Electrocatalytic nitric oxide(NO)reduction reaction(NORR)is a promising and sustainable process that can simultaneously realize green ammonia(NH3)synthesis and hazardous NO removal.However,current NORR performances ar...Electrocatalytic nitric oxide(NO)reduction reaction(NORR)is a promising and sustainable process that can simultaneously realize green ammonia(NH3)synthesis and hazardous NO removal.However,current NORR performances are far from practical needs due to the lack of efficient electrocatalysts.Engineering the lattice of metal-based nanomaterials via phase control has emerged as an effective strategy to modulate their intrinsic electrocatalytic properties.Herein,we realize boron(B)-insertion-induced phase regulation of rhodium(Rh)nanocrystals to obtain amorphous Rh_(4)B nanoparticles(NPs)and hexagonal close-packed(hcp)RhB NPs through a facile wet-chemical method.A high Faradaic efficiency(92.1±1.2%)and NH_(3) yield rate(629.5±11.0μmol h^(−1) cm^(−2))are achieved over hcp RhB NPs,far superior to those of most reported NORR nanocatalysts.In situ spectro-electrochemical analysis and density functional theory simulations reveal that the excellent electrocatalytic performances of hcp RhB NPs are attributed to the upshift of d-band center,enhanced NO adsorption/activation profile,and greatly reduced energy barrier of the rate-determining step.A demonstrative Zn-NO battery is assembled using hcp RhB NPs as the cathode and delivers a peak power density of 4.33 mW cm−2,realizing simultaneous NO removal,NH3 synthesis,and electricity output.展开更多
A modular and efficient synthesis of the biologically significant C-methylisoflavones isosideroxylin（1）,6,8-dimethylgenistein（2） and their analogues（3-8） is established for the first time.The synthesis is realiz...A modular and efficient synthesis of the biologically significant C-methylisoflavones isosideroxylin（1）,6,8-dimethylgenistein（2） and their analogues（3-8） is established for the first time.The synthesis is realized in 7-8 steps in overall yields of 16%-24%from commercially inexpensive phloroglucinol and features a high yielding Vilsmeier-Haack reaction,Friedel-Crafts acylation,Gammill＇s protocol and Suzuki coupling as the pivotal transformations.Next,these compounds evaluated for their inhibitory potency on the production of nitric oxide（NO） in lipopolysaccharide（LPS）-activated RAW-264.7 cells as an indicator of anti-inflammatory activity.The results showed that all the compounds decreased NO production in a dose-dependent manner without marked cytotoxicity and IC_（50） values are found in the range of 10.17-33.88 μmol/L.Of note,compounds 3 followed by 1,7 and 8 show comparable inhibitory activity with positive control（N-monomethyl-L-arginine,L-NMMA）.展开更多
The electrochemical nitric oxide reduction reaction(NORR)to NH_(3)represents a promising avenue for NO removal and NH_(3)synthesis.It is essential to develop catalysts with superior performance for this process.We sys...The electrochemical nitric oxide reduction reaction(NORR)to NH_(3)represents a promising avenue for NO removal and NH_(3)synthesis.It is essential to develop catalysts with superior performance for this process.We systematically studied a series of single-atom alloy catalysts(SAACs)with Pd single-atom dopants using density functional theory(DFT)calculations and machine learning(ML).Based on the energetic span model,we take G_(max)(η)as a descriptor to evaluate the reaction activity of SAACs.After comprehensively considering the stability,activity,and NH_(3)selectivity of SAACs,Cu and Pd/Cu SAAC are screened out as candidate NORR to NH_(3)catalysts.To predict the G_(max)(η)descriptor,the extreme gradient boosting regression(XGBR)ML algorithm was adopted with geometric/electronic properties of the SAACs as input features.Additionally,we proposed a mathematical formula to correlate the crucial features and the G_(max)(η)descriptor using the sure independence screening and sparsifying operator(SISSO)approach.This work provides an understanding of the complex NORR mechanisms and offers a strategy to rationally design highly efficient SAACs.展开更多
Synthesis of ammonia gas through environmental protection and low-cost electrocatalysis is one of the ways to solve the current human energy problems.Herein,through the study of density functional theory(DFT),a series...Synthesis of ammonia gas through environmental protection and low-cost electrocatalysis is one of the ways to solve the current human energy problems.Herein,through the study of density functional theory(DFT),a series of transition metal single atoms are embedded in the defect-containing h-BN to construct a TM@B_(2) N_(2)(TM=Ti-Zn,Nb-Ag) two-dimensional nanostructure.The activation effect of these single-atom catalysts on NO molecules and the electrochemical performance of catalyzing NO reduction reaction(NORR)were explored.All reaction pathways are studied in detail,and competition between hydrogen proton and ammonia(NH3) oxidation with NORRs is also explored.Among the16 transition metal atoms we studied,the intercalation of Pb atom into h-BN has the best catalytic activity.The reaction rate-limiting potential of NORR is only 0.55 eV,and the surface HER reaction and ammonia oxidation can be effectively inhibited.It is hoped that our research can further promote the application of h-BN in the field of catalysis and provide some guidance for experimental workers in the field of ammonia synthesis.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
Designing advanced and cost-effective electrocatalytic system for nitric oxide(NO)reduction reaction(NORR)is vital for sustainable NH_(3) production and NO removal,yet it is a challenging task.Herein,it is shown that ...Designing advanced and cost-effective electrocatalytic system for nitric oxide(NO)reduction reaction(NORR)is vital for sustainable NH_(3) production and NO removal,yet it is a challenging task.Herein,it is shown that phosphorus(P)-doped titania(TiO_(2))nanotubes can be adopted as highly efficient catalyst for NORR.The catalyst demonstrates impressive performance in ionic liquid(IL)-based electrolyte with a remarkable high Faradaic efficiency of 89%and NH3 yield rate of 425μg·h^(−1)·mg_(cat).^(−1),being close to the best-reported results.Noteworthy,the obtained performance metrics are significantly larger than those for N_(2) reduction reaction.It also shows good durability with negligible activity decay even after 10 cycles.Theoretical simulations reveal that the introduction of P dopants tunes the electronic structure of Ti active sites,thereby enhancing the NO adsorption and facilitating the desorption of ^(*)NH_(3).Moreover,the utilization of IL further suppresses the competitive hydrogen evolution reaction.This study highlights the advantage of the catalyst−electrolyte engineering strategy for producing NH_(3) at a high efficiency and rate.展开更多
基金funding support from General Research Fund[Project No.14300525]from the Research Grants Council(RGC)of Hong Kong SAR,Chinafunding support from Natural Science Foundation of China(NSFC)Young Scientists Fund(Project No.22305203)+2 种基金NSFC Projects Nos.22309123,22422303,22303011,22033002,92261112 and U21A20328support from the Hong Kong Branch of National Precious Metals Material Engineering Research Center(NPMM)at City University of Hong Kongsupport from Young Collaborative Research Grant[Project No.C1003-23Y]support from RGC of Hong Kong SAR,China.
文摘Electrocatalytic nitric oxide(NO)reduction reaction(NORR)is a promising and sustainable process that can simultaneously realize green ammonia(NH3)synthesis and hazardous NO removal.However,current NORR performances are far from practical needs due to the lack of efficient electrocatalysts.Engineering the lattice of metal-based nanomaterials via phase control has emerged as an effective strategy to modulate their intrinsic electrocatalytic properties.Herein,we realize boron(B)-insertion-induced phase regulation of rhodium(Rh)nanocrystals to obtain amorphous Rh_(4)B nanoparticles(NPs)and hexagonal close-packed(hcp)RhB NPs through a facile wet-chemical method.A high Faradaic efficiency(92.1±1.2%)and NH_(3) yield rate(629.5±11.0μmol h^(−1) cm^(−2))are achieved over hcp RhB NPs,far superior to those of most reported NORR nanocatalysts.In situ spectro-electrochemical analysis and density functional theory simulations reveal that the excellent electrocatalytic performances of hcp RhB NPs are attributed to the upshift of d-band center,enhanced NO adsorption/activation profile,and greatly reduced energy barrier of the rate-determining step.A demonstrative Zn-NO battery is assembled using hcp RhB NPs as the cathode and delivers a peak power density of 4.33 mW cm−2,realizing simultaneous NO removal,NH3 synthesis,and electricity output.
基金financially supported by industrial co-work program with Sun Chem(Sun Kyung Chemical Co.,South Korea)
文摘A modular and efficient synthesis of the biologically significant C-methylisoflavones isosideroxylin（1）,6,8-dimethylgenistein（2） and their analogues（3-8） is established for the first time.The synthesis is realized in 7-8 steps in overall yields of 16%-24%from commercially inexpensive phloroglucinol and features a high yielding Vilsmeier-Haack reaction,Friedel-Crafts acylation,Gammill＇s protocol and Suzuki coupling as the pivotal transformations.Next,these compounds evaluated for their inhibitory potency on the production of nitric oxide（NO） in lipopolysaccharide（LPS）-activated RAW-264.7 cells as an indicator of anti-inflammatory activity.The results showed that all the compounds decreased NO production in a dose-dependent manner without marked cytotoxicity and IC_（50） values are found in the range of 10.17-33.88 μmol/L.Of note,compounds 3 followed by 1,7 and 8 show comparable inhibitory activity with positive control（N-monomethyl-L-arginine,L-NMMA）.
基金support from the He Bei Natural Science Foundation(Nos.B2022205029 and B2022205013)。
文摘The electrochemical nitric oxide reduction reaction(NORR)to NH_(3)represents a promising avenue for NO removal and NH_(3)synthesis.It is essential to develop catalysts with superior performance for this process.We systematically studied a series of single-atom alloy catalysts(SAACs)with Pd single-atom dopants using density functional theory(DFT)calculations and machine learning(ML).Based on the energetic span model,we take G_(max)(η)as a descriptor to evaluate the reaction activity of SAACs.After comprehensively considering the stability,activity,and NH_(3)selectivity of SAACs,Cu and Pd/Cu SAAC are screened out as candidate NORR to NH_(3)catalysts.To predict the G_(max)(η)descriptor,the extreme gradient boosting regression(XGBR)ML algorithm was adopted with geometric/electronic properties of the SAACs as input features.Additionally,we proposed a mathematical formula to correlate the crucial features and the G_(max)(η)descriptor using the sure independence screening and sparsifying operator(SISSO)approach.This work provides an understanding of the complex NORR mechanisms and offers a strategy to rationally design highly efficient SAACs.
基金financially supported by the Natural Science Foundation of China (No.21603109)Henan Joint Fund of the National Natural Science Foundation of China (No. U1404216)the Scientific Research Program Funded by Shaanxi Provincial Education Department (No.20JK0676)。
文摘Synthesis of ammonia gas through environmental protection and low-cost electrocatalysis is one of the ways to solve the current human energy problems.Herein,through the study of density functional theory(DFT),a series of transition metal single atoms are embedded in the defect-containing h-BN to construct a TM@B_(2) N_(2)(TM=Ti-Zn,Nb-Ag) two-dimensional nanostructure.The activation effect of these single-atom catalysts on NO molecules and the electrochemical performance of catalyzing NO reduction reaction(NORR)were explored.All reaction pathways are studied in detail,and competition between hydrogen proton and ammonia(NH3) oxidation with NORRs is also explored.Among the16 transition metal atoms we studied,the intercalation of Pb atom into h-BN has the best catalytic activity.The reaction rate-limiting potential of NORR is only 0.55 eV,and the surface HER reaction and ammonia oxidation can be effectively inhibited.It is hoped that our research can further promote the application of h-BN in the field of catalysis and provide some guidance for experimental workers in the field of ammonia synthesis.
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financially supported by the National Natural Science Foundation of China(Grant Nos.22075211,21601136,and 21905246)the Key Projects of Zhejiang Natural Science Foundation(Grant No.LZ20E010001).
文摘Designing advanced and cost-effective electrocatalytic system for nitric oxide(NO)reduction reaction(NORR)is vital for sustainable NH_(3) production and NO removal,yet it is a challenging task.Herein,it is shown that phosphorus(P)-doped titania(TiO_(2))nanotubes can be adopted as highly efficient catalyst for NORR.The catalyst demonstrates impressive performance in ionic liquid(IL)-based electrolyte with a remarkable high Faradaic efficiency of 89%and NH3 yield rate of 425μg·h^(−1)·mg_(cat).^(−1),being close to the best-reported results.Noteworthy,the obtained performance metrics are significantly larger than those for N_(2) reduction reaction.It also shows good durability with negligible activity decay even after 10 cycles.Theoretical simulations reveal that the introduction of P dopants tunes the electronic structure of Ti active sites,thereby enhancing the NO adsorption and facilitating the desorption of ^(*)NH_(3).Moreover,the utilization of IL further suppresses the competitive hydrogen evolution reaction.This study highlights the advantage of the catalyst−electrolyte engineering strategy for producing NH_(3) at a high efficiency and rate.
