In recent years,renewable energy sources,which aim to replace rapidly depleting fossil fuels,face challenges due to limited energy storage and conversion technologies.To enhance energy storage and conversion efficienc...In recent years,renewable energy sources,which aim to replace rapidly depleting fossil fuels,face challenges due to limited energy storage and conversion technologies.To enhance energy storage and conversion efficiency,extensive research has been conducted in the academic community on numerous potential materials.Among these materials,metal fluorides have attracted significant attention due to their ionic metal-fluorine bonds and tunable electronic structures,attributed to the highest electronegativity of fluorine in their chemical composition.This makes them promising candidates for future electrochemical applications in various fields.However,metal fluorides encounter various challenges in different application directions.Therefore,we comprehensively review the applications of metal fluorides in the field of energy storage and conversion,aiming to deepen our understanding of their exhibited characteristics in different electrochemical processes.In this paper,we summarize the difficulties and improvement methods encountered in different types of battery applications and several typical electrode optimization strategies in the field of supercapacitors.In the field of water electrolysis,we focus on surface reconstruction and the critical role of fluorine,demonstrating the catalytic performance of metal fluorides from the perspectives of reconstruction mechanism and process analysis.Finally,we provide a summary and outlook for this field,aiming to offer guidance for future breakthroughs in the energy storage and conversion applications of metal fluorides.展开更多
Integrating high-nickel layered oxide cathodes with aqueous slurry electrode preparation routes holds the potential to simultaneously meet the demands for high energy density and low-cost production of lithium-ion bat...Integrating high-nickel layered oxide cathodes with aqueous slurry electrode preparation routes holds the potential to simultaneously meet the demands for high energy density and low-cost production of lithium-ion batteries.However,the influence of dual exposure to air and liquid water as well as the heating treatment during aqueous slurry electrode processing on the high-nickel layered oxide electrode is yet to be understood.In this study,we systematically investigate the structural evolution and electro-chemical behaviors when LiNi_(0.83)Mn_(0.05)Co_(0.12)O_(2)(NMC83)is subjected to aqueous slurry processing.It was observed that the crystal structure near the surface of NMC83 is partially reconstructed to contain a mixture of rock-salt and layered phases when exposed to water,leading to the deteriorated rate capability of the NMC83 electrodes.This partial surface reconstruction layer completely converts into a pure rock-salt phase upon cycling,accompanied by the release of O_(2),Ni leaching,catalyzed decomposition of the electrolyte,and the formation of a thick cathode electrolyte interphase layer.The byproducts of the electrolyte and dissolved Ni could shuttle to the Li metal side,causing a crosstalk effect that results in a thick and unstable solid electrolyte interphase layer on the Li surface.These in combination severely undermined the cycling stability of the NMC83 electrodes obtained from the aqueous slurry.A mitigation strategy using molecular self-assembly technique was demonstrated to enhance the surface stability of water-treated NMC83.Our findings offer new insights for tailoring ambient environment stability and aqueous slurry processability for ultra-high nickel layered oxide and other water-sensitive cathode materials.展开更多
Self-assembled monolayers(SAMs),owing to their amphiphilic nature,tend to aggregate,which impedes the formation of a dense and uniform SAM on the substrate.Additionally,the weak adsorption ability of SAMs on the indiu...Self-assembled monolayers(SAMs),owing to their amphiphilic nature,tend to aggregate,which impedes the formation of a dense and uniform SAM on the substrate.Additionally,the weak adsorption ability of SAMs on the indium tin oxide(ITO)surface and the desorption of hydroxyl(OH)from the ITO surface induced by polar solvents can lead to the formation of vacancies.Herein,a dimethylacridine-based SAM is incorporated into the perovskite precursor solution.This SAM can be extruded from the precursor solution and enriched on the bottom surface of the perovskite,filling the vacancies and in situ forming a mixed SAM with MeO-2PACz as a hole-selective layer(HSL).The in situ formed mixed SAM optimizes the energy level alignment between the HSL and the perovskite,facilitating hole extraction and alleviating the residual strain of the perovskite film.Consequently,the perovskite solar cells(PSCs),based on the mixed SAM,achieve a power conversion efficiency(PCE)of 25.69%and exhibit excellent operational stability.When this approach is applied to 1.78 eV bandgap PSC devices,it yields a PCE of 20.08%.This work presents a unique strategy for fabricating both high-quality perovskite films and superior buried interfaces,which is also applicable to wide-bandgap PSCs.展开更多
Solid polymer electrolytes(SPEs)have attracted much attention for their safety,ease of packaging,costeffectiveness,excellent flexibility and stability.Poly-dioxolane(PDOL)is one of the most promising matrix materials ...Solid polymer electrolytes(SPEs)have attracted much attention for their safety,ease of packaging,costeffectiveness,excellent flexibility and stability.Poly-dioxolane(PDOL)is one of the most promising matrix materials of SPEs due to its remarkable compatibility with lithium metal anodes(LMAs)and suitability for in-situ polymerization.However,poor thermal stability,insufficient ionic conductivity and narrow electrochemical stability window(ESW)hinder its further application in lithium metal batteries(LMBs).To ameliorate these problems,we have successfully synthesized a polymerized-ionic-liquid(PIL)monomer named DIMTFSI by modifying DOL with imidazolium cation coupled with TFSI^(-)anion,which simultaneously inherits the lipophilicity of DOL,high ionic conductivity of imidazole,and excellent stability of PILs.Then the tridentate crosslinker trimethylolpropane tris[3-(2-methyl-1-aziridine)propionate](TTMAP)was introduced to regulate the excessive Li^(+)-O coordination and prepare a flame-retardant SPE(DT-SPE)with prominent thermal stability,wide ESW,high ionic conductivity and abundant Lit transference numbers(t_(Li+)).As a result,the LiFePO_(4)|DT-SPE|Li cell exhibits a high initial discharge specific capacity of 149.60 mAh g^(-1)at 0.2C and 30℃with a capacity retention rate of 98.68%after 500 cycles.This work provides new insights into the structural design of PIL-based electrolytes for long-cycling LMBs with high safety and stability.展开更多
Two-dimensional(2D)heterostructures compris-ing of differently stacking atomic layers are attrac-tive owing to its flexible composition as well as the emerging new physicochemical properties.Howev-er,so far many 2D ve...Two-dimensional(2D)heterostructures compris-ing of differently stacking atomic layers are attrac-tive owing to its flexible composition as well as the emerging new physicochemical properties.Howev-er,so far many 2D vertical heterojunctions are constructed through transfer methods,inevitably introducing interfacial impurities and thus hindering detailed atomic-level studies.In this work,we have developed a clean two-step fabrication strat-egy by combining ultrahigh vacuum(UHV)molecular beam epitaxy(MBE)growth with am-bient chemical vapor deposition(CVD).We first-ly grew single crystalline graphene film on a SiC substrate under UHV condition,and then synthesized MoS_(2)films on the graphene-SiC sur-face through CVD under inert atmosphere,thus successfully realized the construction of a well-defined MoS_(2)-graphene/SiC heterojunction with clean surface.Particularly,we observed the MoS_(2)can not only grow into monolayer flakes but also form spiral structures,the latter showing layer-by-layer stacks with reduced bandgap down to~1.0 eV.展开更多
Photocatalytic seawater splitting is an attractive way for producing green hydrogen.Significant progresses have been made recently in catalytic efficiencies,but the activity of catalysts can only maintain stable for a...Photocatalytic seawater splitting is an attractive way for producing green hydrogen.Significant progresses have been made recently in catalytic efficiencies,but the activity of catalysts can only maintain stable for about 10 h.Here,we develop a vacancy-engineered Ag_(3)PO_(4)/CdS porous microreactor chip photocatalyst,operating in seawater with a performance stability exceeding 300 h.This is achieved by the establishment of both catalytic selectivity for impurity ions and tailored interactions between vacancies and sulfur species.Efficient transport of carriers with strong redox ability is ensured by forming a heterojunction within a space charge region,where the visualization of potential distribution confirms the key design concept of our chip.Moreover,the separation of oxidation and reduction reactions in space inhibits the reverse recombination,making the chip capable of working at atmospheric pressure.Consequently,in the presence of Pt co-catalysts,a high solar-to-hydrogen efficiency of 0.81%can be achieved in the whole durability test.When using a fully solar-driven 256 cm2 hydrogen production prototype,a H_(2) evolution rate of 68.01 mmol h−1 m−2 can be achieved under outdoor insolation.Our findings provide a novel approach to achieve high selectivity,and demonstrate an efficient and scalable prototype suitable for practical solar H_(2) production.展开更多
Orbital angular momentum(OAM)conversion is critical in understanding interactions between a structural sound field and a planar lattice.Herein,we explore the evolution of a monochromatic acoustic vortex beam(AVB)that ...Orbital angular momentum(OAM)conversion is critical in understanding interactions between a structural sound field and a planar lattice.Herein,we explore the evolution of a monochromatic acoustic vortex beam(AVB)that is scattered by a phononic crystal(PnC)or a correlated random lattice.The phenomenon is ascribed to the enhanced orbit–orbit angular momentum coupling induced by the band structure.By modifying the coupling condition,accurate and continuous micromanipulation of AVBs can be achieved,including the transverse/lateral gravity shift,the dynamics of the phase singularities,and the spatial distribution of acoustic pressure,etc.This research provides insight to the inhomogeneous coupling of AVBs with both propagating Bloch waves and localized Anderson modes,and may facilitate development of novel OAM-based acoustic devices for active sound field manipulation.展开更多
电解水技术是一种生产高纯氢燃料的方法,能够增强可再生能源发电系统的消纳能力.相较于质子交换膜(PEM)电解槽,碱性(ALK)电解槽可以使用非贵金属基催化电极,拥有更高的经济效益和市场占有率.然而,由于ALK电解槽处于质子稀缺环境,阴极氢...电解水技术是一种生产高纯氢燃料的方法,能够增强可再生能源发电系统的消纳能力.相较于质子交换膜(PEM)电解槽,碱性(ALK)电解槽可以使用非贵金属基催化电极,拥有更高的经济效益和市场占有率.然而,由于ALK电解槽处于质子稀缺环境,阴极氢气演化反应(HER)动力学变得更加复杂,需要快速解离水分子提供动态质子微环境.硫化钼(MoS_(2))纳米片边缘具有合适的质子吸附和演化的活性位点,是制备HER催化剂的潜力材料.但其二维基面原子由于配位饱和,显示出较弱的质子吸附能力.如何调控MoS_(2)基面以实现水解动力与质子吸附演化动力的集成,提升MoS_(2)纳米片的碱性HER活性,具有重要的科学和应用意义.本文提出了一种Co/O双原子植入策略,精准调控双活性位点及其电子结构,实现了水解离动力和质子吸附演化动力的高效耦联.首先,利用刻蚀和电沉积的两步实验法,在MoS_(2)基面上成功引入O和Co原子;随后,结合高分辨透射电镜、高角环形暗场-扫描透射电子显微镜、同步辐射X射线吸收精细结构谱等表征分析技术,精准识别了掺杂Co/O原子的位置和配位情况:O原子替换部分S原子,Co原子占据Mo原子的上方,构建出立体凸起的“O-Co-S_(2)”配位构型.催化在线的原位表征分析结果表明:该独特的“O-Co-S_(2)”原子基序发挥着水解离与氢演化反应协同催化效应.密度泛函理论计算结果也证实了该协同机制,其中Co位点促进水的解离反应,而S位点则有助于质子的转化生成氢气.因此,Co/O掺杂MoS_(2)催化剂(Co-O@MoS_(2))表现出较好的碱性HER活性:仅需81 mV的过电位,即可达到100 mA cm^(‒2)的电流密度,Tafel斜率低至42 mV dec^(‒1),在600 mA cm^(‒2)的高电流密度测试中运行300 h活性无衰减.上述碱性HER性能不仅远高于原始的MoS_(2)纳米片,而且也领先于部分已报道结果.综上所述,本文在MoS_(2)基面上构筑了原子级协同催化活性中心,显著促进了碱性HER反应性能,为原子活化工程开发先进催化剂提供参考,在原子级基序构造、表征和功能分析方面提供借鉴.展开更多
Surface with well-defined components and structures possesses unique electronic,magnetic,optical and chemical properties.As a result,surface chemistry research plays a crucial role in various fields such as catalysis,...Surface with well-defined components and structures possesses unique electronic,magnetic,optical and chemical properties.As a result,surface chemistry research plays a crucial role in various fields such as catalysis,energy,materials,quantum,and microelectronics.Surface science mainly investigates the correspondence between surface property and functionality.Scanning probe microscopy(SPM)techniques are important tools to characterize surface properties because of the capability of atomic-scale imaging,spectroscopy and manipulation at the single-atom level.In this review,we summarize recent advances in surface electronic,magnetic and optical properties characterized mainly by SPM-based methods.We focus on elucidating theπ-magnetism in graphene-based nanostructures,construction of spin qubits on surfaces,topology properties of surface organic structures,STM-based light emission,tip-enhanced Raman spectroscopy and integration of machine learning in SPM studies.展开更多
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 ...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.展开更多
Surface-supported isolated atoms in single-atom catalysts(SACs)grant maximum utilization of metals in heterogeneous catalysis.Herein,we report a feasible pyrolysis strategy to synthesize Pd single atoms by thermally m...Surface-supported isolated atoms in single-atom catalysts(SACs)grant maximum utilization of metals in heterogeneous catalysis.Herein,we report a feasible pyrolysis strategy to synthesize Pd single atoms by thermally melting Pd nanoparticles on an oxygen-vacancy-rich tungsten-oxide matrix at reduction atmosphere.Near ambient pressure X-ray photoelectron spectroscopy was used to monitor the formation of zero-valence Pd single atoms and the increased metallic feature of WO_(3-x)substrate.Accordingly,the as-obtained zero-valence Pd single-atom catalyst exhibits a markedly boosted HER activity with a low overpotential(η_(10)=70 mV)at the current density of 10 mA/cm2and a small Tafel slope(b=68 mV/dec),nearly 150 mV and a 3,0-fold enhancement than those of Pd nanoparticles(η_(10)=220 mV,b=133 mV/dec)under the same conditions.In addition,quasi in situ XPS results suggest the hydrogen spillover effect is more likely to occur on Pd single atoms during the electrochemical process.Our work may pave an interesting route for the rational design of highly-efficient single-atom catalysts,and the elucidation of corresponding enhanced reaction mechanisms by the utilization of advanced characterization techniques.展开更多
Highly efficient organic solar cells(OSCs)are normally produced using the halogenated solvents chloroform or chlorobenzene,which present challenges for scalable manufacturing due to their toxicity,narrow processing wi...Highly efficient organic solar cells(OSCs)are normally produced using the halogenated solvents chloroform or chlorobenzene,which present challenges for scalable manufacturing due to their toxicity,narrow processing window and low boiling point.Herein,we develop a novel high-speed doctor-blading technique that significantly reduces the required concentration,facilitating the use of eco-friendly,non-halogenated solvents as alternatives to chloroform or chlorobenzene.By utilizing two widely used high-boiling,non-halogenated green solvents-o-xylene(o-XY)and toluene(Tol)-in the fabrication of PM 6:L 8-BO,we achieve power conversion efficiencies(PCEs)of 18.20%and 17.36%,respectively.Additionally,a module fabricated with o-XY demonstrates a notable PCE of 16.07%.In-situ testing and morphological analysis reveal that the o-XY coating process extends the liquid-to-solid transition stage to 6 s,significantly longer than the 1.7 s observed with Tol processing.This prolonged transition phase is crucial for improving the crystallinity of the thin film,reducing defect-mediated recombination,and enhancing carrier mobility,which collectively contribute to superior PCEs.展开更多
Developing wide-temperature and high-safety lithium-ion batteries(LIBs)presents significant challenges attributed to the absence of suitable solvents possessing broad liquid range and non-flammability properties.γ-Bu...Developing wide-temperature and high-safety lithium-ion batteries(LIBs)presents significant challenges attributed to the absence of suitable solvents possessing broad liquid range and non-flammability properties.γ-Butyrolactone(GBL)has emerged as a promising solvent;however,its incompatibility with graphite anode has hindered its application.This limitation necessitates a comprehensive investigation into the underlying mechanisms and potential solutions.In this study,we achieve a molecular-level understanding of the perplexing interphase formation process by employing in-situ spectroelectrochemical techniques and density function calculations.Our findings reveal that,even at high salt concentrations,GBL consistently occupies the primary Li^(+)solvation sheath,leading to extensive GBL decomposition and the formation of a high-impedance and inorganic-poor solid-electrolyte interphase(SEI)layer.Contrary to manipulating solvation structures,our research demonstrates that the utilization of filmforming additives with higher reduction potential facilitates the pre-establishment of a robust SEI film on the graphite anode.This approach effectively inhibits GBL decomposition and significantly enhances the battery's lifespan.This study provides the first reported intrinsic understanding of the unique GBLgraphite incompatibility and offers valuable insights for the development of wide-temperature and high-safety LIBs.展开更多
基金National Natural Science Foundation of China,Grant/Award Number:51073067Scientific and Technological Development Program of Jilin Province,Grant/Award Number:20220201138GX.
文摘In recent years,renewable energy sources,which aim to replace rapidly depleting fossil fuels,face challenges due to limited energy storage and conversion technologies.To enhance energy storage and conversion efficiency,extensive research has been conducted in the academic community on numerous potential materials.Among these materials,metal fluorides have attracted significant attention due to their ionic metal-fluorine bonds and tunable electronic structures,attributed to the highest electronegativity of fluorine in their chemical composition.This makes them promising candidates for future electrochemical applications in various fields.However,metal fluorides encounter various challenges in different application directions.Therefore,we comprehensively review the applications of metal fluorides in the field of energy storage and conversion,aiming to deepen our understanding of their exhibited characteristics in different electrochemical processes.In this paper,we summarize the difficulties and improvement methods encountered in different types of battery applications and several typical electrode optimization strategies in the field of supercapacitors.In the field of water electrolysis,we focus on surface reconstruction and the critical role of fluorine,demonstrating the catalytic performance of metal fluorides from the perspectives of reconstruction mechanism and process analysis.Finally,we provide a summary and outlook for this field,aiming to offer guidance for future breakthroughs in the energy storage and conversion applications of metal fluorides.
基金financially supported by the National Key R&D Program of China(2021YFB3800300)the National Natural Science Foundation of China(22179143 and 22309202)+1 种基金the Jiangsu Funding Program for Excellent Postdoctoral Talentthe Gusu Leading Talents Program(ZXL2023190)。
文摘Integrating high-nickel layered oxide cathodes with aqueous slurry electrode preparation routes holds the potential to simultaneously meet the demands for high energy density and low-cost production of lithium-ion batteries.However,the influence of dual exposure to air and liquid water as well as the heating treatment during aqueous slurry electrode processing on the high-nickel layered oxide electrode is yet to be understood.In this study,we systematically investigate the structural evolution and electro-chemical behaviors when LiNi_(0.83)Mn_(0.05)Co_(0.12)O_(2)(NMC83)is subjected to aqueous slurry processing.It was observed that the crystal structure near the surface of NMC83 is partially reconstructed to contain a mixture of rock-salt and layered phases when exposed to water,leading to the deteriorated rate capability of the NMC83 electrodes.This partial surface reconstruction layer completely converts into a pure rock-salt phase upon cycling,accompanied by the release of O_(2),Ni leaching,catalyzed decomposition of the electrolyte,and the formation of a thick cathode electrolyte interphase layer.The byproducts of the electrolyte and dissolved Ni could shuttle to the Li metal side,causing a crosstalk effect that results in a thick and unstable solid electrolyte interphase layer on the Li surface.These in combination severely undermined the cycling stability of the NMC83 electrodes obtained from the aqueous slurry.A mitigation strategy using molecular self-assembly technique was demonstrated to enhance the surface stability of water-treated NMC83.Our findings offer new insights for tailoring ambient environment stability and aqueous slurry processability for ultra-high nickel layered oxide and other water-sensitive cathode materials.
基金supported by the Young Cross Team Project of CAS(No.JCTD-2021-14)the National Natural Science Foundation of China(51925206)Gusu Innovation and Entrepreneur Leading Talents(ZXL2022466)。
文摘Self-assembled monolayers(SAMs),owing to their amphiphilic nature,tend to aggregate,which impedes the formation of a dense and uniform SAM on the substrate.Additionally,the weak adsorption ability of SAMs on the indium tin oxide(ITO)surface and the desorption of hydroxyl(OH)from the ITO surface induced by polar solvents can lead to the formation of vacancies.Herein,a dimethylacridine-based SAM is incorporated into the perovskite precursor solution.This SAM can be extruded from the precursor solution and enriched on the bottom surface of the perovskite,filling the vacancies and in situ forming a mixed SAM with MeO-2PACz as a hole-selective layer(HSL).The in situ formed mixed SAM optimizes the energy level alignment between the HSL and the perovskite,facilitating hole extraction and alleviating the residual strain of the perovskite film.Consequently,the perovskite solar cells(PSCs),based on the mixed SAM,achieve a power conversion efficiency(PCE)of 25.69%and exhibit excellent operational stability.When this approach is applied to 1.78 eV bandgap PSC devices,it yields a PCE of 20.08%.This work presents a unique strategy for fabricating both high-quality perovskite films and superior buried interfaces,which is also applicable to wide-bandgap PSCs.
基金financially supported by the National Key R&D Program of China(Grant No.2022YFE0207300)National Natural Science Foundation of China(Grant Nos.22179142 and 22075314)+1 种基金Jiangsu Funding Program for Excellent Postdoctoral Talent(Grant No.2024ZB051 and 2023ZB836)the technical support for Nano-X from Suzhou Institute of Nano-Tech and Nano-Bionics,Chinese Academy of Sciences(SINANO).
文摘Solid polymer electrolytes(SPEs)have attracted much attention for their safety,ease of packaging,costeffectiveness,excellent flexibility and stability.Poly-dioxolane(PDOL)is one of the most promising matrix materials of SPEs due to its remarkable compatibility with lithium metal anodes(LMAs)and suitability for in-situ polymerization.However,poor thermal stability,insufficient ionic conductivity and narrow electrochemical stability window(ESW)hinder its further application in lithium metal batteries(LMBs).To ameliorate these problems,we have successfully synthesized a polymerized-ionic-liquid(PIL)monomer named DIMTFSI by modifying DOL with imidazolium cation coupled with TFSI^(-)anion,which simultaneously inherits the lipophilicity of DOL,high ionic conductivity of imidazole,and excellent stability of PILs.Then the tridentate crosslinker trimethylolpropane tris[3-(2-methyl-1-aziridine)propionate](TTMAP)was introduced to regulate the excessive Li^(+)-O coordination and prepare a flame-retardant SPE(DT-SPE)with prominent thermal stability,wide ESW,high ionic conductivity and abundant Lit transference numbers(t_(Li+)).As a result,the LiFePO_(4)|DT-SPE|Li cell exhibits a high initial discharge specific capacity of 149.60 mAh g^(-1)at 0.2C and 30℃with a capacity retention rate of 98.68%after 500 cycles.This work provides new insights into the structural design of PIL-based electrolytes for long-cycling LMBs with high safety and stability.
基金support from the Natural Science Foundation of Jiangsu Province(No.BK20210124)the National Natural Science Foun-dation of China(No.12204512,No.22172152,No.21872130,No.22372193)+3 种基金the National Key Re-search and Development Program of China(No.2021YFA1502801)the joint funds from the Hefei National Synchrotron Radiation Laboratory(No.KY2060000202)We also acknowledge financial support from the CAS Project for Young Scientists in Basic Research(No.YSBR-049)the Fundamental Re-search Funds for the Central Universities(No.WK3510000013,WK2060000066).
文摘Two-dimensional(2D)heterostructures compris-ing of differently stacking atomic layers are attrac-tive owing to its flexible composition as well as the emerging new physicochemical properties.Howev-er,so far many 2D vertical heterojunctions are constructed through transfer methods,inevitably introducing interfacial impurities and thus hindering detailed atomic-level studies.In this work,we have developed a clean two-step fabrication strat-egy by combining ultrahigh vacuum(UHV)molecular beam epitaxy(MBE)growth with am-bient chemical vapor deposition(CVD).We first-ly grew single crystalline graphene film on a SiC substrate under UHV condition,and then synthesized MoS_(2)films on the graphene-SiC sur-face through CVD under inert atmosphere,thus successfully realized the construction of a well-defined MoS_(2)-graphene/SiC heterojunction with clean surface.Particularly,we observed the MoS_(2)can not only grow into monolayer flakes but also form spiral structures,the latter showing layer-by-layer stacks with reduced bandgap down to~1.0 eV.
基金support from the Industry-University Cooperation Project of Fujian Province(2023H6003)F.L.gratefully acknowledges financial support from the Fuzhou Fuzhi Photocatalysis Research Center+1 种基金Q.C.gratefully acknowledges financial support from the National Natural Science Foundation of China(22022205,22372193)the CAS Project for Young Scientists in Basic Research(YSBR-054).
文摘Photocatalytic seawater splitting is an attractive way for producing green hydrogen.Significant progresses have been made recently in catalytic efficiencies,but the activity of catalysts can only maintain stable for about 10 h.Here,we develop a vacancy-engineered Ag_(3)PO_(4)/CdS porous microreactor chip photocatalyst,operating in seawater with a performance stability exceeding 300 h.This is achieved by the establishment of both catalytic selectivity for impurity ions and tailored interactions between vacancies and sulfur species.Efficient transport of carriers with strong redox ability is ensured by forming a heterojunction within a space charge region,where the visualization of potential distribution confirms the key design concept of our chip.Moreover,the separation of oxidation and reduction reactions in space inhibits the reverse recombination,making the chip capable of working at atmospheric pressure.Consequently,in the presence of Pt co-catalysts,a high solar-to-hydrogen efficiency of 0.81%can be achieved in the whole durability test.When using a fully solar-driven 256 cm2 hydrogen production prototype,a H_(2) evolution rate of 68.01 mmol h−1 m−2 can be achieved under outdoor insolation.Our findings provide a novel approach to achieve high selectivity,and demonstrate an efficient and scalable prototype suitable for practical solar H_(2) production.
基金the National Natural Sciencefoundation of China (Grant No. 12174085)the FundamentalResearch Funds for the Central Universities (GrantNo. B220202018)+1 种基金the Basic Science (Natural Science) ResearchProject for the Universities of Jiangsu Province (GrantNo. 23KJD140002)Natural Science Foundation of Nantong(Grant No. JC2023081).
文摘Orbital angular momentum(OAM)conversion is critical in understanding interactions between a structural sound field and a planar lattice.Herein,we explore the evolution of a monochromatic acoustic vortex beam(AVB)that is scattered by a phononic crystal(PnC)or a correlated random lattice.The phenomenon is ascribed to the enhanced orbit–orbit angular momentum coupling induced by the band structure.By modifying the coupling condition,accurate and continuous micromanipulation of AVBs can be achieved,including the transverse/lateral gravity shift,the dynamics of the phase singularities,and the spatial distribution of acoustic pressure,etc.This research provides insight to the inhomogeneous coupling of AVBs with both propagating Bloch waves and localized Anderson modes,and may facilitate development of novel OAM-based acoustic devices for active sound field manipulation.
文摘电解水技术是一种生产高纯氢燃料的方法,能够增强可再生能源发电系统的消纳能力.相较于质子交换膜(PEM)电解槽,碱性(ALK)电解槽可以使用非贵金属基催化电极,拥有更高的经济效益和市场占有率.然而,由于ALK电解槽处于质子稀缺环境,阴极氢气演化反应(HER)动力学变得更加复杂,需要快速解离水分子提供动态质子微环境.硫化钼(MoS_(2))纳米片边缘具有合适的质子吸附和演化的活性位点,是制备HER催化剂的潜力材料.但其二维基面原子由于配位饱和,显示出较弱的质子吸附能力.如何调控MoS_(2)基面以实现水解动力与质子吸附演化动力的集成,提升MoS_(2)纳米片的碱性HER活性,具有重要的科学和应用意义.本文提出了一种Co/O双原子植入策略,精准调控双活性位点及其电子结构,实现了水解离动力和质子吸附演化动力的高效耦联.首先,利用刻蚀和电沉积的两步实验法,在MoS_(2)基面上成功引入O和Co原子;随后,结合高分辨透射电镜、高角环形暗场-扫描透射电子显微镜、同步辐射X射线吸收精细结构谱等表征分析技术,精准识别了掺杂Co/O原子的位置和配位情况:O原子替换部分S原子,Co原子占据Mo原子的上方,构建出立体凸起的“O-Co-S_(2)”配位构型.催化在线的原位表征分析结果表明:该独特的“O-Co-S_(2)”原子基序发挥着水解离与氢演化反应协同催化效应.密度泛函理论计算结果也证实了该协同机制,其中Co位点促进水的解离反应,而S位点则有助于质子的转化生成氢气.因此,Co/O掺杂MoS_(2)催化剂(Co-O@MoS_(2))表现出较好的碱性HER活性:仅需81 mV的过电位,即可达到100 mA cm^(‒2)的电流密度,Tafel斜率低至42 mV dec^(‒1),在600 mA cm^(‒2)的高电流密度测试中运行300 h活性无衰减.上述碱性HER性能不仅远高于原始的MoS_(2)纳米片,而且也领先于部分已报道结果.综上所述,本文在MoS_(2)基面上构筑了原子级协同催化活性中心,显著促进了碱性HER反应性能,为原子活化工程开发先进催化剂提供参考,在原子级基序构造、表征和功能分析方面提供借鉴.
文摘Surface with well-defined components and structures possesses unique electronic,magnetic,optical and chemical properties.As a result,surface chemistry research plays a crucial role in various fields such as catalysis,energy,materials,quantum,and microelectronics.Surface science mainly investigates the correspondence between surface property and functionality.Scanning probe microscopy(SPM)techniques are important tools to characterize surface properties because of the capability of atomic-scale imaging,spectroscopy and manipulation at the single-atom level.In this review,we summarize recent advances in surface electronic,magnetic and optical properties characterized mainly by SPM-based methods.We focus on elucidating theπ-magnetism in graphene-based nanostructures,construction of spin qubits on surfaces,topology properties of surface organic structures,STM-based light emission,tip-enhanced Raman spectroscopy and integration of machine learning in SPM studies.
基金financially supported by the Scientific and Technological Development Program of Jilin Province(20220201138GX)the support of the National Key R&D Program of China(No.2022YFA1503801)+1 种基金CAS Project for Young Scientists in Basic Research(No.YSBR-022)the Young Cross Team Project of CAS(No.JCTD-2021-14)。
文摘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.
基金the support from the National Key R&D Program of China(No.2022YFA1503801)the National Natural Science Foundation of China(No.22172190,No.22202232 and No.22109171)。
文摘Surface-supported isolated atoms in single-atom catalysts(SACs)grant maximum utilization of metals in heterogeneous catalysis.Herein,we report a feasible pyrolysis strategy to synthesize Pd single atoms by thermally melting Pd nanoparticles on an oxygen-vacancy-rich tungsten-oxide matrix at reduction atmosphere.Near ambient pressure X-ray photoelectron spectroscopy was used to monitor the formation of zero-valence Pd single atoms and the increased metallic feature of WO_(3-x)substrate.Accordingly,the as-obtained zero-valence Pd single-atom catalyst exhibits a markedly boosted HER activity with a low overpotential(η_(10)=70 mV)at the current density of 10 mA/cm2and a small Tafel slope(b=68 mV/dec),nearly 150 mV and a 3,0-fold enhancement than those of Pd nanoparticles(η_(10)=220 mV,b=133 mV/dec)under the same conditions.In addition,quasi in situ XPS results suggest the hydrogen spillover effect is more likely to occur on Pd single atoms during the electrochemical process.Our work may pave an interesting route for the rational design of highly-efficient single-atom catalysts,and the elucidation of corresponding enhanced reaction mechanisms by the utilization of advanced characterization techniques.
基金Project(2022YFB3803300)supported by the National Key Research and Development Program of ChinaProjects(U23A20138,52173192)supported by the National Natural Science Foundation of China+1 种基金Project(GZC20233148)supported by the Postdoctoral Fellowship Program of CPSF,ChinaProject(140050043)supported by the Central South University Postdoctoral Research Funding,China。
文摘Highly efficient organic solar cells(OSCs)are normally produced using the halogenated solvents chloroform or chlorobenzene,which present challenges for scalable manufacturing due to their toxicity,narrow processing window and low boiling point.Herein,we develop a novel high-speed doctor-blading technique that significantly reduces the required concentration,facilitating the use of eco-friendly,non-halogenated solvents as alternatives to chloroform or chlorobenzene.By utilizing two widely used high-boiling,non-halogenated green solvents-o-xylene(o-XY)and toluene(Tol)-in the fabrication of PM 6:L 8-BO,we achieve power conversion efficiencies(PCEs)of 18.20%and 17.36%,respectively.Additionally,a module fabricated with o-XY demonstrates a notable PCE of 16.07%.In-situ testing and morphological analysis reveal that the o-XY coating process extends the liquid-to-solid transition stage to 6 s,significantly longer than the 1.7 s observed with Tol processing.This prolonged transition phase is crucial for improving the crystallinity of the thin film,reducing defect-mediated recombination,and enhancing carrier mobility,which collectively contribute to superior PCEs.
基金financially supported by the National Natural Science Foundation of China(21972049,22272175)the National Key R&D Program of China(2022YFA1504002)+3 种基金the“Scientist Studio Funding”from Tianmu Lake Institute of Advanced Energy Storage Technologies Co.,Ltd.Dalian Supports High-Level Talent Innovation and Entrepreneurship Projects(2021RD14)the Dalian Institute of Chemical Physics(DICP I202213)the 21C Innovation Laboratory,Contemporary Ampere Technology Ltd.by project No.21C-OP-202208。
文摘Developing wide-temperature and high-safety lithium-ion batteries(LIBs)presents significant challenges attributed to the absence of suitable solvents possessing broad liquid range and non-flammability properties.γ-Butyrolactone(GBL)has emerged as a promising solvent;however,its incompatibility with graphite anode has hindered its application.This limitation necessitates a comprehensive investigation into the underlying mechanisms and potential solutions.In this study,we achieve a molecular-level understanding of the perplexing interphase formation process by employing in-situ spectroelectrochemical techniques and density function calculations.Our findings reveal that,even at high salt concentrations,GBL consistently occupies the primary Li^(+)solvation sheath,leading to extensive GBL decomposition and the formation of a high-impedance and inorganic-poor solid-electrolyte interphase(SEI)layer.Contrary to manipulating solvation structures,our research demonstrates that the utilization of filmforming additives with higher reduction potential facilitates the pre-establishment of a robust SEI film on the graphite anode.This approach effectively inhibits GBL decomposition and significantly enhances the battery's lifespan.This study provides the first reported intrinsic understanding of the unique GBLgraphite incompatibility and offers valuable insights for the development of wide-temperature and high-safety LIBs.
