Electrochemical reduction of acetonitrile to ethylamine with a high selectivity is a novel approach to manufacture valuable primary amines which are important raw material in organic chemical industry. However, the po...Electrochemical reduction of acetonitrile to ethylamine with a high selectivity is a novel approach to manufacture valuable primary amines which are important raw material in organic chemical industry. However, the poor ethylamine Faradic efficiency(FE_(ethylamine)) and catalyst stability at the high current density prohibit this method from being practically used. Herein, CuNi alloy ultrafine-nano-particles based on the d-orbital coupling modulation were synthesized through the electrodeposition and their catalytic performance towards acetonitrile reduction reaction(ACNRR) has been systematically studied. The highest FE_(ethylamine)(97%) is achieved with the current density of-114 mA cm^(-2). For practical application, the current density can reach-602.8 mA cm^(-2) with 82.8% FE_(ethylamine)maintained. With the appearance of other organics which co-exist with acetonitrile in the SOHIO process, CuNi can also hydrogenate acetonitrile in it with more than 80% FE_(ethylamine). Our in-situ spectroscopy analysis and DFT calculations towards the acetonitrile hydrogenation behavior reveal that the evenly dispersed Ni in Cu modulates the dband so as to endow CuNi with the better acetonitrile adsorption, milder binding energy with the reaction intermediates, smaller barrier for *CH_3CH_2NH_2 desorption and higher ability for H_2O dissociation to provide *H.展开更多
Two-dimensional(2D)layered materials have many potential applications in memristors owing to their unique atomic structures and electronic properties.Memristors can overcome the in-memory bottleneck for use in brain-l...Two-dimensional(2D)layered materials have many potential applications in memristors owing to their unique atomic structures and electronic properties.Memristors can overcome the in-memory bottleneck for use in brain-like neuromorphic computing.However,exploiting additional lateral memtransistors based on 2D layered materials remains challenging.There are few studies on p-type semiconductors that have not been theoretically analyzed.In this study,a lateral memtransistor based on p-type GeSe nanosheets is investigated.A threeterminal GeSe memtransistor that modulated the interfacial barrier height was fabricated using low-energy ion irradiation;the memtransistor exhibited a low operating voltage.The memtransistor successfully mimics biological synapse,including neuroplasticity functions,such as short-term plasticity,long-term plasticity,paired-pulse facilitation,and spike-timing-dependent plasticity.The mechanism of interfacial modulation was verified by experimental results and theoretical calculations.The results show that it is feasible to modulate the interface of 2D GeSe nanosheets using low-energy ion irradiation to realize a lateral memtransistor.This may provide promising opportunities for artificial neuromorphic system applications based on 2D layered materials.展开更多
With the depletion of fossil fuels and environmental pollution, energy storage and conversion have become the focus of current research. Water splitting and fuel cell technologies have made outstanding contributions t...With the depletion of fossil fuels and environmental pollution, energy storage and conversion have become the focus of current research. Water splitting and fuel cell technologies have made outstanding contributions to energy conversion. However, the oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) have slow kinetics, which limit the capacity of fuel cells. It is of great significance to develop catalysts for the OER and ORR and continuously improve their catalytic performance. Many studies have shown that intrinsic defects, especially vacancies (anion and cation vacancies), can effectively improve the efficiency of electrochemical energy storage and conversion. The introduction of intrinsic defects can generally expose more active sites, enhance conductivity, adjust the electronic state, and promote ion diffusion, thereby enhancing the catalytic performance. This review comprehensively summarizes the latest developments regarding the effects of intrinsic defects on the performance of non-noble metal electrocatalysts. According to the type of intrinsic defect, this article reviews in detail the regulation mechanism, preparation methods and advanced characterization techniques of intrinsic defects in different materials (oxides, non-oxides, etc.). Then, the current difficulties and future development of intrinsic defect regulation are analyzed and discussed thoroughly. Finally, the prospect of intrinsic defects in the field of electrochemical energy storage is further explored.展开更多
The oxygen evolution reaction(OER)electrocatalysts,which can keep active for a long time in acidic media,are of great significance to proton exchange membrane water electrolyzers.Here,Ru-Co_(3)O_(4)electrocatalysts wi...The oxygen evolution reaction(OER)electrocatalysts,which can keep active for a long time in acidic media,are of great significance to proton exchange membrane water electrolyzers.Here,Ru-Co_(3)O_(4)electrocatalysts with transition metal oxide Co_(3)O_(4)as matrix and the noble metal Ru as doping element have been prepared through an ion exchange–pyrolysis process mediated by metal-organic framework,in which Ru atoms occupy the octahedral sites of Co_(3)O_(4).Experimental and theoretical studies show that introduced Ru atoms have a passivation effect on lattice oxygen.The strong coupling between Ru and O causes a negative shift in the energy position of the O p-band centers.Therefore,the bonding activity of oxygen in the adsorbed state to the lattice oxygen is greatly passivated during the OER process,thus improving the stability of matrix material.In addition,benefiting from the modulating effect of the introduced Ru atoms on the metal active sites,the thermodynamic and kinetic barriers have been significantly reduced,which greatly enhances both the catalytic stability and reaction efficiency of Co_(3)O_(4).展开更多
基金the National Natural Science Foundation of China (12025503, 12105208)the Fundamental Research Funds for the Central Universities of China (2042022kf1181)China Postdoctoral Science Foundation (2020M682469)。
文摘Electrochemical reduction of acetonitrile to ethylamine with a high selectivity is a novel approach to manufacture valuable primary amines which are important raw material in organic chemical industry. However, the poor ethylamine Faradic efficiency(FE_(ethylamine)) and catalyst stability at the high current density prohibit this method from being practically used. Herein, CuNi alloy ultrafine-nano-particles based on the d-orbital coupling modulation were synthesized through the electrodeposition and their catalytic performance towards acetonitrile reduction reaction(ACNRR) has been systematically studied. The highest FE_(ethylamine)(97%) is achieved with the current density of-114 mA cm^(-2). For practical application, the current density can reach-602.8 mA cm^(-2) with 82.8% FE_(ethylamine)maintained. With the appearance of other organics which co-exist with acetonitrile in the SOHIO process, CuNi can also hydrogenate acetonitrile in it with more than 80% FE_(ethylamine). Our in-situ spectroscopy analysis and DFT calculations towards the acetonitrile hydrogenation behavior reveal that the evenly dispersed Ni in Cu modulates the dband so as to endow CuNi with the better acetonitrile adsorption, milder binding energy with the reaction intermediates, smaller barrier for *CH_3CH_2NH_2 desorption and higher ability for H_2O dissociation to provide *H.
基金National Natural Science Foundation of China,Grant/Award Numbers:12275198,12074293,12025503Fundamental Research Funds for the Center Universities,Grant/Award Numbers:2042023kf0196,2042022kf1181。
文摘Two-dimensional(2D)layered materials have many potential applications in memristors owing to their unique atomic structures and electronic properties.Memristors can overcome the in-memory bottleneck for use in brain-like neuromorphic computing.However,exploiting additional lateral memtransistors based on 2D layered materials remains challenging.There are few studies on p-type semiconductors that have not been theoretically analyzed.In this study,a lateral memtransistor based on p-type GeSe nanosheets is investigated.A threeterminal GeSe memtransistor that modulated the interfacial barrier height was fabricated using low-energy ion irradiation;the memtransistor exhibited a low operating voltage.The memtransistor successfully mimics biological synapse,including neuroplasticity functions,such as short-term plasticity,long-term plasticity,paired-pulse facilitation,and spike-timing-dependent plasticity.The mechanism of interfacial modulation was verified by experimental results and theoretical calculations.The results show that it is feasible to modulate the interface of 2D GeSe nanosheets using low-energy ion irradiation to realize a lateral memtransistor.This may provide promising opportunities for artificial neuromorphic system applications based on 2D layered materials.
基金This work was financially supported by the National Natu-ral Science Foundation of China(12025503,U1867215,11875211,U1932134,12105208)Hubei Provincial Natural Science Foundation(2019CFA036)+1 种基金the Fundamental Research Funds for the Central Universities(2042021kf0068)China Postdoctoral Science Foundation(No.2020M682469).
文摘With the depletion of fossil fuels and environmental pollution, energy storage and conversion have become the focus of current research. Water splitting and fuel cell technologies have made outstanding contributions to energy conversion. However, the oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) have slow kinetics, which limit the capacity of fuel cells. It is of great significance to develop catalysts for the OER and ORR and continuously improve their catalytic performance. Many studies have shown that intrinsic defects, especially vacancies (anion and cation vacancies), can effectively improve the efficiency of electrochemical energy storage and conversion. The introduction of intrinsic defects can generally expose more active sites, enhance conductivity, adjust the electronic state, and promote ion diffusion, thereby enhancing the catalytic performance. This review comprehensively summarizes the latest developments regarding the effects of intrinsic defects on the performance of non-noble metal electrocatalysts. According to the type of intrinsic defect, this article reviews in detail the regulation mechanism, preparation methods and advanced characterization techniques of intrinsic defects in different materials (oxides, non-oxides, etc.). Then, the current difficulties and future development of intrinsic defect regulation are analyzed and discussed thoroughly. Finally, the prospect of intrinsic defects in the field of electrochemical energy storage is further explored.
基金the National Natural Science Foundation of China(Nos.12025503,U23B2072,and 12105208)。
文摘The oxygen evolution reaction(OER)electrocatalysts,which can keep active for a long time in acidic media,are of great significance to proton exchange membrane water electrolyzers.Here,Ru-Co_(3)O_(4)electrocatalysts with transition metal oxide Co_(3)O_(4)as matrix and the noble metal Ru as doping element have been prepared through an ion exchange–pyrolysis process mediated by metal-organic framework,in which Ru atoms occupy the octahedral sites of Co_(3)O_(4).Experimental and theoretical studies show that introduced Ru atoms have a passivation effect on lattice oxygen.The strong coupling between Ru and O causes a negative shift in the energy position of the O p-band centers.Therefore,the bonding activity of oxygen in the adsorbed state to the lattice oxygen is greatly passivated during the OER process,thus improving the stability of matrix material.In addition,benefiting from the modulating effect of the introduced Ru atoms on the metal active sites,the thermodynamic and kinetic barriers have been significantly reduced,which greatly enhances both the catalytic stability and reaction efficiency of Co_(3)O_(4).