Nitric oxide(NO),which generally originates from vehicle exhaust and industrial flue gases,is one of the most serious air pollutants.In this case,the electrochemical NO reduction reaction(NORR)not only removes the atm...Nitric oxide(NO),which generally originates from vehicle exhaust and industrial flue gases,is one of the most serious air pollutants.In this case,the electrochemical NO reduction reaction(NORR)not only removes the atmospheric pollutant NO but also produces valuable ammonia(NH_(3)).Hence,through the synthesis and modification of Fe_(3)C nanocrystal cata-lysts,the as-obtained optimal sample of Fe_(3)C/C-900 was adopted as the NORR catalyst at ambient conditions.As a result,the Fe_(3)C/C-900 catalyst showed an NH_(3)Faraday efficiency of 76.5%and an NH_(3)yield rate of 177.5μmol·h^(-1)·cm^(-2)at the working potentials of-0.8 and-1.2 V versus reversible hydrogen electrode(vs.RHE),respectively.And it delivered a stable NORR activity during the electrolysis.Moreover,we attribute the high NORR properties of Fe_(3)C/C-900 to two aspects:one is the enhanced intrinsic activity of Fe_(3)C nanocrystals,including the lowering of the energy barrier of rate-limiting step(*NOH→*N)and the inhibition of hydrogen evolution;on the other hand,the favorable dispersion of active components,the effective adsorption of gaseous NO,and the release of liquid NH_(3)products facilitated by the porous carbon substrate.展开更多
Activity of three-way palladium catalyst was examined by means of a pulse-flam-microreactor. The effects of cerium on the catalytic properties of gamma-alumina-supported palladium for the reduction of nitric oxide wer...Activity of three-way palladium catalyst was examined by means of a pulse-flam-microreactor. The effects of cerium on the catalytic properties of gamma-alumina-supported palladium for the reduction of nitric oxide were studied with X-ray photoelectron spectroscopy (XPS) and temperature-programmed reduction (TPR). The reduction of nitric oxide on palladium catalysts is inhibited significantly by hydrocarbon. However, the reduction of nitric oxide was improved by the addition of cerium to the catalysts. The XPS and TPR studies showed that the presence of cerium provided, palladium oxide in a hard-reduced state and suppressed the chemisorption of hydrocarbons on the palladium oxide. Additionally,cerium could increase surface specific oxygen storage capacity and decrease the apparent activation energy for the rea;ltion CO+NO-->CO2-+-1/2 N-2. So a high conversion of NOx reduction could shift to higher A/F ratio.展开更多
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
Electrochemical nitrate reduction(eNO_(3)RR)and nitric oxide reduction(eNORR)to ammonia have emerged as promising and sustainable alternatives to the traditional Haber-Bosch method for ammonia production,particularly ...Electrochemical nitrate reduction(eNO_(3)RR)and nitric oxide reduction(eNORR)to ammonia have emerged as promising and sustainable alternatives to the traditional Haber-Bosch method for ammonia production,particularly within the recently proposed reverse artificial nitrogen cycle route:N_(2)→NO_(x)→NH_(3).Notably,experimental studies have demonstrated that eNORR exhibits superior performance over eNO_(3)RR on Cu6Sn5 catalysts.However,the fundamental mechanisms underlying this difference remain poorly understood.Herein,we performed systematic theoretical calculations to explore the reaction pathways,electronic structure effects,and potential-dependent Faradic efficiency associated with ammonia production via these two distinct electrochemical pathways(eNORR and eNO_(3)RR)on Cu6Sn5.By implementing an advanced‘adaptive electric field controlled constant potential(EFC-CP)’methodology combined with microkinetic modeling,we successfully reproduced the experimental observations and identified the key factors affecting ammonia production in both reaction pathways.It was found that eNORR outperforms eNO_(3)RR because it circumvents the ^(*)NO_(2) dissociation and ^(*)NO_(2) desorption steps,leading to distinct surface coverage of key intermediates between the two pathways.Furthermore,the reaction rates were found to exhibit a pronounced dependence on the surface coverage of ^(*)NO in eNORR and ^(*)NO_(2) in eNO_(3)RR.Specifically,the facile desorption of ^(*)NO_(2) on the Cu6Sn5 surface in eNO_(3)RR limits the attainable surface coverage of ^(*)NO,thereby impeding its performance.In contrast,the eNORR can maintain a high surface coverage of adsorbed ^(*)NO species,contributing to its enhanced ammonia production performance.These fundamental insights provide valuable guidance for the rational design of catalysts and the optimization of reaction routes,facilitating the development of more efficient,sustainable,and scalable techniques for ammonia production.展开更多
For cluster catalysts,reducing their size to single atoms gives rise to precise and high-selective catalytic performance,at the cost of losing some tunability.Superatoms,the entirety with atom-like electronic shells a...For cluster catalysts,reducing their size to single atoms gives rise to precise and high-selective catalytic performance,at the cost of losing some tunability.Superatoms,the entirety with atom-like electronic shells and fine-tunable properties as clusters,are promising candidates for cluster catalysts.Here,we predicted a superatom-assembled two-dimension Al_(8)O_(3)superatom-oxide framework(SOF) using first principles calculation,where the Al8core comprises two 8-electron Al4superatoms and further linked by oxygen atoms in a graphene-like lattice,resulting in porous and stable geometry.The Al_(8)O_(3)-SOF serves as an efficient superatomic catalyst for nitric oxide(NO) reduction reaction,where the Al4superatomic unit acts cohesively as the active site throughout the catalytic process and its superatomic P orbital plays an important role in activating NO molecule.Additionally,the catalytic activity of Al_(8)O_(3)-SOF increases when the two central Al atoms of the Al8core are replaced by Ga atoms,reducing the limiting potential to -0.48 V comparable to that of the reported Pt(100).Our work proposes a novel series of superatomic catalysts and reveals the superatomic behavior in the catalytic process,providing references for the development of efficient heterogeneous catalysts.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
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
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
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
基金supported by the Guangxi Natural Science Fund for Distinguished Young Scholars(2024GXNSFFA010008)Shenzhen Science and Technology Program(JCYJ20230807112503008).
文摘Nitric oxide(NO),which generally originates from vehicle exhaust and industrial flue gases,is one of the most serious air pollutants.In this case,the electrochemical NO reduction reaction(NORR)not only removes the atmospheric pollutant NO but also produces valuable ammonia(NH_(3)).Hence,through the synthesis and modification of Fe_(3)C nanocrystal cata-lysts,the as-obtained optimal sample of Fe_(3)C/C-900 was adopted as the NORR catalyst at ambient conditions.As a result,the Fe_(3)C/C-900 catalyst showed an NH_(3)Faraday efficiency of 76.5%and an NH_(3)yield rate of 177.5μmol·h^(-1)·cm^(-2)at the working potentials of-0.8 and-1.2 V versus reversible hydrogen electrode(vs.RHE),respectively.And it delivered a stable NORR activity during the electrolysis.Moreover,we attribute the high NORR properties of Fe_(3)C/C-900 to two aspects:one is the enhanced intrinsic activity of Fe_(3)C nanocrystals,including the lowering of the energy barrier of rate-limiting step(*NOH→*N)and the inhibition of hydrogen evolution;on the other hand,the favorable dispersion of active components,the effective adsorption of gaseous NO,and the release of liquid NH_(3)products facilitated by the porous carbon substrate.
文摘Activity of three-way palladium catalyst was examined by means of a pulse-flam-microreactor. The effects of cerium on the catalytic properties of gamma-alumina-supported palladium for the reduction of nitric oxide were studied with X-ray photoelectron spectroscopy (XPS) and temperature-programmed reduction (TPR). The reduction of nitric oxide on palladium catalysts is inhibited significantly by hydrocarbon. However, the reduction of nitric oxide was improved by the addition of cerium to the catalysts. The XPS and TPR studies showed that the presence of cerium provided, palladium oxide in a hard-reduced state and suppressed the chemisorption of hydrocarbons on the palladium oxide. Additionally,cerium could increase surface specific oxygen storage capacity and decrease the apparent activation energy for the rea;ltion CO+NO-->CO2-+-1/2 N-2. So a high conversion of NOx reduction could shift to higher A/F ratio.
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.
文摘Electrochemical nitrate reduction(eNO_(3)RR)and nitric oxide reduction(eNORR)to ammonia have emerged as promising and sustainable alternatives to the traditional Haber-Bosch method for ammonia production,particularly within the recently proposed reverse artificial nitrogen cycle route:N_(2)→NO_(x)→NH_(3).Notably,experimental studies have demonstrated that eNORR exhibits superior performance over eNO_(3)RR on Cu6Sn5 catalysts.However,the fundamental mechanisms underlying this difference remain poorly understood.Herein,we performed systematic theoretical calculations to explore the reaction pathways,electronic structure effects,and potential-dependent Faradic efficiency associated with ammonia production via these two distinct electrochemical pathways(eNORR and eNO_(3)RR)on Cu6Sn5.By implementing an advanced‘adaptive electric field controlled constant potential(EFC-CP)’methodology combined with microkinetic modeling,we successfully reproduced the experimental observations and identified the key factors affecting ammonia production in both reaction pathways.It was found that eNORR outperforms eNO_(3)RR because it circumvents the ^(*)NO_(2) dissociation and ^(*)NO_(2) desorption steps,leading to distinct surface coverage of key intermediates between the two pathways.Furthermore,the reaction rates were found to exhibit a pronounced dependence on the surface coverage of ^(*)NO in eNORR and ^(*)NO_(2) in eNO_(3)RR.Specifically,the facile desorption of ^(*)NO_(2) on the Cu6Sn5 surface in eNO_(3)RR limits the attainable surface coverage of ^(*)NO,thereby impeding its performance.In contrast,the eNORR can maintain a high surface coverage of adsorbed ^(*)NO species,contributing to its enhanced ammonia production performance.These fundamental insights provide valuable guidance for the rational design of catalysts and the optimization of reaction routes,facilitating the development of more efficient,sustainable,and scalable techniques for ammonia production.
基金supported by the National Natural Science Foundation of China (22103001, U21A20317)the Natural Science Foundation of Anhui Province (2108085QB64)the Fundamental Research Funds for the Central Universities (20720220009)。
文摘For cluster catalysts,reducing their size to single atoms gives rise to precise and high-selective catalytic performance,at the cost of losing some tunability.Superatoms,the entirety with atom-like electronic shells and fine-tunable properties as clusters,are promising candidates for cluster catalysts.Here,we predicted a superatom-assembled two-dimension Al_(8)O_(3)superatom-oxide framework(SOF) using first principles calculation,where the Al8core comprises two 8-electron Al4superatoms and further linked by oxygen atoms in a graphene-like lattice,resulting in porous and stable geometry.The Al_(8)O_(3)-SOF serves as an efficient superatomic catalyst for nitric oxide(NO) reduction reaction,where the Al4superatomic unit acts cohesively as the active site throughout the catalytic process and its superatomic P orbital plays an important role in activating NO molecule.Additionally,the catalytic activity of Al_(8)O_(3)-SOF increases when the two central Al atoms of the Al8core are replaced by Ga atoms,reducing the limiting potential to -0.48 V comparable to that of the reported Pt(100).Our work proposes a novel series of superatomic catalysts and reveals the superatomic behavior in the catalytic process,providing references for the development of efficient heterogeneous catalysts.
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.
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).
