Designing a heterogeneous interface to improve the kinetics of electrocatalysts represents an effective yet challenging approach for enhancing the oxygen reduction reaction(ORR)and oxygen evolution reaction(OER).Herei...Designing a heterogeneous interface to improve the kinetics of electrocatalysts represents an effective yet challenging approach for enhancing the oxygen reduction reaction(ORR)and oxygen evolution reaction(OER).Herein,a simple MOF-assisted etching-pyrolysis strategy is proposed to fabricate an advanced Mott-Schottky(M–S)electrocatalyst composed of Co/CeO_(2)hetero-nanoparticles embedded within N-doped hollow carbon nanoboxes(H-Co/CeO_(2)@NCBs).Notably,the interfacial Co–O–Ce bond bridging productively facilitates the electron transfer and modulates the charge distribution of the active center,thereby contributing to the ORR/OER kinetics.As expected,the optimal M–S H-Co/CeO_(2)@NCBs catalyst exhibits promising bifunctional electrocatalytic activity with a small potential discrepancy of 0.65 V.Theoretical calculations reveal that the built-in electric field in the M–S heterojunction promotes electron transfer in oxygen electrocatalysis and the interfacial bridge-induced electron redistribution optimizes the adsorption/desorption of the oxygen intermediates,leading to reduced activation energy for the bifunctional ORR/OER reactions.Importantly,H-Co/CeO_(2)@NCBs-assembled Zn-air battery(ZAB)delivers high power density(179.8 mW cm^(−2))and long-term stability(400 h).Furthermore,the assembled flexible solid-state ZAB with H-Co/CeO_(2)@NCBs cathode also exhibits excellent charge–discharge reversibility and flexibility at various bending angles.This work provides a novel perspective on developing efficient and stable M–S bifunctional oxygen electrocatalysts.展开更多
The electron configuration of the active sites can be effectively modulated by regulating the inherent nanostructure of the electrocatalysts,thereby enhancing their electrocatalytic performance.To tackle the unexplore...The electron configuration of the active sites can be effectively modulated by regulating the inherent nanostructure of the electrocatalysts,thereby enhancing their electrocatalytic performance.To tackle the unexplored challenge of substantial electrochemical overpotential,surface reconstruction has emerged as a necessary strategy.Focusing on key aspects such as Janus structures,overflow effects,the d-band center displacement hypothesis,and interface coupling related to electrochemical reactions is essential for water electrolysis.Emerging as frontrunners among next-generation electrocatalysts,Mott-Schottky(M-S)catalysts feature a heterojunction formed between a metal and a semiconductor,offering customizable and predictable interfacial synergy.This review offers an in-depth examination of the processes driving the hydrogen and oxygen evolution reactions(HER and OER),highlighting the benefits of employing nanoscale transition metal nitrides,carbides,oxides,and phosphides in M-S heterointerface catalysts.Furthermore,the challenges,limitations,and future prospects of employing M-S heterostructured catalysts for water splitting are thoroughly discussed.展开更多
Levering the local electron density allows for varying the adsorption and/or desorption feature of catalysts,enabling to boost the reaction kinetics.Mott-Schottky barrier,in which it processes different Fermi levels,f...Levering the local electron density allows for varying the adsorption and/or desorption feature of catalysts,enabling to boost the reaction kinetics.Mott-Schottky barrier,in which it processes different Fermi levels,favors the electron transport at the interface.Here,a Mo-doped CoN is coupled with NiFe-LDH for constructing a Mott-Schottky heterojunction,addressing enhanced hydrogen evolution reaction(HER),oxygen evolution reaction(OER),and urea oxidation reaction(UOR)compared with the individual counterparts.The incorporation of high-valence Mo species and the formation of heterostructures significantly improve the corrosion resistance and electrocatalytic performance of Mo-CoN@NiFeLDH,requiring only 76 mV overpotential for HER and 257 mV for OER to achieve a high current density of 100 mA cm^(-2)in 1 M KOH.The advanced nature of our as-prepared Mott-Schottky heterojunction could be further evidenced by its robust nature of a configured alkaline electrolyzer for stable working over666 h at 200 mA cm^(-2).Impressively,only 1.692 V of cell voltage is required to yield a current density of 300 mA cm^(-2)over the as-prepared urea electrolyzer.This strategy for va rying the local electron density via construction of Mott-Schottky barrier could be regarded as a promising routine to achieve low-energy consumption green hydrogen generation.展开更多
The regulation of the interfacial electric field plays a pivotal role in magnifying the electromagnetic en-ergy attenuation capability during the design and synthesis of efficient and tunable absorbers for elec-tromag...The regulation of the interfacial electric field plays a pivotal role in magnifying the electromagnetic en-ergy attenuation capability during the design and synthesis of efficient and tunable absorbers for elec-tromagnetic waves(EMW).Herein,a rational and universally applicable two-step hydrothermal method strategy was proposed to effectively control the electronic structure of Mott-Schottky EMW absorbing materials derived from Co-MOF.The as-synthesized Co_(3)S_(4)@MoS_(2)/NC ensures efficient electron transfer,while the change redistribution leads to the emergence of additional electric dipoles under an external EMM field.In addition,the hierarchical Co_(3)S_(4)@MoS_(2)/NC nano-architecture with a hierarchical arrange-ment in 2D and 3D offers more polarization sites,thereby extending the path for EMW transmission through multiple reflections and scattering.The potential to enhance the EMW absorption performance of Co_(3)S_(4)@MoS_(2)/NC lies in its unique microstructure and substantial surface area,which optimize impedance matching properties through a synergistic effect of dipole and interfacial polarization induced by Mott-Schottky heterointerfaces.As anticipated,the Co_(3)S_(4)@MoS_(2)/NC exhibits a maximum EMW absorption ca-pacity with an RLmin value of-41.97 dB and a broad EAB of 4.24 GHz at a thickness of 2.0 mm.This study provides insights for designing highly efficient Mott-Schottky EMW absorbing materials at the molecular level rationally.展开更多
Lithium-sulfur batteries(LSBs)offer high energy density and low cost but face challenges such as low sulfur utilization,lithium polysulfides(LiPSs)shuttling,and limited reaction kinetics.To address these issues,we rat...Lithium-sulfur batteries(LSBs)offer high energy density and low cost but face challenges such as low sulfur utilization,lithium polysulfides(LiPSs)shuttling,and limited reaction kinetics.To address these issues,we rationally design a Ti_(3)C_(2)T_(x)/SnS Mott-Schottky heterostructure with a built-in electric field.This three-dimensional(3D)porous architecture can enhance sulfur loading,facilitate electrolyte penetration,and expose more adsorption and catalytic sites.More importantly,the built-in electric field facilitates charge transfer and directs LiPSs migration from SnS to Ti_(3)C_(2)T_(x).The oriented migration of LiPSs enables rapid catalytic conversion at the Ti_(3)C_(2)T_(x)/SnS heterogeneous interface,enhancing electrocatalytic activity and sulfur reduction reaction kinetics.The Ti_(3)C_(2)T_(x)/SnS/S cathode achieves a high initial capacity(1367.1 mAh g^(-1)),excellent rate performance(602.7 mAh g^(-1)at 3 C),and stable long cycling performance with an average capacity decay rate of only 0.029%per cycle at 2 C.Additionally,a high-sulfur-loaded 3 Dprinted cathode with loading of 12.7 mg cm^(-2)manufactured using 3D printing exhibits an areal capacity of 15.0 mAh cm^(-2),retaining 8.9 mAh cm^(-2)after 70 cycles.展开更多
Developing an efficient photocatalyst,catalyzing formic acid(FA) dehydrogenation,can satisfy the demand of the H_(2) energy.Herein,a graphitic carbon nitride(gC_(x)N_(4))-based nanosheet(x=3.2,3.6 or 3.8) with melem r...Developing an efficient photocatalyst,catalyzing formic acid(FA) dehydrogenation,can satisfy the demand of the H_(2) energy.Herein,a graphitic carbon nitride(gC_(x)N_(4))-based nanosheet(x=3.2,3.6 or 3.8) with melem rings conjugated by Schiff-base bond(N=C-C=N) was synthesized,tuning the bandgaps(Eg) of graphitic carbon nitride(g-C_(3) N_(4)) in the range of 1.8 400 nm) without any additive at 25℃,which is the best value among ever-reported ones.This work provides a new strategy to boost dehydrogenation photocatalysis of FA,which will be promising for practical application of H2 in future energy field.展开更多
The properties of the passivation film formed on 316L stainless steel were studied by Electrochemical Impedance Spectroscopy （EIS）, Mott-Schottky and Voltammetry measurements in high- temperature acetic acid. The re...The properties of the passivation film formed on 316L stainless steel were studied by Electrochemical Impedance Spectroscopy （EIS）, Mott-Schottky and Voltammetry measurements in high- temperature acetic acid. The results show that the passivation film formed on 316L stainless steel is stable in 60% acetic acid solution from 25 ℃ to 85 ℃. As temperature increased, the polarization resistance decreased but the interface capacitance increased. There was hardly any relation between temperature and the intrinsic property semiconductor. The passivation film represents the p-semiconductor property in the potential interval of -0.5-0.1 V; represents the n-semiconductor property in the potential interval of 0.1-0.9 V; and represents the p-semiconductor property in the potential interval of 0.9-1.1 V. The voltammetry measurements show that the structure of the passivation film is stable when the temperature is lower than 55 ℃ and that its stability decreased when this temperature is exceeded.展开更多
The disparity in the transfer of carriers(electrons/mass)during the reaction in zinc-air batteries(ZABs)results in sluggish kinetics of the oxygen reduction reaction(ORR)and oxygen evolution reaction(OER),along with e...The disparity in the transfer of carriers(electrons/mass)during the reaction in zinc-air batteries(ZABs)results in sluggish kinetics of the oxygen reduction reaction(ORR)and oxygen evolution reaction(OER),along with elevated overpotentials,thereby imposing additional constraints on its utilization.Therefore,the pre-design and target-development of inexpensive,high-performance,and long-term stable bifunctional catalysts are urgently needed.In this work,an apically guiding dual-functional electrocatalyst(Ag-FeN_(x)-N-C)was prepared,in which a hierarchical porous nitrogen-doped carbon with three-dimensional(3D)hollow star-shaped structure is used as a substrate and high-conductivity Ag nanoparticles are coupled with iron nitride(FeN_(x))nanoparticles.Theoretical calculations indicate that the Mott-Schottky heterojunction as an inherent electric field comes from the two-phase bound of Ag and FeN_(x),of which electron accumulation in the FeN_(x)phase region and electron depletion in the Ag phase region promote orientated-guiding charge migration.The effective modulation of local electronic structures felicitously reforms the d-band electron-group distribution,and intellectually tunes the masstransfer reaction energy barriers for both ORR/OER.Additionally,the hollow star-s haped hierarchical porous structure provides an apical region for fast mass transfer.Experimental results show that the halfwave potential for ORR is 0.914 V,and the overpotential for OER is only 327 mV at 10 mA cm^(-2).A rechargeable ZAB with Ag-FeN_(x)-N-C as the air cathode demonstrates long-term cycling performance exceeding 1500 cycles(500 h),with a power density of 180 mW cm^(-2).Moreover,when employing AgFeN_(x)-N-C as the air cathode,flexible ZABs demonstrate a notable open-circuit voltage of 1.42 V and achieve a maximum power density of 65.6 mW cm^(-2).Ag-FeN_(x)-N-C shows guiding electron/mass transfer route and apical reaction microenvironment for the electrocatalyst architecture in the exploration prospects of ZABs.展开更多
Lithium-oxygen batteries(LOBs)with high energy density are a promising advanced energy storage technology.However,the slow cathodic redox kinetics during cycling causes the discharge products to fail to decompose in t...Lithium-oxygen batteries(LOBs)with high energy density are a promising advanced energy storage technology.However,the slow cathodic redox kinetics during cycling causes the discharge products to fail to decompose in time,resulting in large polarization and battery failure in a short time.Therefore,a self-supporting interconnected nanosheet array network NiCo_(2)O_(4)/MnO_(2)with a Mott-Schottky heterostructure on titanium paper(TP-NCO/MO)is ingeniously designed as an efficient cathode catalyst material for LOBs.This heterostructure can accelerate electron transfer and influence the charge transfer process during adsorption of intermediate by triggering the interface disturbance at the heterogeneous interface,thus accelerating oxygen reduction and oxygen evolution kinetics and regulating product decomposition,which is expected to solve the above problems.The meticulously designed unique structural advantages enable the TP-NCO/MO cathode catalyst to exhibit an astounding ultra-long cycle life of 800 cycles and an extraordinarily low overpotential of 0.73 V.This study utilizes a simple method to cleverly regulate the morphology of the discharge products by constructing a Mott-Schottky heterostructure,providing important reference for the design of efficient catalysts aimed at optimizing the adsorption of reaction intermediates.展开更多
The supercapacitor electrode materials suffer from structure pulverization and sluggish electrode kinetics under high current rates.Herein,a unique NiMoO_(4)@Co-B heterostructure composed of highly conductive Co-B nan...The supercapacitor electrode materials suffer from structure pulverization and sluggish electrode kinetics under high current rates.Herein,a unique NiMoO_(4)@Co-B heterostructure composed of highly conductive Co-B nanoflakes and a semiconductive NiMoO_(4) nanorod is designed as an electrode material to exert the energy storage effect on supercapacitors.The formed Mott-Schottky heterostructure is helpful to overcome the ion diffusion barrier and charge transfer resistance during charging and discharging.Moreover,this crystalline-amorphous heterogeneous phase could provide additional ion storage sites and better strain adaptability.Remarkably,the optimized NiMoO_(4)@Co-B hierarchical nanorods(the mass ratio of NiMoO_(4)/Co-B is 3:1)present greatly enhanced electrochemical characteristics compared with other components,and show superior specific capacity of 236.2 mA h g^(-1)at the current density of 0.5 A g^(-1),as well as remarked rate capability.The present work broadens the horizons of advanced electrode design with distinct heterogeneous interface in other energy storage and conversion field.展开更多
The chemical composition and semi-conductive properties of passive film on nickel- based alloy （G3 alloy） in bicarbonate/carbonate buffer solution were investigated by Auger electron spectroscopy （AES）, X-ray phot...The chemical composition and semi-conductive properties of passive film on nickel- based alloy （G3 alloy） in bicarbonate/carbonate buffer solution were investigated by Auger electron spectroscopy （AES）, X-ray photoelectron spectroscopy （XPS）, elec- trochemical impedance spectra （EIS） and Mott-Schottky plot. AES and XPS results showed that the passive film appeared double-layer structure, in which the inner film was composed of nickel oxide, the mixed nickel-chromium-molybdenum-manganese oxides were the major component of the outer film. The electrochemical results revealed that the factors including frequency, potential, time, temperature and pH value can affect the semi-conductive property, the doping densities decreased with increasing potential and pH value, prolonging time and decreasing temperature. According to the above results, it can be concluded that the film protection on the substrate was enhanced with increasing potential and pH value, prolonging time and decreasing temperature.展开更多
Vacancy engineering and Mott-Schottky heterostructure can accelerate charge transfer,regulate adsorption energy of reaction intermediates,and provide additional active sites,which are regarded as valid means for impro...Vacancy engineering and Mott-Schottky heterostructure can accelerate charge transfer,regulate adsorption energy of reaction intermediates,and provide additional active sites,which are regarded as valid means for improving catalytic activity.However,the underlying mechanism of synergistic regulation of interfacial charge transfer and optimization of electrocatalytic activity by combining vacancy and Mott-Schottky junction remains unclear.Herein,the growth of a bifunctional NiCo/NiCoP Mott-Schottky electrode with abundant phosphorus vacancies on foam nickel(NF)has been synthesized through continuous phosphating and reduction processes.The obtained NiCo/NiCoP heterojunctions show remarkable OER and HER activities,and the overpotentials for OER and HER are as low as 117 and 60 mV at 10 mA/cm^(2) in 1 mol/L KOH,respectively.Moreover,as both the cathode and anode of overall water splitting,the voltage of the bifunctional NiCo/NiCoP electrocatalyst is 1.44 V at 10 mA/cm^(2),which are far exceeding the benchmark commercial electrodes.DFT theoretical calculation results confirm that the phosphorus vacancies and build-in electric field can effectively accelerate ion and electron transfer between NiCo alloy and NiCoP semiconductor,tailor the electronic structure of the metal centers and lower the Gibbs free energy of the intermediates.Furthermore,the unique self-supported integrated structure is beneficial to facilitate the exposure of the active site,avoid catalyst shedding,thus improving the activity and structural stability of NiCo/NiCoP.This study provides an avenue for the controllable synthesis and performance optimization of Mott-Schottky electrocatalysts.展开更多
The sufficient utilization of Mott-Schottky effect for boosting alkaline hydrogen evolution reaction(HER)depends upon scale minimizing of interface components and exposure maximizing of Mott-Schottky interface.Here,a ...The sufficient utilization of Mott-Schottky effect for boosting alkaline hydrogen evolution reaction(HER)depends upon scale minimizing of interface components and exposure maximizing of Mott-Schottky interface.Here,a self-standing porous tubular Mott-Schottky electrocatalyst is constructed by a self-template etching strategy,where amorphous WO_(x)(a-WO_(x))nano-matrix connects Co nanoparticles.This novel“Janus”electrocatalyst maximizes the Mott-Schottky effect by not only providing a highly exposed micro interface,but also simultaneously accelerating the water dissociation and optimizing the hydrogen desorption process.Experimental findings and theoretical calculations reveal that Co/a-WO_(x)Mott-Schottky heterointerface triggers the electron redistribution and a build-in electric field,which can not only optimize the adsorption energy of the reaction intermediates,but also facilitate the charge transfer.Thus,Co/a-WO_(x)requires an overpotential of only 36.3 mV at 10 mA·cm^(−2)and shows a small Tafel slope of 53.9 mV·dec^(−1)as well as an excellent 200-h long-term stability.This work provides a novel design strategy for maximizing the Mott-Schottky effect on promoting alkaline HER.展开更多
Integrating heterogeneous interface through nanostructure design and interfacial modification is essential to realize strengthened interfacial polarization relaxation in electromagnetic wave absorption.However,an in-d...Integrating heterogeneous interface through nanostructure design and interfacial modification is essential to realize strengthened interfacial polarization relaxation in electromagnetic wave absorption.However,an in-depth comprehension of the interfacial polarization behavior at hetero-junction/interface is highly desired but remains a great challenge.Herein,a Mott-Schottky heterojunction consisting of honeycomb-like porous N-doped carbon confined CoP nanoparticles(CoP@HNC)is designed to elevate the interfacial polarization strength.Simultaneously,corresponding electron migration and redistribution between the heterointerface of defective carbon and CoP nanoparticles are revealed.The significant difference in the work function on both sides of heterogeneous interface boosts the interfacial polarization in high frequency region.Furthermore,the relevant spectroscopic characterizations demonstrate that electron spontaneously migrates from CoP to N-doped carbon at the heterointerface,thereby contributing to the accumulation of electron on defective carbon side and the distribution of hole on CoP side.Impressively,benefitting from the synergistic effects of three-dimensional porous conductive carbon skeleton,foreign N heteroatoms,special CoP nanoparticles,and the resultant CoP/N-doped carbon Mott-Schottky heterojunction,the CoP@HNC exhibits remarkable electromagnetic wave absorption performances with minimum reflection loss up to−60.8 dB and the maximum effective absorption bandwidth of 4.96 GHz,which is superior to most of recently reported transition metal phosphides microwave absorbing composites.The present work opens a new avenue for designing heterogeneous interface to realize strengthened microwave absorption capability and also reveals the in-depth influence of interface structure on electromagnetic wave absorption.展开更多
基金supported by the National Natural Science Foundation of China(U24A20550,52273264 and 52470073)the Key Project of the Heilongjiang Provincial Natural Science Foundation(ZD2024B001)Outstanding Youth Fund of Heilongjiang Province(JQ2022E005).
文摘Designing a heterogeneous interface to improve the kinetics of electrocatalysts represents an effective yet challenging approach for enhancing the oxygen reduction reaction(ORR)and oxygen evolution reaction(OER).Herein,a simple MOF-assisted etching-pyrolysis strategy is proposed to fabricate an advanced Mott-Schottky(M–S)electrocatalyst composed of Co/CeO_(2)hetero-nanoparticles embedded within N-doped hollow carbon nanoboxes(H-Co/CeO_(2)@NCBs).Notably,the interfacial Co–O–Ce bond bridging productively facilitates the electron transfer and modulates the charge distribution of the active center,thereby contributing to the ORR/OER kinetics.As expected,the optimal M–S H-Co/CeO_(2)@NCBs catalyst exhibits promising bifunctional electrocatalytic activity with a small potential discrepancy of 0.65 V.Theoretical calculations reveal that the built-in electric field in the M–S heterojunction promotes electron transfer in oxygen electrocatalysis and the interfacial bridge-induced electron redistribution optimizes the adsorption/desorption of the oxygen intermediates,leading to reduced activation energy for the bifunctional ORR/OER reactions.Importantly,H-Co/CeO_(2)@NCBs-assembled Zn-air battery(ZAB)delivers high power density(179.8 mW cm^(−2))and long-term stability(400 h).Furthermore,the assembled flexible solid-state ZAB with H-Co/CeO_(2)@NCBs cathode also exhibits excellent charge–discharge reversibility and flexibility at various bending angles.This work provides a novel perspective on developing efficient and stable M–S bifunctional oxygen electrocatalysts.
基金supported by the Scientific and Technological Innovation Programs of Higher Education Institutions in Shanxi(2021L574)the Guizhou Provincial Science and Technology Foundation([2024]ZK General 425 and 438)+1 种基金the National Natural Science Foundation of China(22309033)the Academic Young Talent Foundation of Guizhou Normal University([2022]B05 and B06)。
文摘The electron configuration of the active sites can be effectively modulated by regulating the inherent nanostructure of the electrocatalysts,thereby enhancing their electrocatalytic performance.To tackle the unexplored challenge of substantial electrochemical overpotential,surface reconstruction has emerged as a necessary strategy.Focusing on key aspects such as Janus structures,overflow effects,the d-band center displacement hypothesis,and interface coupling related to electrochemical reactions is essential for water electrolysis.Emerging as frontrunners among next-generation electrocatalysts,Mott-Schottky(M-S)catalysts feature a heterojunction formed between a metal and a semiconductor,offering customizable and predictable interfacial synergy.This review offers an in-depth examination of the processes driving the hydrogen and oxygen evolution reactions(HER and OER),highlighting the benefits of employing nanoscale transition metal nitrides,carbides,oxides,and phosphides in M-S heterointerface catalysts.Furthermore,the challenges,limitations,and future prospects of employing M-S heterostructured catalysts for water splitting are thoroughly discussed.
基金financially supported by the National Key Research and Development Program of China(Grant No.2022YFB3807201)the National Natural Science Foundation of China(Grants Nos.52462035+6 种基金52272202W242102712464010)the Bituan Science and Technology Program(Grants No.2022DB009)project supported by the Jiangxi Provincial Natural Science Foundation(Grants No.20242BAB21002)the Project of Science and Technology Innovation and Entrepreneurship Fund of China Coal Technology&Engineering Group Co.,Ltd.(2022-MS0022023-TDMS007)。
文摘Levering the local electron density allows for varying the adsorption and/or desorption feature of catalysts,enabling to boost the reaction kinetics.Mott-Schottky barrier,in which it processes different Fermi levels,favors the electron transport at the interface.Here,a Mo-doped CoN is coupled with NiFe-LDH for constructing a Mott-Schottky heterojunction,addressing enhanced hydrogen evolution reaction(HER),oxygen evolution reaction(OER),and urea oxidation reaction(UOR)compared with the individual counterparts.The incorporation of high-valence Mo species and the formation of heterostructures significantly improve the corrosion resistance and electrocatalytic performance of Mo-CoN@NiFeLDH,requiring only 76 mV overpotential for HER and 257 mV for OER to achieve a high current density of 100 mA cm^(-2)in 1 M KOH.The advanced nature of our as-prepared Mott-Schottky heterojunction could be further evidenced by its robust nature of a configured alkaline electrolyzer for stable working over666 h at 200 mA cm^(-2).Impressively,only 1.692 V of cell voltage is required to yield a current density of 300 mA cm^(-2)over the as-prepared urea electrolyzer.This strategy for va rying the local electron density via construction of Mott-Schottky barrier could be regarded as a promising routine to achieve low-energy consumption green hydrogen generation.
基金supported by the National Natural Science Foundation of China(Nos.22271178,22301239)Science and Technology New Star in Shaanxi Province(No.2023KJXX-045)+3 种基金the Youth Talent Promotion Project of Science and Technology Association of Universities of Shaanxi Province(No.20240601)Shaanxi Provincial Department of Education service local special project,industrialization cultivation project(No.23JC007)the Research Program of the Shaanxi Provincial Department of Education(Nos.23JK0596,23JP135)the Open Foundation of Xi’an Key Laboratory of Functional Supramolecular Structure and Materials(No.CFZKFKT23003).
文摘The regulation of the interfacial electric field plays a pivotal role in magnifying the electromagnetic en-ergy attenuation capability during the design and synthesis of efficient and tunable absorbers for elec-tromagnetic waves(EMW).Herein,a rational and universally applicable two-step hydrothermal method strategy was proposed to effectively control the electronic structure of Mott-Schottky EMW absorbing materials derived from Co-MOF.The as-synthesized Co_(3)S_(4)@MoS_(2)/NC ensures efficient electron transfer,while the change redistribution leads to the emergence of additional electric dipoles under an external EMM field.In addition,the hierarchical Co_(3)S_(4)@MoS_(2)/NC nano-architecture with a hierarchical arrange-ment in 2D and 3D offers more polarization sites,thereby extending the path for EMW transmission through multiple reflections and scattering.The potential to enhance the EMW absorption performance of Co_(3)S_(4)@MoS_(2)/NC lies in its unique microstructure and substantial surface area,which optimize impedance matching properties through a synergistic effect of dipole and interfacial polarization induced by Mott-Schottky heterointerfaces.As anticipated,the Co_(3)S_(4)@MoS_(2)/NC exhibits a maximum EMW absorption ca-pacity with an RLmin value of-41.97 dB and a broad EAB of 4.24 GHz at a thickness of 2.0 mm.This study provides insights for designing highly efficient Mott-Schottky EMW absorbing materials at the molecular level rationally.
基金the financial support from the National Natural Science Foundation of China(52203340)the Guangdong Basic and Applied Basic Research Foundation(2025A1515012287)+1 种基金the Natural Science Foundation of Hubei Province(Joint Fund,2025AFD334)the Hubei Key Laboratory of Energy Storage and Power Battery(Hubei University of Automotive Technology,ZDK22024B06)。
文摘Lithium-sulfur batteries(LSBs)offer high energy density and low cost but face challenges such as low sulfur utilization,lithium polysulfides(LiPSs)shuttling,and limited reaction kinetics.To address these issues,we rationally design a Ti_(3)C_(2)T_(x)/SnS Mott-Schottky heterostructure with a built-in electric field.This three-dimensional(3D)porous architecture can enhance sulfur loading,facilitate electrolyte penetration,and expose more adsorption and catalytic sites.More importantly,the built-in electric field facilitates charge transfer and directs LiPSs migration from SnS to Ti_(3)C_(2)T_(x).The oriented migration of LiPSs enables rapid catalytic conversion at the Ti_(3)C_(2)T_(x)/SnS heterogeneous interface,enhancing electrocatalytic activity and sulfur reduction reaction kinetics.The Ti_(3)C_(2)T_(x)/SnS/S cathode achieves a high initial capacity(1367.1 mAh g^(-1)),excellent rate performance(602.7 mAh g^(-1)at 3 C),and stable long cycling performance with an average capacity decay rate of only 0.029%per cycle at 2 C.Additionally,a high-sulfur-loaded 3 Dprinted cathode with loading of 12.7 mg cm^(-2)manufactured using 3D printing exhibits an areal capacity of 15.0 mAh cm^(-2),retaining 8.9 mAh cm^(-2)after 70 cycles.
基金financially supported by Heilongjiang Science Foundation(No.LH2020B006)the National Natural Science Foundation of China(Nos.51871078,21871221 and 21602175)+1 种基金the Fundamental Research Funds for the Central Universities(No.3102017jc01001)Start-Up Funding for Class D Talent of Xi’an University of Architecture and Technology(No.1608720038)。
文摘Developing an efficient photocatalyst,catalyzing formic acid(FA) dehydrogenation,can satisfy the demand of the H_(2) energy.Herein,a graphitic carbon nitride(gC_(x)N_(4))-based nanosheet(x=3.2,3.6 or 3.8) with melem rings conjugated by Schiff-base bond(N=C-C=N) was synthesized,tuning the bandgaps(Eg) of graphitic carbon nitride(g-C_(3) N_(4)) in the range of 1.8 400 nm) without any additive at 25℃,which is the best value among ever-reported ones.This work provides a new strategy to boost dehydrogenation photocatalysis of FA,which will be promising for practical application of H2 in future energy field.
基金the National R&D Infrastructure and Facility Development Program of China(No.2005DKA10400)
文摘The properties of the passivation film formed on 316L stainless steel were studied by Electrochemical Impedance Spectroscopy （EIS）, Mott-Schottky and Voltammetry measurements in high- temperature acetic acid. The results show that the passivation film formed on 316L stainless steel is stable in 60% acetic acid solution from 25 ℃ to 85 ℃. As temperature increased, the polarization resistance decreased but the interface capacitance increased. There was hardly any relation between temperature and the intrinsic property semiconductor. The passivation film represents the p-semiconductor property in the potential interval of -0.5-0.1 V; represents the n-semiconductor property in the potential interval of 0.1-0.9 V; and represents the p-semiconductor property in the potential interval of 0.9-1.1 V. The voltammetry measurements show that the structure of the passivation film is stable when the temperature is lower than 55 ℃ and that its stability decreased when this temperature is exceeded.
基金the financial support of the National Natural Science Foundation of China(52002079,22378074,22179025 and U20A20340)the Guangdong Basic and Applied Basic Research Foundation(2022A1515140085)+2 种基金the Research Fund Program of Guangdong Provincial Key Laboratory of Fuel Cell Technology(FC202209)the Guangzhou Hongmian Project(HMJH-20200012)the Foshan Introducing Innovative and Entrepreneurial Teams(1920001000108)。
文摘The disparity in the transfer of carriers(electrons/mass)during the reaction in zinc-air batteries(ZABs)results in sluggish kinetics of the oxygen reduction reaction(ORR)and oxygen evolution reaction(OER),along with elevated overpotentials,thereby imposing additional constraints on its utilization.Therefore,the pre-design and target-development of inexpensive,high-performance,and long-term stable bifunctional catalysts are urgently needed.In this work,an apically guiding dual-functional electrocatalyst(Ag-FeN_(x)-N-C)was prepared,in which a hierarchical porous nitrogen-doped carbon with three-dimensional(3D)hollow star-shaped structure is used as a substrate and high-conductivity Ag nanoparticles are coupled with iron nitride(FeN_(x))nanoparticles.Theoretical calculations indicate that the Mott-Schottky heterojunction as an inherent electric field comes from the two-phase bound of Ag and FeN_(x),of which electron accumulation in the FeN_(x)phase region and electron depletion in the Ag phase region promote orientated-guiding charge migration.The effective modulation of local electronic structures felicitously reforms the d-band electron-group distribution,and intellectually tunes the masstransfer reaction energy barriers for both ORR/OER.Additionally,the hollow star-s haped hierarchical porous structure provides an apical region for fast mass transfer.Experimental results show that the halfwave potential for ORR is 0.914 V,and the overpotential for OER is only 327 mV at 10 mA cm^(-2).A rechargeable ZAB with Ag-FeN_(x)-N-C as the air cathode demonstrates long-term cycling performance exceeding 1500 cycles(500 h),with a power density of 180 mW cm^(-2).Moreover,when employing AgFeN_(x)-N-C as the air cathode,flexible ZABs demonstrate a notable open-circuit voltage of 1.42 V and achieve a maximum power density of 65.6 mW cm^(-2).Ag-FeN_(x)-N-C shows guiding electron/mass transfer route and apical reaction microenvironment for the electrocatalyst architecture in the exploration prospects of ZABs.
基金the financial support from the National Natural Science Foundation of China (grant nos. 51971184 and 51931006)the Natural Science Foundation of Fujian Province of China (no. 2023J01033)+1 种基金the Fundamental Research Funds for the Central Universities of China (Xiamen University: no. 20 720 200 068)the “Double First Class” Foundation of Materials Intelligent Manufacturing Discipline of Xiamen University
文摘Lithium-oxygen batteries(LOBs)with high energy density are a promising advanced energy storage technology.However,the slow cathodic redox kinetics during cycling causes the discharge products to fail to decompose in time,resulting in large polarization and battery failure in a short time.Therefore,a self-supporting interconnected nanosheet array network NiCo_(2)O_(4)/MnO_(2)with a Mott-Schottky heterostructure on titanium paper(TP-NCO/MO)is ingeniously designed as an efficient cathode catalyst material for LOBs.This heterostructure can accelerate electron transfer and influence the charge transfer process during adsorption of intermediate by triggering the interface disturbance at the heterogeneous interface,thus accelerating oxygen reduction and oxygen evolution kinetics and regulating product decomposition,which is expected to solve the above problems.The meticulously designed unique structural advantages enable the TP-NCO/MO cathode catalyst to exhibit an astounding ultra-long cycle life of 800 cycles and an extraordinarily low overpotential of 0.73 V.This study utilizes a simple method to cleverly regulate the morphology of the discharge products by constructing a Mott-Schottky heterostructure,providing important reference for the design of efficient catalysts aimed at optimizing the adsorption of reaction intermediates.
基金supported by the National Natural Science Foundation of China(52261040,51971104)the Outstanding Postgraduate Innovation Star Project of Gansu Provincial Department of Education(2022CXZX-383)。
文摘The supercapacitor electrode materials suffer from structure pulverization and sluggish electrode kinetics under high current rates.Herein,a unique NiMoO_(4)@Co-B heterostructure composed of highly conductive Co-B nanoflakes and a semiconductive NiMoO_(4) nanorod is designed as an electrode material to exert the energy storage effect on supercapacitors.The formed Mott-Schottky heterostructure is helpful to overcome the ion diffusion barrier and charge transfer resistance during charging and discharging.Moreover,this crystalline-amorphous heterogeneous phase could provide additional ion storage sites and better strain adaptability.Remarkably,the optimized NiMoO_(4)@Co-B hierarchical nanorods(the mass ratio of NiMoO_(4)/Co-B is 3:1)present greatly enhanced electrochemical characteristics compared with other components,and show superior specific capacity of 236.2 mA h g^(-1)at the current density of 0.5 A g^(-1),as well as remarked rate capability.The present work broadens the horizons of advanced electrode design with distinct heterogeneous interface in other energy storage and conversion field.
文摘The chemical composition and semi-conductive properties of passive film on nickel- based alloy （G3 alloy） in bicarbonate/carbonate buffer solution were investigated by Auger electron spectroscopy （AES）, X-ray photoelectron spectroscopy （XPS）, elec- trochemical impedance spectra （EIS） and Mott-Schottky plot. AES and XPS results showed that the passive film appeared double-layer structure, in which the inner film was composed of nickel oxide, the mixed nickel-chromium-molybdenum-manganese oxides were the major component of the outer film. The electrochemical results revealed that the factors including frequency, potential, time, temperature and pH value can affect the semi-conductive property, the doping densities decreased with increasing potential and pH value, prolonging time and decreasing temperature. According to the above results, it can be concluded that the film protection on the substrate was enhanced with increasing potential and pH value, prolonging time and decreasing temperature.
基金financially supported by the National Natural Science Foundation of China(NSFC,Nos.22269015,22205119)Natural Science Foundation of Inner Mongolia Autonomous Region of China(Nos.2021ZD11,2019BS02015).
文摘Vacancy engineering and Mott-Schottky heterostructure can accelerate charge transfer,regulate adsorption energy of reaction intermediates,and provide additional active sites,which are regarded as valid means for improving catalytic activity.However,the underlying mechanism of synergistic regulation of interfacial charge transfer and optimization of electrocatalytic activity by combining vacancy and Mott-Schottky junction remains unclear.Herein,the growth of a bifunctional NiCo/NiCoP Mott-Schottky electrode with abundant phosphorus vacancies on foam nickel(NF)has been synthesized through continuous phosphating and reduction processes.The obtained NiCo/NiCoP heterojunctions show remarkable OER and HER activities,and the overpotentials for OER and HER are as low as 117 and 60 mV at 10 mA/cm^(2) in 1 mol/L KOH,respectively.Moreover,as both the cathode and anode of overall water splitting,the voltage of the bifunctional NiCo/NiCoP electrocatalyst is 1.44 V at 10 mA/cm^(2),which are far exceeding the benchmark commercial electrodes.DFT theoretical calculation results confirm that the phosphorus vacancies and build-in electric field can effectively accelerate ion and electron transfer between NiCo alloy and NiCoP semiconductor,tailor the electronic structure of the metal centers and lower the Gibbs free energy of the intermediates.Furthermore,the unique self-supported integrated structure is beneficial to facilitate the exposure of the active site,avoid catalyst shedding,thus improving the activity and structural stability of NiCo/NiCoP.This study provides an avenue for the controllable synthesis and performance optimization of Mott-Schottky electrocatalysts.
基金supported by the National Natural Science Foundation of China(Nos.51972349,U1801255,and 51972350)the National Natural Science Foundation of Guangdong Province(No.2022A1515011596).T。
文摘The sufficient utilization of Mott-Schottky effect for boosting alkaline hydrogen evolution reaction(HER)depends upon scale minimizing of interface components and exposure maximizing of Mott-Schottky interface.Here,a self-standing porous tubular Mott-Schottky electrocatalyst is constructed by a self-template etching strategy,where amorphous WO_(x)(a-WO_(x))nano-matrix connects Co nanoparticles.This novel“Janus”electrocatalyst maximizes the Mott-Schottky effect by not only providing a highly exposed micro interface,but also simultaneously accelerating the water dissociation and optimizing the hydrogen desorption process.Experimental findings and theoretical calculations reveal that Co/a-WO_(x)Mott-Schottky heterointerface triggers the electron redistribution and a build-in electric field,which can not only optimize the adsorption energy of the reaction intermediates,but also facilitate the charge transfer.Thus,Co/a-WO_(x)requires an overpotential of only 36.3 mV at 10 mA·cm^(−2)and shows a small Tafel slope of 53.9 mV·dec^(−1)as well as an excellent 200-h long-term stability.This work provides a novel design strategy for maximizing the Mott-Schottky effect on promoting alkaline HER.
基金supported by the National Natural Science Foundation of China(Nos.51872002 and 52172174)Open Project of Provincial and Ministerial Scientific Research Platform,and Fuyang Normal University(No.FSKFKT009D).
文摘Integrating heterogeneous interface through nanostructure design and interfacial modification is essential to realize strengthened interfacial polarization relaxation in electromagnetic wave absorption.However,an in-depth comprehension of the interfacial polarization behavior at hetero-junction/interface is highly desired but remains a great challenge.Herein,a Mott-Schottky heterojunction consisting of honeycomb-like porous N-doped carbon confined CoP nanoparticles(CoP@HNC)is designed to elevate the interfacial polarization strength.Simultaneously,corresponding electron migration and redistribution between the heterointerface of defective carbon and CoP nanoparticles are revealed.The significant difference in the work function on both sides of heterogeneous interface boosts the interfacial polarization in high frequency region.Furthermore,the relevant spectroscopic characterizations demonstrate that electron spontaneously migrates from CoP to N-doped carbon at the heterointerface,thereby contributing to the accumulation of electron on defective carbon side and the distribution of hole on CoP side.Impressively,benefitting from the synergistic effects of three-dimensional porous conductive carbon skeleton,foreign N heteroatoms,special CoP nanoparticles,and the resultant CoP/N-doped carbon Mott-Schottky heterojunction,the CoP@HNC exhibits remarkable electromagnetic wave absorption performances with minimum reflection loss up to−60.8 dB and the maximum effective absorption bandwidth of 4.96 GHz,which is superior to most of recently reported transition metal phosphides microwave absorbing composites.The present work opens a new avenue for designing heterogeneous interface to realize strengthened microwave absorption capability and also reveals the in-depth influence of interface structure on electromagnetic wave absorption.
