Thermally activated delayed fluorescence(TADF)materials driven by a through-space charge transfer(TSCT)mechanism have garnered wide interest.However,access of TSCT-TADF molecules with longwavelength emission remains a...Thermally activated delayed fluorescence(TADF)materials driven by a through-space charge transfer(TSCT)mechanism have garnered wide interest.However,access of TSCT-TADF molecules with longwavelength emission remains a formidable challenge.In this study,we introduce a novel V-type DA-D-A’emitter,Trz-mCzCbCz,by using a carborane scaffold.This design strategically incorporates carbazole(Cz)and 2,4,6-triphenyl-1,3,5-triazine(Trz)as donor and acceptor moieties,respectively.Theoretical calculations alongside experimental validations affirm the typical TSCT-TADF characteristics of this luminogen.Owing to the unique structural and electronic attributes of carboranes,Trz-mCzCbCz exhibits an orange-red emission,markedly diverging from the traditional blue-to-green emissions observed in classical Cz and Trz-based TADF molecules.Moreover,bright emission in aggregates was observed for Trz-mCzCbCz with absolute photoluminescence quantum yield(PLQY)of up to 88.8%.As such,we have successfully fabricated five organic light-emitting diodes(OLEDs)by utilizing Trz-mCzCbCz as the emitting layer.It is important to note that both the reverse intersystem crossing process and the TADF properties are profoundly influenced by host materials.The fabricated OLED devices reached a maximum external quantum efficiency(EQE)of 12.7%,with an emission peak at 592 nm.This represents the highest recorded efficiency for TSCT-TADF OLEDs employing carborane derivatives as emitting layers.展开更多
Boron is an element that has ability to build strong and highly directional bonds with boron itself. As a result, boron atoms form diverse structural motifs, ultimately can yield distinct nano structures, such as plan...Boron is an element that has ability to build strong and highly directional bonds with boron itself. As a result, boron atoms form diverse structural motifs, ultimately can yield distinct nano structures, such as planar, quasi-planar, convex, cage, open-cage, tubular, spherical, ring, dome-like, shell, capsule, and so on, i.e., it can take almost any shape. Therefore, a deep understanding of the physical and chemical properties becomes important in boron cluster chemistry. Electronic and geometric structures, total and binding energies, harmonic frequencies, point symmetries, charge distributions, dipole moments, chemical bondings and the highest occupied molecular orbital-lowest unoccupied molecular orbital energy gaps of neutral Bn （n=13-20） clusters have been investigated by density functional theory （DFT）, B3LYP with 6-311＋＋G（d,p） basis set. Furthermore, the first and the second energy differences are used to obtain the most stable sizes. We have observed that almost all physical properties are size dependent, and double-ring tubular form of B20 has the highest binding energy per atom. The icosahedral structure with an inside atom is found as impossible as a stable structure for the size thirteen. This structure transforms to an open-cage form. The structural transition from two-dimensional to three-dimensional is found at the size of 20 and consistent with the literature. The calculated charges by the Mulliken analysis show that there is a symmetry pattern with respect to the x-z and y-z planes for the charge distributions. The unusual planar stability of the boron clusters may be explained by the delocalized π and σ bonding characteristic together with the existence of the multicentered bonding. The results have been compared to available studies in the literature.展开更多
The thermal stability and bonding characteristics of the larger boron clusters B n and their corresponding boranes with T d , O h or I h symmetries were studied by means of ab initio...The thermal stability and bonding characteristics of the larger boron clusters B n and their corresponding boranes with T d , O h or I h symmetries were studied by means of ab initio method. The results obtained from the calculation show that the clusters and boranes are all thermally stable to a different extent. The number of the skeletal bonding orbitals of B n H 2- n satisfies the Wades rule, but this kind of clusters need not be a complete triangular face polyhedron. The results also indicate that the larger neutral boranes B n H n may exist.展开更多
Under hydrothermal and solvothermal conditions,two novel cobalt-based complexes,{[Co_(2)(CIA)(OH)(1,4-dtb)]·3.2H_(2)O}n(HU23)and{[Co_(2)(CIA)(OH)(1,4-dib)]·3.5H2O·DMF}n(HU24),were successfully construct...Under hydrothermal and solvothermal conditions,two novel cobalt-based complexes,{[Co_(2)(CIA)(OH)(1,4-dtb)]·3.2H_(2)O}n(HU23)and{[Co_(2)(CIA)(OH)(1,4-dib)]·3.5H2O·DMF}n(HU24),were successfully constructed by coordinatively assembling the semi-rigid multidentate ligand 5-(1-carboxyethoxy)isophthalic acid(H₃CIA)with the Nheterocyclic ligands 1,4-di(4H-1,2,4-triazol-4-yl)benzene(1,4-dtb)and 1,4-di(1H-imidazol-1-yl)benzene(1,4-dib),respectively,around Co^(2+)ions.Single-crystal X-ray diffraction analysis revealed that in both complexes HU23 and HU24,the CIA^(3-)anions adopt aκ^(7)-coordination mode,bridging six Co^(2+)ions via their five carboxylate oxygen atoms and one ether oxygen atom.This linkage forms tetranuclear[Co4(μ3-OH)2]^(6+)units.These Co-oxo cluster units were interconnected by CIA^(3-)anions to assemble into 2D kgd-type structures featuring a 3,6-connected topology.The 2D layers were further connected by 1,4-dtb and 1,4-dib,resulting in 3D pillar-layered frameworks for HU23 and HU24.Notably,despite the similar configurations of 1,4-dtb and 1,4-dib,differences in their coordination spatial orientations lead to topological divergence in the 3D frameworks of HU23 and HU24.Topological analysis indicates that the frameworks of HU23 and HU24 can be simplified into a 3,10-connected net(point symbol:(4^(10).6^(3).8^(2))(4^(3))_(2))and a 3,8-connected tfz-d net(point symbol:(4^(3))_(2)((4^(6).6^(18).8^(4)))),respectively.This structural differentiation confirms the precise regulatory role of ligands on the topology of metal-organic frameworks.Moreover,the ultraviolet-visible absorption spectra confirmed that HU23 and HU24 have strong absorption capabilities for ultraviolet and visible light.According to the Kubelka-Munk method,their bandwidths were 2.15 and 2.08 eV,respectively,which are consistent with those of typical semiconductor materials.Variable-temperature magnetic susceptibility measurements(2-300 K)revealed significant antiferromagnetic coupling in both complexes,with their effective magnetic moments decreasing markedly as the temperature lowered.CCDC:2457554,HU23;2457553,HU24.展开更多
The effect of Co addition on the formation of Ni-Ti clusters in maraging stainless steel was studied by three dimensional atom probe（3 DAP） and first-principles calculation. The cluster analysis based on the maximum...The effect of Co addition on the formation of Ni-Ti clusters in maraging stainless steel was studied by three dimensional atom probe（3 DAP） and first-principles calculation. The cluster analysis based on the maximum separation approach showed an increase in size but a decrease in density of Ni-Ti clusters with increasing the Co content. The first-principles calculation indicated weaker Co-Ni（Co-Ti） interactions than Co-Ti（Fe-Ti） interactions, which should be the essential reason for the change of distribution characteristics of Ni-Ti clusters in bcc Fe caused by Co addition.展开更多
Au is considered as one of the most promising catalysts for nitrogen reduction reaction(NRR),however maximizing the activity utilization rate of Au and understanding the synergistic effects between Au and carriers pos...Au is considered as one of the most promising catalysts for nitrogen reduction reaction(NRR),however maximizing the activity utilization rate of Au and understanding the synergistic effects between Au and carriers pose ongoing challenges.Herein,we systematically explore the synergistic catalytic effect of incorporating Au with boron clusters for accelerating NRR kinetics.An in-situ abinitio strategy is employed to construct B-doped Au nanoparticles(2-6 nm in diameter)loaded on BO_(x) substrates(AuBO_(x)),in which B not only modulates the surface electronic structure of Au but also forms strong coupling interactions to stabilize the nanoparticles.The electrochemical results show that Au-BO_(x) possesses excellent NRR activity(NH_(3) yield of 48.52μg h^(-1)mg_(cat)^(-1),Faraday efficiency of 56.18%),and exhibits high stability and reproducibility throughout the electrocatalytic NRR process.Theoretical calculations reveal that the introduction of B induces the formation of both Au dangling bond and Au-B coupling bond.which considerably facilitates the hydrogenation of~*N_(2)^(-)~*NH_(3).The present work provides a new avenue for the preparation of metal-boron materials achieved by one-step reduction and doping process,utilizing boron clusters as reducing and stabilizing agents.展开更多
Three-dimensional distribution of solute elements in an Mg–Zn–Gd alloy during ageing process is quantitatively characterized by three-dimensional atom probe(3DAP) tomography. Based on the radius distribution functio...Three-dimensional distribution of solute elements in an Mg–Zn–Gd alloy during ageing process is quantitatively characterized by three-dimensional atom probe(3DAP) tomography. Based on the radius distribution function, it is found that Zn–Gd solute pairs in Mg matrix appear mainly at two peaks at early stage of ageing, and the separation distance between Zn and Gd atoms could be well rationalized by the first-principle calculation. Moreover, the fraction of Zn–Gd solute pairs increases first and then decreases due to the precipitation of long-period stacking ordered(LPSO) structures. Both the composition of the structural unit in LPSO structure and the solute enrichment around it are quantified. It is found that Zn and Gd elements are synchronized in the LPSO structure, and solute segregation of pure Zn or Gd is not observed at the transformation front of the LPSO structure in this alloy. In addition, the crystallography of transformation front is further determined by 3DAP data.展开更多
Our purpose in this study was to develop an automated method for measuring three-dimensional (3D) cerebral cortical thicknesses in patients with Alzheimer’s disease (AD) using magnetic resonance (MR) images. Our prop...Our purpose in this study was to develop an automated method for measuring three-dimensional (3D) cerebral cortical thicknesses in patients with Alzheimer’s disease (AD) using magnetic resonance (MR) images. Our proposed method consists of mainly three steps. First, a brain parenchymal region was segmented based on brain model matching. Second, a 3D fuzzy membership map for a cerebral cortical region was created by applying a fuzzy c-means (FCM) clustering algorithm to T1-weighted MR images. Third, cerebral cortical thickness was three- dimensionally measured on each cortical surface voxel by using a localized gradient vector trajectory in a fuzzy membership map. Spherical models with 3 mm artificial cortical regions, which were produced using three noise levels of 2%, 5%, and 10%, were employed to evaluate the proposed method. We also applied the proposed method to T1-weighted images obtained from 20 cases, i.e., 10 clinically diagnosed AD cases and 10 clinically normal (CN) subjects. The thicknesses of the 3 mm artificial cortical regions for spherical models with noise levels of 2%, 5%, and 10% were measured by the proposed method as 2.953 ± 0.342, 2.953 ± 0.342 and 2.952 ± 0.343 mm, respectively. Thus the mean thicknesses for the entire cerebral lobar region were 3.1 ± 0.4 mm for AD patients and 3.3 ± 0.4 mm for CN subjects, respectively (p < 0.05). The proposed method could be feasible for measuring the 3D cerebral cortical thickness on individual cortical surface voxels as an atrophy feature in AD.展开更多
Gobi spans a large area of China,surpassing the combined expanse of mobile dunes and semi-fixed dunes.Its presence significantly influences the movement of sand and dust.However,the complex origins and diverse materia...Gobi spans a large area of China,surpassing the combined expanse of mobile dunes and semi-fixed dunes.Its presence significantly influences the movement of sand and dust.However,the complex origins and diverse materials constituting the Gobi result in notable differences in saltation processes across various Gobi surfaces.It is challenging to describe these processes according to a uniform morphology.Therefore,it becomes imperative to articulate surface characteristics through parameters such as the three-dimensional(3D)size and shape of gravel.Collecting morphology information for Gobi gravels is essential for studying its genesis and sand saltation.To enhance the efficiency and information yield of gravel parameter measurements,this study conducted field experiments in the Gobi region across Dunhuang City,Guazhou County,and Yumen City(administrated by Jiuquan City),Gansu Province,China in March 2023.A research framework and methodology for measuring 3D parameters of gravel using point cloud were developed,alongside improved calculation formulas for 3D parameters including gravel grain size,volume,flatness,roundness,sphericity,and equivalent grain size.Leveraging multi-view geometry technology for 3D reconstruction allowed for establishing an optimal data acquisition scheme characterized by high point cloud reconstruction efficiency and clear quality.Additionally,the proposed methodology incorporated point cloud clustering,segmentation,and filtering techniques to isolate individual gravel point clouds.Advanced point cloud algorithms,including the Oriented Bounding Box(OBB),point cloud slicing method,and point cloud triangulation,were then deployed to calculate the 3D parameters of individual gravels.These systematic processes allow precise and detailed characterization of individual gravels.For gravel grain size and volume,the correlation coefficients between point cloud and manual measurements all exceeded 0.9000,confirming the feasibility of the proposed methodology for measuring 3D parameters of individual gravels.The proposed workflow yields accurate calculations of relevant parameters for Gobi gravels,providing essential data support for subsequent studies on Gobi environments.展开更多
Four isomers of the three-dimensionally connected bare boron cationic cluster B were investigated by using ab initio molecular orbital theory at the HF/6-31G level. The results show that the D5h symmetric isomer of B ...Four isomers of the three-dimensionally connected bare boron cationic cluster B were investigated by using ab initio molecular orbital theory at the HF/6-31G level. The results show that the D5h symmetric isomer of B is a possible isomer candidate of its stable geometries with closed structure.展开更多
The geometrical structures, relative stabilities, electronic and magnetic properties of small BnAl-（2〈n〈9）clusters are systematicalyy investigated by using the first-principles density functional theory. The resul...The geometrical structures, relative stabilities, electronic and magnetic properties of small BnAl-（2〈n〈9）clusters are systematicalyy investigated by using the first-principles density functional theory. The results show that the A1 atom prefers to reside either on the outer-side or above the surface, but not in the centre of the clusters in all of the most stable BnAl-（2〈n〈9） isomers and the one excess electron is strong enough to modify the geometries of some specific sizes of the neutral clusters. All the results of the analysis for the fragmentation energies, the second-order difference of energies, and the highest occupied-lowest unoccupied molecular orbital energy gaps show that B4A1- and B8A1- clusters each have a higher relative stability. Especially, the BsA1-cluster has the most enhanced chemical stability. Furthermore, both the local magnetic moments and the total magnetic moments display a pronounced oddeven oscillation with the number of boron atoms, and the magnetic effects arise mainly from the boron atoms except for the B7A1- and BgA1- clusters.展开更多
Solid electrolytes are the most promising candidate for replacing liquid electrolytes due to their safetyand chemical stability advantages. However, a single inorganic or organic solid electrolyte cannot meetthe requi...Solid electrolytes are the most promising candidate for replacing liquid electrolytes due to their safetyand chemical stability advantages. However, a single inorganic or organic solid electrolyte cannot meetthe requirements of commercial all-solid-state batteries (ASSBs), which motivates the composite polymerelectrolyte (CPE). Herein, a CPE of boron nitride nanofiber (BNNF) with a high specific surface area, richpore structure, and poly (ethylene oxide) (PEO) are reported. Anions strongly adsorb on the surface ofBNNF through electrostatic interactions based on oxygen vacancies, promoting the dissociation of lithiumsalts at the two-phase interface. The three-dimensional (3D) BNNF network provides three advantagesin the CPE, including (i) improving ionic conductivity through strong interaction between polymers andfillers, (ii) improving mechanical properties through weaving a robust skeleton, and (iii) improving stability through a rapid and uniform thermal dispersion pathway. Therefore, the CPE with BNNF delivers highionic conduction of 4.21 × 10^(−4) S cm^(−1) at 60 ℃ and excellent cycling stability (plating/stripping cyclesfor 2000 h with a low overpotential of ∼40 mV), which results in excellent electrochemical performanceof LiFePO_(4) (LFP) full cell assembled with CPE-5BNNF-1300 (152.7 mAh g^(−1) after 200 cycles at 0.5 C, and134.8 mAh g^(−1) at 2.0 C). Furthermore, when matched with high-voltage LiNi_(0.6)Co_(0.2)Mn_(0.2)O_(2) (NCM622), italso exhibits an outstanding rate capacity of 120.4 mAh g^(−1) at 1.0 C. This work provides insight into theBNNF composite electrolyte and promotes its practical application for ASSBs.展开更多
Cluster science as a bridge linking atomic molecular physics and condensed matter inspired the nanomaterials development in the past decades, ranging from the single-atom catalysis to ligand-protected noble metal clus...Cluster science as a bridge linking atomic molecular physics and condensed matter inspired the nanomaterials development in the past decades, ranging from the single-atom catalysis to ligand-protected noble metal clusters. The corresponding studies not only have been restricted to the search for the geometrical structures of clusters, but also have promoted the development of cluster-assembled materials as the building blocks. The CALYPSO cluster prediction method combined with other computational techniques have significantly stimulated the development of the cluster-based nanomaterials. In this review, we will summarize some good cases of cluster structure by CALYPSO method, which have also been successfully identified by the photoelectron spectra experiments. Beginning with the alkali-metal clusters, which serve as benchmarks, a series of studies are performed on the size-dependent elemental clusters which possess relatively high stability and interesting chemical physical properties. Special attentions are paid to the boron-based clusters because of their promising applications. The NbSi12 and BeB16 clusters, for example, are two classic representatives of the silicon-and boron-based clusters, which can be viewed as building blocks of nanotubes and borophene. This review offers a detailed description of the structural evolutions and electronic properties of medium-sized pure and doped clusters, which will advance fundamental knowledge of cluster-based nanomaterials and provide valuable information for further theoretical and experimental studies.展开更多
Achieving thermal management composite material with isotropic thermal dissipation property by using an environmentally friendly and efficient method is one of the most challenging techniques as a traditional approach...Achieving thermal management composite material with isotropic thermal dissipation property by using an environmentally friendly and efficient method is one of the most challenging techniques as a traditional approach tending to form a horizontally arranged network within the polymer matrix or the preparation steps which are unduly cumbersome.What presented here is a closestack thermally conductive three-dimensional(3D)hybrid network structure prepared by a simple and green strategy that intercalating the modified aluminum oxide(m-Al_(2)O_(3))spheres of different sizes into the modified two-dimensional(2D)boron nitride(m-h-BN)flakes.An effective 3D network is created by the multi-dimensional fillers through volume exclusion and synergistic effects.The m-h-BN flakes facilitate in-plane heat transfer,while the variously sized m-Al_(2)O_(3)spheres insert into the gaps between adjacent m-h-BN flakes,which is conducive to the heat transfer in the out-of-plane direction.Additionally,strong interactions between the m-Al_(2)O_(3)and m-h-BN promote the effective heat flux inside the 3D hybrid network structure.The 3D hybrid composite displays favorable quasi-isotropic heat dissipation property(through-plane thermal conductivity of 2.2 W·m^(-1)·K^(-1)and in-plane thermal conductivity of 11.6 W·m^(-1)·K^(-1))in comparison with the single-filler composites.Furthermore,the hybrid-filler composite has excellent mechanical properties and thermal stability.The efficient heat dissipation capacity of the hybrid composite is further confirmed by a finite element simulation,which indicates that the sphere-flake hybrid structure possesses a higher thermal conductivity and faster thermal response performance than the single-filler system.The composite material has great potential in meeting the needs of emerging and advancing power systems.展开更多
The effects of ion doses on the properties of boron implanted Si for n-type solar cell application were investigated with doses ranging from 5×10^14cm^-2 to 2×10^15cm^-2 and a subsequent two-step annealing p...The effects of ion doses on the properties of boron implanted Si for n-type solar cell application were investigated with doses ranging from 5×10^14cm^-2 to 2×10^15cm^-2 and a subsequent two-step annealing process in a tube furnace.With the help of the TCAD process simulation tool, knowledge on diffusion kinetics of dopants and damage evolution was obtained by fitting SIMS measured boron profiles. Due to insufficient elimination of the residual damage, the implanted emitter was found to have a higher saturation current density（J0e） and a poorer crystallographic quality. Consistent with this observation, V oc, J sc, and the efficiency of the all-implanted p^＋–n–n^＋solar cells followed a decreasing trend with an increase of the implantation dose. The obtained maximum efficiency was 19.59% at a low dose of 5×10^14cm^-2. The main efficiency loss under high doses came not only from increased recombination of carriers in the space charge region revealed by double-diode parameters of dark I–V curves, but also from the degraded minority carrier diffusion length in the emitter and base evidenced by IQE data. These experimental results indicated that clusters and dislocation loops had appeared at high implantation doses, which acted as effective recombination centers for photogenerated carriers.展开更多
We have developed a fast and efficient route to obtain perfunctionalized ether-linked alkyl and benzyl derivatives of the closo-[B_(12)(OH)_(12)]^(2−)icosahedral dodecaborate cluster via microwave-assisted synthesis.T...We have developed a fast and efficient route to obtain perfunctionalized ether-linked alkyl and benzyl derivatives of the closo-[B_(12)(OH)_(12)]^(2−)icosahedral dodecaborate cluster via microwave-assisted synthesis.These icosahedral boron clusters exhibit three-dimensional delocalization of the cage-bonding electrons,tunable photophysical properties,and a high degree of stability in air in both the solid state and in solution.A series of closo-[B_(12)(OR)_(12)]^(2−).展开更多
The separation of acetylene (C_(2)H_(2)) from carbon dioxide (CO_(2)) and ethylene (C_(2)H_(4)) is important in industry but challenging due to their similar physical properties. Herein, a novel microporous boron clus...The separation of acetylene (C_(2)H_(2)) from carbon dioxide (CO_(2)) and ethylene (C_(2)H_(4)) is important in industry but challenging due to their similar physical properties. Herein, a novel microporous boron cluster pillared metal–organic framework BSF-10 was synthesized with ligand inclusion for efficient C_(2)H_(2)/CO_(2) and C_(2)H_(2)/C_(2)H_(4) adsorption separation. The free dipyridyl ligands in the large pore reduce the porosity of BSF-10 but stabilize the framework. The available narrow pores without inclusion of ligands are suited for the accommodation of C_(2)H_(2) by cooperative dihydrogen bonding. High C_(2)H_(2) capacity and high C_(2)H_(2) selectivity over CO_(2) and C_(2)H_(4) are achieved. The practical separation ability was confirmed by the breakthroughs using C_(2)H_(2)/CO_(2) and C_(2)H_(2)/C_(2)H_(4) gas mixtures with good recyclability. The dynamic separation factor of 2.8 for the equimolar C_(2)H_(2)/CO_(2) mixture is comparable to those of many benchmark materials.展开更多
基金supported by the Natural Science Foundation of Jiangsu Province(No.BZ2022007)the National Natural Science Foundation of China(No.92261202)+1 种基金the Ministry of Science and Technology of the People’s Republic of China(No.2021YFE0114800)the Ministry of Science and Higher Education of the Russian Federation(No.075-15-2021-1027).
文摘Thermally activated delayed fluorescence(TADF)materials driven by a through-space charge transfer(TSCT)mechanism have garnered wide interest.However,access of TSCT-TADF molecules with longwavelength emission remains a formidable challenge.In this study,we introduce a novel V-type DA-D-A’emitter,Trz-mCzCbCz,by using a carborane scaffold.This design strategically incorporates carbazole(Cz)and 2,4,6-triphenyl-1,3,5-triazine(Trz)as donor and acceptor moieties,respectively.Theoretical calculations alongside experimental validations affirm the typical TSCT-TADF characteristics of this luminogen.Owing to the unique structural and electronic attributes of carboranes,Trz-mCzCbCz exhibits an orange-red emission,markedly diverging from the traditional blue-to-green emissions observed in classical Cz and Trz-based TADF molecules.Moreover,bright emission in aggregates was observed for Trz-mCzCbCz with absolute photoluminescence quantum yield(PLQY)of up to 88.8%.As such,we have successfully fabricated five organic light-emitting diodes(OLEDs)by utilizing Trz-mCzCbCz as the emitting layer.It is important to note that both the reverse intersystem crossing process and the TADF properties are profoundly influenced by host materials.The fabricated OLED devices reached a maximum external quantum efficiency(EQE)of 12.7%,with an emission peak at 592 nm.This represents the highest recorded efficiency for TSCT-TADF OLEDs employing carborane derivatives as emitting layers.
文摘Boron is an element that has ability to build strong and highly directional bonds with boron itself. As a result, boron atoms form diverse structural motifs, ultimately can yield distinct nano structures, such as planar, quasi-planar, convex, cage, open-cage, tubular, spherical, ring, dome-like, shell, capsule, and so on, i.e., it can take almost any shape. Therefore, a deep understanding of the physical and chemical properties becomes important in boron cluster chemistry. Electronic and geometric structures, total and binding energies, harmonic frequencies, point symmetries, charge distributions, dipole moments, chemical bondings and the highest occupied molecular orbital-lowest unoccupied molecular orbital energy gaps of neutral Bn （n=13-20） clusters have been investigated by density functional theory （DFT）, B3LYP with 6-311＋＋G（d,p） basis set. Furthermore, the first and the second energy differences are used to obtain the most stable sizes. We have observed that almost all physical properties are size dependent, and double-ring tubular form of B20 has the highest binding energy per atom. The icosahedral structure with an inside atom is found as impossible as a stable structure for the size thirteen. This structure transforms to an open-cage form. The structural transition from two-dimensional to three-dimensional is found at the size of 20 and consistent with the literature. The calculated charges by the Mulliken analysis show that there is a symmetry pattern with respect to the x-z and y-z planes for the charge distributions. The unusual planar stability of the boron clusters may be explained by the delocalized π and σ bonding characteristic together with the existence of the multicentered bonding. The results have been compared to available studies in the literature.
文摘The thermal stability and bonding characteristics of the larger boron clusters B n and their corresponding boranes with T d , O h or I h symmetries were studied by means of ab initio method. The results obtained from the calculation show that the clusters and boranes are all thermally stable to a different extent. The number of the skeletal bonding orbitals of B n H 2- n satisfies the Wades rule, but this kind of clusters need not be a complete triangular face polyhedron. The results also indicate that the larger neutral boranes B n H n may exist.
文摘Under hydrothermal and solvothermal conditions,two novel cobalt-based complexes,{[Co_(2)(CIA)(OH)(1,4-dtb)]·3.2H_(2)O}n(HU23)and{[Co_(2)(CIA)(OH)(1,4-dib)]·3.5H2O·DMF}n(HU24),were successfully constructed by coordinatively assembling the semi-rigid multidentate ligand 5-(1-carboxyethoxy)isophthalic acid(H₃CIA)with the Nheterocyclic ligands 1,4-di(4H-1,2,4-triazol-4-yl)benzene(1,4-dtb)and 1,4-di(1H-imidazol-1-yl)benzene(1,4-dib),respectively,around Co^(2+)ions.Single-crystal X-ray diffraction analysis revealed that in both complexes HU23 and HU24,the CIA^(3-)anions adopt aκ^(7)-coordination mode,bridging six Co^(2+)ions via their five carboxylate oxygen atoms and one ether oxygen atom.This linkage forms tetranuclear[Co4(μ3-OH)2]^(6+)units.These Co-oxo cluster units were interconnected by CIA^(3-)anions to assemble into 2D kgd-type structures featuring a 3,6-connected topology.The 2D layers were further connected by 1,4-dtb and 1,4-dib,resulting in 3D pillar-layered frameworks for HU23 and HU24.Notably,despite the similar configurations of 1,4-dtb and 1,4-dib,differences in their coordination spatial orientations lead to topological divergence in the 3D frameworks of HU23 and HU24.Topological analysis indicates that the frameworks of HU23 and HU24 can be simplified into a 3,10-connected net(point symbol:(4^(10).6^(3).8^(2))(4^(3))_(2))and a 3,8-connected tfz-d net(point symbol:(4^(3))_(2)((4^(6).6^(18).8^(4)))),respectively.This structural differentiation confirms the precise regulatory role of ligands on the topology of metal-organic frameworks.Moreover,the ultraviolet-visible absorption spectra confirmed that HU23 and HU24 have strong absorption capabilities for ultraviolet and visible light.According to the Kubelka-Munk method,their bandwidths were 2.15 and 2.08 eV,respectively,which are consistent with those of typical semiconductor materials.Variable-temperature magnetic susceptibility measurements(2-300 K)revealed significant antiferromagnetic coupling in both complexes,with their effective magnetic moments decreasing markedly as the temperature lowered.CCDC:2457554,HU23;2457553,HU24.
基金sponsored by Youth Innovation Promotion Association of Chinese Academy of Sciences (2017233)National Natural Science Foundation of C hina (No. 51472249)+2 种基金Innovation Project of Institute of Metal Research (2015-ZD04)National Natural Science Foundation of China Research Fund for International Young Scientists (No. 51750110515)the Special Program for Applied Research on Super Computation of the NSFCGuangdong Joint Fund (second phase) under Grant No. U1501501
文摘The effect of Co addition on the formation of Ni-Ti clusters in maraging stainless steel was studied by three dimensional atom probe（3 DAP） and first-principles calculation. The cluster analysis based on the maximum separation approach showed an increase in size but a decrease in density of Ni-Ti clusters with increasing the Co content. The first-principles calculation indicated weaker Co-Ni（Co-Ti） interactions than Co-Ti（Fe-Ti） interactions, which should be the essential reason for the change of distribution characteristics of Ni-Ti clusters in bcc Fe caused by Co addition.
基金supported by the National Natural Science Foundation of China(22075133,62288102,22375091,21971114,and 21701086)the Jiangsu Provincial Funds(BX2022013)。
文摘Au is considered as one of the most promising catalysts for nitrogen reduction reaction(NRR),however maximizing the activity utilization rate of Au and understanding the synergistic effects between Au and carriers pose ongoing challenges.Herein,we systematically explore the synergistic catalytic effect of incorporating Au with boron clusters for accelerating NRR kinetics.An in-situ abinitio strategy is employed to construct B-doped Au nanoparticles(2-6 nm in diameter)loaded on BO_(x) substrates(AuBO_(x)),in which B not only modulates the surface electronic structure of Au but also forms strong coupling interactions to stabilize the nanoparticles.The electrochemical results show that Au-BO_(x) possesses excellent NRR activity(NH_(3) yield of 48.52μg h^(-1)mg_(cat)^(-1),Faraday efficiency of 56.18%),and exhibits high stability and reproducibility throughout the electrocatalytic NRR process.Theoretical calculations reveal that the introduction of B induces the formation of both Au dangling bond and Au-B coupling bond.which considerably facilitates the hydrogenation of~*N_(2)^(-)~*NH_(3).The present work provides a new avenue for the preparation of metal-boron materials achieved by one-step reduction and doping process,utilizing boron clusters as reducing and stabilizing agents.
基金supported by a Grant-in-Aid for Scientific Research on Innovative Areas,‘‘Synchronized Long-Period Stacking Ordered Structure’’,from the Ministry of Education,Culture,Sports,Science and Technology,Japan(No.23109006)Fundamental Research Funds for the Central Universities(No.FRFTP-17-003A1)
文摘Three-dimensional distribution of solute elements in an Mg–Zn–Gd alloy during ageing process is quantitatively characterized by three-dimensional atom probe(3DAP) tomography. Based on the radius distribution function, it is found that Zn–Gd solute pairs in Mg matrix appear mainly at two peaks at early stage of ageing, and the separation distance between Zn and Gd atoms could be well rationalized by the first-principle calculation. Moreover, the fraction of Zn–Gd solute pairs increases first and then decreases due to the precipitation of long-period stacking ordered(LPSO) structures. Both the composition of the structural unit in LPSO structure and the solute enrichment around it are quantified. It is found that Zn and Gd elements are synchronized in the LPSO structure, and solute segregation of pure Zn or Gd is not observed at the transformation front of the LPSO structure in this alloy. In addition, the crystallography of transformation front is further determined by 3DAP data.
文摘Our purpose in this study was to develop an automated method for measuring three-dimensional (3D) cerebral cortical thicknesses in patients with Alzheimer’s disease (AD) using magnetic resonance (MR) images. Our proposed method consists of mainly three steps. First, a brain parenchymal region was segmented based on brain model matching. Second, a 3D fuzzy membership map for a cerebral cortical region was created by applying a fuzzy c-means (FCM) clustering algorithm to T1-weighted MR images. Third, cerebral cortical thickness was three- dimensionally measured on each cortical surface voxel by using a localized gradient vector trajectory in a fuzzy membership map. Spherical models with 3 mm artificial cortical regions, which were produced using three noise levels of 2%, 5%, and 10%, were employed to evaluate the proposed method. We also applied the proposed method to T1-weighted images obtained from 20 cases, i.e., 10 clinically diagnosed AD cases and 10 clinically normal (CN) subjects. The thicknesses of the 3 mm artificial cortical regions for spherical models with noise levels of 2%, 5%, and 10% were measured by the proposed method as 2.953 ± 0.342, 2.953 ± 0.342 and 2.952 ± 0.343 mm, respectively. Thus the mean thicknesses for the entire cerebral lobar region were 3.1 ± 0.4 mm for AD patients and 3.3 ± 0.4 mm for CN subjects, respectively (p < 0.05). The proposed method could be feasible for measuring the 3D cerebral cortical thickness on individual cortical surface voxels as an atrophy feature in AD.
基金funded by the National Natural Science Foundation of China(42071014).
文摘Gobi spans a large area of China,surpassing the combined expanse of mobile dunes and semi-fixed dunes.Its presence significantly influences the movement of sand and dust.However,the complex origins and diverse materials constituting the Gobi result in notable differences in saltation processes across various Gobi surfaces.It is challenging to describe these processes according to a uniform morphology.Therefore,it becomes imperative to articulate surface characteristics through parameters such as the three-dimensional(3D)size and shape of gravel.Collecting morphology information for Gobi gravels is essential for studying its genesis and sand saltation.To enhance the efficiency and information yield of gravel parameter measurements,this study conducted field experiments in the Gobi region across Dunhuang City,Guazhou County,and Yumen City(administrated by Jiuquan City),Gansu Province,China in March 2023.A research framework and methodology for measuring 3D parameters of gravel using point cloud were developed,alongside improved calculation formulas for 3D parameters including gravel grain size,volume,flatness,roundness,sphericity,and equivalent grain size.Leveraging multi-view geometry technology for 3D reconstruction allowed for establishing an optimal data acquisition scheme characterized by high point cloud reconstruction efficiency and clear quality.Additionally,the proposed methodology incorporated point cloud clustering,segmentation,and filtering techniques to isolate individual gravel point clouds.Advanced point cloud algorithms,including the Oriented Bounding Box(OBB),point cloud slicing method,and point cloud triangulation,were then deployed to calculate the 3D parameters of individual gravels.These systematic processes allow precise and detailed characterization of individual gravels.For gravel grain size and volume,the correlation coefficients between point cloud and manual measurements all exceeded 0.9000,confirming the feasibility of the proposed methodology for measuring 3D parameters of individual gravels.The proposed workflow yields accurate calculations of relevant parameters for Gobi gravels,providing essential data support for subsequent studies on Gobi environments.
文摘Four isomers of the three-dimensionally connected bare boron cationic cluster B were investigated by using ab initio molecular orbital theory at the HF/6-31G level. The results show that the D5h symmetric isomer of B is a possible isomer candidate of its stable geometries with closed structure.
基金supported by the National Natural Science Foundation of China (Grant Nos. 10974139 and 10964002) the Doctoral Program Foundation of the Institution of Higher Education of China (Grant No. 20050610010)
文摘The geometrical structures, relative stabilities, electronic and magnetic properties of small BnAl-（2〈n〈9）clusters are systematicalyy investigated by using the first-principles density functional theory. The results show that the A1 atom prefers to reside either on the outer-side or above the surface, but not in the centre of the clusters in all of the most stable BnAl-（2〈n〈9） isomers and the one excess electron is strong enough to modify the geometries of some specific sizes of the neutral clusters. All the results of the analysis for the fragmentation energies, the second-order difference of energies, and the highest occupied-lowest unoccupied molecular orbital energy gaps show that B4A1- and B8A1- clusters each have a higher relative stability. Especially, the BsA1-cluster has the most enhanced chemical stability. Furthermore, both the local magnetic moments and the total magnetic moments display a pronounced oddeven oscillation with the number of boron atoms, and the magnetic effects arise mainly from the boron atoms except for the B7A1- and BgA1- clusters.
基金financially supported by the Science and Tech-nology Innovation Base Project(No.226Z3606G)the National Natural Science Foundation of China(No.51802073)+3 种基金the Hebei Province Graduate Student Innovation Ability Training Project(No.CXZZBS2023040)the Hebei Province Eighth Batch of“100 People Plan”Project(No.E2018050008)the Natural Science Foundation of Hebei Province(No.E2018202129)Hebei Key Laboratory of Boron Nitride and Nano Materials.
文摘Solid electrolytes are the most promising candidate for replacing liquid electrolytes due to their safetyand chemical stability advantages. However, a single inorganic or organic solid electrolyte cannot meetthe requirements of commercial all-solid-state batteries (ASSBs), which motivates the composite polymerelectrolyte (CPE). Herein, a CPE of boron nitride nanofiber (BNNF) with a high specific surface area, richpore structure, and poly (ethylene oxide) (PEO) are reported. Anions strongly adsorb on the surface ofBNNF through electrostatic interactions based on oxygen vacancies, promoting the dissociation of lithiumsalts at the two-phase interface. The three-dimensional (3D) BNNF network provides three advantagesin the CPE, including (i) improving ionic conductivity through strong interaction between polymers andfillers, (ii) improving mechanical properties through weaving a robust skeleton, and (iii) improving stability through a rapid and uniform thermal dispersion pathway. Therefore, the CPE with BNNF delivers highionic conduction of 4.21 × 10^(−4) S cm^(−1) at 60 ℃ and excellent cycling stability (plating/stripping cyclesfor 2000 h with a low overpotential of ∼40 mV), which results in excellent electrochemical performanceof LiFePO_(4) (LFP) full cell assembled with CPE-5BNNF-1300 (152.7 mAh g^(−1) after 200 cycles at 0.5 C, and134.8 mAh g^(−1) at 2.0 C). Furthermore, when matched with high-voltage LiNi_(0.6)Co_(0.2)Mn_(0.2)O_(2) (NCM622), italso exhibits an outstanding rate capacity of 120.4 mAh g^(−1) at 1.0 C. This work provides insight into theBNNF composite electrolyte and promotes its practical application for ASSBs.
基金Project supported by the National Natural Science Foundation of China(Grant Nos.U1804121 and 11304167)
文摘Cluster science as a bridge linking atomic molecular physics and condensed matter inspired the nanomaterials development in the past decades, ranging from the single-atom catalysis to ligand-protected noble metal clusters. The corresponding studies not only have been restricted to the search for the geometrical structures of clusters, but also have promoted the development of cluster-assembled materials as the building blocks. The CALYPSO cluster prediction method combined with other computational techniques have significantly stimulated the development of the cluster-based nanomaterials. In this review, we will summarize some good cases of cluster structure by CALYPSO method, which have also been successfully identified by the photoelectron spectra experiments. Beginning with the alkali-metal clusters, which serve as benchmarks, a series of studies are performed on the size-dependent elemental clusters which possess relatively high stability and interesting chemical physical properties. Special attentions are paid to the boron-based clusters because of their promising applications. The NbSi12 and BeB16 clusters, for example, are two classic representatives of the silicon-and boron-based clusters, which can be viewed as building blocks of nanotubes and borophene. This review offers a detailed description of the structural evolutions and electronic properties of medium-sized pure and doped clusters, which will advance fundamental knowledge of cluster-based nanomaterials and provide valuable information for further theoretical and experimental studies.
基金financially supported by the National Natural Science Foundation of China(No.51972162)。
文摘Achieving thermal management composite material with isotropic thermal dissipation property by using an environmentally friendly and efficient method is one of the most challenging techniques as a traditional approach tending to form a horizontally arranged network within the polymer matrix or the preparation steps which are unduly cumbersome.What presented here is a closestack thermally conductive three-dimensional(3D)hybrid network structure prepared by a simple and green strategy that intercalating the modified aluminum oxide(m-Al_(2)O_(3))spheres of different sizes into the modified two-dimensional(2D)boron nitride(m-h-BN)flakes.An effective 3D network is created by the multi-dimensional fillers through volume exclusion and synergistic effects.The m-h-BN flakes facilitate in-plane heat transfer,while the variously sized m-Al_(2)O_(3)spheres insert into the gaps between adjacent m-h-BN flakes,which is conducive to the heat transfer in the out-of-plane direction.Additionally,strong interactions between the m-Al_(2)O_(3)and m-h-BN promote the effective heat flux inside the 3D hybrid network structure.The 3D hybrid composite displays favorable quasi-isotropic heat dissipation property(through-plane thermal conductivity of 2.2 W·m^(-1)·K^(-1)and in-plane thermal conductivity of 11.6 W·m^(-1)·K^(-1))in comparison with the single-filler composites.Furthermore,the hybrid-filler composite has excellent mechanical properties and thermal stability.The efficient heat dissipation capacity of the hybrid composite is further confirmed by a finite element simulation,which indicates that the sphere-flake hybrid structure possesses a higher thermal conductivity and faster thermal response performance than the single-filler system.The composite material has great potential in meeting the needs of emerging and advancing power systems.
基金supported by the National Natural Science Foundation of China(Grant Nos.61275040,60976046,and 61021003)the National Basic Research Program of China(Grant No.2012CB934200)
文摘The effects of ion doses on the properties of boron implanted Si for n-type solar cell application were investigated with doses ranging from 5×10^14cm^-2 to 2×10^15cm^-2 and a subsequent two-step annealing process in a tube furnace.With the help of the TCAD process simulation tool, knowledge on diffusion kinetics of dopants and damage evolution was obtained by fitting SIMS measured boron profiles. Due to insufficient elimination of the residual damage, the implanted emitter was found to have a higher saturation current density（J0e） and a poorer crystallographic quality. Consistent with this observation, V oc, J sc, and the efficiency of the all-implanted p^＋–n–n^＋solar cells followed a decreasing trend with an increase of the implantation dose. The obtained maximum efficiency was 19.59% at a low dose of 5×10^14cm^-2. The main efficiency loss under high doses came not only from increased recombination of carriers in the space charge region revealed by double-diode parameters of dark I–V curves, but also from the degraded minority carrier diffusion length in the emitter and base evidenced by IQE data. These experimental results indicated that clusters and dislocation loops had appeared at high implantation doses, which acted as effective recombination centers for photogenerated carriers.
基金acknowledge Department of Chemistry and Biochemistry at UCLA for start-up funds.Portions of this material are based upon work supported by the National Science Foundation(CHE-1048804)E.A.Q.acknowledges the USPHS of the National Institutes of Heath(NIH)for the predoctoral training fellowship through the UCLA Chemistry-Biology Interface Training Program under the National Research Service Award(T32GM008496)C.W.M.and C.P.K.acknowledge support for this work from the AFOSR through a Basic Research Initiative(BRI)grant(FA9550-12-1-0414).
文摘We have developed a fast and efficient route to obtain perfunctionalized ether-linked alkyl and benzyl derivatives of the closo-[B_(12)(OH)_(12)]^(2−)icosahedral dodecaborate cluster via microwave-assisted synthesis.These icosahedral boron clusters exhibit three-dimensional delocalization of the cage-bonding electrons,tunable photophysical properties,and a high degree of stability in air in both the solid state and in solution.A series of closo-[B_(12)(OR)_(12)]^(2−).
基金support of the Natural Science Foundation of China(No.21908193)Jinhua Industrial Key Project(2021A22648)+2 种基金support of Open Research Fund of Key Laboratory of the Ministry of Education for Advanced Catalysis Materials and Zhejiang Key Laboratory for Reactive Chemistry on Solid Surfaces,Zhejiang Normal University(KLMEACM202111)support of the National Natural Science Foundation of China(No.21871231)the Special Funds for Basic Scientific Research of Zhejiang University(No.2019QNA3010 and K20210335).
文摘The separation of acetylene (C_(2)H_(2)) from carbon dioxide (CO_(2)) and ethylene (C_(2)H_(4)) is important in industry but challenging due to their similar physical properties. Herein, a novel microporous boron cluster pillared metal–organic framework BSF-10 was synthesized with ligand inclusion for efficient C_(2)H_(2)/CO_(2) and C_(2)H_(2)/C_(2)H_(4) adsorption separation. The free dipyridyl ligands in the large pore reduce the porosity of BSF-10 but stabilize the framework. The available narrow pores without inclusion of ligands are suited for the accommodation of C_(2)H_(2) by cooperative dihydrogen bonding. High C_(2)H_(2) capacity and high C_(2)H_(2) selectivity over CO_(2) and C_(2)H_(4) are achieved. The practical separation ability was confirmed by the breakthroughs using C_(2)H_(2)/CO_(2) and C_(2)H_(2)/C_(2)H_(4) gas mixtures with good recyclability. The dynamic separation factor of 2.8 for the equimolar C_(2)H_(2)/CO_(2) mixture is comparable to those of many benchmark materials.
