Nano-Au-decorated hierarchical porous cobalt sulfide derived from ZIF-67 toward optimized oxygen evolution catalysis:Important roles of microstructures and electronic modulation

Enhancing both the number of active sites available and the intrinsic activity of Co-based electrocatalysts simultaneously is a desirable goal.Herein,a ZIF-67-derived hierarchical porous cobalt sulfide decorated by Au nanoparticles(NPs)(denoted as HP-Au@CoxSy@ZIF-67)hybrid is synthesized by low-temperature sulfuration treatment.The well-defined macroporous-mesoporous-microporous structure is obtained based on the combination of polystyrene spheres,as-formed CoxSy nanosheets,and ZIF-67 frameworks.This novel three-dimensional hierarchical structure significantly enlarges the three-phase interfaces,accelerating the mass transfer and exposing the active centers for oxygen evolution reaction.The electronic structure of Co is modulated by Au through charge transfer,and a series of experiments,together with theoretical analysis,is performed to ascertain the electronic modulation of Co by Au.Meanwhile,HP-Au@CoxSy@ZIF-67 catalysts with different amounts of Au were synthesized,wherein Au and NaBH4 reductant result in an interesting“competition effect”to regulate the relative ratio of Co^(2+)/Co^(3+),and moderate Au assists the electrochemical performance to reach the highest value.Consequently,the optimized HP-Au@CoxSy@ZIF-67 exhibits a low overpotential of 340 mV at 10 mA cm^(-2)and a Tafel slope of 42 mV dec-1 for OER in 0.1 M aqueous KOH,enabling efficient water splitting and Zn-air battery performance.The work here highlights the pivotal roles of both microstructural and electronic modulation in enhancing electrocatalytic activity and presents a feasible strategy for designing and optimizing advanced electrocatalysts.

Interfacial Electronic Modulation of Dual-Monodispersed Pt–Ni_(3)S_(2) as Efficacious Bi-Functional Electrocatalysts for Concurrent H_(2) Evolution and Methanol Selective Oxidation

Constructing the efficacious and applicable bifunctional electrocatalysts and establishing out the mechanisms of organic electro-oxidation by replacing anodic oxygen evolution reaction(OER) are critical to the development of electrochemicallydriven technologies for efficient hydrogen production and avoid CO_(2) emission. Herein, the hetero-nanocrystals between monodispersed Pt(~ 2 nm) and Ni_(3)S_(2)(~ 9.6 nm) are constructed as active electrocatalysts through interfacial electronic modulation, which exhibit superior bi-functional activities for methanol selective oxidation and H_(2) generation. The experimental and theoretical studies reveal that the asymmetrical charge distribution at Pt–Ni_(3)S_(2) could be modulated by the electronic interaction at the interface of dual-monodispersed heterojunctions, which thus promote the adsorption/desorption of the chemical intermediates at the interface. As a result, the selective conversion from CH_(3)OH to formate is accomplished at very low potentials(1.45 V) to attain 100 m A cm^(-2) with high electronic utilization rate(~ 98%) and without CO_(2) emission. Meanwhile, the Pt–Ni_(3)S_(2) can simultaneously exhibit a broad potential window with outstanding stability and large current densities for hydrogen evolution reaction(HER) at the cathode. Further, the excellent bi-functional performance is also indicated in the coupled methanol oxidation reaction(MOR)//HER reactor by only requiring a cell voltage of 1.60 V to achieve a current density of 50 m A cm^(-2) with good reusability.

Exploring the role of iron in Fe_(5)Ni_(4)S_(8)toward oxygen evolution through modulation of electronic orbital occupancy

Ni-Fe-based catalysts are considered to be among the most active catalysts for the oxygen evolution reaction(OER)under alkaline conditions,with Fe playing a crucial role.However,Fe leaching occurs during the reaction due to thermodynamic instability,which has resulted in conflicting reports within the literature regarding its role.To clarify this point,we propose a strategy consisting of modulating the electronic orbital occupancy to suppress the extensive loss of Fe atoms during the OER process.Theoretical calculations,in-situ X-ray photoelectron spectroscopy,molecular dynamics simulations,and a series of characterization showed that the stable presence of Fe not only accelerates the electron transfer process but also optimizes the reaction barriers of the oxygen evolution intermediates,promoting the phase transition of Fe_(5)Ni_(4)S_(8)to highly active catalytic species.The modulated Fe_(5)Ni_(4)S_(8)-based pre-catalysts exhibit improved OER activity and long-term durability.This study provides a novel perspective for understanding the role of Fe in the OER process.

Integrated power electronics module based on chip scale packaged power devices

High performance can be obtained for the integrated power electronics module（IPEM） by using a three-dimensional packaging structure instead of a planar structure. A three- dimensional packaged half bridge-IPEM （HB-IPEM）, consisting of two chip scale packaged MOSFETs and the corresponding gate driver and protection circuits, is fabricated at the laboratory. The reliability of the IPEM is controlled from the shape design of solder joints and the control of assembly process parameters. The parasitic parameters are extracted using Agilent 4395A impedance analyzer for building the parasitic parameter model of the HB- IPEM. A 12 V/3 A output synchronous rectifier Buck converter using the HB-IPEM is built to test the electrical performance of the HB-IPEM. Low voltage spikes on two MOSFETs illustrate that the three-dimensional package of the HB-IPEM can decrease parasitic inductance. Temperature distribution simulation results of the HB-IPEM using FLOTHERM are given. Heat dissipation of the solder joints makes the peak junction temperature of the chip drop obviously. The package realizes three-dimensional heat dissipation and has better thermal management.

Boron modulating electronic structure of FeN4C to initiate high-efficiency oxygen reduction reaction and high-performance zinc-air battery

The biggest challenge is to develop a low cost and readily available catalyst to replace expensive commercial Pt/C for efficient electrochemical oxygen reduction reaction(ORR).In this research,closo-[B_(12)H_(12)]^(2−)and 1,10-phenanthroline-iron complexes were introduced into the porous metal-organic framework by impregnation method,and further annealing treatment achieved the successful anchoring of single-atom-Fe in B-doped CN Matrix(FeN4CB).The ORR activity of FeN4CB is comparable to the widely used commercial 20 wt%Pt/C.Where the half-wave potential(E_(1/2))in alkaline medium up to 0.84 V,and even in the face of challenging ORR in acidic medium,the E_(1/2)of ORR driven by FeN4CB is still as high as 0.81 V.When FeN4CB was used as air cathode,the open circuit voltage of Zn-air battery reaches 1.435 V,and the power density and specific capacity are as high as 177 mW cm^(−2)and 800 mAh g_(Zn)^(−1)(theoretical value:820 mAh g_(Zn)^(−1)),respectively.The dazzling point of FeN4CB also appears in the high ORR stability,whether in alkaline or acidic media,E_(1/2)and limiting current density are still close to the initial value after 5000 times cycles.After continuously running the charge-discharge test for 220 h,the charge voltage and discharge voltage of the rechargeable zinc-air battery with FeN4CB as the air cathode maintained the initial state.Density functional theory calculations reveals that introducing B atom to Fe–N4–C can adjust the electronic structure to easily break O=O bond and significantly reduce the energy barrier of the rate-determining step resulting in an improved ORR activity.

Electronic modulation and interface engineering of electrospun nanomaterials‐based electrocatalysts toward water splitting

Nowdays,electrocatalytic water splitting has been regarded as one of the most efficient means to approach the urgent energy crisis and environmental issues.However,to speed up the electrocatalytic conversion efficiency of their half reactions including hydrogen evolution reaction(HER)and oxygen evolution reaction(OER),electrocatalysts are usually essential to reduce their kinetic energy barriers.Electrospun nanomaterials possess a unique one‐dimensional structure for outstanding electron and mass transportation,large specific surface area,and the possibilities of flexibility with the porous feature,which are good candidates as efficient electrocatalysts for water splitting.In this review,we focus on the recent research progress on the electrospun nanomaterials‐based electrocatalysts for HER,OER,and overall water splitting reaction.Specifically,the insights of the influence of the electronic modulation and interface engineering of these electrocatalysts on their electrocatalytic activities will be deeply discussed and highlighted.Furthermore,the challenges and development opportunities of the electrospun nanomaterials‐based electrocatalysts for water splitting are featured.Based on the achievements of the significantly enhanced performance from the electronic modulation and interface engineering of these electrocatalysts,full utilization of these materials for practical energy conversion is anticipated.

Electronic structure modulation with ultrafine Fe_(3)O_(4) nanoparticles on 2D Ni-based metal-organic framework layers for enhanced oxygen evolution reaction

Two-dimensional(2D)metal organic frameworks(MOFs)are emerging as low-cost oxygen evolution reaction(OER)electrocatalysts,however,suffering aggregation and poor operation stability.Herein,ultrafine Fe_(3)O_(4) nanoparticles(diameter:6±2 nm)are homogeneously immobilized on 2D Ni based MOFs(Ni-BDC,thickness:5±1 nm)to improve the OER stability.Electronic structure modulation for enhanced catalytic activity is studied via adjusting the amount of Fe_(3)O_(4) nanoparticles on Ni-BDC.The optimal Fe_(3)O_(4)/Ni-BDC achieves the best OER performance with an overpotential of 295 mV at 10 mA cm^(-2),a Tafel slope of 47.8 mV dec^(-1) and a considerable catalytic durability of more than 40 h(less than 5 h for Ni-BDC alone).DFT calculations confirm that the active sites for Fe_(3)O_(4)/Ni-BDC are mainly contributed by Fe species with a higher oxidation state,and the potential-determining step(PDS)is the formation of the adsorbed O*species,which are facilitated in the composite.

Boosting oxygen evolution reactivity by modulating electronic structure and honeycomb-like architecture in Ni_(2)P/N,P-codoped carbon hybrids

Oxygen evolution reaction(OER)as the foremost stumbling block to generate cost-effective clean fuels has received extensive attention in recent years.But,it still maintains the challenge to manipulate the geometric and electronic structure during single reaction process under the same conditions.Herein,we report a simple self-template strategy to generate honeycomb-like Ni_(2)P/N,P-C hybrids with preferred electronic architecture.Experiments coupled with theoretical results revealed that the synthesized catalyst has two characteristics:firstly,the unique honeycomb-like morphology not only enables the fully utilization of catalytic active sites but also optimizes the mass/electron transportation pathway,which favor the diffusion of electrolyte to accessible active sites.Secondly,N,P-C substrate,on the one hand,largely contributes the electronic distribution near Fermi level(E_(F))thus boosting its electrical conductivity.On the other hand,the support effect result in the upshift of d-band center and electropositivity of Ni sites,which attenuates the energy barrier for the adsorption of OH~àand the formation of*OOH.In consequence,the optimized Ni_(2)P/N,P-C catalysts feature high electrocatalytic activity towards OER(a low overpotential of 252 m V to achieve10 m A cm^(-2))and 10 h long-term stability,the outstanding performance is comparable to most of transition metal catalysts.This work gives a innovative tactics for contriving original OER electrocatalysts,inspirng deeper understanding of fabricating catalysts by combining theoretical simulation and experiment design.

Magnetic field‐enhanced water splitting enabled by bifunctional molybdenum‐doped nickel sulfide on nickel foam

Herein,we report bifunctional molybdenum-doped nickel sulfide on nickel foam(Mo-NiS_(x)/NF)for magnetic field-enhanced overall water splitting under alkaline conditions.Proper doping of Mo can lead to optimization of the electronic structure of NiS_(x),which accelerates the dissociation of H2O and the adsorption of OH−in the hydrogen evolution reaction(HER)and the oxygen evolution reaction(OER)processes,respectively.In addition,the magnetically active Mo-NiS_(x)/NF can further enhance the HER and OER activity under an applied magnetic field due to the magnetoresistance effect and the ferromagnetic(FM)exchange-field penetration effect.As a result,Mo-NiS_(x)/NF requires low overpotentials of 307 mV at 50mA cm^(−2)(for OER)and 136 mV at 10mA cm^(−2)(for HER)under a magnetic field of 10000 G.Furthermore,the electrolytic cell constructed by the bifunctional Mo-NiS_(x)/NFs as both the cathode and the anode shows a low cell voltage of 1.594 V at 10 mA cm^(−2)with optimal stability over 60 h under the magnetic field.Simultaneous enhancement of the HER and OER processes by an external magnetic field through rational design of electrocatalysts might be promising for overall water splitting applications.

Modulation of Electronic States in Bimetallic-doped Nitrogen-Carbon Based Nanoparticles for Enhanced Oxygen Reduction Kinetics

Controlling the local electronic structure of active ingredients to improve the adsorption desorption characteristics of oxygen-containing intermediates over the electrochemical liquid-solid interfaces is a critical challenge in the field of oxygen reduction reaction(ORR)catalysis.Here,we offer a simple approach for modulating the electronic states of metal nanocrystals by bimetal co-doping into carbon-nitrogen substrate,allowing us to modulate the electronic structure of catalytic active centers.To test our strategy,we designed a typical bimetallic nanoparticle catalyst(Fe-Co NP/NC)to flexibly alter the reaction kinetics of ORR.Our results from synchrotron Xray absorption spectroscopy and X-ray photoelectron spectroscopy showed that the co-doping of iron and cobalt could optimize the intrinsic charge distribution of Fe-Co NP/NC catalyst,promoting the oxygen reduction kinetics and ultimately achieving remarkable ORR activity.Consequently,the carefully designed Fe-Co NP/NC exhibits an ultra-high kinetic current density at the operating voltage(71.94 mA/cm^(2)at 0.80 V),and the half-wave potential achieves 0.915 V,which is obviously better than that of the corresponding controls including Fe NP/NC,Co NP/NC.Our findings provide a unique perspective for optimizing the electronic structure of active centers to achieve higher ORR catalytic activity and faster kinetics.

Self-supporting NiFe LDH-MoS_(x) integrated electrode for highly efficient water splitting at the industrial electrolysis conditions

Developing effective and practical electrocatalyst under industrial electrolysis conditions is critical for renewable hydrogen production.Herein,we report the self-supporting NiFe LDH-MoS_(x) integrated electrode for water oxidation under normal alkaline test condition(1 M KOH at 25℃)and simulated industrial electrolysis conditions(5 M KOH at 65℃).Such optimized electrode exhibits excellent oxygen evolution reaction(OER)performance with overpotential of 195 and 290 mV at current density of 100 and 400 mA·cm^(-2) under normal alkaline test condition.Notably,only over-potential of 156 and 201 mV were required to achieve the current density of 100 and 400mA·cm^(-2) under simulated industrial electrolysis conditions.No significant degradations were observed after long-term durability tests for both conditions.When using in two-electrode system,the operational voltages of 1.44 and 1.72 V were required to achieve a current density of 10 and 100 mA·cm^(-2) for the overall water splitting test(NiFe LDH-MoS_(x)/INF||20%Pt/C).Additionally,the operational voltage of employing NiFe LDH-MoS_(x)/INF as both cathode and anode merely require 1.52 V at 50mA·cm^(-2) at simulated industrial electrolysis conditions.Notably,a membrane electrode assembly(MEA)for anion exchange membrane water electrolysis(AEMWEs)using NiFe LDH-MoS_(x)/INF as an anode catalyst exhibited an energy conversion efficiency of 71.8%at current density of 400 mA·cm^(-2)in 1 M KOH at 60℃.Further experimental results reveal that sulfurized substrate not only improved the conductivity of NiFe LDH,but also regulated its electronic configurations and atomic composition,leading to the excellent activity.The easy-obtained and cost-effective integrated electrodes are expected to meet the large-scale application of industrial water electrolysis.

Nest-type NCM ■ Pt/C with oxygen capture character as advanced electrocatalyst for oxygen reduction reaction

A unique nest-type catalyst has been designed with a nest of oxygen capture surrounding catalytic Pt centers, which shows much promoted performance, on the base of Pt/C catalyst, for oxygen reduction reaction(ORR). The nest is constructed with nitrogen-doped carbon matrix(NCM), derived from the controlled carbonization of PANI precursor, to cover Pt/C catalyst. The unique structure of the catalyst(denoted as NCM■ Pt/C) has many merits. Firstly, it can capture oxygen both in air and in acidic electrolyte. Compared with naked Pt/C, it is found that, in air, the oxygen concentration within the porous nest of NCM surrounding Pt/C particles is ~13 times higher than atmospheric oxygen concentration and, in acidic electrolyte, the concentration of activated oxygen over the catalyst NCM■ Pt/C rise to~1.9 times. Secondly, the NCM nest offers a special electronic modulation on Pt centers toward modified ORR kinetics and then catalytic performances. With these merits, compared with Pt/C, the NCM■ Pt/C catalyst shows 3.2 times higher turnover frequency value and 2.9 times enhanced specific activity for ORR with half-wave potential at 0.894 V. After 50,000 sweeping cycles, the NCM■ Pt/C catalyst retains~66% mass activity and still has advantages over the fresh Pt/C catalyst. We envision that the nest-type catalyst provides a new idea for progress of practical Pt/C ORR catalyst.

High rate and ultralong life flexible all-solid-state zinc ion battery based on electron density modulated NiCo_(2)O_(4) nanosheets

The development of zinc ion batteries (ZIBs) with large capacity,high rate,and durable cathode material is a crucial and urgent task.Ni Co_(2)O_(4)(NCO) has received ever-growing interest as a potential cathode material for ZIBs,owing to the high theoretical capacity,rich source,cost-effective,and versatile redox nature.However,due to the slow dynamics of the NCO electrodes,its practical application in highperformance systems is severely limited.Herein,we report an electron density modulated NCO nanosheets (N-NCO NSs) with high-kinetics Zn^(2+)-storage capability as an additive-free cathode for flexible all-solid-state (ASS) ZIBs.By virtue of the enhanced electronic conductivity,improved reaction kinetics,and increased active sites,the optimized N-NCO NSs electrode delivers a high capacity of 357.7 m Ah g^(-1)at 1.0 A g^(-1)and a superior rate capacity of 201.4 m Ah g^(-1)at 20 A g^(-1).More importantly,a flexible ASS ZIBs device is manufactured using a solid polymer electrolyte of a poly (vinylidene fluoride hexafluoropropylene)(PVDF-HFP) film.The flexible ASS ZIBs device shows superb durability with 80.2%capacity retention after 20,000 cycles and works well in the range of-20–70℃.Furthermore,the flexible ASS ZIBs achieves an impressive energy density as high as 578.1 W h kg^(-1)with a peak power density of 33.6 k W kg^(-1),substantially outperforming those latest ZIBs.This work could provide valuable insights for constructing high-kinetics and high-capability cathodes with long-term stability for flexible ASS ZIBs.

Electromagnetic Compatibility Design for Powertrain Control Module

In order to improve the electromagnetic compatibility of powertrain control module （PCM）, a system procedure of vehicular PCM electromagnetic alteration is presented in this paper. First of all, the box of the PCM is divided into different cabins to eliminate interferences between power supply circuit, analog circuit and digital circuit. Secondly, the working principle and electromagnetic （EM） characters of all the signals adopted by a typical PCM are analyzed. Then according to specific electromagnetic characters, different measures are adopted in corresponding signal process circuits or signal transfer cables, such as ground layout designing, power supply protecting, signal shielding and drive cable interference suppressing. Finally, further improvement may also needed regarding to practical electromagnetic compatibility test effects. The final test shows that, with all the measures mentioned above, the conducted emission of a PCM can be reduced by 20 dB; meanwhile, the radiated emission can be reduced by 30 dB comparing to the original system.

Research on performance testing of radio fuse based on virtual separation technology

The conception of virtual separation technology about high low frequency of electronic module was put forward based on the analysis of tactical performance testing of radio fuse.By means of the principle of fuse Doppler signal acquisition and injection,the high low frequency of electronic module was virtually separated,and one of important parameters—burst height of radio fuse is tested precisely.

Physical model for the exotic ultraviolet photo-conductivity of ZnO nanowire films

Employing a simple and efficient method of electro-chemical anodization, ZnO nanowire films are fabricated on Zn foil, and an ultraviolet （UV） sensor prototype is formed for investigating the electronic transport through back-to-back double junctions. The UV （365 nm） responses of surface-contacted ZnO film are provided by I-V measurement, along with the current evolution process by on/off of UV illumination. In this paper, the back-to-back metal-seconductor-metal （M-S-M） model is used to explain the electronic transport of a ZnO nanowire film based structure. A thermionic-field electron emission mechanism is employed to fit and explain the as-observed UV sensitive electronic transport properties of ZnO film with surface-modulation by oxygen and water molecular coverage.

On the Time Fractional Modulation for Electron Acoustic Shock Waves

Nonlinear features of electron-acoustic shock waves are studied. The Burgers equation is derived and converted to the time fractional Burgers equation by Agrawal＇s method. Using the Adomian decomposition method, the shock wave solutions of the time fractional Burgers equation are constructed. The effect of time fractional parameter on the shock wave properties in auroral plasma ＆ investigated.

Recent progress of cobalt-based electrocatalysts for water splitting: Electron modulation, surface reconstitution, and applications

Electrocatalytic water splitting is an essential and effective means to produce green hydrogen energy structures,so it is necessary to develop non-precious metal catalysts to replace precious metals.Cobalt-based catalysts present effective alternatives due to the diverse valence states,adjustable electronic structures,and plentiful components.In this review,the catalytic mechanisms of hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)for electrocatalytic water splitting are described.Then,the synthesis strategies of various cobalt-based catalysts are systematically summarized,followed by the relationships between the structure and performance clarified.Subsequently,the effects of d-band center and spin regulation for cobalt-based catalysts are also discussed.Furthermore,the dynamic electronic and structural devolution of cobalt-based catalysts are elucidated by combining a series of in-situ characterizations.Finally,we highlight the challenges and future developed directions of cobalt-based catalysts for electrocatalytic water splitting.

Amorphous high-entropy phosphoxides for efficient overall alkaline water/seawater splitting

Designing and synthesizing cost-effective bifunctional catalysts for overall alkaline water/seawater splitting is still a huge challenge for hydrogen production.Herein,Co/Ni/Fe/Mn based-amorphous high-entropy phosphoxide self-standing electrode(CNFMPO)is synthesized by the facile and fast electrodeposition method.CNFMPO exhibits excellent bifunctional electrocatalytic performances on alkaline water/seawater electrolysis.The hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)overpotentials of CNFMPO in alkaline water/seawater are as low as 43/73 and 252/282 mV to reach a current density of 10 mA cm^(-2),respectively.Additionally,two-electrode electrolyzers with CNFMPO||CNFMPO successfully achieve the current density of 10 mA cm^(-2) at low voltages of 1.54 and 1.56 V for overall alkaline water/seawater splitting,respectively.CNFMPO exhibits satisfactory long-term stability on overall alkaline water/seawater splitting for the surface reconstruction into active metal hydroxide/(oxy)hydroxide,phosphite,and phosphate.Moreover,no hypochlorite is detected during seawater electrolysis for the beneficial chlorite oxidation inhibition of the reconstructed phosphite and phosphate.The excellent catalytic performances of CNFMPO are due to the unique amorphous structure,multi-component synergistic effect,beneficial electronic structure modulation,and surface reconstruction during the catalytic reaction process.Therefore,CNFMPO has shown potential promotion to the development of the water/seawater splitting industry as a promising substituent for noble-metal electrocatalysts.This work provides new insights into the design of efficient bifunctional catalysts for overall water/seawater splitting.

通过与钌合金化来调控铂的电子结构促进以水为质子源的光催化选择性加氢

调控金属活性位点的电子结构来发展高活性的选择性加氢反应催化剂对于可持续有机合成非常重要.但时至今日,这仍然是非常具有挑战性的课题.在本文中,我们将具有电子结构调节特性的超细PtRu合金纳米颗粒负载在CdS纳米棒上,成功构建了PtRu/CdS复合催化剂并研究了其光催化芳香族硝基化合物氢化还原性能.我们发现当以水为质子源时,所得复合催化剂表现出高效的光催化加氢活性.超快光谱研究和密度泛函理论计算揭示了合金的形成促进了光生载流子的分离并降低了氢化还原反应中决速步的能垒,从而显著提高了加氢活性.本研究通过合金化效应调节助催化剂的电子结构,为高活性助催化剂/光催化剂体系的理性设计开辟了一条新途径.