to 5,140.8mg·h^(-1)·mg_(cat).^(-1))at-0.6 V vs.reversible hydrogen electrode in acid medium.Meanwhile,this catalyst maintains an excellent activity with negligible current density and NH_(3)yield rate decays over 40 h.Moreover,as a proof-of-concept of Zn-NO battery,it delivers a high power density of 2.0 mW·cm^(-2)and a large NH_(3)yield rate of 0.22×10^(-7)mol·cm^(-2)·s^(-1)(corresponding to 1,077.1mg·h^(-1)·mg_(cat).^(-1)),both of which are comparable to the best-reported results.Theoretical analyses confirm that the VN surface favors the activation and hydrogenation of NO by suppressing the hydrogen evolution.This work highlights that the electrochemical NO reduction is an eco-friendly and energy-efficient strategy to produce NH_(3).展开更多
The potential application of monolayer MS2(M?Mo,W)as thermoelectric material has been widely studied since the first report of successful fabrication.However,their performances are hindered by the considerable band ga...The potential application of monolayer MS2(M?Mo,W)as thermoelectric material has been widely studied since the first report of successful fabrication.However,their performances are hindered by the considerable band gap and the large lattice thermal conductivity in the pristine 2H phase.Recent discoveries of polymorphism in MS2s provide new opportunities for materials engineering.In this work,phonon and electron transport properties of both 2H and 1T0 phases were investigated by first-principle calculations.It is found that upon the phase transition from 2H to 1T0 in MS2,the electron transport is greatly enhanced,while the lattice thermal conductivity is reduced by several times.These features lead to a significant enhancement of power factor by one order of magnitude in MoS2 and by three times in WS2.Meanwhile,the figure of merit can reach up to 0.33 for 1T0eMoS2 and 0.68 for 1T0eWS2 at low temperature.These findings indicate that monolayer MS2 in the 1T0 phase can be promising materials for thermoelectric devices application.Meanwhile,this work demonstrates that phase engineering techniques can bring in one important control parameter in materials design.展开更多
基金supported by the National Natural Science Foundation of China(Nos.22075211 and 51971157)the Guangzhou Basic&Applied Basic Research Project(No.202201011853)+2 种基金the Shenzhen Science and Technology Program(Nos.JCYJ20210324115412035,JCYJ20210324123202008,JCYJ20210324122803009,and ZDSYS20210813095534001)the Guangdong Basic and Applied Basic Research Foundation(No.2021A1515110880)the Tianjin Science Fund for Distinguished Young Scholars(No.19JCJQJC61800).
文摘Electrocatalytic nitrate reduction reaction(NO_(3)RR)offers a unique rationale for green NH_(3) synthesis,yet the lack of high-efficiency NO_(3)RR catalysts remains a great challenge.In this work,we show that Au nanoclusters anchored on TiO_(2) nanosheets can efficiently catalyze the conversion of NO_(3)RR-to-NH_(3) under ambient conditions,achieving a maximal Faradic efficiency of 91%,a peak yield rate of 1923μg·h^(-1)·mgcat.-1,and high durability over 10 consecutive cycles,all of which are comparable to the recently reported metrics(including transition metal and noble metal-based catalysts)and exceed those of pristine TiO_(2).Moreover,a galvanic Zn-nitrate battery using the catalyst as the cathode was proposed,which shows a power density of 3.62 mW·cm^(-2) and a yield rate of 452μg·h^(-1)·mgcat.-1.Theoretical simulations further indicate that the atomically dispersed Au clusters can promote the adsorption and activation of NO_(3)-species,and reduce the NO_(3)RR-to-NH_(3) barrier,thus leading to an accelerated cathodic reaction.This work highlights the importance of metal clusters for the NH_(3) electrosynthesis and nitrate removal.
基金supported by the National Natural Science Foundation of China(Grant No.22075211)Guangxi Natural Science Fund for Distinguished Young Scholars(2024GXNSFFA010008).
文摘Electrocatalytic NO reduction reaction offers a sustainable route to achieving environmental protection and NH3 production targets as well.In this work,a class of dealloyed Ti_(60)Cu_(33)Mn_(7)ribbons with enough nanoparticles for the high-efficient NO reduction reaction to NH_(3)is fabricated,reaching an excellent Faradaic efficiency of 93.2%at–0.5 V vs reversible hydrogen electrode and a high NH_(3) synthesis rate of 717.4μmol·h^(-1)·mg_(cat).^(-1) at–0.6 V vs reversible hydrogen electrode.The formed nanoparticles on the surface of the catalyst could facilitate the exposure of active sites and the transportation of various reactive ions and gases.Meanwhile,the Mn content in the TiCuMn ribbons modulates the chemical and physical properties of its surface,such as modifying the electronic structure of the Cu species,optimizing the adsorption energy of N^(*)atoms,decreasing the strength of the NO adsorption,and eliminating the thermodynamic energy barrier,thus improving the NO reduction reaction catalytic performance.Moreover,a Zn-NO battery was fabricated using the catalyst and Zn plates,generating an NH_(3) yield of 129.1µmol·h^(-1)·cm^(-2)while offering a peak power density of 1.45 mW·cm^(-2).
基金supported by National Natural Science Foundation of China(Nos.22075211,22109118,21601136,51971157,and 51621003).
文摘Electrochemical nitric oxide reduction reaction(NORR)to produce ammonia(NH3)under ambient conditions is a promising alternative to the energy and carbon-intensive Haber–Bosch approach,but its performance is still improved.Herein,molybdenum carbides(MoC)nanocrystals confined by nitrogen-doped carbon nanosheets are first designed as an efficient and durable electrocatalyst for catalyzing the reduction of NO to NH3 with maximal Faradaic efficiency of 89%±2%and a yield rate of 1,350±15μg·h^(−1)·cm^(−2) at the applied potential of−0.8 V vs.reversible hydrogen electrode(RHE)as well as high stable activity with negligible current density and NH3 yield rate decays over a 30 h continue the test.Moreover,as a proof-of-concept of Zn–NO battery,it achieves a peak power density of 1.8 mW·cm^(−2) and a large NH3 yield rate of 782±10μg·h^(−1)·cm^(−2),which are comparable to the best-reported results.Theoretical calculations reveal that the MoC(111)has a strong electronic interaction with NO molecules and thus lowering the energy barrier of the potential-determining step and suppressing hydrogen evolution kinetics.This work suggests that Mo-based materials are a powerful platform providing great opportunities to explore highly selective and active catalysts for NH3 production.
基金supported by the Zhejiang Provincial Natural Science Foundation of China(No.LZ21E020003)the National Natural Science Foundation of China(Nos.21905246,22075211,21601136,51971157,and 51621003)Tianjin Science Fund for Distinguished Young Scholars(No.19JCJQJC61800).
文摘Aqueous rechargeable Zn–gas batteries are regarded as promising energy storage and conversion devices due to their high safety and inherent environmental friendliness.However,the energy efficiency and power density of Zn–gas batteries are restricted by the kinetically sluggish cathode reactions,such as oxygen evolution reaction(OER)during charging and oxygen reduction reaction(ORR)/carbon dioxide reduction reaction(CO_(2)RR)/nitrogen reduction reaction(NRR)/nitric oxide reduction reaction(NORR)during discharge.In this review,battery configurations and fundamental reactions in Zn–gas batteries are first introduced,including Zn–air,Zn-CO_(2),Zn-N_(2),and Zn-NO batteries.Afterward,recent advances in active site engineering for enhancing the intrinsic catalytic activities of cathode catalysts are summarized.Subsequently,the structure and surface regulation strategies of cathode materials for optimizing the three-phase interface and improving the performance of Zn–gas batteries are discussed.Finally,some personal perspectives for the future development of Zn–gas batteries are presented.
基金This work was financially supported by the National Natural Science Foundation of China(Nos.22075211,22109118,21601136,51971157,51621003,and 21905246)Tianjin Science Fund for Distinguished Young Scholars(No.19JCJQJC61800)The authors would also like to express their gratitude to Deanship of Scientific Research at King Khalid University,Abha,Saudi Arabia for funding this work through the Research Group Program under No.RGP.2/79/43.
文摘Electrocatalytic NO reduction reaction to generate NH_(3)under ambient conditions offers an attractive alternative to the energy-extensive Haber-Bosch route;however,the challenge still lies in the development of cost-effective and high-performance electrocatalysts.Herein,nanoporous VN film is first designed as a highly selective and stable electrocatalyst for catalyzing reduction of NO to NH_(3)with a maximal Faradaic efficiency of 85%and a peak yield rate of 1.05×10^(-7)mol·cm^(-2)·s^(-1)(corresponding to 5,140.8mg·h^(-1)·mg_(cat).^(-1))at-0.6 V vs.reversible hydrogen electrode in acid medium.Meanwhile,this catalyst maintains an excellent activity with negligible current density and NH_(3)yield rate decays over 40 h.Moreover,as a proof-of-concept of Zn-NO battery,it delivers a high power density of 2.0 mW·cm^(-2)and a large NH_(3)yield rate of 0.22×10^(-7)mol·cm^(-2)·s^(-1)(corresponding to 1,077.1mg·h^(-1)·mg_(cat).^(-1)),both of which are comparable to the best-reported results.Theoretical analyses confirm that the VN surface favors the activation and hydrogenation of NO by suppressing the hydrogen evolution.This work highlights that the electrochemical NO reduction is an eco-friendly and energy-efficient strategy to produce NH_(3).
基金the Jiangsu provincial natural science funding Project(No.BK20160308)the NSF of Heilongjiang Province of China under Grants No.QC2015001.
文摘The potential application of monolayer MS2(M?Mo,W)as thermoelectric material has been widely studied since the first report of successful fabrication.However,their performances are hindered by the considerable band gap and the large lattice thermal conductivity in the pristine 2H phase.Recent discoveries of polymorphism in MS2s provide new opportunities for materials engineering.In this work,phonon and electron transport properties of both 2H and 1T0 phases were investigated by first-principle calculations.It is found that upon the phase transition from 2H to 1T0 in MS2,the electron transport is greatly enhanced,while the lattice thermal conductivity is reduced by several times.These features lead to a significant enhancement of power factor by one order of magnitude in MoS2 and by three times in WS2.Meanwhile,the figure of merit can reach up to 0.33 for 1T0eMoS2 and 0.68 for 1T0eWS2 at low temperature.These findings indicate that monolayer MS2 in the 1T0 phase can be promising materials for thermoelectric devices application.Meanwhile,this work demonstrates that phase engineering techniques can bring in one important control parameter in materials design.
