D-π hybridization is a key structural feature that may significantly affect the intrinsic electronic properties of metallopolymers.Herein,we present the electrosynthesis and memristive properties of metallopolymers u...D-π hybridization is a key structural feature that may significantly affect the intrinsic electronic properties of metallopolymers.Herein,we present the electrosynthesis and memristive properties of metallopolymers using the distinct d-π hybridization monomers R_(1) and R_(2).R_(1)(Ru^(Ⅱ)-(tpz)Cl_(2))features tetradentate ligands(tpz,6,6'-di(1H-pyrazol-1-yl)-2,2'-bipyridine)enforcing quasi-octahedral geometry;R_(2)(Ru^(Ⅱ)-(bpp)_(2))incorporates tridentate ligands(bpp,2,6-di(1H-pyrazol-1-yl)pyridine)inducing pronounced geometric distortion.The planar ligand(tpz)in R_(1) facilitates ordered molecular assembly through high conformational rigidity and extensive π-π stacking,resulting in increased molecular densities and enhanced morphological uniformity compared to R_(2) metallopolymers.Due to pyrazole’s weaker π-acceptance and strongerσ-donation compared to pyridine,R_(1) exhibits a 119 nm red-shift in metal-to-ligand charge transfer(MLCT)band and a 30 mV anodic shift in Ru^(+2/+3)redox potential relative to R_(2).Coupled with a reduced HOMO-LUMO gap,the uniform and ordered structure leads to a lower conductance decay constant in R_(1).Additionally,R_(2) metallopolymers exhibit superior memristive performance(characterized by lower switching voltage and higher switching ratio)via redox-induced aromatic transitions in axial ligands enhancing electronic delocalization.This work compares two metallopolymers with different ligand geometries,revealing how this difference leads to distinct charge transport and memristive behaviors.展开更多
The design and fabrication of ordered epitaxial MOF-on-MOF heterostructures as highly efficient electrocatalysts for water splitting is crucial but still challenging.In this study,a simple coordination-driven self-ass...The design and fabrication of ordered epitaxial MOF-on-MOF heterostructures as highly efficient electrocatalysts for water splitting is crucial but still challenging.In this study,a simple coordination-driven self-assembly method is used to fabricate controllable MOF-on-MOF multiscale heterostructures,where triangular host MOF(ZIF-67)nanosheets undergo in situ epitaxial growth to form uniform orthogonal vip MOF(CoFe PBA)nanosheets.Phosphorus(P)is further introduced in situ to fabricate CoP and Fe_(2)P heterostructured nanosheets(CoFe-P-NS),which exhibit excellent bifunctional electrocatalytic performance due to the enhancement of intrinsic electrocatalytic activity by p-d orbital hybridization.Specifically,the CoFe-P-NS requires low overpotential of 259 and 307 mV to reach 500 mA cm−2 for HER and OER,respectively.Remarkably,the assembled electrolysis cell maintained a large current density of 300 mA cm−2 for over 360 h with negligible voltage increase during alkaline seawater electrolysis.Experiments and theoretical calculations show that the synergistic catalytic activity of bimetallic phosphides arises from p-d orbital hybridization,where the CoP-P sites enhance HER by optimizing H*adsorption in the Volmer-Heyrovsky steps,while the Fe_(2)P-Fe sites accelerate OER by lowering the energy barrier of the rate-determining step from O*to OOH*.This study provides valuable insights into the design of a controllable MOF-on-MOF-based electrocatalyst toward alkaline seawater splitting.展开更多
Hard carbon is a vital anode material for sodium-ion batteries;however,the nonuniform growth of solid electrolyte interphase(SEI)film substantially diminishes its initial coulombic efficiency(ICE)and cycle life.The ch...Hard carbon is a vital anode material for sodium-ion batteries;however,the nonuniform growth of solid electrolyte interphase(SEI)film substantially diminishes its initial coulombic efficiency(ICE)and cycle life.The chemical and morphological properties of surface highly influence the electrode/electrolyte interfacial reactions.In this study,we have tuned orbital hybridization states forming an interface enriched with sp^(2) hybridized carbon(sp^(2)-C),which decreases the binding energy to solvent molecules and inhibits excessive solvent decomposition during SEI formation.Benefiting from successfully constructed inorganic-rich SEI,the ICE increased to 91%and sodium storage capacity reached 346 mAh/g.Besides,the capacity retention rate was 90.7%after 700 cycles at 1 A/g higher than pristine electrode(83.8%).展开更多
The hybridization gap in strained-layer InAs/In_(x)Ga_(1−x) Sb quantum spin Hall insulators(QSHIs)is significantly enhanced compared to binary InAs/GaSb QSHI structures,where the typical indium composition,x,ranges be...The hybridization gap in strained-layer InAs/In_(x)Ga_(1−x) Sb quantum spin Hall insulators(QSHIs)is significantly enhanced compared to binary InAs/GaSb QSHI structures,where the typical indium composition,x,ranges between 0.2 and 0.4.This enhancement prompts a critical question:to what extent can quantum wells(QWs)be strained while still preserving the fundamental QSHI phase?In this study,we demonstrate the controlled molecular beam epitaxial growth of highly strained-layer QWs with an indium composition of x=0.5.These structures possess a substantial compressive strain within the In_(0.5)Ga_(0.5)Sb QW.Detailed crystal structure analyses confirm the exceptional quality of the resulting epitaxial films,indicating coherent lattice structures and the absence of visible dislocations.Transport measurements further reveal that the QSHI phase in InAs/In_(0.5)Ga_(0.5)Sb QWs is robust and protected by time-reversal symmetry.Notably,the edge states in these systems exhibit giant magnetoresistance when subjected to a modest perpendicular magnetic field.This behavior is in agreement with the𝑍2 topological property predicted by the Bernevig–Hughes–Zhang model,confirming the preservation of topologically protected edge transport in the presence of enhanced bulk strain.展开更多
Developing high-performance Ni cathodes and understanding the relationship between electron states of Ni 3d orbital and energy storage mechanism from an atomic-orbital perspective are crucial yet challenging for alkal...Developing high-performance Ni cathodes and understanding the relationship between electron states of Ni 3d orbital and energy storage mechanism from an atomic-orbital perspective are crucial yet challenging for alkaline nickel-zinc batteries.Herein,we innovatively design P-NiMoO_(4)/NiSe_(2)heterostructures with rich oxygen vacancy via a selective component segregation.The P substitution in NiMoO_(4)activate Ni atoms,leading to the spin-state transition of Ni-3d orbitals from high-spin to low-spin,which promote the uniform and rapid nucleation of NiSe_(2)on the surface of NiMoO_(4)during subsequent selenization process.After selenization,the in situ formed P-NiMoO_(4)/NiSe_(2)heterostructures exhibits continuous increased unoccupied states of Ni 3d-orbitals and higher Ni valence state.The synergistic effect of P doping and selenization modulate the d-band center(ɛd)level of Ni 3d,thereby promoting d-p orbital hybridization between Ni 3d and O 2p of OH−as well as OH−adsorption ability.Consequently,the P-NiMoO_(4)/NiSe_(2)exhibits a top-level specific capacity of 390.7 mA h g^(−1)at 1 A g^(−1),2.8-fold higher than that of pristine NiMoO_(4),accompanied by remarkable rate capability and structural stability.Moreover,the assembled pouch-type battery and flexible devices demonstrate the practical application potential.This work provides fundamental insights into orbital-level engineering of battery materials for enhanced redox kinetics and cycling stability.展开更多
In multi-orbital systems,the correlation strength is typically attributed to Coulomb interactions and Hund's couplings.However,this study demonstrates that on-site inter-orbital hybridization can also significant ...In multi-orbital systems,the correlation strength is typically attributed to Coulomb interactions and Hund's couplings.However,this study demonstrates that on-site inter-orbital hybridization can also significant influence the correlation strength of the system.We investigate the impact of on-site inter-orbital hybridization on the correlation strength of a two-orbital Hubbard model on a square lattice using the dynamical mean-field theory combined with Lanczos exact diagonalization.Our findings reveal a distinct Janus effect:on-site inter-orbital hybridization enhances correlation strength in the non-half-filled regime while suppresses it at half-filling.This dual role of on-site inter-orbital hybridization provides a fundamental mechanism for tuning the strength of correlations in multi-orbital systems.展开更多
With the continuous advancement of bionanomaterial technology,the design and fabrication strategies of biomimetic nanocarriers have undergone significant strategic transformations and innovations.This article systemat...With the continuous advancement of bionanomaterial technology,the design and fabrication strategies of biomimetic nanocarriers have undergone significant strategic transformations and innovations.This article systematically reviews the evolution from single-cell membrane nanovesicles to hybrid cell membrane nanovesicles integrating multiple cell membranes,culminating in cell membrane hybrid lipid nanoparticles(CM-LNPs)combining natural cell membranes or membrane proteins with engineered synthetic phospholipids.This technological progression enables the synergistic retention of multicellular biological functions and the incorporation of advantageous synthetic material properties,such as enhanced engineering flexibility and surface modifiability.Additionally,the article discusses the advantages and limitations of traditional extrusion and ultrasonication methods in the preparation of cell membrane nanovesicles,highlights the benefits and development prospects of novel microfluidic techniques in the preparation of CM-LNPs,and explores the future application prospects and challenges of CM-LNPs in the biomedical field.展开更多
The hybridization between oxygen 2p and transition-metal 3d states largely determines the electronic structure near the Fermi level and related functionalities of transition-metal oxides(TMOs).Considerable efforts hav...The hybridization between oxygen 2p and transition-metal 3d states largely determines the electronic structure near the Fermi level and related functionalities of transition-metal oxides(TMOs).Considerable efforts have been made to manipulate the p-d hybridization in TMOs by tailoring the spatial orbital overlap via structural engineering.Here,we demonstrate enhanced p-d hybridization in Ba^(2+)-doped LaNiO_(3)epitaxial films by simultaneously modifying both the spatial and energetic overlaps between the O-2p and Ni-3d orbitals.Combining x-ray absorption spectroscopy and firstprinciples calculations,we reveal that the enhanced hybridization stems from the synergistic effects of a reduced chargetransfer energy due to hole injection and an increased spatial orbital overlap due to straightening of Ni-O-Ni bonds.We further show that the enhanced p-d hybridization can be utilized to promote the oxygen evolution activity of LaNiO_(3).This work sheds new insights into the fine-tuning of the electronic structures of TMOs for enhanced functionalities.展开更多
Introduction Early cancer detection represents a critical evolution in healthcare,addressing a significant pain point in cancer treatment:the tendency for diagnoses to occur at advanced stages.Traditionally,many cance...Introduction Early cancer detection represents a critical evolution in healthcare,addressing a significant pain point in cancer treatment:the tendency for diagnoses to occur at advanced stages.Traditionally,many cancers are not identified until they have progressed to late stages,where treatment options become limited,less effective,and more costly.This late detection results in poorer prognoses,higher mortality rates,and increased healthcare costs.Without early detection tools like Fluorescence In Situ Hybridization(FISH),these challenges persist,leaving patients with fewer opportunities for successful outcomes.展开更多
The biological species concept defines species as groups of actually or potentially interbreeding natural populations that are reproductively isolated from other such groups(Mayr,1942).Reproductive isolation,whether p...The biological species concept defines species as groups of actually or potentially interbreeding natural populations that are reproductively isolated from other such groups(Mayr,1942).Reproductive isolation,whether prezygotic or postzygotic,plays a central role in maintaining species boundaries.However,hybridization between closely related taxa can challenge these boundaries and provide insight into speciation,gene flow,and evolutionary processes(Coyne and Orr,2004).展开更多
Photocatalytic hydrogen(H_(2))production using solar energy is a cutting-edge green technology that holds great potential for addressing the urgent fuel and environmental crises[1–3].To achieve high-efficiency H_(2) ...Photocatalytic hydrogen(H_(2))production using solar energy is a cutting-edge green technology that holds great potential for addressing the urgent fuel and environmental crises[1–3].To achieve high-efficiency H_(2) production,cocatalyst modification is commonly employed to provide active sites for the hydrogen evolution reaction(HER)[4,5].In this context,the kinetics of hydrogen adsorption and desorption at these active sites play a crucial role in enhancing overall photocatalytic H_(2) production efficiency.However,the H adsorption/desorption kinetics often exhibit a trade-off,presenting a significant challenge in achieving an optimal equilibrium between Hads and Hdes in many cocatalyst systems.Therefore,fine-tuning the active sites to optimize the H_(2) evolution kinetics is essential for improving photocatalytic activity[6].展开更多
Layered double hydroxides(LDHs)are potential cathode materials for aqueous magnesium-ion batteries(AMIBs).However,the low capacity and sluggish kinetics significantly limit their electrochemical performance in AMIBs.H...Layered double hydroxides(LDHs)are potential cathode materials for aqueous magnesium-ion batteries(AMIBs).However,the low capacity and sluggish kinetics significantly limit their electrochemical performance in AMIBs.Herein,we find that oxygen vacancies can significantly boost the capacity,electrochemical kinetics,and structure stability of LDHs.The corresponding structure-performance relationship and energy storage mechanism are elaborated through exhaustive in/ex-situ experimental characterizations and density functional theory(DFT)calculations.Specially,in-situ Raman and DFT calculations reveal that oxygen vacancies elevate orbital energy of O 2p and electron density of O atoms,thereby enhancing the orbital hybridization of O 2p with Ni/Co 3d.This facilitates electron transfer between O and adjacent Ni/Co atoms and improves the covalency of Ni–O and Co–O bonds,which activates Ni/Co atoms to release more capacity and stabilizes the Ov-NiCo-LDH structure.Moreover,the distribution of relaxation times(DRT)and molecular dynamics(MD)simulations disclose that the enhanced d-p orbital hybridization optimizes the electronic structure of Ov-NiCo-LDH,which distinctly reduces the diffusion energy barriers of Mg^(2+)and improves the charge transfer kinetics of Ov-NiCo-LDH.Consequently,the assembled Ov-NiCo-LDH//active carbon(AC)and Ov-NiCo-LDH//perylenediimide(PTCDI)AMIBs can both deliver high specific discharge capacity(182.7 and 59.4 mAh g^(−1)at 0.5 A g^(−1),respectively)and long-term cycling stability(85.4%and 89.0%of capacity retentions after 2500 and 2400 cycles at 1.0 A g^(−1),respectively).In addition,the practical prospects for Ov-NiCo-LDH-based AMIBs have been demonstrated in different application scenarios.This work not only provides an effective strategy for obtaining high-performance cathodes of AMIBs,but also fundamentally elucidates the inherent mechanisms.展开更多
Defect engineering significantly enhances electrocatalytic performance by modulating electronic structures and interfacial coordination,yet the dynamic correlation between defect evolution and catalytic activity durin...Defect engineering significantly enhances electrocatalytic performance by modulating electronic structures and interfacial coordination,yet the dynamic correlation between defect evolution and catalytic activity during reactions remains unclear.Herein,density functional theory(DFT)calculations first reveal the modulation of sulfur vacancy concentrations on Co_(9)S_(8)electronic structures,predicting that optimized vacancy concentrations enable highly efficient electrocatalytic water splitting.Experimentally fabricated Co_(9)S_(8)with appropriate sulfur vacancies exhibits superior bifunctional activity(HER:164 mV@_(η10);OER:297 mV@_(η100)).The MCS-assembled overall water splitting system demonstrates stable operation at 1.57 V(10 mA cm^(−2))for over 60 h.Experimental studies illustrate that sulfur vacancies preferentially adsorb OH^(−)during reactions,inducing the formation of CoOOH active phases.DFT analysis further indicates that OH^(−)adsorption weakens d-p orbital hybridization,optimizing hydrogen/oxygen intermediate adsorption energy barriers and ultimately enhancing catalytic performance.This work establishes novel paradigms for systematic development of catalysts through synergistic analysis of defect dynamics,electronic structures and catalytic performance.展开更多
Asymmetric single-atom catalysts(ASACs)have attracted much attention owing to their excellent catalytic properties.However,the relationship between asymmetric coordination and the spin states of metal sites remains un...Asymmetric single-atom catalysts(ASACs)have attracted much attention owing to their excellent catalytic properties.However,the relationship between asymmetric coordination and the spin states of metal sites remains unclear.Additionally,the modulation of reactive oxygen species in Fenton-like reactions remains challenging.Herein,a novel strategy is reported for the rational design of highly loaded Co ASACs(CoN_(1)C_(2)/C_(2)N)immobilized on three-dimensional flower-like C_(2)N using an in situ-generated carbon defect method.In particular,the asymmetrically tricoordinated CoN_(1)C_(2)/C_(2)N exhibited excellent catalytic activity for sulfachloropyridazine degradation,with a turnover frequency of 36.8 min^(–1).Experimental results and theoretical calculations revealed that the electron spin state of the Co-active sites was transferred from the low-spin configuration(t_(2g)^(6)e_(g)^(1))to the high-spin configuration(t_(2g)^(5)e_(g)^(2))owing to asymmetric coordination.The high-spin Co 3d orbital in CoN_(1)C_(2)/C_(2)N possessed more unpaired electrons and therefore,had a strong ability to gain electrons from the O 2p orbitals of HSO_(5)^(–),boosting d-p orbital hybridization.More importantly,the spin-electron filling in theσ^(*)orbital of high-spin Co 3d−O 2p accelerated the desorption of^(*)SO_(5)•^(−),which acted as a rate-limiting step in the reaction,thus facilitating more^(1)O_(2)generation.This study provides an innovative synthetic route for practical ASACs and clarifies the critical relationship between structure and spin state,paving the way for advancements in environmental remediation and energy conversion applications.展开更多
Hybridization is a driving force in ecological transitions and speciation,yet direct evidence linking it to adaptive differentiation in natural systems remains limited.This study evaluates the role of hybridization in...Hybridization is a driving force in ecological transitions and speciation,yet direct evidence linking it to adaptive differentiation in natural systems remains limited.This study evaluates the role of hybridization in the speciation of Pinus densata,a keystone forest species on the southeastern Tibetan Plateau.By creating artificialinterspecificF1s and a long-term common garden experiment on the plateau,we provide in situ assessments on 44 growth and physiological traits across four seasons,along with RNA sequencing.We found significantphenotypic divergence between P.densata and its putative parental species P.tabuliformis and P.yunnanensis,with P.densata demonstrating superior growth and dynamic balance between photosynthesis and photoprotection.The F1s closely resembled P.densata in most traits.Gene expression revealed 19%–10%of 34,000 examined genes as differentially expressed in P.densata and F1s relative to mid-parent expression values.Both additive(4%)and non-additive gene actions(5%–6%in F1s,10%–12%in P.densata)were common,while transgressive expression occurred more frequently in the stabilized natural hybrids,illustrating transcriptomic reprogramming brought by hybridization and further divergence by natural selection.We provide compelling evidence for hybridization-derived phenotypic divergence at both physiological and gene expression levels that could have contributed to the adaptation of P.densata to high plateau habitat where both parental species have low fitness.The altered physiology and gene expression in hybrids serve both as a substrate for novel ecological adaptation and as a mechanism for the initiation of reproductive isolation.展开更多
文摘D-π hybridization is a key structural feature that may significantly affect the intrinsic electronic properties of metallopolymers.Herein,we present the electrosynthesis and memristive properties of metallopolymers using the distinct d-π hybridization monomers R_(1) and R_(2).R_(1)(Ru^(Ⅱ)-(tpz)Cl_(2))features tetradentate ligands(tpz,6,6'-di(1H-pyrazol-1-yl)-2,2'-bipyridine)enforcing quasi-octahedral geometry;R_(2)(Ru^(Ⅱ)-(bpp)_(2))incorporates tridentate ligands(bpp,2,6-di(1H-pyrazol-1-yl)pyridine)inducing pronounced geometric distortion.The planar ligand(tpz)in R_(1) facilitates ordered molecular assembly through high conformational rigidity and extensive π-π stacking,resulting in increased molecular densities and enhanced morphological uniformity compared to R_(2) metallopolymers.Due to pyrazole’s weaker π-acceptance and strongerσ-donation compared to pyridine,R_(1) exhibits a 119 nm red-shift in metal-to-ligand charge transfer(MLCT)band and a 30 mV anodic shift in Ru^(+2/+3)redox potential relative to R_(2).Coupled with a reduced HOMO-LUMO gap,the uniform and ordered structure leads to a lower conductance decay constant in R_(1).Additionally,R_(2) metallopolymers exhibit superior memristive performance(characterized by lower switching voltage and higher switching ratio)via redox-induced aromatic transitions in axial ligands enhancing electronic delocalization.This work compares two metallopolymers with different ligand geometries,revealing how this difference leads to distinct charge transport and memristive behaviors.
基金financial support of the National Natural Science Foundation of China (21875247,21072221, 21172252)the Project of Talent Cultivation for Carbon Peak and Carbon Neutrality of the University of Chinese of Academy of Science
文摘The design and fabrication of ordered epitaxial MOF-on-MOF heterostructures as highly efficient electrocatalysts for water splitting is crucial but still challenging.In this study,a simple coordination-driven self-assembly method is used to fabricate controllable MOF-on-MOF multiscale heterostructures,where triangular host MOF(ZIF-67)nanosheets undergo in situ epitaxial growth to form uniform orthogonal vip MOF(CoFe PBA)nanosheets.Phosphorus(P)is further introduced in situ to fabricate CoP and Fe_(2)P heterostructured nanosheets(CoFe-P-NS),which exhibit excellent bifunctional electrocatalytic performance due to the enhancement of intrinsic electrocatalytic activity by p-d orbital hybridization.Specifically,the CoFe-P-NS requires low overpotential of 259 and 307 mV to reach 500 mA cm−2 for HER and OER,respectively.Remarkably,the assembled electrolysis cell maintained a large current density of 300 mA cm−2 for over 360 h with negligible voltage increase during alkaline seawater electrolysis.Experiments and theoretical calculations show that the synergistic catalytic activity of bimetallic phosphides arises from p-d orbital hybridization,where the CoP-P sites enhance HER by optimizing H*adsorption in the Volmer-Heyrovsky steps,while the Fe_(2)P-Fe sites accelerate OER by lowering the energy barrier of the rate-determining step from O*to OOH*.This study provides valuable insights into the design of a controllable MOF-on-MOF-based electrocatalyst toward alkaline seawater splitting.
基金support from the Heilongjiang Province"Double First Class"Discipline Collaborative Innovation Project(No.LJGXCG2023-061).
文摘Hard carbon is a vital anode material for sodium-ion batteries;however,the nonuniform growth of solid electrolyte interphase(SEI)film substantially diminishes its initial coulombic efficiency(ICE)and cycle life.The chemical and morphological properties of surface highly influence the electrode/electrolyte interfacial reactions.In this study,we have tuned orbital hybridization states forming an interface enriched with sp^(2) hybridized carbon(sp^(2)-C),which decreases the binding energy to solvent molecules and inhibits excessive solvent decomposition during SEI formation.Benefiting from successfully constructed inorganic-rich SEI,the ICE increased to 91%and sodium storage capacity reached 346 mAh/g.Besides,the capacity retention rate was 90.7%after 700 cycles at 1 A/g higher than pristine electrode(83.8%).
基金supported by the Strategic Priority Research Program of Chinese Academy of Sciences (Grant Nos.XDB28000000 and XDB0460000)the Quantum Science and Technology-National Science and Technology Major Project (Grant No.2021ZD0302600)the National Key Research and Development Program of China(Grant No.2024YFA1409002)。
文摘The hybridization gap in strained-layer InAs/In_(x)Ga_(1−x) Sb quantum spin Hall insulators(QSHIs)is significantly enhanced compared to binary InAs/GaSb QSHI structures,where the typical indium composition,x,ranges between 0.2 and 0.4.This enhancement prompts a critical question:to what extent can quantum wells(QWs)be strained while still preserving the fundamental QSHI phase?In this study,we demonstrate the controlled molecular beam epitaxial growth of highly strained-layer QWs with an indium composition of x=0.5.These structures possess a substantial compressive strain within the In_(0.5)Ga_(0.5)Sb QW.Detailed crystal structure analyses confirm the exceptional quality of the resulting epitaxial films,indicating coherent lattice structures and the absence of visible dislocations.Transport measurements further reveal that the QSHI phase in InAs/In_(0.5)Ga_(0.5)Sb QWs is robust and protected by time-reversal symmetry.Notably,the edge states in these systems exhibit giant magnetoresistance when subjected to a modest perpendicular magnetic field.This behavior is in agreement with the𝑍2 topological property predicted by the Bernevig–Hughes–Zhang model,confirming the preservation of topologically protected edge transport in the presence of enhanced bulk strain.
基金supported by the National Natural Science Foundation of China (Grant no. 22209083)
文摘Developing high-performance Ni cathodes and understanding the relationship between electron states of Ni 3d orbital and energy storage mechanism from an atomic-orbital perspective are crucial yet challenging for alkaline nickel-zinc batteries.Herein,we innovatively design P-NiMoO_(4)/NiSe_(2)heterostructures with rich oxygen vacancy via a selective component segregation.The P substitution in NiMoO_(4)activate Ni atoms,leading to the spin-state transition of Ni-3d orbitals from high-spin to low-spin,which promote the uniform and rapid nucleation of NiSe_(2)on the surface of NiMoO_(4)during subsequent selenization process.After selenization,the in situ formed P-NiMoO_(4)/NiSe_(2)heterostructures exhibits continuous increased unoccupied states of Ni 3d-orbitals and higher Ni valence state.The synergistic effect of P doping and selenization modulate the d-band center(ɛd)level of Ni 3d,thereby promoting d-p orbital hybridization between Ni 3d and O 2p of OH−as well as OH−adsorption ability.Consequently,the P-NiMoO_(4)/NiSe_(2)exhibits a top-level specific capacity of 390.7 mA h g^(−1)at 1 A g^(−1),2.8-fold higher than that of pristine NiMoO_(4),accompanied by remarkable rate capability and structural stability.Moreover,the assembled pouch-type battery and flexible devices demonstrate the practical application potential.This work provides fundamental insights into orbital-level engineering of battery materials for enhanced redox kinetics and cycling stability.
基金Project supported by the National Natural Science Foundation of China(Grant No.12174327)the Natural Science Foundation of Shandong Province,China(Grant No.ZR2023ZD09)。
文摘In multi-orbital systems,the correlation strength is typically attributed to Coulomb interactions and Hund's couplings.However,this study demonstrates that on-site inter-orbital hybridization can also significant influence the correlation strength of the system.We investigate the impact of on-site inter-orbital hybridization on the correlation strength of a two-orbital Hubbard model on a square lattice using the dynamical mean-field theory combined with Lanczos exact diagonalization.Our findings reveal a distinct Janus effect:on-site inter-orbital hybridization enhances correlation strength in the non-half-filled regime while suppresses it at half-filling.This dual role of on-site inter-orbital hybridization provides a fundamental mechanism for tuning the strength of correlations in multi-orbital systems.
基金financially supported by the National Natural Science Foundation of China(32371475)。
文摘With the continuous advancement of bionanomaterial technology,the design and fabrication strategies of biomimetic nanocarriers have undergone significant strategic transformations and innovations.This article systematically reviews the evolution from single-cell membrane nanovesicles to hybrid cell membrane nanovesicles integrating multiple cell membranes,culminating in cell membrane hybrid lipid nanoparticles(CM-LNPs)combining natural cell membranes or membrane proteins with engineered synthetic phospholipids.This technological progression enables the synergistic retention of multicellular biological functions and the incorporation of advantageous synthetic material properties,such as enhanced engineering flexibility and surface modifiability.Additionally,the article discusses the advantages and limitations of traditional extrusion and ultrasonication methods in the preparation of cell membrane nanovesicles,highlights the benefits and development prospects of novel microfluidic techniques in the preparation of CM-LNPs,and explores the future application prospects and challenges of CM-LNPs in the biomedical field.
基金supported by the National Key R&D Program of China(Grant No.2022YFA1402902)the National Natural Science Foundation of China(Grant Nos.12374179,12074119,12374145,051B22001,12104157,12134003,and 12304218)the Shanghai Pujiang Program(Grant No.23PJ1402200).
文摘The hybridization between oxygen 2p and transition-metal 3d states largely determines the electronic structure near the Fermi level and related functionalities of transition-metal oxides(TMOs).Considerable efforts have been made to manipulate the p-d hybridization in TMOs by tailoring the spatial orbital overlap via structural engineering.Here,we demonstrate enhanced p-d hybridization in Ba^(2+)-doped LaNiO_(3)epitaxial films by simultaneously modifying both the spatial and energetic overlaps between the O-2p and Ni-3d orbitals.Combining x-ray absorption spectroscopy and firstprinciples calculations,we reveal that the enhanced hybridization stems from the synergistic effects of a reduced chargetransfer energy due to hole injection and an increased spatial orbital overlap due to straightening of Ni-O-Ni bonds.We further show that the enhanced p-d hybridization can be utilized to promote the oxygen evolution activity of LaNiO_(3).This work sheds new insights into the fine-tuning of the electronic structures of TMOs for enhanced functionalities.
基金supported by Guangzhou Development Zone Science and Technology(2021GH10,2020GH10,2023GH02)the University of Macao(MYRG2022-00271-FST)The Science and Technology Development Fund(FDCT)of Macao(0032/2022/A).
文摘Introduction Early cancer detection represents a critical evolution in healthcare,addressing a significant pain point in cancer treatment:the tendency for diagnoses to occur at advanced stages.Traditionally,many cancers are not identified until they have progressed to late stages,where treatment options become limited,less effective,and more costly.This late detection results in poorer prognoses,higher mortality rates,and increased healthcare costs.Without early detection tools like Fluorescence In Situ Hybridization(FISH),these challenges persist,leaving patients with fewer opportunities for successful outcomes.
基金supported by the National Natural Science Foundation of China(No.32161143024,31970405)Iran National Science Foundation,Iran-China(INSF-NSFC)joint project(No.4002006).
文摘The biological species concept defines species as groups of actually or potentially interbreeding natural populations that are reproductively isolated from other such groups(Mayr,1942).Reproductive isolation,whether prezygotic or postzygotic,plays a central role in maintaining species boundaries.However,hybridization between closely related taxa can challenge these boundaries and provide insight into speciation,gene flow,and evolutionary processes(Coyne and Orr,2004).
文摘Photocatalytic hydrogen(H_(2))production using solar energy is a cutting-edge green technology that holds great potential for addressing the urgent fuel and environmental crises[1–3].To achieve high-efficiency H_(2) production,cocatalyst modification is commonly employed to provide active sites for the hydrogen evolution reaction(HER)[4,5].In this context,the kinetics of hydrogen adsorption and desorption at these active sites play a crucial role in enhancing overall photocatalytic H_(2) production efficiency.However,the H adsorption/desorption kinetics often exhibit a trade-off,presenting a significant challenge in achieving an optimal equilibrium between Hads and Hdes in many cocatalyst systems.Therefore,fine-tuning the active sites to optimize the H_(2) evolution kinetics is essential for improving photocatalytic activity[6].
基金financial support of the National Natural Science Foundation of China (22379063)
文摘Layered double hydroxides(LDHs)are potential cathode materials for aqueous magnesium-ion batteries(AMIBs).However,the low capacity and sluggish kinetics significantly limit their electrochemical performance in AMIBs.Herein,we find that oxygen vacancies can significantly boost the capacity,electrochemical kinetics,and structure stability of LDHs.The corresponding structure-performance relationship and energy storage mechanism are elaborated through exhaustive in/ex-situ experimental characterizations and density functional theory(DFT)calculations.Specially,in-situ Raman and DFT calculations reveal that oxygen vacancies elevate orbital energy of O 2p and electron density of O atoms,thereby enhancing the orbital hybridization of O 2p with Ni/Co 3d.This facilitates electron transfer between O and adjacent Ni/Co atoms and improves the covalency of Ni–O and Co–O bonds,which activates Ni/Co atoms to release more capacity and stabilizes the Ov-NiCo-LDH structure.Moreover,the distribution of relaxation times(DRT)and molecular dynamics(MD)simulations disclose that the enhanced d-p orbital hybridization optimizes the electronic structure of Ov-NiCo-LDH,which distinctly reduces the diffusion energy barriers of Mg^(2+)and improves the charge transfer kinetics of Ov-NiCo-LDH.Consequently,the assembled Ov-NiCo-LDH//active carbon(AC)and Ov-NiCo-LDH//perylenediimide(PTCDI)AMIBs can both deliver high specific discharge capacity(182.7 and 59.4 mAh g^(−1)at 0.5 A g^(−1),respectively)and long-term cycling stability(85.4%and 89.0%of capacity retentions after 2500 and 2400 cycles at 1.0 A g^(−1),respectively).In addition,the practical prospects for Ov-NiCo-LDH-based AMIBs have been demonstrated in different application scenarios.This work not only provides an effective strategy for obtaining high-performance cathodes of AMIBs,but also fundamentally elucidates the inherent mechanisms.
基金financially supported by National Natural Science Foundation of China(No.52473327,51572295,21273285 and 21003157)National Key R&D Program of China(No.2021YFA1501300,2019YFC1907602).
文摘Defect engineering significantly enhances electrocatalytic performance by modulating electronic structures and interfacial coordination,yet the dynamic correlation between defect evolution and catalytic activity during reactions remains unclear.Herein,density functional theory(DFT)calculations first reveal the modulation of sulfur vacancy concentrations on Co_(9)S_(8)electronic structures,predicting that optimized vacancy concentrations enable highly efficient electrocatalytic water splitting.Experimentally fabricated Co_(9)S_(8)with appropriate sulfur vacancies exhibits superior bifunctional activity(HER:164 mV@_(η10);OER:297 mV@_(η100)).The MCS-assembled overall water splitting system demonstrates stable operation at 1.57 V(10 mA cm^(−2))for over 60 h.Experimental studies illustrate that sulfur vacancies preferentially adsorb OH^(−)during reactions,inducing the formation of CoOOH active phases.DFT analysis further indicates that OH^(−)adsorption weakens d-p orbital hybridization,optimizing hydrogen/oxygen intermediate adsorption energy barriers and ultimately enhancing catalytic performance.This work establishes novel paradigms for systematic development of catalysts through synergistic analysis of defect dynamics,electronic structures and catalytic performance.
文摘Asymmetric single-atom catalysts(ASACs)have attracted much attention owing to their excellent catalytic properties.However,the relationship between asymmetric coordination and the spin states of metal sites remains unclear.Additionally,the modulation of reactive oxygen species in Fenton-like reactions remains challenging.Herein,a novel strategy is reported for the rational design of highly loaded Co ASACs(CoN_(1)C_(2)/C_(2)N)immobilized on three-dimensional flower-like C_(2)N using an in situ-generated carbon defect method.In particular,the asymmetrically tricoordinated CoN_(1)C_(2)/C_(2)N exhibited excellent catalytic activity for sulfachloropyridazine degradation,with a turnover frequency of 36.8 min^(–1).Experimental results and theoretical calculations revealed that the electron spin state of the Co-active sites was transferred from the low-spin configuration(t_(2g)^(6)e_(g)^(1))to the high-spin configuration(t_(2g)^(5)e_(g)^(2))owing to asymmetric coordination.The high-spin Co 3d orbital in CoN_(1)C_(2)/C_(2)N possessed more unpaired electrons and therefore,had a strong ability to gain electrons from the O 2p orbitals of HSO_(5)^(–),boosting d-p orbital hybridization.More importantly,the spin-electron filling in theσ^(*)orbital of high-spin Co 3d−O 2p accelerated the desorption of^(*)SO_(5)•^(−),which acted as a rate-limiting step in the reaction,thus facilitating more^(1)O_(2)generation.This study provides an innovative synthetic route for practical ASACs and clarifies the critical relationship between structure and spin state,paving the way for advancements in environmental remediation and energy conversion applications.
基金supported by the National Natural Science Foundation of China(32171816)T4F program Sweden.
文摘Hybridization is a driving force in ecological transitions and speciation,yet direct evidence linking it to adaptive differentiation in natural systems remains limited.This study evaluates the role of hybridization in the speciation of Pinus densata,a keystone forest species on the southeastern Tibetan Plateau.By creating artificialinterspecificF1s and a long-term common garden experiment on the plateau,we provide in situ assessments on 44 growth and physiological traits across four seasons,along with RNA sequencing.We found significantphenotypic divergence between P.densata and its putative parental species P.tabuliformis and P.yunnanensis,with P.densata demonstrating superior growth and dynamic balance between photosynthesis and photoprotection.The F1s closely resembled P.densata in most traits.Gene expression revealed 19%–10%of 34,000 examined genes as differentially expressed in P.densata and F1s relative to mid-parent expression values.Both additive(4%)and non-additive gene actions(5%–6%in F1s,10%–12%in P.densata)were common,while transgressive expression occurred more frequently in the stabilized natural hybrids,illustrating transcriptomic reprogramming brought by hybridization and further divergence by natural selection.We provide compelling evidence for hybridization-derived phenotypic divergence at both physiological and gene expression levels that could have contributed to the adaptation of P.densata to high plateau habitat where both parental species have low fitness.The altered physiology and gene expression in hybrids serve both as a substrate for novel ecological adaptation and as a mechanism for the initiation of reproductive isolation.
