For dissimilar metal welds(DMWs)involving nickel-based weld metal(WM)and ferritic heat resistant steel base metal(BM)in power plants,there must be an interface between WM and BM,and this interface suffers mechanical a...For dissimilar metal welds(DMWs)involving nickel-based weld metal(WM)and ferritic heat resistant steel base metal(BM)in power plants,there must be an interface between WM and BM,and this interface suffers mechanical and microstructure mismatches and is often the rupture location of premature failure.In this study,a new form of WM/BM interface form,namely double Y-type interface was designed for the DMWs.Creep behaviors and life of DMWs containing double Y-type interface and conventional I-type interface were compared by finite element analysis and creep tests,and creep failure mechanisms were investigated by stress-strain analysis and microstructure characterization.By applying double Y-type interface instead of conventional I-type interface,failure location of DMW could be shifted from the WM/ferritic heat-affected zone(HAZ)interface into the ferritic HAZ or even the ferritic BM,and the failure mode change improved the creep life of DMW.The interface premature failure of I-type interface DMW was related to the coupling effect of microstructure degradation,stress and strain concentrations,and oxide notch on the WM/HAZ interface.The creep failure of double Y-type interface DMW was the result of Type IV fracture due to the creep voids and micro-cracks on fine-grain boundaries in HAZ,which was a result of the matrix softening of HAZ and lack of precipitate pinning at fine-grain boundaries.The double Y-type interface form separated the stress and strain concentrations in DMW from the WM/HAZ interface,preventing the trigger effect of oxide notch on interface failure and inhibiting the interfacial microstructure cracking.It is a novel scheme to prolong creep life and enhance reliability of DMW,by means of optimizing the interface form,decoupling the damage factors from WM/HAZ interface,and then changing the failure mechanism and shifting the failure location.展开更多
The widespread adoption of lithium-ion batteries has been driven by the proliferation of portable electronic devices and electric vehicles,which have increasingly stringent energy density requirements.Lithium metal ba...The widespread adoption of lithium-ion batteries has been driven by the proliferation of portable electronic devices and electric vehicles,which have increasingly stringent energy density requirements.Lithium metal batteries(LMBs),with their ultralow reduction potential and high theoretical capacity,are widely regarded as the most promising technical pathway for achieving high energy density batteries.In this review,we provide a comprehensive overview of fundamental issues related to high reactivity and migrated interfaces in LMBs.Furthermore,we propose improved strategies involving interface engineering,3D current collector design,electrolyte optimization,separator modification,application of alloyed anodes,and external field regulation to address these challenges.The utilization of solid-state electrolytes can significantly enhance the safety of LMBs and represents the only viable approach for advancing them.This review also encompasses the variation in fundamental issues and design strategies for the transition from liquid to solid electrolytes.Particularly noteworthy is that the introduction of SSEs will exacerbate differences in electrochemical and mechanical properties at the interface,leading to increased interface inhomogeneity—a critical factor contributing to failure in all-solidstate lithium metal batteries.Based on recent research works,this perspective highlights the current status of research on developing high-performance LMBs.展开更多
Engineering transition metal compounds(TMCs)catalysts with excellent adsorption-catalytic ability has been one of the most effec-tive strategies to accelerate the redox kinetics of sulfur cathodes.Herein,this review f...Engineering transition metal compounds(TMCs)catalysts with excellent adsorption-catalytic ability has been one of the most effec-tive strategies to accelerate the redox kinetics of sulfur cathodes.Herein,this review focuses on engineering TMCs catalysts by cation doping/anion doping/dual doping,bimetallic/bi-anionic TMCs,and TMCs-based heterostructure composites.It is obvious that introducing cations/anions to TMCs or constructing heterostructure can boost adsorption-catalytic capacity by regulating the electronic structure including energy band,d/p-band center,electron filling,and valence state.Moreover,the elec-tronic structure of doped/dual-ionic TMCs are adjusted by inducing ions with different electronegativity,electron filling,and ion radius,resulting in electron redistribution,bonds reconstruction,induced vacancies due to the electronic interaction and changed crystal structure such as lat-tice spacing and lattice distortion.Different from the aforementioned two strategies,heterostructures are constructed by two types of TMCs with different Fermi energy levels,which causes built-in electric field and electrons transfer through the interface,and induces electron redistribution and arranged local atoms to regulate the electronic structure.Additionally,the lacking studies of the three strategies to comprehensively regulate electronic structure for improving catalytic performance are pointed out.It is believed that this review can guide the design of advanced TMCs catalysts for boosting redox of lithium sulfur batteries.展开更多
The development of a durable metallic coating on diverse substrates is both intriguing and challenging,particularly in the research of metal-conductive materials for applications such as batteries,soft electronics,and...The development of a durable metallic coating on diverse substrates is both intriguing and challenging,particularly in the research of metal-conductive materials for applications such as batteries,soft electronics,and beyond.Herein,by learning from the pencil-writing process,a facile solid-ink rubbing technology(SIR-tech)is invented to address the above challenge.The solid-ink is exampled by rational combination of liquid metal and graphite particles.By harnessing the synergistic effects between rubbing and adhesion,controllable metallic skin is successfully formed onto metals,woods,ceramics,and plastics without limitation in size and shape.Moreover,outperforming pure liquid-metal coating,the composite metallic skin by SIR-tech is very robust due to the self-lamination of graphite nanoplate exfoliated by liquid-metal rubbing.The critical factors controlling the structures-properties of the composite metallic skin have been systematically investigated as well.For applications,the SIR-tech is demonstrated to fabricate high-performance composite current collectors for next-generation batteries without traditional metal foils.Meanwhile,advanced skin-electrodes are further demonstrated for stable triboelectricity generation even under temperature fluctuation from-196 to 120℃.This facile and highly-flexible SIR-tech may work as a powerful platform for the studies on functional coatings by liquid metals and beyond.展开更多
Lithium metal batteries(LMBs) promise energy density over 400 Wh kg^(-1).However,they suffer severe electrochemical performance deterioration at sub-zero temperatures.Such failure behavior highly correlates to inferio...Lithium metal batteries(LMBs) promise energy density over 400 Wh kg^(-1).However,they suffer severe electrochemical performance deterioration at sub-zero temperatures.Such failure behavior highly correlates to inferior lithium metal anode(LMA) compatibility and sluggish Li^(+) desolvation.Here,we demonstrate that cyclopentylmethyl ether(CPME) based diluted high-concentration electrolyte(DHCE)enables-60℃ LMBs operation.By leveraging the loose coordination between Li^(+) and CPME,such developed electrolyte boosts the formation of ion clusters to derive anion-dominant interfacial chemistry for enhancing LMA compatibility and greatly accelerates Li^(+) desolvation kinetics.The resulting electrolyte demonstrates high Coulombic efficiencies(CE),providing over 99.5%,99.1%,98.5% and 95% at 25,-20,-40,and-60℃respectively.The assembled Li-S battery exhibits remarkable cyclic stability in-20,and-40℃ at 0.2 C charging and 0.5 C discharging.Even at-60℃,Li-S cell with this designed electrolyte retains> 70% of the initial capacity over 170 cycles.Besides,lithium metal coin cell and pouch cell with10 mg cm^(-2) high S cathode loading exhibit cycling stability at-20℃.This work offers an opportunity for rational designing electrolytes toward low temperature LMBs.展开更多
Advancements in sensor technology have significantly enhanced atmospheric monitoring.Notably,metal oxide and carbon(MO_(x)/C)hybrids have gained attention for their exceptional sensitivity and room-temperature sensing...Advancements in sensor technology have significantly enhanced atmospheric monitoring.Notably,metal oxide and carbon(MO_(x)/C)hybrids have gained attention for their exceptional sensitivity and room-temperature sensing performance.However,previous methods of synthesizing MO_(x)/C composites suffer from problems,including inhomogeneity,aggregation,and challenges in micropatterning.Herein,we introduce a refined method that employs a metal–organic framework(MOF)as a precursor combined with direct laser writing.The inherent structure of MOFs ensures a uniform distribution of metal ions and organic linkers,yielding homogeneous MO_(x)/C structures.The laser processing facilitates precise micropatterning(<2μm,comparable to typical photolithography)of the MO_(x)/C crystals.The optimized MOF-derived MO_(x)/C sensor rapidly detected ethanol gas even at room temperature(105 and 18 s for response and recovery,respectively),with a broad range of sensing performance from 170 to 3,400 ppm and a high response value of up to 3,500%.Additionally,this sensor exhibited enhanced stability and thermal resilience compared to previous MOF-based counterparts.This research opens up promising avenues for practical applications in MOF-derived sensing devices.展开更多
The valence states and coordination structures of doped heterometal atoms in two-dimensional(2D)nanomaterials lack predictable regulation strategies.Hence,a robust method is proposed to form unsaturated heteroatom clu...The valence states and coordination structures of doped heterometal atoms in two-dimensional(2D)nanomaterials lack predictable regulation strategies.Hence,a robust method is proposed to form unsaturated heteroatom clusters via the metal-vacancy restraint mechanism,which can precisely regulate the bonding and valence state of heterometal atoms doped in 2D molybdenum disulfide.The unsaturated valence state of heterometal Pt and Ru cluster atoms form a spatial coordination structure with Pt–S and Ru–O–S as catalytically active sites.Among them,the strong binding energy of negatively charged suspended S and O sites for H+,as well as the weak adsorption of positively charged unsaturated heterometal atoms for H*,reduces the energy barrier of the hydrogen evolution reaction proved by theoretical calculation.Whereupon,the electrocatalytic hydrogen evolution performance is markedly improved by the ensemble effect of unsaturated heterometal atoms and highlighted with an overpotential of 84 mV and Tafel slope of 68.5 mV dec^(−1).In brief,this metal vacancy-induced valence state regulation of heterometal can manipulate the coordination structure and catalytic activity of heterometal atoms doped in the 2D atomic lattice but not limited to 2D nanomaterials.展开更多
Owning various crystal structures and high theoretical capacity,metal tellurides are emerging as promising electrode materials for high-performance metal-ion batteries(MBs).Since metal telluride-based MBs are quite ne...Owning various crystal structures and high theoretical capacity,metal tellurides are emerging as promising electrode materials for high-performance metal-ion batteries(MBs).Since metal telluride-based MBs are quite new,fundamental issues raise regarding the energy storage mechanism and other aspects affecting electrochemical performance.Severe volume expansion,low intrinsic conductivity and slow ion diffusion kinetics jeopardize the performance of metal tellurides,so that rational design and engineering are crucial to circumvent these disadvantages.Herein,this review provides an in-depth discussion of recent investigations and progresses of metal tellurides,beginning with a critical discussion on the energy storage mechanisms of metal tellurides in various MBs.In the following,recent design and engineering strategies of metal tellurides,including morphology engineering,compositing,defect engineering and heterostructure construction,for high-performance MBs are summarized.The primary focus is to present a comprehensive understanding of the structural evolution based on the mechanism and corresponding effects of dimension control,composition,electron configuration and structural complexity on the electrochemical performance.In closing,outlooks and prospects for future development of metal tellurides are proposed.This work also highlights the promising directions of design and engineering strategies of metal tellurides with high performance and low cost.展开更多
Owing to the utilization of lithium metal as anode with the ultrahigh theoretical capacity density of 3860 mA h g^(-1)and oxide-based ceramic solid-state electrolytes(SE),e.g.,garnet-type Li7La_(3)Zr_(2)O_(12)(LLZO),a...Owing to the utilization of lithium metal as anode with the ultrahigh theoretical capacity density of 3860 mA h g^(-1)and oxide-based ceramic solid-state electrolytes(SE),e.g.,garnet-type Li7La_(3)Zr_(2)O_(12)(LLZO),all-state-state lithium metal batteries(ASLMBs)have been widely accepted as the promising alternatives for providing the satisfactory energy density and safety.However,its applications are still challenged by plenty of technical and scientific issues.In this contribution,the co-sintering temperature at 500℃is proved as a compromise method to fabricate the composite cathode with structural integrity and declined capacity fading of LiNi_(0.5)Co_(0.2)Mn_(0.3)O_(2)(NCM).On the other hand,it tends to form weaker grain boundary(GB)inside polycrystalline LLZO at inadequate sintering temperature for LLZO,which can induce the intergranular failure of SE during the growth of Li filament inside the unavoidable defect on the interface of SE.Therefore,increasing the strength of GB,refining the grain to 0.4μm,and precluding the interfacial defect are suggested to postpone the electro-chemo-mechanical failure of SE with weak GB.Moreover,the advanced sintering techniques to lower the co-sintering temperature for both NCM-LLZO composite cathode and LLZO SE can be posted out to realize the viability of state-of-the-art ASLMBs with higher energy density as well as the guaranteed safety.展开更多
The metal-organic framework(MOF)derived Ni–Co–C–N composite alloys(NiCCZ)were“embedded”inside the carbon cloth(CC)strands as opposed to the popular idea of growing them upward to realize ultrastable energy storag...The metal-organic framework(MOF)derived Ni–Co–C–N composite alloys(NiCCZ)were“embedded”inside the carbon cloth(CC)strands as opposed to the popular idea of growing them upward to realize ultrastable energy storage and conversion application.The NiCCZ was then oxygen functionalized,facilitating the next step of stoichiometric sulfur anion diffusion during hydrothermal sulfurization,generating a flower-like metal hydroxysulfide structure(NiCCZOS)with strong partial implantation inside CC.Thus obtained NiCCZOS shows an excellent capacity when tested as a supercapacitor electrode in a three-electrode configuration.Moreover,when paired with the biomass-derived nitrogen-rich activated carbon,the asymmetric supercapacitor device shows almost 100%capacity retention even after 45,000 charge–discharge cycles with remarkable energy density(59.4 Wh kg^(-1)/263.8μWh cm^(–2))owing to a uniquely designed cathode.Furthermore,the same electrode performed as an excellent bifunctional water-splitting electrocatalyst with an overpotential of 271 mV for oxygen evolution reaction(OER)and 168.4 mV for hydrogen evolution reaction(HER)at 10 mA cm−2 current density along with 30 h of unhinged chronopotentiometric stability performance for both HER and OER.Hence,a unique metal chalcogenide composite electrode/substrate configuration has been proposed as a highly stable electrode material for flexible energy storage and conversion applications.展开更多
Transition metal phosphides(TMPs)have been regarded as alternative hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)catalysts owing to their comparable activity to those of noble metal-based catalysts...Transition metal phosphides(TMPs)have been regarded as alternative hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)catalysts owing to their comparable activity to those of noble metal-based catalysts.TMPs have been produced in various morphologies,including hollow and porous nanostructures,which are features deemed desirable for electrocatalytic materials.Templated synthesis routes are often responsible for such morphologies.This paper reviews the latest advances and existing challenges in the synthesis of TMP-based OER and HER catalysts through templated methods.A comprehensive review of the structure-property-performance of TMP-based HER and OER catalysts prepared using different templates is presented.The discussion proceeds according to application,first by HER and further divided among the types of templates used-from hard templates,sacrificial templates,and soft templates to the emerging dynamic hydrogen bubble template.OER catalysts are then reviewed and grouped according to their morphology.Finally,prospective research directions for the synthesis of hollow and porous TMP-based catalysts,such as improvements on both activity and stability of TMPs,design of environmentally benign templates and processes,and analysis of the reaction mechanism through advanced material characterization techniques and theoretical calculations,are suggested.展开更多
In this paper,tannic acid(TA)and Fe~(3+)were added to form a layer of metal-polyphenol network structure on the surface of the nanoparticles which were fabricated by zein and carbon quantum dots(CQDs)encapsulating phl...In this paper,tannic acid(TA)and Fe~(3+)were added to form a layer of metal-polyphenol network structure on the surface of the nanoparticles which were fabricated by zein and carbon quantum dots(CQDs)encapsulating phlorotannins(PTN).pH-Responsive nanoparticles were prepared successfully(zein-PTN-CQDs-Fe-~Ⅲ).Further,the formation of composite nanoparticles was confirmed by a series of characterization methods.The zeta-potential and Fourier transform infrared spectroscopy data proved that electrostatic interaction and hydrogen bonding are dominant forces to form nanoparticles.The encapsulation efficiency(EE)revealed that metal-polyphenol network structure could improve the EE of PTN.Thermogravimetric analysis and differential scanning calorimetry experiment indicated the thermal stability of zein-PTN-CQDs-Fe~Ⅲnanoparticles increased because of metal-polyphenol network structure.The pH-responsive nanoparticles greatly increased the release rate of active substances and achieved targeted release.展开更多
Melt treatment is well known to have an important influence on the properties of metallic glasses(MGs).However,for the MGs quenched from different melt temperatures with a quartz tube,the underlying physical origin re...Melt treatment is well known to have an important influence on the properties of metallic glasses(MGs).However,for the MGs quenched from different melt temperatures with a quartz tube,the underlying physical origin responsible for the variation of properties remains poorly understood.In the present work,we systematically studied the influence of melt treatment on the thermal properties of a Zr50Cu36Al14 glass-forming alloy and unveiled the microscopic origins.Specifically,we quenched the melt at different temperatures ranging from 1.1Tl to 1.5Tl(Tl is the liquidus temperature)to obtain melt-spun MG ribbons and investigated the variation of thermal properties of the MGs upon heating.We found that glass transition temperature,Tg,increases by as much as 36 K,and the supercooled liquid region disappears in the curve of differential scanning calorimetry when the melt is quenched at a high temperature up to 1.5Tl.The careful chemical analyses indicate that the change in glass transition behavior originates from the incorporation of oxygen and silicon in the molten alloys.The incorporated oxygen and silicon can both enhance the interactions between atoms,which renders the cooperative rearrangements of atoms difficult,and thus enhances the kinetic stability of the MGs.展开更多
Surface metallization of glass fiber(GF)/polyetheretherketone(PEEK)[GF/PEEK] is conducted by coating copper using electroplating and magnetron sputtering and the properties are determined by X-ray diffraction(XRD), sc...Surface metallization of glass fiber(GF)/polyetheretherketone(PEEK)[GF/PEEK] is conducted by coating copper using electroplating and magnetron sputtering and the properties are determined by X-ray diffraction(XRD), scanning electron microscopy(SEM), and electron backscatter diffraction(EBSD).The coating bonding strength is assessed by pull-out tests and scribing in accordance with GB/T 9286-1998.The results show that the Cu coating with a thickness of 30 μm deposited on GF/PEEK by magnetron sputtering has lower roughness, finer grain size, higher crystallinity, as well as better macroscopic compressive stress,bonding strength, and electrical conductivity than the Cu coating deposited by electroplating.展开更多
Zeolite-encapsulated metal nanoclusters are at the heart of bifunctional catalysts,which hold great potential for petrochemical conversion and the emerging sustainable biorefineries.Nevertheless,efficient encapsulatio...Zeolite-encapsulated metal nanoclusters are at the heart of bifunctional catalysts,which hold great potential for petrochemical conversion and the emerging sustainable biorefineries.Nevertheless,efficient encapsulation of metal nanoclusters into a high-silica zeolite Y in particular with good structural integrity still remains a significant challenge.Herein,we have constructed Ru nanoclusters(~1 nm)encapsulated inside a high-silica zeolite Y(SY)with a SiO_(2)/Al_(2)O_(3) ratio(SAR)of 10 via a cooperative strategy for direct zeolite synthesis and a consecutive impregnation for metal encapsulation.Compared with the benchmark Ru/H-USY and other analogues,the as-prepared Ru/H-SY markedly boosts the yields of pentanoic biofuels and stability in the direct hydrodeoxygenation of biomass-derived levulinate even at a mild temperature of 180℃,which are attributed to the notable stabilization of transition states by the enhanced acid accessibility and properly sized constraints of zeolite cavities owing to the good structural integrity.展开更多
Electrolyte design holds the greatest opportunity for the development of batteries that are capable of sub-zero temperature operation.To get the most energy storage out of the battery at low temperatures,improvements ...Electrolyte design holds the greatest opportunity for the development of batteries that are capable of sub-zero temperature operation.To get the most energy storage out of the battery at low temperatures,improvements in electrolyte chemistry need to be coupled with optimized electrode materials and tailored electrolyte/electrode interphases.Herein,this review critically outlines electrolytes’limiting factors,including reduced ionic conductivity,large de-solvation energy,sluggish charge transfer,and slow Li-ion transportation across the electrolyte/electrode interphases,which affect the low-temperature performance of Li-metal batteries.Detailed theoretical derivations that explain the explicit influence of temperature on battery performance are presented to deepen understanding.Emerging improvement strategies from the aspects of electrolyte design and electrolyte/electrode interphase engineering are summarized and rigorously compared.Perspectives on future research are proposed to guide the ongoing exploration for better low-temperature Li-metal batteries.展开更多
Metallic lithium(Li)is considered the“Holy Grail”anode material for the nextgeneration of Li batteries with high energy density owing to the extraordinary theoretical specific capacity and the lowest negative electr...Metallic lithium(Li)is considered the“Holy Grail”anode material for the nextgeneration of Li batteries with high energy density owing to the extraordinary theoretical specific capacity and the lowest negative electrochemical potential.However,owing to inhomogeneous Li-ion flux,Li anodes undergo uncontrollable Li deposition,leading to limited power output and practical applications.Carbon materials and their composites with controllable structures and properties have received extensive attention to guide the homogeneous growth of Li to achieve high-performance Li anodes.In this review,the correlation between the behavior of Li anode and the properties of carbon materials is proposed.Subsequently,we review emerging strategies for rationally designing high-performance Li anodes with carbon materials,including interface engineering(stabilizing solid electrolyte interphase layer and other functionalized interfacial layer)and architecture design of host carbon(constructing three-dimension structure,preparing hollow structure,introducing lithiophilic sites,optimizing geometric effects,and compositing with Li).Based on the insights,some prospects on critical challenges and possible future research directions in this field are concluded.It is anticipated that further innovative works on the fundamental chemistry and theoretical research of Li anodes are needed.展开更多
The sluggish kinetics of the oxygen reduction reaction(ORR)is the bottleneck for various electrochemical energy conversion devices.Regulating the electronic structure of electrocatalysts by ligands has received partic...The sluggish kinetics of the oxygen reduction reaction(ORR)is the bottleneck for various electrochemical energy conversion devices.Regulating the electronic structure of electrocatalysts by ligands has received particular attention in deriving valid ORR electrocatalysts.Here,the surface electronic structure of Ptbased noble metal aerogels(NMAs)was modulated by various organic ligands,among which the electron-withdrawing ligand of 4-methylphenylene effectively boosted the ORR electrocatalysis.Theoretical calculations suggested the smaller energy barrier for the transformation of O^(*) to OH^(*) and downshift the d-band center of Pt due to the interaction between 4-methylphenylene and the surface metals,thus enhancing the ORR intrinsic activity.Both Pt3Ni and Pt Pd aerogels with 4-methylphenylene decoration performed significant enhancement in ORR activity and durability in different media.Remarkably,the 4-methylphenylene modified Pt Pd aerogel exhibited the higher halfwave potential of 0.952 V and the mass activity of 10.2 times of commercial Pt/C.This work explained the effect of electronic structure on ORR electrocatalytic properties and would promote functionalized NMAs as efficient ORR electrocatalysts.展开更多
Traditional selection of combustion catalysis is time-consuming and labor-intensive.Theoretical calculation is expected to resolve this problem.The adsorption energy of HMX and O atoms on 13 metal oxides was calculate...Traditional selection of combustion catalysis is time-consuming and labor-intensive.Theoretical calculation is expected to resolve this problem.The adsorption energy of HMX and O atoms on 13 metal oxides was calculated using DMol3,since HMX and O are key substances in decomposition process.And the relationship between the adsorption energy of HMX,O on metal oxides(TiO_(2),Al_(2)O_(3),PbO,CuO,Fe_(2)O_(3),Co_(3)O_(4),Bi_(2)O_(3),NiO)and experimental T30 values(time required for the decomposition depth of HMX to reach 30%)was depicted as volcano plot.Thus,the T30 values of other metal oxides was predicted based on their adsorption energy on volcano plot and validated by previous experimental data.Further,the adsorption energy of HMX on ZrO_(2)and MnO_(2)was predicted based on the linear relationship between surface energy and adsorption energy,and T30 values were estimated based on volcano plot.The apparent activation energy data of HMX/MgO,HMX/SnO_(2),HMX/ZrO_(2),and HMX/MnO_(2)obtained from DSC experiments are basically consistent with our predicted T30 values,indicating that it is feasible to predict the catalytic activity based on the adsorption calculation,and it is expected that these simple structural properties can predict adsorption energy to reduce the large quantities of computation and experiment cost.展开更多
The exploitation of electrocatalysts with high activity and durability for HER is desirable for future energy systems,but it is still a challenge.NMPs have attracted increasing attentions,but the preparation process o...The exploitation of electrocatalysts with high activity and durability for HER is desirable for future energy systems,but it is still a challenge.NMPs have attracted increasing attentions,but the preparation process often needs toxic regents or dangerous reaction conditions.Herein,we develop a general green method to fabricate metal-rich NMPs anchored on NPG through pyrolyzing DNA cross-linked complexes.The obtained Ru_(2) P-NPG exhibits an ultrasmall overpotential of 7 mV at 10 mA cm^(2) and ultralow Tafel slope of 33 mV dec^(-1) in 1.0 mol L?1 KOH,even better than that of commercial Pt/C.In addition,Ru 2 P-NPG also shows low overpotentials of 29 and 78 mV in 0.5 mol L^(-1) H_(2)SO_(4) and 1.0 mol L^(-1) PBS,respectively.The superior activity can be attributed to the ultrafine dispersion of Ru 2 P nanoparticles for more accessible sites,more defects formed for abundant active sites,the two-dimensional plane structure for accelerated electron transfer and mass transport,as well as the regulation of electron distribution of the catalyst.Moreover,the synthetic method can also be applied to prepare other metal-rich noble metal phosphides(Pd_(3)P-NPG and Rh_(2)P-NPG),which also exhibits high activity for HER.This work provides an effective strategy for designing NMP-based electrocatalysts.展开更多
基金Supported by Youth Elite Project of CNNC and Modular HTGR Super-critical Power Generation Technology Collaborative Project between CNNC and Tsinghua University Project of China(Grant No.ZHJTIZYFGWD20201).
文摘For dissimilar metal welds(DMWs)involving nickel-based weld metal(WM)and ferritic heat resistant steel base metal(BM)in power plants,there must be an interface between WM and BM,and this interface suffers mechanical and microstructure mismatches and is often the rupture location of premature failure.In this study,a new form of WM/BM interface form,namely double Y-type interface was designed for the DMWs.Creep behaviors and life of DMWs containing double Y-type interface and conventional I-type interface were compared by finite element analysis and creep tests,and creep failure mechanisms were investigated by stress-strain analysis and microstructure characterization.By applying double Y-type interface instead of conventional I-type interface,failure location of DMW could be shifted from the WM/ferritic heat-affected zone(HAZ)interface into the ferritic HAZ or even the ferritic BM,and the failure mode change improved the creep life of DMW.The interface premature failure of I-type interface DMW was related to the coupling effect of microstructure degradation,stress and strain concentrations,and oxide notch on the WM/HAZ interface.The creep failure of double Y-type interface DMW was the result of Type IV fracture due to the creep voids and micro-cracks on fine-grain boundaries in HAZ,which was a result of the matrix softening of HAZ and lack of precipitate pinning at fine-grain boundaries.The double Y-type interface form separated the stress and strain concentrations in DMW from the WM/HAZ interface,preventing the trigger effect of oxide notch on interface failure and inhibiting the interfacial microstructure cracking.It is a novel scheme to prolong creep life and enhance reliability of DMW,by means of optimizing the interface form,decoupling the damage factors from WM/HAZ interface,and then changing the failure mechanism and shifting the failure location.
基金This work is supported by the Technologies R&D Program of Huzhou City(No.2022JB01)the Key Research and Development Program of Zhejiang Province(No.2023C01127)the Highstar Corporation HSD20210118.
文摘The widespread adoption of lithium-ion batteries has been driven by the proliferation of portable electronic devices and electric vehicles,which have increasingly stringent energy density requirements.Lithium metal batteries(LMBs),with their ultralow reduction potential and high theoretical capacity,are widely regarded as the most promising technical pathway for achieving high energy density batteries.In this review,we provide a comprehensive overview of fundamental issues related to high reactivity and migrated interfaces in LMBs.Furthermore,we propose improved strategies involving interface engineering,3D current collector design,electrolyte optimization,separator modification,application of alloyed anodes,and external field regulation to address these challenges.The utilization of solid-state electrolytes can significantly enhance the safety of LMBs and represents the only viable approach for advancing them.This review also encompasses the variation in fundamental issues and design strategies for the transition from liquid to solid electrolytes.Particularly noteworthy is that the introduction of SSEs will exacerbate differences in electrochemical and mechanical properties at the interface,leading to increased interface inhomogeneity—a critical factor contributing to failure in all-solidstate lithium metal batteries.Based on recent research works,this perspective highlights the current status of research on developing high-performance LMBs.
基金The authors acknowledge funding from National Natural Science Foundation of China(52302307)Shaanxi Province(2023-ZDLGY-24,2023-JC-QN-0473)+2 种基金project funded by China Postdoctoral Science Foundation(2023MD734210)the Open Foundation of State Key Laboratory for Advanced Metals and Materials(2022-Z01)Shaanxi Provincial Department of Education industrialization project(21JC018).
文摘Engineering transition metal compounds(TMCs)catalysts with excellent adsorption-catalytic ability has been one of the most effec-tive strategies to accelerate the redox kinetics of sulfur cathodes.Herein,this review focuses on engineering TMCs catalysts by cation doping/anion doping/dual doping,bimetallic/bi-anionic TMCs,and TMCs-based heterostructure composites.It is obvious that introducing cations/anions to TMCs or constructing heterostructure can boost adsorption-catalytic capacity by regulating the electronic structure including energy band,d/p-band center,electron filling,and valence state.Moreover,the elec-tronic structure of doped/dual-ionic TMCs are adjusted by inducing ions with different electronegativity,electron filling,and ion radius,resulting in electron redistribution,bonds reconstruction,induced vacancies due to the electronic interaction and changed crystal structure such as lat-tice spacing and lattice distortion.Different from the aforementioned two strategies,heterostructures are constructed by two types of TMCs with different Fermi energy levels,which causes built-in electric field and electrons transfer through the interface,and induces electron redistribution and arranged local atoms to regulate the electronic structure.Additionally,the lacking studies of the three strategies to comprehensively regulate electronic structure for improving catalytic performance are pointed out.It is believed that this review can guide the design of advanced TMCs catalysts for boosting redox of lithium sulfur batteries.
基金the financial support from the National Natural Science Foundation of China (52125301 and 52203123)the Fundamental Research Funds for the Central Universitiespartially sponsored by the Double First-Class Construction Funds of Sichuan University。
文摘The development of a durable metallic coating on diverse substrates is both intriguing and challenging,particularly in the research of metal-conductive materials for applications such as batteries,soft electronics,and beyond.Herein,by learning from the pencil-writing process,a facile solid-ink rubbing technology(SIR-tech)is invented to address the above challenge.The solid-ink is exampled by rational combination of liquid metal and graphite particles.By harnessing the synergistic effects between rubbing and adhesion,controllable metallic skin is successfully formed onto metals,woods,ceramics,and plastics without limitation in size and shape.Moreover,outperforming pure liquid-metal coating,the composite metallic skin by SIR-tech is very robust due to the self-lamination of graphite nanoplate exfoliated by liquid-metal rubbing.The critical factors controlling the structures-properties of the composite metallic skin have been systematically investigated as well.For applications,the SIR-tech is demonstrated to fabricate high-performance composite current collectors for next-generation batteries without traditional metal foils.Meanwhile,advanced skin-electrodes are further demonstrated for stable triboelectricity generation even under temperature fluctuation from-196 to 120℃.This facile and highly-flexible SIR-tech may work as a powerful platform for the studies on functional coatings by liquid metals and beyond.
基金supported by the National Natural Science Foundation of China(Nos.21975087,22008082)。
文摘Lithium metal batteries(LMBs) promise energy density over 400 Wh kg^(-1).However,they suffer severe electrochemical performance deterioration at sub-zero temperatures.Such failure behavior highly correlates to inferior lithium metal anode(LMA) compatibility and sluggish Li^(+) desolvation.Here,we demonstrate that cyclopentylmethyl ether(CPME) based diluted high-concentration electrolyte(DHCE)enables-60℃ LMBs operation.By leveraging the loose coordination between Li^(+) and CPME,such developed electrolyte boosts the formation of ion clusters to derive anion-dominant interfacial chemistry for enhancing LMA compatibility and greatly accelerates Li^(+) desolvation kinetics.The resulting electrolyte demonstrates high Coulombic efficiencies(CE),providing over 99.5%,99.1%,98.5% and 95% at 25,-20,-40,and-60℃respectively.The assembled Li-S battery exhibits remarkable cyclic stability in-20,and-40℃ at 0.2 C charging and 0.5 C discharging.Even at-60℃,Li-S cell with this designed electrolyte retains> 70% of the initial capacity over 170 cycles.Besides,lithium metal coin cell and pouch cell with10 mg cm^(-2) high S cathode loading exhibit cycling stability at-20℃.This work offers an opportunity for rational designing electrolytes toward low temperature LMBs.
基金supported by the National Research Foundation of Korea(NRF)grants funded by the Ministry of Science and ICT(MSIT)(RS-2023-00251283,and 2022M3D1A2083618)by the Ministry of Education(2020R1A6A1A03040516).
文摘Advancements in sensor technology have significantly enhanced atmospheric monitoring.Notably,metal oxide and carbon(MO_(x)/C)hybrids have gained attention for their exceptional sensitivity and room-temperature sensing performance.However,previous methods of synthesizing MO_(x)/C composites suffer from problems,including inhomogeneity,aggregation,and challenges in micropatterning.Herein,we introduce a refined method that employs a metal–organic framework(MOF)as a precursor combined with direct laser writing.The inherent structure of MOFs ensures a uniform distribution of metal ions and organic linkers,yielding homogeneous MO_(x)/C structures.The laser processing facilitates precise micropatterning(<2μm,comparable to typical photolithography)of the MO_(x)/C crystals.The optimized MOF-derived MO_(x)/C sensor rapidly detected ethanol gas even at room temperature(105 and 18 s for response and recovery,respectively),with a broad range of sensing performance from 170 to 3,400 ppm and a high response value of up to 3,500%.Additionally,this sensor exhibited enhanced stability and thermal resilience compared to previous MOF-based counterparts.This research opens up promising avenues for practical applications in MOF-derived sensing devices.
基金supported by the National Natural Science Foundation of China(22205209,52202373 and U21A200972)China Postdoctoral Science Foundation(2022M722867)Key Research Project of Higher Education Institutions in Henan Province(23A530001)。
文摘The valence states and coordination structures of doped heterometal atoms in two-dimensional(2D)nanomaterials lack predictable regulation strategies.Hence,a robust method is proposed to form unsaturated heteroatom clusters via the metal-vacancy restraint mechanism,which can precisely regulate the bonding and valence state of heterometal atoms doped in 2D molybdenum disulfide.The unsaturated valence state of heterometal Pt and Ru cluster atoms form a spatial coordination structure with Pt–S and Ru–O–S as catalytically active sites.Among them,the strong binding energy of negatively charged suspended S and O sites for H+,as well as the weak adsorption of positively charged unsaturated heterometal atoms for H*,reduces the energy barrier of the hydrogen evolution reaction proved by theoretical calculation.Whereupon,the electrocatalytic hydrogen evolution performance is markedly improved by the ensemble effect of unsaturated heterometal atoms and highlighted with an overpotential of 84 mV and Tafel slope of 68.5 mV dec^(−1).In brief,this metal vacancy-induced valence state regulation of heterometal can manipulate the coordination structure and catalytic activity of heterometal atoms doped in the 2D atomic lattice but not limited to 2D nanomaterials.
基金supported by the International Collaboration Program of Jilin Provincial Department of Science and Technology,China(20230402051GH)the National Natural Science Foundation of China(51932003,51902050)+2 种基金the Open Project Program of Key Laboratory of Preparation and Application of Environmental friendly Materials(Jilin Normal University)of Ministry of China(2021006)the Fundamental Research Funds for the Central Universities JLU“Double-First Class”Discipline for Materials Science&Engineering。
文摘Owning various crystal structures and high theoretical capacity,metal tellurides are emerging as promising electrode materials for high-performance metal-ion batteries(MBs).Since metal telluride-based MBs are quite new,fundamental issues raise regarding the energy storage mechanism and other aspects affecting electrochemical performance.Severe volume expansion,low intrinsic conductivity and slow ion diffusion kinetics jeopardize the performance of metal tellurides,so that rational design and engineering are crucial to circumvent these disadvantages.Herein,this review provides an in-depth discussion of recent investigations and progresses of metal tellurides,beginning with a critical discussion on the energy storage mechanisms of metal tellurides in various MBs.In the following,recent design and engineering strategies of metal tellurides,including morphology engineering,compositing,defect engineering and heterostructure construction,for high-performance MBs are summarized.The primary focus is to present a comprehensive understanding of the structural evolution based on the mechanism and corresponding effects of dimension control,composition,electron configuration and structural complexity on the electrochemical performance.In closing,outlooks and prospects for future development of metal tellurides are proposed.This work also highlights the promising directions of design and engineering strategies of metal tellurides with high performance and low cost.
基金the National Natural Science Foundation of China(12102328)for supporting this work。
文摘Owing to the utilization of lithium metal as anode with the ultrahigh theoretical capacity density of 3860 mA h g^(-1)and oxide-based ceramic solid-state electrolytes(SE),e.g.,garnet-type Li7La_(3)Zr_(2)O_(12)(LLZO),all-state-state lithium metal batteries(ASLMBs)have been widely accepted as the promising alternatives for providing the satisfactory energy density and safety.However,its applications are still challenged by plenty of technical and scientific issues.In this contribution,the co-sintering temperature at 500℃is proved as a compromise method to fabricate the composite cathode with structural integrity and declined capacity fading of LiNi_(0.5)Co_(0.2)Mn_(0.3)O_(2)(NCM).On the other hand,it tends to form weaker grain boundary(GB)inside polycrystalline LLZO at inadequate sintering temperature for LLZO,which can induce the intergranular failure of SE during the growth of Li filament inside the unavoidable defect on the interface of SE.Therefore,increasing the strength of GB,refining the grain to 0.4μm,and precluding the interfacial defect are suggested to postpone the electro-chemo-mechanical failure of SE with weak GB.Moreover,the advanced sintering techniques to lower the co-sintering temperature for both NCM-LLZO composite cathode and LLZO SE can be posted out to realize the viability of state-of-the-art ASLMBs with higher energy density as well as the guaranteed safety.
基金supported by the Basic Science Research Program through the National Research Foundation of Korea(NRF)grant funded by the Korean government(MSIT)(2021R1A4A2000934).
文摘The metal-organic framework(MOF)derived Ni–Co–C–N composite alloys(NiCCZ)were“embedded”inside the carbon cloth(CC)strands as opposed to the popular idea of growing them upward to realize ultrastable energy storage and conversion application.The NiCCZ was then oxygen functionalized,facilitating the next step of stoichiometric sulfur anion diffusion during hydrothermal sulfurization,generating a flower-like metal hydroxysulfide structure(NiCCZOS)with strong partial implantation inside CC.Thus obtained NiCCZOS shows an excellent capacity when tested as a supercapacitor electrode in a three-electrode configuration.Moreover,when paired with the biomass-derived nitrogen-rich activated carbon,the asymmetric supercapacitor device shows almost 100%capacity retention even after 45,000 charge–discharge cycles with remarkable energy density(59.4 Wh kg^(-1)/263.8μWh cm^(–2))owing to a uniquely designed cathode.Furthermore,the same electrode performed as an excellent bifunctional water-splitting electrocatalyst with an overpotential of 271 mV for oxygen evolution reaction(OER)and 168.4 mV for hydrogen evolution reaction(HER)at 10 mA cm−2 current density along with 30 h of unhinged chronopotentiometric stability performance for both HER and OER.Hence,a unique metal chalcogenide composite electrode/substrate configuration has been proposed as a highly stable electrode material for flexible energy storage and conversion applications.
基金the support from the CIPHER Project(IIID 2018-008)funded by the Commission on Higher Education-Philippine California Advanced Research Institutes(CHED-PCARI)。
文摘Transition metal phosphides(TMPs)have been regarded as alternative hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)catalysts owing to their comparable activity to those of noble metal-based catalysts.TMPs have been produced in various morphologies,including hollow and porous nanostructures,which are features deemed desirable for electrocatalytic materials.Templated synthesis routes are often responsible for such morphologies.This paper reviews the latest advances and existing challenges in the synthesis of TMP-based OER and HER catalysts through templated methods.A comprehensive review of the structure-property-performance of TMP-based HER and OER catalysts prepared using different templates is presented.The discussion proceeds according to application,first by HER and further divided among the types of templates used-from hard templates,sacrificial templates,and soft templates to the emerging dynamic hydrogen bubble template.OER catalysts are then reviewed and grouped according to their morphology.Finally,prospective research directions for the synthesis of hollow and porous TMP-based catalysts,such as improvements on both activity and stability of TMPs,design of environmentally benign templates and processes,and analysis of the reaction mechanism through advanced material characterization techniques and theoretical calculations,are suggested.
基金supported by the National Key R&D Program of China (2018YFD0901106)the Wenzhou Major Science and Technology Project (ZN2021002)the Ningbo“3315 series program”for high-level talents (2020B-34-G)。
文摘In this paper,tannic acid(TA)and Fe~(3+)were added to form a layer of metal-polyphenol network structure on the surface of the nanoparticles which were fabricated by zein and carbon quantum dots(CQDs)encapsulating phlorotannins(PTN).pH-Responsive nanoparticles were prepared successfully(zein-PTN-CQDs-Fe-~Ⅲ).Further,the formation of composite nanoparticles was confirmed by a series of characterization methods.The zeta-potential and Fourier transform infrared spectroscopy data proved that electrostatic interaction and hydrogen bonding are dominant forces to form nanoparticles.The encapsulation efficiency(EE)revealed that metal-polyphenol network structure could improve the EE of PTN.Thermogravimetric analysis and differential scanning calorimetry experiment indicated the thermal stability of zein-PTN-CQDs-Fe~Ⅲnanoparticles increased because of metal-polyphenol network structure.The pH-responsive nanoparticles greatly increased the release rate of active substances and achieved targeted release.
基金The work was financially supported by the National Key Research and Development Program of China(Grant Nos.2018YFA0703600,2021YFA0716302,and 2021YFA0718703)the National Natural Science Foundation of China(Grant Nos.51825104 and 52192602)China Postdoctoral Science Foundation(Grant No.2022T150691).
文摘Melt treatment is well known to have an important influence on the properties of metallic glasses(MGs).However,for the MGs quenched from different melt temperatures with a quartz tube,the underlying physical origin responsible for the variation of properties remains poorly understood.In the present work,we systematically studied the influence of melt treatment on the thermal properties of a Zr50Cu36Al14 glass-forming alloy and unveiled the microscopic origins.Specifically,we quenched the melt at different temperatures ranging from 1.1Tl to 1.5Tl(Tl is the liquidus temperature)to obtain melt-spun MG ribbons and investigated the variation of thermal properties of the MGs upon heating.We found that glass transition temperature,Tg,increases by as much as 36 K,and the supercooled liquid region disappears in the curve of differential scanning calorimetry when the melt is quenched at a high temperature up to 1.5Tl.The careful chemical analyses indicate that the change in glass transition behavior originates from the incorporation of oxygen and silicon in the molten alloys.The incorporated oxygen and silicon can both enhance the interactions between atoms,which renders the cooperative rearrangements of atoms difficult,and thus enhances the kinetic stability of the MGs.
基金Funded by Shenzhen-Hong Kong Innovative Collaborative Research and Development Program (Nos.SGLH20181109 110802117, CityU 9240014)Innovation Project of Southwestern Institute of Physics (Nos.202001XWCXYD002, 202301XWCX003)CNNC Young Talent Program (No.2023JZYF-01)。
文摘Surface metallization of glass fiber(GF)/polyetheretherketone(PEEK)[GF/PEEK] is conducted by coating copper using electroplating and magnetron sputtering and the properties are determined by X-ray diffraction(XRD), scanning electron microscopy(SEM), and electron backscatter diffraction(EBSD).The coating bonding strength is assessed by pull-out tests and scribing in accordance with GB/T 9286-1998.The results show that the Cu coating with a thickness of 30 μm deposited on GF/PEEK by magnetron sputtering has lower roughness, finer grain size, higher crystallinity, as well as better macroscopic compressive stress,bonding strength, and electrical conductivity than the Cu coating deposited by electroplating.
基金supported by the National Natural Science Foundation of China (22288101,21991090,21991091,22078316,22272171 and 22109167)the Sino-French International Research Network (Zeolites)+2 种基金the BL01B1 beamline of SPring-8 and the 1W1B station of Beijing Synchrotron Radiation Facility (BSRF)for the support of XAS measurementsthe Division of Energy Research Resources of Dalian Institute of Chemical Physics for the support of iDPC-STEM measurementsthe support of the Alexander von Humboldt Foundation (CHN 1220532 HFST-P)。
文摘Zeolite-encapsulated metal nanoclusters are at the heart of bifunctional catalysts,which hold great potential for petrochemical conversion and the emerging sustainable biorefineries.Nevertheless,efficient encapsulation of metal nanoclusters into a high-silica zeolite Y in particular with good structural integrity still remains a significant challenge.Herein,we have constructed Ru nanoclusters(~1 nm)encapsulated inside a high-silica zeolite Y(SY)with a SiO_(2)/Al_(2)O_(3) ratio(SAR)of 10 via a cooperative strategy for direct zeolite synthesis and a consecutive impregnation for metal encapsulation.Compared with the benchmark Ru/H-USY and other analogues,the as-prepared Ru/H-SY markedly boosts the yields of pentanoic biofuels and stability in the direct hydrodeoxygenation of biomass-derived levulinate even at a mild temperature of 180℃,which are attributed to the notable stabilization of transition states by the enhanced acid accessibility and properly sized constraints of zeolite cavities owing to the good structural integrity.
基金The work described in this paper was fully supported by a Grant from the City University of Hong Kong(Project No.9610641).
文摘Electrolyte design holds the greatest opportunity for the development of batteries that are capable of sub-zero temperature operation.To get the most energy storage out of the battery at low temperatures,improvements in electrolyte chemistry need to be coupled with optimized electrode materials and tailored electrolyte/electrode interphases.Herein,this review critically outlines electrolytes’limiting factors,including reduced ionic conductivity,large de-solvation energy,sluggish charge transfer,and slow Li-ion transportation across the electrolyte/electrode interphases,which affect the low-temperature performance of Li-metal batteries.Detailed theoretical derivations that explain the explicit influence of temperature on battery performance are presented to deepen understanding.Emerging improvement strategies from the aspects of electrolyte design and electrolyte/electrode interphase engineering are summarized and rigorously compared.Perspectives on future research are proposed to guide the ongoing exploration for better low-temperature Li-metal batteries.
基金supported by the China Petrochemical Corporation(222260).
文摘Metallic lithium(Li)is considered the“Holy Grail”anode material for the nextgeneration of Li batteries with high energy density owing to the extraordinary theoretical specific capacity and the lowest negative electrochemical potential.However,owing to inhomogeneous Li-ion flux,Li anodes undergo uncontrollable Li deposition,leading to limited power output and practical applications.Carbon materials and their composites with controllable structures and properties have received extensive attention to guide the homogeneous growth of Li to achieve high-performance Li anodes.In this review,the correlation between the behavior of Li anode and the properties of carbon materials is proposed.Subsequently,we review emerging strategies for rationally designing high-performance Li anodes with carbon materials,including interface engineering(stabilizing solid electrolyte interphase layer and other functionalized interfacial layer)and architecture design of host carbon(constructing three-dimension structure,preparing hollow structure,introducing lithiophilic sites,optimizing geometric effects,and compositing with Li).Based on the insights,some prospects on critical challenges and possible future research directions in this field are concluded.It is anticipated that further innovative works on the fundamental chemistry and theoretical research of Li anodes are needed.
基金supported by the National Natural Science Foundation of China(22374119,21902128)the China Postdoctoral Science Foundation(2021M692620)+1 种基金the Research Fund of the State Key Laboratory of Solidification Processing(NPU),China(2021-QZ-01)the Key Project of Natural Science Fund of Shaanxi Province(2023-JC-ZD-06)。
文摘The sluggish kinetics of the oxygen reduction reaction(ORR)is the bottleneck for various electrochemical energy conversion devices.Regulating the electronic structure of electrocatalysts by ligands has received particular attention in deriving valid ORR electrocatalysts.Here,the surface electronic structure of Ptbased noble metal aerogels(NMAs)was modulated by various organic ligands,among which the electron-withdrawing ligand of 4-methylphenylene effectively boosted the ORR electrocatalysis.Theoretical calculations suggested the smaller energy barrier for the transformation of O^(*) to OH^(*) and downshift the d-band center of Pt due to the interaction between 4-methylphenylene and the surface metals,thus enhancing the ORR intrinsic activity.Both Pt3Ni and Pt Pd aerogels with 4-methylphenylene decoration performed significant enhancement in ORR activity and durability in different media.Remarkably,the 4-methylphenylene modified Pt Pd aerogel exhibited the higher halfwave potential of 0.952 V and the mass activity of 10.2 times of commercial Pt/C.This work explained the effect of electronic structure on ORR electrocatalytic properties and would promote functionalized NMAs as efficient ORR electrocatalysts.
基金supported by Key Science and Technology Innovation Team of Shaanxi Province(No.2022TD-33)National Natural Science Foundation of China(Grant Nos.21373161,21504067)。
文摘Traditional selection of combustion catalysis is time-consuming and labor-intensive.Theoretical calculation is expected to resolve this problem.The adsorption energy of HMX and O atoms on 13 metal oxides was calculated using DMol3,since HMX and O are key substances in decomposition process.And the relationship between the adsorption energy of HMX,O on metal oxides(TiO_(2),Al_(2)O_(3),PbO,CuO,Fe_(2)O_(3),Co_(3)O_(4),Bi_(2)O_(3),NiO)and experimental T30 values(time required for the decomposition depth of HMX to reach 30%)was depicted as volcano plot.Thus,the T30 values of other metal oxides was predicted based on their adsorption energy on volcano plot and validated by previous experimental data.Further,the adsorption energy of HMX on ZrO_(2)and MnO_(2)was predicted based on the linear relationship between surface energy and adsorption energy,and T30 values were estimated based on volcano plot.The apparent activation energy data of HMX/MgO,HMX/SnO_(2),HMX/ZrO_(2),and HMX/MnO_(2)obtained from DSC experiments are basically consistent with our predicted T30 values,indicating that it is feasible to predict the catalytic activity based on the adsorption calculation,and it is expected that these simple structural properties can predict adsorption energy to reduce the large quantities of computation and experiment cost.
基金This work was supported by the Fundamental Research Funds for the Central Universities(No.2022XJHH02)the National Key Research and Development Program of China(No.2019YFC1907602).
文摘The exploitation of electrocatalysts with high activity and durability for HER is desirable for future energy systems,but it is still a challenge.NMPs have attracted increasing attentions,but the preparation process often needs toxic regents or dangerous reaction conditions.Herein,we develop a general green method to fabricate metal-rich NMPs anchored on NPG through pyrolyzing DNA cross-linked complexes.The obtained Ru_(2) P-NPG exhibits an ultrasmall overpotential of 7 mV at 10 mA cm^(2) and ultralow Tafel slope of 33 mV dec^(-1) in 1.0 mol L?1 KOH,even better than that of commercial Pt/C.In addition,Ru 2 P-NPG also shows low overpotentials of 29 and 78 mV in 0.5 mol L^(-1) H_(2)SO_(4) and 1.0 mol L^(-1) PBS,respectively.The superior activity can be attributed to the ultrafine dispersion of Ru 2 P nanoparticles for more accessible sites,more defects formed for abundant active sites,the two-dimensional plane structure for accelerated electron transfer and mass transport,as well as the regulation of electron distribution of the catalyst.Moreover,the synthetic method can also be applied to prepare other metal-rich noble metal phosphides(Pd_(3)P-NPG and Rh_(2)P-NPG),which also exhibits high activity for HER.This work provides an effective strategy for designing NMP-based electrocatalysts.