Carbon superstructures with multiscale hierarchies and functional attributes represent an appealing cathode candidate for zinc hybrid capacitors,but their tailor-made design to optimize the capacitive activity remains...Carbon superstructures with multiscale hierarchies and functional attributes represent an appealing cathode candidate for zinc hybrid capacitors,but their tailor-made design to optimize the capacitive activity remains a confusing topic.Here we develop a hydrogen-bond-oriented interfacial super-assembly strategy to custom-tailor nanosheet-intertwined spherical carbon superstructures(SCSs)for Zn-ion storage with double-high capacitive activity and durability.Tetrachlorobenzoquinone(H-bond acceptor)and dimethylbenzidine(H-bond donator)can interact to form organic nanosheet modules,which are sequentially assembled,orientally compacted and densified into well-orchestrated superstructures through multiple H-bonds(N-H···O).Featured with rich surface-active heterodiatomic motifs,more exposed nanoporous channels,and successive charge migration paths,SCSs cathode promises high accessibility of built-in zincophilic sites and rapid ion diffusion with low energy barriers(3.3Ωs-0.5).Consequently,the assembled Zn||SCSs capacitor harvests all-round improvement in Zn-ion storage metrics,including high energy density(166 Wh kg-1),high-rate performance(172 m Ah g^(-1)at 20 A g^(-1)),and long-lasting cycling lifespan(95.5%capacity retention after 500,000 cycles).An opposite chargecarrier storage mechanism is rationalized for SCSs cathode to maximize spatial capacitive charge storage,involving high-kinetics physical Zn^(2+)/CF_(3)SO_(3)-adsorption and chemical Zn^(2+)redox with carbonyl/pyridine groups.This work gives insights into H-bond-guided interfacial superassembly design of superstructural carbons toward advanced energy storage.展开更多
Presently,financial portfolio managers lack a solid basis for building a reliable risk management strategy for green debt instrument investments due to the lack of compelling growth and resilience data.Therefore,this ...Presently,financial portfolio managers lack a solid basis for building a reliable risk management strategy for green debt instrument investments due to the lack of compelling growth and resilience data.Therefore,this study assesses the role of green bonds in financial markets by assessing and correlating their complex scaling behaviors across multiple periods with those of key benchmark assets(e.g.,conventional bonds,high-yield bonds,Euro-Dollar exchange,Dow Jones Industrial Index,Bitcoin,and Gold).Specifically,we explore linear and nonlinear correlation patterns using crosscorrelation tests and the dynamic conditional correlation model,focusing on bond interactions under various degrees of freedom.Our analysis reveals that although most assets exhibit nonlinear correlations,Bitcoin uniquely aligns linearly with U.S.bonds under certain conditions.Green bonds,however,display nonlinear correlations with Bitcoin and stand out for their distinct upward financial persistence.We find also that green bonds are primary drivers in the financial domain,highlighted by their pronounced interactions and the consistent cross-correlation with the Euro-Dollar exchange rate.Moreover,green bonds have the lowest multifractality,showing persistent upward trends and antipersistent downward trends,rendering them quite resilient during periods of high volatility.These results imply that green bonds may be advantageous to portfolio risk management strategies,especially during crises when diversification and hedging tactics are needed.展开更多
The non-additivity of the methyl groups in the single-electron lithium bond was investigated using ab initio calculations at the B3LYP/6-311＋＋G＊＊ and UMP2/6-311＋＋G＊＊ levels. The strength of the interaction in ...The non-additivity of the methyl groups in the single-electron lithium bond was investigated using ab initio calculations at the B3LYP/6-311＋＋G＊＊ and UMP2/6-311＋＋G＊＊ levels. The strength of the interaction in the H3C… LiH, H3CH2C… LiH, （H3C）2HC… LiH, and u v （H3C）3C… LiH complexes was analyzed in term of the geometries, energies, frequency shifts, stabilization energies, charges, and topological parameters. It is shown that （H3C）3C radical with LiH forms the strongest single-electron lithium bond, followed by （H3C）2HC radical, then H3CH2C radical, and H3C radical forms the weakest single-electron lithium bond. A positive non-additivity is present among methyl groups. Natural bond orbital and atoms in molecules analyses were used to estimate such conclusions. Furthermore, there are few linear/nonlinear relationships in the system and the interaction mode of single-electron Li- bond is different from the single-electron H-bond and single-electron halogen bond.展开更多
The excellent irradiation resistance,high strength and plasticity exhibited by high-entropy alloys(HEAs)make it candidate for engin-eering applications.Diffusion bonding of Al_(0.3)CoCrFeNi single-phase HEAs was carri...The excellent irradiation resistance,high strength and plasticity exhibited by high-entropy alloys(HEAs)make it candidate for engin-eering applications.Diffusion bonding of Al_(0.3)CoCrFeNi single-phase HEAs was carried out using electric-assisted diffusion bonding(EADB),and the effect of bonding temperature on the evolution of the interfacial microstructure and the mechanical properties was investigated.The results indicate that as the bonding temperature increases,the pores at the interface gradually decrease in size and undergo closure.The electric current significantly promotes the pore closure mechanism dominated by plastic deformation at the diffusion interface and promotes the recrystallisation behavior at the interface,and the fracture mode changes from intergranular fracture at the interface to jagged fracture along the grains spanning the weld parent material.Due to the activation effect of EADB,higher-strength diffusion bonding of high-entropy alloys can be achieved at the same temperature compared with the conventional hot-pressure diffusion bonding(HPDB)process.展开更多
Cebu Province,a key hub in the Philippine archipelago,is known for its strategic location,abundant natural resources,and rich cultural heritage.Far across the sea in southern China,Guangxi Zhuang Autonomous Region shi...Cebu Province,a key hub in the Philippine archipelago,is known for its strategic location,abundant natural resources,and rich cultural heritage.Far across the sea in southern China,Guangxi Zhuang Autonomous Region shines with picturesque landscapes,vibrant ethnic cultures,and dynamic growth.Separated by vast waters yet linked through the China-ASEAN Expo(CAEXPO)in Nanning,the two regions have forged a strong bond of friendship.展开更多
Surface chemistry plays a critical role in the fields of electrochemistry,heterogeneous catalysis,adsorption,etc.[1–4].The representative D-band center theory reported through Hammer and Nørskov in surface chemi...Surface chemistry plays a critical role in the fields of electrochemistry,heterogeneous catalysis,adsorption,etc.[1–4].The representative D-band center theory reported through Hammer and Nørskov in surface chemistry has been widely used in early studies to predict adsorption strength[5,6].Generally,the adsorption strength of active sites correlates inversely with the downward shift of the D-band center(εd)relative to the Fermi level,as lower-energy positioning increases anti-bonding orbital occupancy,weakening surface interactions(Fig.1(a)).展开更多
Surface tension-induced shrinkage of heterogeneously bonded interfaces is a key factor in limiting the performance of nanostructures.Herein,we demonstrate a laser-induced thermo-compression bonding technology to suppr...Surface tension-induced shrinkage of heterogeneously bonded interfaces is a key factor in limiting the performance of nanostructures.Herein,we demonstrate a laser-induced thermo-compression bonding technology to suppress surface tension-induced shrinkage of Cu-Au bonded interface.A focused laser beam is used to apply localized heating and scattering force to the exposed Cu nanowire.The laser-induced scattering force and the heating can be adjusted by regulating the exposure intensity.When the ratio of scattering forces to the gravity of the exposed nanowire reaches 3.6×10^(3),the molten Cu nanowire is compressed into flattened shape rather than shrinking into nanosphere by the surface tension.As a result,the Cu-Au bonding interface is broadened fourfold by the scattering force,leading to a reduction in contact resistance of approximately 56%.This noncontact thermo-compression bonding technology provides significant possibilities for the interconnect packaging and integration of nanodevices.展开更多
Organofluorines play a crucial role in medicine,agrochemicals,and materials science.Adding fluorine to molecules creates structures with specific beneficial properties or tunes properties through interactions with the...Organofluorines play a crucial role in medicine,agrochemicals,and materials science.Adding fluorine to molecules creates structures with specific beneficial properties or tunes properties through interactions with their environment.Many popular pharmaceuticals and agrochemicals contain fluorine because it enhances hydrogen bonding at protein’s active sites.展开更多
Due to its superior nanoscale properties,cobalt(Co)is highly desirable for ultrahigh-density 3D integration into materials through metal/dielectric hybrid bonding.However,this process is very challenging through Co/Si...Due to its superior nanoscale properties,cobalt(Co)is highly desirable for ultrahigh-density 3D integration into materials through metal/dielectric hybrid bonding.However,this process is very challenging through Co/SiO_(2)hybrid bonding,as very hydrophilic SiO_(2)surfaces are needed for bonding during dehydration reactions and oxidation of the Co surfaces must be avoided.Additionally,the substantial coefficient of thermal expansion mismatch between the robust capping layers(Co and SiO_(2)layers)necessitates hybrid bonding with minimal thermal input and compression.In this study,we introduce a ternary plasma activation strategy employing an Ar/NH_(3)/H_(2)O gas mixture to facilitate Co/SiO_(2)hybrid bonding at temperatures as low as~200℃,which is markedly lower than the melting point of Co(~1500℃).Intriguingly,non-oxide metallization at the Co-Co interface can be realized without the hindrance of a bonding barrier,thereby reducing the electrical resistance by over 40%and compression force requirements.Moreover,the enhancement in the SiO_(2)surface energy through active group terminations fosters extensive interfacial hydration and strengthens the mechanical properties.This research paves the way for fine-tuning bonding surfaces using a material-selective strategy which should advance metal/dielectric hybrid bonding for future integration applications.展开更多
As more and more studies have shown that lipid molecules play an important role in the whole biology,in-depth analysis of lipid structure has become particularly important in lipidomics.Mass spectrometry(MS),as the pr...As more and more studies have shown that lipid molecules play an important role in the whole biology,in-depth analysis of lipid structure has become particularly important in lipidomics.Mass spectrometry(MS),as the preferred tool for lipid analysis,has greatly promoted the development of this field.However,the existing MS methods still face many difficulties in the in-depth or even comprehensive analysis of lipid structure.In this review,we discuss recent advances in MS methods based on double bond-specific chemistries for the resolving of C=C location and geometry isomers of lipids.This progress has greatly advanced the lipidomics analysis to a deeper structural level and facilitated the development of structural lipid biology.展开更多
The most widely used bisphenol A-type epoxy resin(DGEBA)in electrical engineering demonstrates excellent mechanical and electrical properties.However,the insoluble and infusible characteristics of cured DGEBA make it ...The most widely used bisphenol A-type epoxy resin(DGEBA)in electrical engineering demonstrates excellent mechanical and electrical properties.However,the insoluble and infusible characteristics of cured DGEBA make it difficult to efficiently degrade and recycle decommissioned electrical equipment.In this study,a degradable itaconic acid-based epoxy resin incorporating dynamic covalent bonds was prepared through the integration of ester bonds and disulfide bonds,with itaconic acid as the precursor.The covalent bonding effects on the mechanical,thermal,electrical,and degradation characteristics were systematically evaluated.The experimental results revealed that the introduction of dynamic ester bonds enhanced the mechanical properties and thermal stability of the resin system,achieving a flexural strength of 141.57 MPa and an initial decomposition temperature T_(5%)of up to 344.9℃.The resin system containing dynamic disulfide bonds exhibited a dielectric breakdown strength of 41.11 k V/mm.Simultaneously,the incorporation of disulfide bonds endowed the epoxy resin with remarkable degradability,enabling complete dissolution within 1.5 h at 90℃ in a mixed solution of dithiothreitol(DTT)and N-methylpyrrolidone(NMP).This research provides a valuable reference for the application of itaconic acid-based vitrimer with dynamic covalent bonds in electrical materials,contributing to the development and utilization of environmentally friendly electrical equipment.展开更多
The activation of the N≡N triple bond in N_(2) is a fascinating topic in nitrogen chemistry.The transition metals have been demonstrated to effectively modulate the reactivity of N_(2) molecules under high pressure,l...The activation of the N≡N triple bond in N_(2) is a fascinating topic in nitrogen chemistry.The transition metals have been demonstrated to effectively modulate the reactivity of N_(2) molecules under high pressure,leading to nitrogen-rich compounds.However,their use often results in a significant reduction in energy density.In this work,we propose a series of low-enthalpy nitrogen-rich phases in CN_(x)(x=3,...,7)compounds using a first-principles crystal structure search method.The results of calculations reveal that all these CN compounds are assembled from both CN_(4) tetrahedra and N_(x)(x=1,2,or 5)species.Strikingly,we find that the CN_(4) tetrahedron can effectively activate the N≡N bond through weakening of the π orbital of N_(2) under a pressure of 40 GPa,leading to stable CN polynitrides.The robust structural framework of CN polynitrides containing C-N and N-N bonds plays a crucial role in enhancing their structural stability,energy density,and hardness.Among these polynitrides,CN_(6) possesses not only a very high mass density of 3.19 g/cm^(3),but also an ultrahigh energy density of 28.94 kJ/cm^(3),which represents a significant advance in the development of energetic materials using high-pressure methods.This work provides new insights into the mechanism of N_(2) activation under high pressure,and offers a promising pathway to realize high-performance energetic materials.展开更多
Interfacial evolution and bonding mechanism of reduced activation ferritic/martensitic(RAFM)steel were systematically investigated through a series of hot compression tests conducted at various strains(0.15-0.8),strai...Interfacial evolution and bonding mechanism of reduced activation ferritic/martensitic(RAFM)steel were systematically investigated through a series of hot compression tests conducted at various strains(0.15-0.8),strain rates(0.001-1 s^(-1)),and temperatures(950-1050℃).Interfacial microstructural analysis revealed that plastic deformation of surface asperities effectively removes interfacial voids,and the evolution of dynamic recrystallization(DRX)aids in achieving a joint characterized by homogeneously refined microstructure and adequate interfacial grain boundary(IGB)migration.Electron backscattered diffraction analysis demonstrated that the continuous dynamic recrystallization,characterized by progressive subgrain rotation,is the prevailing DRX nucleation mechanism in RAFM steel during hot compression bonding.During DRX evolution,emerging DRX grains in the interfacial region expand into adjacent areas,transforming T-type triple junction grain boundaries into equal form,and resulting in a serrated and intricate interface.Elevated temperatures and strains,coupled with reduced strain rates,augment DRX grain nucleation and IGB migration,thus enhancing RAFM joint quality with regard to the interface bonding ratio and the interface migration ratio.展开更多
Silicene,a silicon analog of graphene,holds promise for next-generation electronics due to its tunable bandgap and larger spin-orbit coupling.Despite extensive efforts to synthesize and characterize silicene on metal ...Silicene,a silicon analog of graphene,holds promise for next-generation electronics due to its tunable bandgap and larger spin-orbit coupling.Despite extensive efforts to synthesize and characterize silicene on metal substrates,bondresolved imaging of its atomic structure has remained elusive.Here,we report the fabrication and bond-resolved characterization of silicene on Au(111)substrate.Three silicene phases tuned by surface reconstruction and annealing temperatures are achieved.Using CO-terminated scanning tunneling microscopy(STM)tips,we resolve these silicene phases with atomic precision,determining their bond lengths,local strain,and geometric configurations.Furthermore,we correlate these structural features with their electronic properties,revealing the effect of strain and substrate interactions on the electronic properties of silicene.This work establishes silicene's intrinsic bonding topology and resolves longstanding controversies in silicene research.展开更多
Efficient conversion and synergistic solar energy utilization are critical for advancing low-carbon and sustainable development.In this study,two Pt(Ⅱ)-based metal/halogen-bonded organic frameworks(MXOFBen and MXOF-A...Efficient conversion and synergistic solar energy utilization are critical for advancing low-carbon and sustainable development.In this study,two Pt(Ⅱ)-based metal/halogen-bonded organic frameworks(MXOFBen and MXOF-Anth)were designed to enhance photoconversion efficiency and enable multifunctional integration.The ligand L-terpyr is formed by coupling tripyridine with diphenylamine dipyridine,in which the tripyridine effectively acts as a metal-ligand to lower the band gap and promote nonradiative leaps,thereby enhancing the photoconversion ability.Meanwhile,diphenylamine dipyridine serves as a[N…I^(+)…N]halogen-bonding acceptor,imparting superhydrophilicity to the materials and increasing carrier density,further improving photocatalytic performance.Experimental results demonstrate that these two MXOFs achieve impressive interfacial water evaporation efficiencies of up to87.8%and 94.0%,respectively.Additionally,the materials exhibit excellent performance in photothermal power generation and photocatalysis of H_(2)O_(2).Notably,the MXOFs also deliver strong overall performance in integrated systems combining interfacial water evaporation with photothermal power generation or photocatalysis,underscoring their exceptional photoconversion efficiency and multifunctional potential.This work introduces a novel strategy by incorporating metal-ligand and halogen bonds,offering a pathway to enhance photoconversion efficiency and develop versatile materials for advanced solar energy applications,thereby fostering the progress of high-efficiency solar energy conversion and multifunctional organic materials.展开更多
The intrinsic symmetrical electron distribution in crystalline metal sulfides usually causes an improper electronic configuration between catalytic S atoms and H intermediates(H_(ad))to form strong S-H_(ad) bonds,resu...The intrinsic symmetrical electron distribution in crystalline metal sulfides usually causes an improper electronic configuration between catalytic S atoms and H intermediates(H_(ad))to form strong S-H_(ad) bonds,resulting in a low photocatalytic H_(2) evolution activity.Herein,a cobalt-induced asymmetric electronic distribution is justified as an effective strategy to optimize the electronic configuration of catalytic S sites in NiCoS cocatalysts for highly active photocatalytic H_(2) evolution.To this end,Co atoms are uniformly incorporated in NiS nanoparticles to fabricate homogeneous NiCoS cocatalyst on TiO_(2) surface by a facile photosynthesis strategy.It is revealed that the incorporated Co atoms break the electron distribution symmetry in NiS,thus essentially increasing the electron density of S atoms to form active electron-enriched S^(2+δ)–sites.The electron-enriched S^(2+δ)–sites could interact with Had via an increased antibonding orbital occupancy,which weakens S–Had bonds for efficient H_(ad) adsorption and desorption,endowing the NiCoS cocatalysts with a highly active H_(2) evolution process.Consequently,the optimized NiCoS/TiO_(2)(1:2)photocatalyst displays the highest H_(2) production performance,outperforming the NiS/TiO_(2) and CoS/TiO_(2) samples by factors of 2.1 and 2.5,respectively.This work provides novel insights on breaking electron distribution symmetry to optimize catalytic efficiency of active sites.展开更多
Acidic-stable oxygen evolution reaction(OER)catalysts based on earth-abundant materials are important but rare for the proton exchange membrane-based water electrolysis.In this study,a metal-containing hydrogen-bonded...Acidic-stable oxygen evolution reaction(OER)catalysts based on earth-abundant materials are important but rare for the proton exchange membrane-based water electrolysis.In this study,a metal-containing hydrogen-bonded organic framework(HOF)of manganese coordinated with 2,2'-bipyridine-6,6'-dicarboxylate ligands,Mn(bda),interconnected through hydrogen bonding and π-π stacking is used as a heterogeneous OER catalyst(Mn(bda)-HOF)for acidic water oxidation and exhibits a considerable OER performance.Electrochemical results show that Mn(bda)-HOF displays a turn of frequency of 1 s^(-1) at an overpotential of 870 mV.Meanwhile,this Mn(bda)-HOF shows an unusual pH dependence on performance,where the reaction rate increases with the decrease of pH.A comprehensive mechanistic study reveals that the charge transfer triggered coupling of two metal-oxo species Mn^(5+)(O)is the rate-determining step,which leads to this unusual pH dependence on the OER performance.展开更多
The regioselective carbon-hydrogen bond functionalization reaction in atom-and step-economy holds significant potential for the late-stage elaboration of complex molecules and natural products.In recent years,the hydr...The regioselective carbon-hydrogen bond functionalization reaction in atom-and step-economy holds significant potential for the late-stage elaboration of complex molecules and natural products.In recent years,the hydrogen atom transfer strategy involving radicals has garnered considerable attention from chemists due to its high chemoselectivity and regioselectivity.However,owing to the marginal differences in bond dissociation energies(BDEs)among C(sp^(3))—H bonds,hydrogen atom transfer reactions mediated by alkyl radicals remain less-developed.A copper-catalyzed sulfone-induced regioselective C(sp^(3))—H bond heteroarylation reaction was reported.This strategy utilizes theα-alkyl radical of sulfone as an intramolecular hydrogen abstraction reagent,enabling the regioselective formation of carbon-nitrogen bonds under copper catalysis.展开更多
The persistent stability of ruthenium dioxide(RuO_(2))in acidic oxygen evolution reactions(OER)is compromised by the involvement of lattice oxygen(LO)and metal dissolution during the OER process.Heteroatom doping has ...The persistent stability of ruthenium dioxide(RuO_(2))in acidic oxygen evolution reactions(OER)is compromised by the involvement of lattice oxygen(LO)and metal dissolution during the OER process.Heteroatom doping has been recognized as a viable strategy to foster the stability of RuO_(2)for acidic OER applications.This study presented an ion that does not readily gain or lose electrons,Ba^(2+),into RuO_(2)(Ba-RuO_(2))nanosheet(NS)catalyst that increased the number of exposed active sites,achieving a current density of 10 mA/cm^(2)with an overpotential of only 229 mV and sustaining this output for over 250 h.According to density functional theory(DFT)and X-ray absorption spectroscopy,Ba doping resulted in a longer Ru-O bond length,which in turn diminished the covalency of the bond.This alteration curtailed the involvement of LO and the dissolution of ruthenium(Ru),thereby markedly improving the durability of the catalyst over extended periods.Additionally,attenuated total reflectance-surface enhanced infrared absorption spectroscopy analysis substantiated that the OER mechanism shifted from a LO-mediated pathway to an adsorbate evolution pathway due to Ba doping,thereby circumventing Ru over-oxidation and further enhancing the stability of RuO_(2).Furthermore,DFT findings uncovered that Ba doping optimizes the adsorption energy of intermediates,thus enhancing the OER activity in acidic environments.This study offers a potent strategy to guide future developments on Ru-based oxide catalysts'stability in an acidic environment.展开更多
基金financially supported by the National Natural Science Foundation of China(Nos.22272118,22172111,and 22309134)the Science and Technology Commission of Shanghai Municipality,China(Nos.22ZR1464100,20ZR1460300,and 19DZ2271500)+2 种基金the China Postdoctoral Science Foundation(2022M712402),the Shanghai Rising-Star Program(23YF1449200)the Zhejiang Provincial Science and Technology Project(2022C01182)the Fundamental Research Funds for the Central Universities(2023-3-YB-07)。
文摘Carbon superstructures with multiscale hierarchies and functional attributes represent an appealing cathode candidate for zinc hybrid capacitors,but their tailor-made design to optimize the capacitive activity remains a confusing topic.Here we develop a hydrogen-bond-oriented interfacial super-assembly strategy to custom-tailor nanosheet-intertwined spherical carbon superstructures(SCSs)for Zn-ion storage with double-high capacitive activity and durability.Tetrachlorobenzoquinone(H-bond acceptor)and dimethylbenzidine(H-bond donator)can interact to form organic nanosheet modules,which are sequentially assembled,orientally compacted and densified into well-orchestrated superstructures through multiple H-bonds(N-H···O).Featured with rich surface-active heterodiatomic motifs,more exposed nanoporous channels,and successive charge migration paths,SCSs cathode promises high accessibility of built-in zincophilic sites and rapid ion diffusion with low energy barriers(3.3Ωs-0.5).Consequently,the assembled Zn||SCSs capacitor harvests all-round improvement in Zn-ion storage metrics,including high energy density(166 Wh kg-1),high-rate performance(172 m Ah g^(-1)at 20 A g^(-1)),and long-lasting cycling lifespan(95.5%capacity retention after 500,000 cycles).An opposite chargecarrier storage mechanism is rationalized for SCSs cathode to maximize spatial capacitive charge storage,involving high-kinetics physical Zn^(2+)/CF_(3)SO_(3)-adsorption and chemical Zn^(2+)redox with carbonyl/pyridine groups.This work gives insights into H-bond-guided interfacial superassembly design of superstructural carbons toward advanced energy storage.
基金Benjamin M.Tabak(Grant no.305485/2022-9)gratefully acknowledges financial support from the CNPq foundation and CAPES Foundation。
文摘Presently,financial portfolio managers lack a solid basis for building a reliable risk management strategy for green debt instrument investments due to the lack of compelling growth and resilience data.Therefore,this study assesses the role of green bonds in financial markets by assessing and correlating their complex scaling behaviors across multiple periods with those of key benchmark assets(e.g.,conventional bonds,high-yield bonds,Euro-Dollar exchange,Dow Jones Industrial Index,Bitcoin,and Gold).Specifically,we explore linear and nonlinear correlation patterns using crosscorrelation tests and the dynamic conditional correlation model,focusing on bond interactions under various degrees of freedom.Our analysis reveals that although most assets exhibit nonlinear correlations,Bitcoin uniquely aligns linearly with U.S.bonds under certain conditions.Green bonds,however,display nonlinear correlations with Bitcoin and stand out for their distinct upward financial persistence.We find also that green bonds are primary drivers in the financial domain,highlighted by their pronounced interactions and the consistent cross-correlation with the Euro-Dollar exchange rate.Moreover,green bonds have the lowest multifractality,showing persistent upward trends and antipersistent downward trends,rendering them quite resilient during periods of high volatility.These results imply that green bonds may be advantageous to portfolio risk management strategies,especially during crises when diversification and hedging tactics are needed.
文摘The non-additivity of the methyl groups in the single-electron lithium bond was investigated using ab initio calculations at the B3LYP/6-311＋＋G＊＊ and UMP2/6-311＋＋G＊＊ levels. The strength of the interaction in the H3C… LiH, H3CH2C… LiH, （H3C）2HC… LiH, and u v （H3C）3C… LiH complexes was analyzed in term of the geometries, energies, frequency shifts, stabilization energies, charges, and topological parameters. It is shown that （H3C）3C radical with LiH forms the strongest single-electron lithium bond, followed by （H3C）2HC radical, then H3CH2C radical, and H3C radical forms the weakest single-electron lithium bond. A positive non-additivity is present among methyl groups. Natural bond orbital and atoms in molecules analyses were used to estimate such conclusions. Furthermore, there are few linear/nonlinear relationships in the system and the interaction mode of single-electron Li- bond is different from the single-electron H-bond and single-electron halogen bond.
基金support from National Natural Science Foundation of China(NSFC,Grant numbers U22A20185,U21A20128,52175302 and 52305353)Aeronautical Science Foundation(ASFC-20230036077001)Fundamental Research Funds for the Central Universities(2022FRFK060009,HIT.DZI1.2023012).
文摘The excellent irradiation resistance,high strength and plasticity exhibited by high-entropy alloys(HEAs)make it candidate for engin-eering applications.Diffusion bonding of Al_(0.3)CoCrFeNi single-phase HEAs was carried out using electric-assisted diffusion bonding(EADB),and the effect of bonding temperature on the evolution of the interfacial microstructure and the mechanical properties was investigated.The results indicate that as the bonding temperature increases,the pores at the interface gradually decrease in size and undergo closure.The electric current significantly promotes the pore closure mechanism dominated by plastic deformation at the diffusion interface and promotes the recrystallisation behavior at the interface,and the fracture mode changes from intergranular fracture at the interface to jagged fracture along the grains spanning the weld parent material.Due to the activation effect of EADB,higher-strength diffusion bonding of high-entropy alloys can be achieved at the same temperature compared with the conventional hot-pressure diffusion bonding(HPDB)process.
文摘Cebu Province,a key hub in the Philippine archipelago,is known for its strategic location,abundant natural resources,and rich cultural heritage.Far across the sea in southern China,Guangxi Zhuang Autonomous Region shines with picturesque landscapes,vibrant ethnic cultures,and dynamic growth.Separated by vast waters yet linked through the China-ASEAN Expo(CAEXPO)in Nanning,the two regions have forged a strong bond of friendship.
文摘Surface chemistry plays a critical role in the fields of electrochemistry,heterogeneous catalysis,adsorption,etc.[1–4].The representative D-band center theory reported through Hammer and Nørskov in surface chemistry has been widely used in early studies to predict adsorption strength[5,6].Generally,the adsorption strength of active sites correlates inversely with the downward shift of the D-band center(εd)relative to the Fermi level,as lower-energy positioning increases anti-bonding orbital occupancy,weakening surface interactions(Fig.1(a)).
基金supported by the National Natural Science Foundation of China(Nos.52305612 and U20A6004)Open Fund of Hubei Key Laboratory of Electronic Manufacturing and Packaging Integration(Wuhan University)(NO.EMPI2023015).
文摘Surface tension-induced shrinkage of heterogeneously bonded interfaces is a key factor in limiting the performance of nanostructures.Herein,we demonstrate a laser-induced thermo-compression bonding technology to suppress surface tension-induced shrinkage of Cu-Au bonded interface.A focused laser beam is used to apply localized heating and scattering force to the exposed Cu nanowire.The laser-induced scattering force and the heating can be adjusted by regulating the exposure intensity.When the ratio of scattering forces to the gravity of the exposed nanowire reaches 3.6×10^(3),the molten Cu nanowire is compressed into flattened shape rather than shrinking into nanosphere by the surface tension.As a result,the Cu-Au bonding interface is broadened fourfold by the scattering force,leading to a reduction in contact resistance of approximately 56%.This noncontact thermo-compression bonding technology provides significant possibilities for the interconnect packaging and integration of nanodevices.
文摘Organofluorines play a crucial role in medicine,agrochemicals,and materials science.Adding fluorine to molecules creates structures with specific beneficial properties or tunes properties through interactions with their environment.Many popular pharmaceuticals and agrochemicals contain fluorine because it enhances hydrogen bonding at protein’s active sites.
基金supported by the National Natural Science Foundation of China(Grant Nos.92164105 and 51975151)the Heilongjiang Provincial Natural Science Foundation of China under grant LH2019E041+1 种基金the Heilongjiang Touyan Innovation Team Program(HITTY-20190013)State Key Laboratory of Precision Welding&Joining of Materials and Structures(No.24-T-04)。
文摘Due to its superior nanoscale properties,cobalt(Co)is highly desirable for ultrahigh-density 3D integration into materials through metal/dielectric hybrid bonding.However,this process is very challenging through Co/SiO_(2)hybrid bonding,as very hydrophilic SiO_(2)surfaces are needed for bonding during dehydration reactions and oxidation of the Co surfaces must be avoided.Additionally,the substantial coefficient of thermal expansion mismatch between the robust capping layers(Co and SiO_(2)layers)necessitates hybrid bonding with minimal thermal input and compression.In this study,we introduce a ternary plasma activation strategy employing an Ar/NH_(3)/H_(2)O gas mixture to facilitate Co/SiO_(2)hybrid bonding at temperatures as low as~200℃,which is markedly lower than the melting point of Co(~1500℃).Intriguingly,non-oxide metallization at the Co-Co interface can be realized without the hindrance of a bonding barrier,thereby reducing the electrical resistance by over 40%and compression force requirements.Moreover,the enhancement in the SiO_(2)surface energy through active group terminations fosters extensive interfacial hydration and strengthens the mechanical properties.This research paves the way for fine-tuning bonding surfaces using a material-selective strategy which should advance metal/dielectric hybrid bonding for future integration applications.
基金financially supported by the National Natural Science Foundation of China(No.22074111)National Key Research and Development Program of China(No.2021YFC2700700)the Opening fund of Hubei Key Laboratory of Bioinorganic Chemistry&Materia Medica(No.BCMM202303)。
文摘As more and more studies have shown that lipid molecules play an important role in the whole biology,in-depth analysis of lipid structure has become particularly important in lipidomics.Mass spectrometry(MS),as the preferred tool for lipid analysis,has greatly promoted the development of this field.However,the existing MS methods still face many difficulties in the in-depth or even comprehensive analysis of lipid structure.In this review,we discuss recent advances in MS methods based on double bond-specific chemistries for the resolving of C=C location and geometry isomers of lipids.This progress has greatly advanced the lipidomics analysis to a deeper structural level and facilitated the development of structural lipid biology.
基金financially supported by the National Natural Science Foundation of China(No.52377025)。
文摘The most widely used bisphenol A-type epoxy resin(DGEBA)in electrical engineering demonstrates excellent mechanical and electrical properties.However,the insoluble and infusible characteristics of cured DGEBA make it difficult to efficiently degrade and recycle decommissioned electrical equipment.In this study,a degradable itaconic acid-based epoxy resin incorporating dynamic covalent bonds was prepared through the integration of ester bonds and disulfide bonds,with itaconic acid as the precursor.The covalent bonding effects on the mechanical,thermal,electrical,and degradation characteristics were systematically evaluated.The experimental results revealed that the introduction of dynamic ester bonds enhanced the mechanical properties and thermal stability of the resin system,achieving a flexural strength of 141.57 MPa and an initial decomposition temperature T_(5%)of up to 344.9℃.The resin system containing dynamic disulfide bonds exhibited a dielectric breakdown strength of 41.11 k V/mm.Simultaneously,the incorporation of disulfide bonds endowed the epoxy resin with remarkable degradability,enabling complete dissolution within 1.5 h at 90℃ in a mixed solution of dithiothreitol(DTT)and N-methylpyrrolidone(NMP).This research provides a valuable reference for the application of itaconic acid-based vitrimer with dynamic covalent bonds in electrical materials,contributing to the development and utilization of environmentally friendly electrical equipment.
基金supported by the Higher Educational Youth Innovation Science and Technology Program Shandong Province(Grant Nos.2022KJ183 and 2022KJ175)the Natural Science Foundation of Shandong Province(Grant Nos.ZR2023MA016 and ZR2023JQ001)+1 种基金the National Natural Science Foundation of China(Grant Nos.11974208 and 12374012)financial support from the award of Taishan Scholar(Grant No.tsqn202211128).
文摘The activation of the N≡N triple bond in N_(2) is a fascinating topic in nitrogen chemistry.The transition metals have been demonstrated to effectively modulate the reactivity of N_(2) molecules under high pressure,leading to nitrogen-rich compounds.However,their use often results in a significant reduction in energy density.In this work,we propose a series of low-enthalpy nitrogen-rich phases in CN_(x)(x=3,...,7)compounds using a first-principles crystal structure search method.The results of calculations reveal that all these CN compounds are assembled from both CN_(4) tetrahedra and N_(x)(x=1,2,or 5)species.Strikingly,we find that the CN_(4) tetrahedron can effectively activate the N≡N bond through weakening of the π orbital of N_(2) under a pressure of 40 GPa,leading to stable CN polynitrides.The robust structural framework of CN polynitrides containing C-N and N-N bonds plays a crucial role in enhancing their structural stability,energy density,and hardness.Among these polynitrides,CN_(6) possesses not only a very high mass density of 3.19 g/cm^(3),but also an ultrahigh energy density of 28.94 kJ/cm^(3),which represents a significant advance in the development of energetic materials using high-pressure methods.This work provides new insights into the mechanism of N_(2) activation under high pressure,and offers a promising pathway to realize high-performance energetic materials.
基金The authors are grateful to the National Natural Science Foundation of China(Grant Nos.52034004 and 52271111)the National Key R&D Program of China(2022YFB3705300)for grant and financial support.
文摘Interfacial evolution and bonding mechanism of reduced activation ferritic/martensitic(RAFM)steel were systematically investigated through a series of hot compression tests conducted at various strains(0.15-0.8),strain rates(0.001-1 s^(-1)),and temperatures(950-1050℃).Interfacial microstructural analysis revealed that plastic deformation of surface asperities effectively removes interfacial voids,and the evolution of dynamic recrystallization(DRX)aids in achieving a joint characterized by homogeneously refined microstructure and adequate interfacial grain boundary(IGB)migration.Electron backscattered diffraction analysis demonstrated that the continuous dynamic recrystallization,characterized by progressive subgrain rotation,is the prevailing DRX nucleation mechanism in RAFM steel during hot compression bonding.During DRX evolution,emerging DRX grains in the interfacial region expand into adjacent areas,transforming T-type triple junction grain boundaries into equal form,and resulting in a serrated and intricate interface.Elevated temperatures and strains,coupled with reduced strain rates,augment DRX grain nucleation and IGB migration,thus enhancing RAFM joint quality with regard to the interface bonding ratio and the interface migration ratio.
基金Project supported by the National Natural Science Foundation of China(Grant No.12474181)the Guangdong Basic and Applied Basic Research Foundation(Grant Nos.2021B0301030002 and 2024A1515010656)the Guangdong Science and Technology Project(Grant No.2021QN02X859)。
文摘Silicene,a silicon analog of graphene,holds promise for next-generation electronics due to its tunable bandgap and larger spin-orbit coupling.Despite extensive efforts to synthesize and characterize silicene on metal substrates,bondresolved imaging of its atomic structure has remained elusive.Here,we report the fabrication and bond-resolved characterization of silicene on Au(111)substrate.Three silicene phases tuned by surface reconstruction and annealing temperatures are achieved.Using CO-terminated scanning tunneling microscopy(STM)tips,we resolve these silicene phases with atomic precision,determining their bond lengths,local strain,and geometric configurations.Furthermore,we correlate these structural features with their electronic properties,revealing the effect of strain and substrate interactions on the electronic properties of silicene.This work establishes silicene's intrinsic bonding topology and resolves longstanding controversies in silicene research.
基金supported by the National Natural Science Foundation of China(Nos.22371218,21702153,52270070,and 21801194)the Wuhan Science and Technology Bureau(No.whkxjsj009)+1 种基金support of the Core Facility of Wuhan Universitythe Large-scale Instrument and Equipment Sharing Foundation of Wuhan University。
文摘Efficient conversion and synergistic solar energy utilization are critical for advancing low-carbon and sustainable development.In this study,two Pt(Ⅱ)-based metal/halogen-bonded organic frameworks(MXOFBen and MXOF-Anth)were designed to enhance photoconversion efficiency and enable multifunctional integration.The ligand L-terpyr is formed by coupling tripyridine with diphenylamine dipyridine,in which the tripyridine effectively acts as a metal-ligand to lower the band gap and promote nonradiative leaps,thereby enhancing the photoconversion ability.Meanwhile,diphenylamine dipyridine serves as a[N…I^(+)…N]halogen-bonding acceptor,imparting superhydrophilicity to the materials and increasing carrier density,further improving photocatalytic performance.Experimental results demonstrate that these two MXOFs achieve impressive interfacial water evaporation efficiencies of up to87.8%and 94.0%,respectively.Additionally,the materials exhibit excellent performance in photothermal power generation and photocatalysis of H_(2)O_(2).Notably,the MXOFs also deliver strong overall performance in integrated systems combining interfacial water evaporation with photothermal power generation or photocatalysis,underscoring their exceptional photoconversion efficiency and multifunctional potential.This work introduces a novel strategy by incorporating metal-ligand and halogen bonds,offering a pathway to enhance photoconversion efficiency and develop versatile materials for advanced solar energy applications,thereby fostering the progress of high-efficiency solar energy conversion and multifunctional organic materials.
文摘The intrinsic symmetrical electron distribution in crystalline metal sulfides usually causes an improper electronic configuration between catalytic S atoms and H intermediates(H_(ad))to form strong S-H_(ad) bonds,resulting in a low photocatalytic H_(2) evolution activity.Herein,a cobalt-induced asymmetric electronic distribution is justified as an effective strategy to optimize the electronic configuration of catalytic S sites in NiCoS cocatalysts for highly active photocatalytic H_(2) evolution.To this end,Co atoms are uniformly incorporated in NiS nanoparticles to fabricate homogeneous NiCoS cocatalyst on TiO_(2) surface by a facile photosynthesis strategy.It is revealed that the incorporated Co atoms break the electron distribution symmetry in NiS,thus essentially increasing the electron density of S atoms to form active electron-enriched S^(2+δ)–sites.The electron-enriched S^(2+δ)–sites could interact with Had via an increased antibonding orbital occupancy,which weakens S–Had bonds for efficient H_(ad) adsorption and desorption,endowing the NiCoS cocatalysts with a highly active H_(2) evolution process.Consequently,the optimized NiCoS/TiO_(2)(1:2)photocatalyst displays the highest H_(2) production performance,outperforming the NiS/TiO_(2) and CoS/TiO_(2) samples by factors of 2.1 and 2.5,respectively.This work provides novel insights on breaking electron distribution symmetry to optimize catalytic efficiency of active sites.
基金supported by the National Natural Science Foundation of China(Nos.22172011,22088102,and 22301248)the National Key R&D Program of China(2022YFA0911900)the Fundamental Research Funds for the Central Universities(DUT23LAB611).
文摘Acidic-stable oxygen evolution reaction(OER)catalysts based on earth-abundant materials are important but rare for the proton exchange membrane-based water electrolysis.In this study,a metal-containing hydrogen-bonded organic framework(HOF)of manganese coordinated with 2,2'-bipyridine-6,6'-dicarboxylate ligands,Mn(bda),interconnected through hydrogen bonding and π-π stacking is used as a heterogeneous OER catalyst(Mn(bda)-HOF)for acidic water oxidation and exhibits a considerable OER performance.Electrochemical results show that Mn(bda)-HOF displays a turn of frequency of 1 s^(-1) at an overpotential of 870 mV.Meanwhile,this Mn(bda)-HOF shows an unusual pH dependence on performance,where the reaction rate increases with the decrease of pH.A comprehensive mechanistic study reveals that the charge transfer triggered coupling of two metal-oxo species Mn^(5+)(O)is the rate-determining step,which leads to this unusual pH dependence on the OER performance.
文摘The regioselective carbon-hydrogen bond functionalization reaction in atom-and step-economy holds significant potential for the late-stage elaboration of complex molecules and natural products.In recent years,the hydrogen atom transfer strategy involving radicals has garnered considerable attention from chemists due to its high chemoselectivity and regioselectivity.However,owing to the marginal differences in bond dissociation energies(BDEs)among C(sp^(3))—H bonds,hydrogen atom transfer reactions mediated by alkyl radicals remain less-developed.A copper-catalyzed sulfone-induced regioselective C(sp^(3))—H bond heteroarylation reaction was reported.This strategy utilizes theα-alkyl radical of sulfone as an intramolecular hydrogen abstraction reagent,enabling the regioselective formation of carbon-nitrogen bonds under copper catalysis.
基金supported by Young Project of Education Department in Guizhou Province(No.2022099)the Natural Science Special of Guizhou University(No.X202220 Special Post A)the National Natural Science Foundation of China(Grant No.22208071)。
文摘The persistent stability of ruthenium dioxide(RuO_(2))in acidic oxygen evolution reactions(OER)is compromised by the involvement of lattice oxygen(LO)and metal dissolution during the OER process.Heteroatom doping has been recognized as a viable strategy to foster the stability of RuO_(2)for acidic OER applications.This study presented an ion that does not readily gain or lose electrons,Ba^(2+),into RuO_(2)(Ba-RuO_(2))nanosheet(NS)catalyst that increased the number of exposed active sites,achieving a current density of 10 mA/cm^(2)with an overpotential of only 229 mV and sustaining this output for over 250 h.According to density functional theory(DFT)and X-ray absorption spectroscopy,Ba doping resulted in a longer Ru-O bond length,which in turn diminished the covalency of the bond.This alteration curtailed the involvement of LO and the dissolution of ruthenium(Ru),thereby markedly improving the durability of the catalyst over extended periods.Additionally,attenuated total reflectance-surface enhanced infrared absorption spectroscopy analysis substantiated that the OER mechanism shifted from a LO-mediated pathway to an adsorbate evolution pathway due to Ba doping,thereby circumventing Ru over-oxidation and further enhancing the stability of RuO_(2).Furthermore,DFT findings uncovered that Ba doping optimizes the adsorption energy of intermediates,thus enhancing the OER activity in acidic environments.This study offers a potent strategy to guide future developments on Ru-based oxide catalysts'stability in an acidic environment.
