Metallene has been widely considered as an advanced electrocatalytic material due to its large specific surface area and highly active reaction sites.Herein,we design and synthesize ultrathin rhodium metallene(Rh ML)w...Metallene has been widely considered as an advanced electrocatalytic material due to its large specific surface area and highly active reaction sites.Herein,we design and synthesize ultrathin rhodium metallene(Rh ML)with abundant wrinkles to supply surface-strained Rh sites for driving acetonitrile electroreduction to ethylamine(AER).The electrochemical tests indicate that Rh ML shows an ethylamine yield rate of 137.1 mmol gcat^(-1) h^(-1) in an acidic solution,with stability lasting up to 200 h.Theoretical calculations reveal that Rh ML with wrinkle-induced compressive strain not only shows a lower energy barrier in the rate-determining step but also facilitates the ethylamine desorption process compared to wrinkle-free Rh ML and commercial Rh black.The assembled electrolyzer with bifunctional Rh ML shows an electrolysis voltage of 0.41 V at 10 mA cm^(-2),enabling simultaneous ethylamine production and hydrazine waste treatment.Furthermore,the voltage of an assembled hybrid zinc-acetonitrile battery can effectively drive this electrolyzer to achieve the dual AER process.This study provides guidance for improving the catalytic efficiency of surface atoms in two-dimensional materials,as well as the electrochemical synthesis technology for series-connected battery-electrolyzer systems.展开更多
The electrochemical hydrogenation(ECH)of 5-hydroxymethylfurfural(HMF)to 2,5-dihydroxymethylfuran(DHMF)represents a pivotal pathway for the electrocatalytic upgrading of biomass-based organic small molecules,offering s...The electrochemical hydrogenation(ECH)of 5-hydroxymethylfurfural(HMF)to 2,5-dihydroxymethylfuran(DHMF)represents a pivotal pathway for the electrocatalytic upgrading of biomass-based organic small molecules,offering significant reductions in energy consumption while producing value-added chemicals.The conversion of HMF to DHMF is challenging due to the high reduction potential and complex intermediates of HMF ECH under neutral environment.Also,the total efficiency is hindered by sluggish anodic oxygen evolution reaction(OER)kinetics.Herein,we report a synthesis of highly alloyed Pd-Pt bimetallene(Pd3Pt1 BML)for HMF ECH coupled with formic acid oxidation reaction(FAOR).Through a combination of in-situ Raman spectroscopy,electron paramagnetic resonance analysis,and theoretical calculations,we elucidate that the HMF adsorption on Pd atoms,strategically separated by Pt atoms,is weakened compared to pure Pd surfaces.Additionally,Pt atoms serve as crucial providers of active hydrogen to neighboring Pd atoms,synergistically enhancing the reaction kinetics of HMF conversion with a Faradaic efficiency>93%.Meanwhile,the atomically dispersed Pt atoms endow Pd_(3)Pt_(1) BML with high electrochemical performance for the direct pathway of FAOR at the anode.As a result,a FAOR-assisted HMF ECH system equipped with bifunctional Pd3Pt1 BML achieves the energy-efficient conversion of HMF to DHMF at electrolysis voltage of 0.72 V at 10 mA cm^(–2).This work provides insights into the rational design of bifunctional catalysts featuring two distinct types of active sites for advanced energy electrocatalysis and ECH.展开更多
The exploitation of competent electrocatalysts is a key issue of the broad application of many promising electrochemical processes,including the hydrogen evolution reaction(HER),the oxygen evolution reaction(OER),the ...The exploitation of competent electrocatalysts is a key issue of the broad application of many promising electrochemical processes,including the hydrogen evolution reaction(HER),the oxygen evolution reaction(OER),the oxygen reduction reaction(ORR),the CO_(2) reduction reaction(CO_(2)RR)and the nitrogen reduction reaction(NRR).The traditional searches for good electrocatalysts rely on the trial-and-error approaches,which are typically tedious and inefficient.In the past decades,some fundamental principles,activity descriptors and catalytic mechanisms have been established to accelerate the discovery of advanced electrocatalysts.Hence,it is time to summarize these theory-related research advances that unravel the structure-performance relationships and enables predictive ability in electrocatalysis studies.In this review,we summarize some basic aspects of catalytic theories that are commonly used in the design of electrocatalysts(e.g.,Sabatier principle,d-band theory,adsorption-energy scaling relation,activity descriptors)and their relevance.Then,we briefly introduced the fundamental mechanisms and central challenges of HER,OER,ORR,CO_(2)RR and NRR electrocatalysts,and highlight the theory-based efforts used to address the challenges facing these electrocatalysis processes.Finally,we propose the key challenges and opportunities of theory-driven electrocatalysis on their future.展开更多
We present a strategy that effectively modulate the d-band electronic structure of the active center by strain effect and interatomic orbital hybridization.This strategy efficiently promotes the kinetic process of the...We present a strategy that effectively modulate the d-band electronic structure of the active center by strain effect and interatomic orbital hybridization.This strategy efficiently promotes the kinetic process of the ethanol oxidation reaction(EOR)in alkaline media.In the intermetallic Pd_(3)Pb nanowires,the introduction of Pb not only causes the lattice expansion of Pd but also achieves the interatomic orbital hybridization bonding with Pd.Such interatomic orbital hybridization effect and tensile strain effect can effectively achieve a co-regulation of the d-band electronic structure of Pd,which directly affects the adsorption behavior of intermediate on Pd for EOR.Hence,the intermetallic Pd_(3)Pb nanowires demonstrate enhanced EOR activity and anti-poisoning ability against CO_(ads).Theoretical calculations show that the enhanced OH^(*)adsorption ability and the low energy barrier for the oxidative dehydrogenation of ethanol are the keys to high EOR activity and stability of the intermetallic Pd_(3)Pb nanowires.展开更多
Electrochemical reduction of acetonitrile(ACN)to ethylamine(ETA)is a new strategy for producing high-value chemicals.Herein,the ultrathin nickel sulfide nanosheets(Ni_(x)S_(y)NSs)anchored on nickel foam(NF)nanohybrid(...Electrochemical reduction of acetonitrile(ACN)to ethylamine(ETA)is a new strategy for producing high-value chemicals.Herein,the ultrathin nickel sulfide nanosheets(Ni_(x)S_(y)NSs)anchored on nickel foam(NF)nanohybrid(Ni_(x)S_(y)NSs/NF)were designed as an efficient bifunctional electrocatalyst for the waste conversion.Owing to the introduction of the S element,the ultrathin nanosheet structure,and the three-dimensional architecture,Ni_(x)S_(y)NSs/NF simultaneously reveals excellent electrocatalytic activity for both electrochemical ACN reduction reaction(EACNRR)at the cathode and electrochemical sulfur ion(S^(2-))oxidation reaction(ESOR)at the anode.For the EACNRR,Ni_(x)S_(y)NSs/NF exhibits a Faradaic efficiency of 95.5%and the ETA yield of 923.1 mmol h^(-1)g^(-1)at-0.05 V potential.For the ESOR,the S^(2-)ion is oxidized to the value-added S_8 product,in which the oxidation potential is only 0.16 V at 50 mA cm^(-2).Consequently,the assembled Ni_(x)S_(y)NS s/NF||Ni_(x)S_(y)NSs/NF electrolytic cell is successfully established for the ESOR-assisted EACNRR system that only needs a cell voltage of 0.32 V to reach the 50 mA cm^(-2)current density.This work provides an effective and energy-saving strategy for the co-production of value-added chemicals from pollutants.展开更多
The construction of bimetallic sites with strong interaction can effectively regulate the electronic structure and modulate the adsorption behavior of adsorbate species on bimetallic catalysts,thereby overcoming catal...The construction of bimetallic sites with strong interaction can effectively regulate the electronic structure and modulate the adsorption behavior of adsorbate species on bimetallic catalysts,thereby overcoming catalytic bottlenecks.Herein,an RhPb bimetallene(RhPb b-ML)with the strong d-p orbital hybridization is proposed for efficiently catalyzing ethanol oxidation reaction(EOR).Notably,the specific EOR activity of RhPb b-ML is 32 and 6.8 times higher than those of Rh metallene and commercial Pt/C,respectively.Theoretical calculation analysis reveals that the introduction of Pb atoms into the Rh lattice leads to an upward shift of the d-band center of Rh on RhPb(111).The shift in the d-band center is primarily attributed to the different degrees of hybridization between the d sub-orbitals of Rh and the p-orbitals of Pb,which enhance the adsorption of key species and improve EOR activity and selectivity.In-situ infrared tests and high-performance liquid chromatography tests together confirm that RhPb b-ML not only exhibits enhanced ability for the breakage of C-C bonds but also effectively suppresses the generation of absorbed CO.Furthermore,the strategy of enhancing catalyst performance through the strong d-p orbital hybridization has been demonstrated to be scalable to other bimetallic catalysts,providing valuable insights for the design of advanced catalysts.展开更多
Glycerol,a byproduct of biodiesel production,can be efficiently converted into valuable chemicals through electrocatalytic reaction.In this study,platinum(Pt)nanocrystals decorated on bismuth oxide(Bi_(2)O_(3))nanoshe...Glycerol,a byproduct of biodiesel production,can be efficiently converted into valuable chemicals through electrocatalytic reaction.In this study,platinum(Pt)nanocrystals decorated on bismuth oxide(Bi_(2)O_(3))nanosheets(PtBi DONS)with an optimal Pt_(1)Bi_(1) ratio of 1:1 were successfully synthesized using a galvanic replacement method.Pt,Bi,DONS exhibit remarkable electrocatalytic performance for glycerol electrooxidation,achieving an excellent catalytic activity(current of 0.82 A mg_(Pt)^(-1) at 0.67 V vs.reversible hydrogen electrode(RHE))and an exceptional selectivity of 96.6%for C_(3) products,particularly glyceric acid.The superior performance stems from two key factors:(1)electron transfer from Bi_(2)O_(3) to Pt creates electron-rich Pt sites that suppress C-C bond cleavage and(2)Bi_(2)O_(3) facilitates favorable glycerol adsorption configurations through multiple hydroxyl group interactions.Mechanistic studies using operando spectroscopy and electrochemical impedance spectroscopy revealed that the synergistic effect between Pt and Bi_(2)O_(3) promotes rapid charge transfer and stable intermediate formation.Moreover,PtBi DONS showed excellent versatility in oxidizing other polyols compared with monoalcohols.展开更多
基金supported by the National Natural Science Foundation of China(22272103)the National Natural Science Foundation of China for the Youth(22309108,22202076)+3 种基金the Science and Technology Innovation Team of Shaanxi Province(2023-CX-TD-27)the China Postdoctoral Science Foundation(2023TQ0204)the Young Scientist Initiative Project of School of Materials Science and Engineering at Shaanxi Normal University(2024YSIP-MSE-SNNU008)Sanqin Scholars Innovation Teams in Shaanxi Province in China.
文摘Metallene has been widely considered as an advanced electrocatalytic material due to its large specific surface area and highly active reaction sites.Herein,we design and synthesize ultrathin rhodium metallene(Rh ML)with abundant wrinkles to supply surface-strained Rh sites for driving acetonitrile electroreduction to ethylamine(AER).The electrochemical tests indicate that Rh ML shows an ethylamine yield rate of 137.1 mmol gcat^(-1) h^(-1) in an acidic solution,with stability lasting up to 200 h.Theoretical calculations reveal that Rh ML with wrinkle-induced compressive strain not only shows a lower energy barrier in the rate-determining step but also facilitates the ethylamine desorption process compared to wrinkle-free Rh ML and commercial Rh black.The assembled electrolyzer with bifunctional Rh ML shows an electrolysis voltage of 0.41 V at 10 mA cm^(-2),enabling simultaneous ethylamine production and hydrazine waste treatment.Furthermore,the voltage of an assembled hybrid zinc-acetonitrile battery can effectively drive this electrolyzer to achieve the dual AER process.This study provides guidance for improving the catalytic efficiency of surface atoms in two-dimensional materials,as well as the electrochemical synthesis technology for series-connected battery-electrolyzer systems.
文摘The electrochemical hydrogenation(ECH)of 5-hydroxymethylfurfural(HMF)to 2,5-dihydroxymethylfuran(DHMF)represents a pivotal pathway for the electrocatalytic upgrading of biomass-based organic small molecules,offering significant reductions in energy consumption while producing value-added chemicals.The conversion of HMF to DHMF is challenging due to the high reduction potential and complex intermediates of HMF ECH under neutral environment.Also,the total efficiency is hindered by sluggish anodic oxygen evolution reaction(OER)kinetics.Herein,we report a synthesis of highly alloyed Pd-Pt bimetallene(Pd3Pt1 BML)for HMF ECH coupled with formic acid oxidation reaction(FAOR).Through a combination of in-situ Raman spectroscopy,electron paramagnetic resonance analysis,and theoretical calculations,we elucidate that the HMF adsorption on Pd atoms,strategically separated by Pt atoms,is weakened compared to pure Pd surfaces.Additionally,Pt atoms serve as crucial providers of active hydrogen to neighboring Pd atoms,synergistically enhancing the reaction kinetics of HMF conversion with a Faradaic efficiency>93%.Meanwhile,the atomically dispersed Pt atoms endow Pd_(3)Pt_(1) BML with high electrochemical performance for the direct pathway of FAOR at the anode.As a result,a FAOR-assisted HMF ECH system equipped with bifunctional Pd3Pt1 BML achieves the energy-efficient conversion of HMF to DHMF at electrolysis voltage of 0.72 V at 10 mA cm^(–2).This work provides insights into the rational design of bifunctional catalysts featuring two distinct types of active sites for advanced energy electrocatalysis and ECH.
文摘The exploitation of competent electrocatalysts is a key issue of the broad application of many promising electrochemical processes,including the hydrogen evolution reaction(HER),the oxygen evolution reaction(OER),the oxygen reduction reaction(ORR),the CO_(2) reduction reaction(CO_(2)RR)and the nitrogen reduction reaction(NRR).The traditional searches for good electrocatalysts rely on the trial-and-error approaches,which are typically tedious and inefficient.In the past decades,some fundamental principles,activity descriptors and catalytic mechanisms have been established to accelerate the discovery of advanced electrocatalysts.Hence,it is time to summarize these theory-related research advances that unravel the structure-performance relationships and enables predictive ability in electrocatalysis studies.In this review,we summarize some basic aspects of catalytic theories that are commonly used in the design of electrocatalysts(e.g.,Sabatier principle,d-band theory,adsorption-energy scaling relation,activity descriptors)and their relevance.Then,we briefly introduced the fundamental mechanisms and central challenges of HER,OER,ORR,CO_(2)RR and NRR electrocatalysts,and highlight the theory-based efforts used to address the challenges facing these electrocatalysis processes.Finally,we propose the key challenges and opportunities of theory-driven electrocatalysis on their future.
基金sponsored by the National Natural Science Foundation of China(22272103)the Science and Technology Innovation Team of Shaanxi Province(2022TD-35and 2023-CX-TD-27)+1 种基金Fundamental Research Funds for the Central Universities(GK202202001)Sanqin Scholars Innovation Teams in Shaanxi Province,China.
文摘We present a strategy that effectively modulate the d-band electronic structure of the active center by strain effect and interatomic orbital hybridization.This strategy efficiently promotes the kinetic process of the ethanol oxidation reaction(EOR)in alkaline media.In the intermetallic Pd_(3)Pb nanowires,the introduction of Pb not only causes the lattice expansion of Pd but also achieves the interatomic orbital hybridization bonding with Pd.Such interatomic orbital hybridization effect and tensile strain effect can effectively achieve a co-regulation of the d-band electronic structure of Pd,which directly affects the adsorption behavior of intermediate on Pd for EOR.Hence,the intermetallic Pd_(3)Pb nanowires demonstrate enhanced EOR activity and anti-poisoning ability against CO_(ads).Theoretical calculations show that the enhanced OH^(*)adsorption ability and the low energy barrier for the oxidative dehydrogenation of ethanol are the keys to high EOR activity and stability of the intermetallic Pd_(3)Pb nanowires.
基金supported by the National Natural Science Foundation of China (22309108)the Science and Technology Innovation Team of Shaanxi Province (2023-CX-TD-27)+1 种基金the Fundamental Research Funds for the Central Universities (GK202202001)Sanqin Scholars Innovation Teams in Shaanxi Province,China。
文摘Electrochemical reduction of acetonitrile(ACN)to ethylamine(ETA)is a new strategy for producing high-value chemicals.Herein,the ultrathin nickel sulfide nanosheets(Ni_(x)S_(y)NSs)anchored on nickel foam(NF)nanohybrid(Ni_(x)S_(y)NSs/NF)were designed as an efficient bifunctional electrocatalyst for the waste conversion.Owing to the introduction of the S element,the ultrathin nanosheet structure,and the three-dimensional architecture,Ni_(x)S_(y)NSs/NF simultaneously reveals excellent electrocatalytic activity for both electrochemical ACN reduction reaction(EACNRR)at the cathode and electrochemical sulfur ion(S^(2-))oxidation reaction(ESOR)at the anode.For the EACNRR,Ni_(x)S_(y)NSs/NF exhibits a Faradaic efficiency of 95.5%and the ETA yield of 923.1 mmol h^(-1)g^(-1)at-0.05 V potential.For the ESOR,the S^(2-)ion is oxidized to the value-added S_8 product,in which the oxidation potential is only 0.16 V at 50 mA cm^(-2).Consequently,the assembled Ni_(x)S_(y)NS s/NF||Ni_(x)S_(y)NSs/NF electrolytic cell is successfully established for the ESOR-assisted EACNRR system that only needs a cell voltage of 0.32 V to reach the 50 mA cm^(-2)current density.This work provides an effective and energy-saving strategy for the co-production of value-added chemicals from pollutants.
基金supported by the National Natural Science Foundation of China(22309108,22202076,22272103)the China Postdoctoral Science Foundation(2022M711231,2023TQ0204)+3 种基金the Science and Technology Innovation Team of Shaanxi Province(2023-CX-TD27)the Fundamental Research Funds for the Central Universities(GK202202001)the 111 Project(B14041)Sanqin scholars'innovation teams in Shaanxi Province,China。
文摘The construction of bimetallic sites with strong interaction can effectively regulate the electronic structure and modulate the adsorption behavior of adsorbate species on bimetallic catalysts,thereby overcoming catalytic bottlenecks.Herein,an RhPb bimetallene(RhPb b-ML)with the strong d-p orbital hybridization is proposed for efficiently catalyzing ethanol oxidation reaction(EOR).Notably,the specific EOR activity of RhPb b-ML is 32 and 6.8 times higher than those of Rh metallene and commercial Pt/C,respectively.Theoretical calculation analysis reveals that the introduction of Pb atoms into the Rh lattice leads to an upward shift of the d-band center of Rh on RhPb(111).The shift in the d-band center is primarily attributed to the different degrees of hybridization between the d sub-orbitals of Rh and the p-orbitals of Pb,which enhance the adsorption of key species and improve EOR activity and selectivity.In-situ infrared tests and high-performance liquid chromatography tests together confirm that RhPb b-ML not only exhibits enhanced ability for the breakage of C-C bonds but also effectively suppresses the generation of absorbed CO.Furthermore,the strategy of enhancing catalyst performance through the strong d-p orbital hybridization has been demonstrated to be scalable to other bimetallic catalysts,providing valuable insights for the design of advanced catalysts.
基金supported by the National Natural Science Foundation of China(22272103)Science and Technology Innovation Team of Shaanxi Province(2023-CX-TD-27 and 2022TD-35)+1 种基金the Technology Innovation Leading Program of Shaanxi in China,Sanqin Scholars Innovation Teams in Shaanxi Province in China,the Young Scientist Initiative Project of School of Materials Science and Engineering at Shaanxi Normal University(2023YSIP-MSESNNU008)Shaanxi Province Postdoctoral Science Foundation(2024BSHSDZZ080).
文摘Glycerol,a byproduct of biodiesel production,can be efficiently converted into valuable chemicals through electrocatalytic reaction.In this study,platinum(Pt)nanocrystals decorated on bismuth oxide(Bi_(2)O_(3))nanosheets(PtBi DONS)with an optimal Pt_(1)Bi_(1) ratio of 1:1 were successfully synthesized using a galvanic replacement method.Pt,Bi,DONS exhibit remarkable electrocatalytic performance for glycerol electrooxidation,achieving an excellent catalytic activity(current of 0.82 A mg_(Pt)^(-1) at 0.67 V vs.reversible hydrogen electrode(RHE))and an exceptional selectivity of 96.6%for C_(3) products,particularly glyceric acid.The superior performance stems from two key factors:(1)electron transfer from Bi_(2)O_(3) to Pt creates electron-rich Pt sites that suppress C-C bond cleavage and(2)Bi_(2)O_(3) facilitates favorable glycerol adsorption configurations through multiple hydroxyl group interactions.Mechanistic studies using operando spectroscopy and electrochemical impedance spectroscopy revealed that the synergistic effect between Pt and Bi_(2)O_(3) promotes rapid charge transfer and stable intermediate formation.Moreover,PtBi DONS showed excellent versatility in oxidizing other polyols compared with monoalcohols.
