Formic acid oxidation reaction(FAOR),as the anodic reaction in direct formic acid fuel cells,has attracted much attention but increasing the mass activity and stability of catalysts still face a bottleneck to meet the...Formic acid oxidation reaction(FAOR),as the anodic reaction in direct formic acid fuel cells,has attracted much attention but increasing the mass activity and stability of catalysts still face a bottleneck to meet the requirements of practical applications.In the past decades,researchers developed many strategies to fix these issues by improving the structure of catalysts and the newly raised single atom catalysts(SACs)show the high mass activity and stability in FAOR.This review first summarized the reaction mechanism involved in FAOR.The mass activity as well as stability of catalysts reported in the past five years have been outlined.Moreover,the synthetic strategies to improve the catalytic performance of catalysts are also reviewed in this work.Finally,we proposed the research directions to guide the rational design of new FAOR catalysts in the future.展开更多
The supported isolated Pt atoms(Pt iso)and other rare metals have attracted intensive concern due to their maximized metal utilization efficiency,unique reactivity or selectivity,connection to organometallic catalysis...The supported isolated Pt atoms(Pt iso)and other rare metals have attracted intensive concern due to their maximized metal utilization efficiency,unique reactivity or selectivity,connection to organometallic catalysis and the potential for making well-defined active sites[1-3].As catalytic active sites,oxide-supported isolated Pt-group metal atoms are well known for their unique reactivity and efficient metal utilization[4-6].Even continuous efforts have been made,it is still challenging to characterize the intrinsic ca-talytic activity of these dispersed active sites on oxide supports at a level that relates local electronic and geometric structure to function,because of their atomic dispersion,heterogeneity in the local coordination,dynamic changes in local coordination under reactive environments and low loading of metal[7-9].展开更多
A localized parametric time-sheared Gabor atom is derived by convolving a linear frequency modulated factor, modulating in frequency and translating in time to a dilated Gaussian function, which is the generalization ...A localized parametric time-sheared Gabor atom is derived by convolving a linear frequency modulated factor, modulating in frequency and translating in time to a dilated Gaussian function, which is the generalization of Gabor atom and is more delicate for matching most of the signals encountered in practice, especially for those having frequency dispersion characteristics. The time-frequency distribution of this atom concentrates in its time center and frequency center along energy curve, with the curve being oblique to a certain extent along the time axis. A novel parametric adaptive time-frequency distribution based on a set of the derived atoms is then proposed using a adaptive signal subspace decomposition method in frequency domain, which is non-negative time-frequency energy distribution and free of cross-term interference for multicomponent signals. The results of numerical simulation manifest the effectiveness of the approach in time-frequency representation and signal de-noising processing.展开更多
A quantitative structure-spectrum relationship (QSSR) model was developed to simulate 13C nuclear magnetic resonance (NMR) spectra of carbinol carbon atoms for 55 alcohols. The proposed model,using multiple linear reg...A quantitative structure-spectrum relationship (QSSR) model was developed to simulate 13C nuclear magnetic resonance (NMR) spectra of carbinol carbon atoms for 55 alcohols. The proposed model,using multiple linear regression,contained four descriptors solely extracted from the molecular structure of compounds. The statistical results of the final model show that R2= 0.982 4 and S=0.869 8 (where R is the correlation coefficient and S is the standard deviation). To test its predictive ability,the model was further used to predict the 13C NMR spectra of the carbinol carbon atoms of other nine compounds which were not included in the developed model. The average relative errors are 0.94% and 1.70%,respectively,for the training set and the predictive set. The model is statistically significant and shows good stability for data variation as tested by the leave-one-out (LOO) cross-validation. The comparison with other approaches also reveals good performance of this method.展开更多
A new iterative algorithm is proposed to reconstruct an unknown sparse signal from a set of projected measurements. Unlike existing greedy pursuit methods which only consider the atoms having the highest correlation w...A new iterative algorithm is proposed to reconstruct an unknown sparse signal from a set of projected measurements. Unlike existing greedy pursuit methods which only consider the atoms having the highest correlation with the residual signal, the proposed algorithm not only considers the higher correlation atoms but also reserves the lower correlation atoms with the residual signal. In the lower correlation atoms, only a few are correct which usually impact the reconstructive performance and decide the reconstruction dynamic range of greedy pursuit methods. The others are redundant. In order to avoid redundant atoms impacting the reconstructive accuracy, the Bayesian pursuit algorithm is used to eliminate them. Simulation results show that the proposed algorithm can improve the reconstructive dynamic range and the reconstructive accuracy. Furthermore, better noise immunity compared with the existing greedy pursuit methods can be obtained.展开更多
The design of cost-effective and efficient metal-free carbon-based catalysts for the hydrogen evolution reaction(HER)is of great significance for increasing the production of clean hydrogen by the electrolysis of alka...The design of cost-effective and efficient metal-free carbon-based catalysts for the hydrogen evolution reaction(HER)is of great significance for increasing the production of clean hydrogen by the electrolysis of alkaline water.Precise control of the electronic structure by heteroatom doping has proven to be efficient for increasing catalytic activity.Nevertheless,both the structural characteristics and the underlying mechanism are not well understood,especially for doping with two different atoms,thus limiting the use of these catalysts.We report the production of phosphorus and nitrogen co-doped hollow carbon nanospheres(HCNs)by the copolymerization of pyrrole and aniline at a Triton X-100 micelle-interface,followed by doping with phytic acid and carbonization.The unique pore structure and defect-rich framework of the HCNs expose numerous active sites.Crucially,the combined effect of graphitic nitrogen and phosphorus-carbon bonds modulate the local electronic structure of adjacent C atoms and facilitates electron transfer.As a res-ult,the HCN carbonized at 1100°C exhibited superior HER activity and an outstanding stability(70 h at a current density of 10 mA cm^(−2))in alkaline water,because of the large number of graphitic nitrogen and phosphorus-carbon bonds.展开更多
Broadband transparent films play a pivotal role in various applications such as lenses and solar cells,particularly porous structured transparent films exhibit significant potential.This study investigates a porous Si...Broadband transparent films play a pivotal role in various applications such as lenses and solar cells,particularly porous structured transparent films exhibit significant potential.This study investigates a porous SiO_(2) refractive index gradient anti-reflective film prepared by atomic layer deposition(ALD).A porous SiO_(2) film with gradual porosity was obtained by phosphoric acid etching of Al_(2)O_(3)/SiO_(2) multilayers with gradient Al2O3 ratios,achieving a gradual decrease in refractive index from the substrate to the surface.The film exhibited an average transmittance as high as 97.8%within the wavelength range from 320 nm to 1200 nm.The environmental adaptability was further enhanced by surface modification using rare earth oxide(REO)La_(2)O_(3),resulting in formation of a lotus leaf-like structure and achieving a water contact angle of 100.0°.These data proved that the modification significantly improved hydrophobic self-cleaning capability while maintaining exceptional transparency of the film.The surface structure of the modified film remained undamaged even after undergoing wipe testing,demonstrating its excellent surface durability.展开更多
Polymeric perylene diimide(PDI)has been evidenced as a good candidate for photocatalytic water oxidation,yet the origin of the photocatalytic oxygen evolution activity remains unclear and needs further exploration.Her...Polymeric perylene diimide(PDI)has been evidenced as a good candidate for photocatalytic water oxidation,yet the origin of the photocatalytic oxygen evolution activity remains unclear and needs further exploration.Herein,with crystal and atomic structures of the self-assembled PDI revealed from the X-ray diffraction pattern,the electronic structure is theoretically illustrated by the first-principles density functional theory calculations,suggesting the suitable band structure and the direct electronic transition for efficient photocatalytic oxygen evolution over PDI.It is confirmed that the carbonyl O atoms on the conjugation structure serve as the active sites for oxygen evolution reaction by the crystal orbital Hamiltonian group analysis.The calculations of reaction free energy changes indicate that the oxygen evolution reaction should follow the reaction pathway of H_(2)O→^(*)OH→^(*)O→^(*)OOH→^(*)O_(2)with an overpotential of 0.81 V.Through an in-depth theoretical computational analysis in the atomic and electronic structures,the origin of photocatalytic oxygen evolution activity for PDI is well illustrated,which would help the rational design and modification of polymeric photocatalysts for efficient oxygen evolution.展开更多
This work presents a method for the three-dimensional localization of individual shallow NV center in diamond,leveraging the near-field quenching effect of a gold tip.Our experimental setup involves the use of an atom...This work presents a method for the three-dimensional localization of individual shallow NV center in diamond,leveraging the near-field quenching effect of a gold tip.Our experimental setup involves the use of an atomic force microscope to precisely move the gold tip close to the NV center,while simultaneously employing a home-made confocal microscope to monitor the fluorescence of the NV center.This approach allows for lateral super-resolution,achieving a full width at half maximum(FWHM)of 38.0 nm and a location uncertainty of 0.7 nm.Additionally,we show the potential of this method for determining the depth of the NV centers.We also attempt to determine the depth of the NV centers in combination with finite-difference time-domain(FDTD)simulations.Compared to other depth determination methods,this approach allows for simultaneous lateral and longitudinal localization of individual NV centers,and holds promise for facilitating manipulation of the local environment surrounding the NV center.展开更多
Electrocatalytic reduction of carbon dioxide(CO_(2))to carbon monoxide(CO)is an effective strategy to achieve carbon neutrality.High selective and low-cost catalysts for the electrocatalytic reduction of CO_(2)have re...Electrocatalytic reduction of carbon dioxide(CO_(2))to carbon monoxide(CO)is an effective strategy to achieve carbon neutrality.High selective and low-cost catalysts for the electrocatalytic reduction of CO_(2)have received increasing attention.In contrast to the conventional tube furnace method,the high-temperature shock(HTS)method enables ultra-fast thermal processing,superior atomic efficiency,and a streamlined synthesis protocol,offering a simplified method for the preparation of high-performance single-atom catalysts(SACs).The reports have shown that nickel-based SACs can be synthesized quickly and conveniently using the HTS method,making their application in CO_(2)reduction reactions(CO_(2)RR)a viable and promising avenue for further exploration.In this study,the effect of heating temperature,metal loading and different nitrogen(N)sources on the catalyst morphology,coordination environment and electrocatalytic performance were investigated.Under optimal conditions,0.05Ni-DCD-C-1050 showed excellent performance in reducing CO_(2)to CO,with CO selectivity close to 100%(−0.7 to−1.0 V vs RHE)and current density as high as 130 mA/cm^(2)(−1.1 V vs RHE)in a flow cell under alkaline environment.展开更多
Effects of ultrasonic bonding parameters on atomic diffusion, microstructure at the Al-Au interface, and shear strength of Al-Au ultrasonic bonding were investigated by the combining experiments and finite element (FE...Effects of ultrasonic bonding parameters on atomic diffusion, microstructure at the Al-Au interface, and shear strength of Al-Au ultrasonic bonding were investigated by the combining experiments and finite element (FE) simulation. The quantitative model of atomic diffusion, which is related to the ultrasonic bonding parameters, time and distance, is established to calculate the atomic diffusion of the Al-Au interface. The maximum relative error between the calculated and experimental fraction of Al atom is 7.35%, indicating high prediction accuracy of this model. During the process of ultrasonic bonding, Au8Al3 is the main intermetallic compound (IMC) at the Al-Au interface. With larger bonding forces, higher ultrasonic powers and longer bonding time, it is more difficult to remove the oxide particles from the Al-Au interface, which hinders the atomic diffusion. Therefore, the complicated stress state and the existence of oxide particles both promotes the formation of holes. The shear strength of Al-Au ultrasonic bonding increases with increasing bonding force, ultrasonic power and bonding time. However, combined with the presence of holes at especial parameters, the optimal ultrasonic bonding parameter is confirmed to be a bonding force of 23 gf, ultrasonic power of 75 mW and bonding time of 21 ms.展开更多
Materials with low thermal conductivity are applied extensively in energy management,and breaking the amorphous limits of thermal conductivity to solids has attracted widespread attention from scientists.Doping is a c...Materials with low thermal conductivity are applied extensively in energy management,and breaking the amorphous limits of thermal conductivity to solids has attracted widespread attention from scientists.Doping is a common strategy for achieving low thermal conductivity that can offer abundant scattering centers in which heavier dopants always result in lower phonon group velocities and lower thermal conductivities.However,the amount of equivalent heavyatom single dopant available is limited.Unfortunately,nonequivalent heavy dopants have finite solubility because of charge imbalance.Here,we propose a charge balance strategy for SnS by substituting Sn2+with Ag^(+)and heavy Bi^(3+),improving the doping limit of Ag from 2%to 3%.Ag and Bi codoping increases the point defect concentration and introduces abundant boundaries simultaneously,scattering the phonons at both the atomic scale and nanoscale.The thermal conductivity of Ag0.03Bi0.03Sn0.94S decreased to 0.535 W·m^(−1)·K^(−1)at room temperature and 0.388 W·m^(−1)·K^(−1)at 275°C,which is below the amorphous limit of 0.450 W·m^(−1)·K^(−1)for SnS.This strategy offers a simple way to enhance the doping limit and achieve ultralow thermal conductivity in solids below the amorphous limit without precise structural modification.展开更多
In this paper,we study the accuracy of delay-Doppler parameter estimation of targets in a passive radar using orthogonal frequency division multiplexing(OFDM)signal.A coarse-fine joint estimation method is proposed to...In this paper,we study the accuracy of delay-Doppler parameter estimation of targets in a passive radar using orthogonal frequency division multiplexing(OFDM)signal.A coarse-fine joint estimation method is proposed to achieve better estimation accuracy of target parameters without excessive computational burden.Firstly,the modulation symbol domain(MSD)method is used to roughly estimate the delay and Doppler of targets.Then,to obtain high-precision Doppler estimation,the atomic norm(AN)based on the multiple measurement vectors(MMV)model(MMV-AN)is used to manifest the signal sparsity in the continuous Doppler domain.At the same time,a reference signal compensation(RSC)method is presented to obtain highprecision delay estimation.Simulation results based on the OFDM signal show that the coarse-fine joint estimation method based on AN-RSC can obtain a more accurate estimation of target parameters compared with other algorithms.In addition,the proposed method also possesses computational advantages compared with the joint parameter estimation.展开更多
new coordination polymer {[Zn(CF3COO)2(C5H5ON)]·H2O}n was synthesized based on the reaction of zinc(Ⅱ) trifluoroacetate and 3-hydroxypyridine(C5H5ON) in methanol medium for the first time. The structure of the c...new coordination polymer {[Zn(CF3COO)2(C5H5ON)]·H2O}n was synthesized based on the reaction of zinc(Ⅱ) trifluoroacetate and 3-hydroxypyridine(C5H5ON) in methanol medium for the first time. The structure of the coordination polymer was confirmed by IR, 1H NMR, elemental analysis and thermal analysis. The crystal structure of the coordination polymer was also determined by X-ray single crystal diffraction. The crystal belongs to monoclinic system with space group P21/m, and crystallographic data of the coordination polymer are: a= 0.863 1(4) nm, b=0.717 7(3) nm, c=1.116 4(5) nm, α=γ=90°, β=107.542(6)°, V=0.659 4(5) nm3; Dc=2.037 g·cm-3; Z=2; F(000)=400; μ=1.969 mm-1. Zinc(Ⅱ) atom lies at the center of an octahedron formed by the coordination of zinc atom and six O atoms which come from four different trifluoroacetate ions and two different 3-hydroxypyridine molecules where each trifluoroacetate ion and 3-hydroxypyridine are coordinated to two different zinc ions to form coordination polymer. CCDC: 253909.展开更多
A new binuclear copper(Ⅱ) complex, [Cu2(phen)2(H2O)2( μ2-C2O4)](NO3)2, has been synthesized and characterized by elemental analysis, IR and UV-Vis spectrum. Its crystal structure was determined by single crystal X-r...A new binuclear copper(Ⅱ) complex, [Cu2(phen)2(H2O)2( μ2-C2O4)](NO3)2, has been synthesized and characterized by elemental analysis, IR and UV-Vis spectrum. Its crystal structure was determined by single crystal X-ray diffraction techniques. Crystal data: monoclinic, space group P21/c, a=0.712 21(8) nm, b=1.170 93(14) nm, c=1.783 7(2) nm, β=111.828(2)°, and V=1.380 8(3) nm3, Dc=1.769 Mg·m-3, Z=2, F(000)=744, R1=0.025 4, wR2=0.069 5, Gof=1.077, Δρ=328^-455 e·nm-3. The complex is packed by one centrosymmetry binuclear copper(Ⅱ) unit, oxalate dianion and NO3- anion. In the molecule structure of the title complex, two Cu(Ⅱ) ions are bridged by oxalate dianion and each Cu(Ⅱ) ions coordinates with two nitrogen atoms from 1,10-phenanthroline ligand and one oxygen atom from water to form a five-coordinate distorted square-pyramidal configuration. The hydrogen bonds are observed between coordinated water molecules and NO3- anions. The analysis of the crystal structure indicates that the complex has a two-dimensional stacking network structure, which is formed by intramolecular hydrogen bonds, intermolecular hydrogen bonds and stacking effect of aromatic ring. CCDC: 255345.展开更多
The μ-oxygen-bis[tri(p-fluorobenzyl)tin] was synthesized. The structure were characterized by elementary analysis, IR and 1H NMR and the crystal structure were determined by X-ray single crystal diffraction. The crys...The μ-oxygen-bis[tri(p-fluorobenzyl)tin] was synthesized. The structure were characterized by elementary analysis, IR and 1H NMR and the crystal structure were determined by X-ray single crystal diffraction. The crystal of the title compound belongs to rhombohedral with space group R, a=1.346 4(4), b=1.346 4(4), c=1.772 9(7) nm, α=90°, β=90°, γ=120°, Z=3, V=2.783 2(15) nm3, Dc=1.625 g·cm-3, μ(Mo Kα)=1.408 mm-1, S=1.088, F(000)=1 350, R1=0.027 5, wR2=0.065 9. In compound, the tin atom has a distorted tetrahedral coordination configuration. CCDC: 257079.展开更多
Diorganotin(Ⅳ) compound [(p-CNC6H4CH2)2Sn(C9H7N3O3)(H2O)]2 was synthesized by the reaction of tri-p-cyanobenzyltin chloride with Schiff base ligand pyruvic acid isonicotinyl hydrazone. The compound was characterized ...Diorganotin(Ⅳ) compound [(p-CNC6H4CH2)2Sn(C9H7N3O3)(H2O)]2 was synthesized by the reaction of tri-p-cyanobenzyltin chloride with Schiff base ligand pyruvic acid isonicotinyl hydrazone. The compound was characterized by elemental analysis, IR, 1H NMR. The crystal structure was determined by X-ray single crystal diffraction. The crystal belongs to monoclinic space group C2/c, with a=3.143 1(3) nm, b=0.989 99(10) nm, c=1.785 68(18) nm, β=114.908 0(13)°, V=5.039 6(9) nm3, Z=4, μ=1.054 mm-1, Dc=1.513 Mg·m-3, F(000)=2 304, R=0.042 8, wR=0.090 3, GOF=0.997. In this compound, the Sn atom exists in a distorted octahedral coordination environment in which one water molecule, one tridentate pyruvic acid isonicotinyl hydrazone ligand, and two trans p-cyanobenzyl groups coordinate to each Sn center, the angle of the axial C10-Sn1-C18 is 166.1(2)°. Two molecules form a weak-bridged dimmer with weak interactions of Sn...O bonding and hydrogen bonds. CCDC: 270796.展开更多
基金Project(22102218)supported by the National Natural Science Foundation of ChinaProject(2022RC1110)supported by the Science and Technology Innovation Program of Hunan Province,ChinaProject(2022QNRC001)supported by the Young Elite Scientists Sponsorship Program by CAST,China。
文摘Formic acid oxidation reaction(FAOR),as the anodic reaction in direct formic acid fuel cells,has attracted much attention but increasing the mass activity and stability of catalysts still face a bottleneck to meet the requirements of practical applications.In the past decades,researchers developed many strategies to fix these issues by improving the structure of catalysts and the newly raised single atom catalysts(SACs)show the high mass activity and stability in FAOR.This review first summarized the reaction mechanism involved in FAOR.The mass activity as well as stability of catalysts reported in the past five years have been outlined.Moreover,the synthetic strategies to improve the catalytic performance of catalysts are also reviewed in this work.Finally,we proposed the research directions to guide the rational design of new FAOR catalysts in the future.
文摘The supported isolated Pt atoms(Pt iso)and other rare metals have attracted intensive concern due to their maximized metal utilization efficiency,unique reactivity or selectivity,connection to organometallic catalysis and the potential for making well-defined active sites[1-3].As catalytic active sites,oxide-supported isolated Pt-group metal atoms are well known for their unique reactivity and efficient metal utilization[4-6].Even continuous efforts have been made,it is still challenging to characterize the intrinsic ca-talytic activity of these dispersed active sites on oxide supports at a level that relates local electronic and geometric structure to function,because of their atomic dispersion,heterogeneity in the local coordination,dynamic changes in local coordination under reactive environments and low loading of metal[7-9].
基金This project was supported by the National Natural Science Foundation of China (60472102)Shanghai Leading Academic Discipline Project (T0103).
文摘A localized parametric time-sheared Gabor atom is derived by convolving a linear frequency modulated factor, modulating in frequency and translating in time to a dilated Gaussian function, which is the generalization of Gabor atom and is more delicate for matching most of the signals encountered in practice, especially for those having frequency dispersion characteristics. The time-frequency distribution of this atom concentrates in its time center and frequency center along energy curve, with the curve being oblique to a certain extent along the time axis. A novel parametric adaptive time-frequency distribution based on a set of the derived atoms is then proposed using a adaptive signal subspace decomposition method in frequency domain, which is non-negative time-frequency energy distribution and free of cross-term interference for multicomponent signals. The results of numerical simulation manifest the effectiveness of the approach in time-frequency representation and signal de-noising processing.
基金Projects(20775010, 21075011) supported by the National Natural Science Foundation of ChinaProject(2008AA05Z405) supported by the National High-tech Research and Development Program of China+2 种基金Project(09JJ3016) supported by the Natural Science Foundation of Hunan Province, ChinaProject(09C066) supported by the Scientific Research Fund of Hunan Provincial Education Department, ChinaProject(2010CL01) supported by the Foundation of Hunan Provincial Key Laboratory of Materials Protection for Electric Power and Transportation, China
文摘A quantitative structure-spectrum relationship (QSSR) model was developed to simulate 13C nuclear magnetic resonance (NMR) spectra of carbinol carbon atoms for 55 alcohols. The proposed model,using multiple linear regression,contained four descriptors solely extracted from the molecular structure of compounds. The statistical results of the final model show that R2= 0.982 4 and S=0.869 8 (where R is the correlation coefficient and S is the standard deviation). To test its predictive ability,the model was further used to predict the 13C NMR spectra of the carbinol carbon atoms of other nine compounds which were not included in the developed model. The average relative errors are 0.94% and 1.70%,respectively,for the training set and the predictive set. The model is statistically significant and shows good stability for data variation as tested by the leave-one-out (LOO) cross-validation. The comparison with other approaches also reveals good performance of this method.
基金supported by the National Natural Science Foundation of China (61172138)the Specialized Research Fund for the Doctoral Program of Higher Education (200807011007)the Natural Science Basic Research Program in Shannxi Province of China (2013JQ8040)
文摘A new iterative algorithm is proposed to reconstruct an unknown sparse signal from a set of projected measurements. Unlike existing greedy pursuit methods which only consider the atoms having the highest correlation with the residual signal, the proposed algorithm not only considers the higher correlation atoms but also reserves the lower correlation atoms with the residual signal. In the lower correlation atoms, only a few are correct which usually impact the reconstructive performance and decide the reconstruction dynamic range of greedy pursuit methods. The others are redundant. In order to avoid redundant atoms impacting the reconstructive accuracy, the Bayesian pursuit algorithm is used to eliminate them. Simulation results show that the proposed algorithm can improve the reconstructive dynamic range and the reconstructive accuracy. Furthermore, better noise immunity compared with the existing greedy pursuit methods can be obtained.
基金financially supported by the project of the National Natural Science Foundation of China(52322203)the Key Research and Development Program of Shaanxi Province(2024GHZDXM-21)。
文摘The design of cost-effective and efficient metal-free carbon-based catalysts for the hydrogen evolution reaction(HER)is of great significance for increasing the production of clean hydrogen by the electrolysis of alkaline water.Precise control of the electronic structure by heteroatom doping has proven to be efficient for increasing catalytic activity.Nevertheless,both the structural characteristics and the underlying mechanism are not well understood,especially for doping with two different atoms,thus limiting the use of these catalysts.We report the production of phosphorus and nitrogen co-doped hollow carbon nanospheres(HCNs)by the copolymerization of pyrrole and aniline at a Triton X-100 micelle-interface,followed by doping with phytic acid and carbonization.The unique pore structure and defect-rich framework of the HCNs expose numerous active sites.Crucially,the combined effect of graphitic nitrogen and phosphorus-carbon bonds modulate the local electronic structure of adjacent C atoms and facilitates electron transfer.As a res-ult,the HCN carbonized at 1100°C exhibited superior HER activity and an outstanding stability(70 h at a current density of 10 mA cm^(−2))in alkaline water,because of the large number of graphitic nitrogen and phosphorus-carbon bonds.
文摘Broadband transparent films play a pivotal role in various applications such as lenses and solar cells,particularly porous structured transparent films exhibit significant potential.This study investigates a porous SiO_(2) refractive index gradient anti-reflective film prepared by atomic layer deposition(ALD).A porous SiO_(2) film with gradual porosity was obtained by phosphoric acid etching of Al_(2)O_(3)/SiO_(2) multilayers with gradient Al2O3 ratios,achieving a gradual decrease in refractive index from the substrate to the surface.The film exhibited an average transmittance as high as 97.8%within the wavelength range from 320 nm to 1200 nm.The environmental adaptability was further enhanced by surface modification using rare earth oxide(REO)La_(2)O_(3),resulting in formation of a lotus leaf-like structure and achieving a water contact angle of 100.0°.These data proved that the modification significantly improved hydrophobic self-cleaning capability while maintaining exceptional transparency of the film.The surface structure of the modified film remained undamaged even after undergoing wipe testing,demonstrating its excellent surface durability.
基金supported by National Natural Science Foundation of China(No.523B2070,No.52225606).
文摘Polymeric perylene diimide(PDI)has been evidenced as a good candidate for photocatalytic water oxidation,yet the origin of the photocatalytic oxygen evolution activity remains unclear and needs further exploration.Herein,with crystal and atomic structures of the self-assembled PDI revealed from the X-ray diffraction pattern,the electronic structure is theoretically illustrated by the first-principles density functional theory calculations,suggesting the suitable band structure and the direct electronic transition for efficient photocatalytic oxygen evolution over PDI.It is confirmed that the carbonyl O atoms on the conjugation structure serve as the active sites for oxygen evolution reaction by the crystal orbital Hamiltonian group analysis.The calculations of reaction free energy changes indicate that the oxygen evolution reaction should follow the reaction pathway of H_(2)O→^(*)OH→^(*)O→^(*)OOH→^(*)O_(2)with an overpotential of 0.81 V.Through an in-depth theoretical computational analysis in the atomic and electronic structures,the origin of photocatalytic oxygen evolution activity for PDI is well illustrated,which would help the rational design and modification of polymeric photocatalysts for efficient oxygen evolution.
基金supported by the National Natural Science Foundation of China(T2325023,92265204,12104447)the National Key R&D Program of China(2023YFF0718400)+1 种基金the Innovation Program for Quantum Science and Technology(2021ZD0302200)the Fundamental Research Funds for the Central Universities。
文摘This work presents a method for the three-dimensional localization of individual shallow NV center in diamond,leveraging the near-field quenching effect of a gold tip.Our experimental setup involves the use of an atomic force microscope to precisely move the gold tip close to the NV center,while simultaneously employing a home-made confocal microscope to monitor the fluorescence of the NV center.This approach allows for lateral super-resolution,achieving a full width at half maximum(FWHM)of 38.0 nm and a location uncertainty of 0.7 nm.Additionally,we show the potential of this method for determining the depth of the NV centers.We also attempt to determine the depth of the NV centers in combination with finite-difference time-domain(FDTD)simulations.Compared to other depth determination methods,this approach allows for simultaneous lateral and longitudinal localization of individual NV centers,and holds promise for facilitating manipulation of the local environment surrounding the NV center.
基金supported by the National Key R&D Program of China(2024YFB4106400)National Natural Science Foundation of China(22209200,52302331)。
文摘Electrocatalytic reduction of carbon dioxide(CO_(2))to carbon monoxide(CO)is an effective strategy to achieve carbon neutrality.High selective and low-cost catalysts for the electrocatalytic reduction of CO_(2)have received increasing attention.In contrast to the conventional tube furnace method,the high-temperature shock(HTS)method enables ultra-fast thermal processing,superior atomic efficiency,and a streamlined synthesis protocol,offering a simplified method for the preparation of high-performance single-atom catalysts(SACs).The reports have shown that nickel-based SACs can be synthesized quickly and conveniently using the HTS method,making their application in CO_(2)reduction reactions(CO_(2)RR)a viable and promising avenue for further exploration.In this study,the effect of heating temperature,metal loading and different nitrogen(N)sources on the catalyst morphology,coordination environment and electrocatalytic performance were investigated.Under optimal conditions,0.05Ni-DCD-C-1050 showed excellent performance in reducing CO_(2)to CO,with CO selectivity close to 100%(−0.7 to−1.0 V vs RHE)and current density as high as 130 mA/cm^(2)(−1.1 V vs RHE)in a flow cell under alkaline environment.
基金Project(2022YFB3707201) supported by the National Key R&D Program of ChinaProject(U2341254) supported by the Ye Qisun Science Foundation of National Natural Science Foundation of China+1 种基金Projects(0604022GH0202143,0604022SH0201143) supported by the NPU Aoxiang Distinguished Young Scholars,ChinaProject supported by the Funding of Young Top-notch Talent of the National Ten Thousand Talent Program,China。
文摘Effects of ultrasonic bonding parameters on atomic diffusion, microstructure at the Al-Au interface, and shear strength of Al-Au ultrasonic bonding were investigated by the combining experiments and finite element (FE) simulation. The quantitative model of atomic diffusion, which is related to the ultrasonic bonding parameters, time and distance, is established to calculate the atomic diffusion of the Al-Au interface. The maximum relative error between the calculated and experimental fraction of Al atom is 7.35%, indicating high prediction accuracy of this model. During the process of ultrasonic bonding, Au8Al3 is the main intermetallic compound (IMC) at the Al-Au interface. With larger bonding forces, higher ultrasonic powers and longer bonding time, it is more difficult to remove the oxide particles from the Al-Au interface, which hinders the atomic diffusion. Therefore, the complicated stress state and the existence of oxide particles both promotes the formation of holes. The shear strength of Al-Au ultrasonic bonding increases with increasing bonding force, ultrasonic power and bonding time. However, combined with the presence of holes at especial parameters, the optimal ultrasonic bonding parameter is confirmed to be a bonding force of 23 gf, ultrasonic power of 75 mW and bonding time of 21 ms.
基金supported by the CAS Project for Young Scientists in Basic Research(YSBR-070)the National Natural Science Foundation of China(21925110,21890750,U2032161,12147105)+8 种基金the USTC Research Funds of the Double First-Class Initiative(YD2060002004)the National Key Research and Development Program of China(2022YFA1203600,2022YFA1203601,2022YFA1203602)the Natural Science Foundation of China-Anhui Joint Fund(U23A20121)the Outstanding Youth Foundation of Anhui Province(2208085J14)the Anhui Provincial Key Research and Development Project(202004a050200760)the Key R&D Program of Shandong Province(2021CXGC010302)the Users with Excellence Project of Hefei Science Center CAS(2021HSC-UE004)the Fellowship of the China Postdoctoral Science Foundation(2022M710141)the open foundation of the Key Laboratory of the Engineering Research Center of Building Energy Efficiency Control and Evaluation,Ministry of Education(AHJZNX-2023-04).
文摘Materials with low thermal conductivity are applied extensively in energy management,and breaking the amorphous limits of thermal conductivity to solids has attracted widespread attention from scientists.Doping is a common strategy for achieving low thermal conductivity that can offer abundant scattering centers in which heavier dopants always result in lower phonon group velocities and lower thermal conductivities.However,the amount of equivalent heavyatom single dopant available is limited.Unfortunately,nonequivalent heavy dopants have finite solubility because of charge imbalance.Here,we propose a charge balance strategy for SnS by substituting Sn2+with Ag^(+)and heavy Bi^(3+),improving the doping limit of Ag from 2%to 3%.Ag and Bi codoping increases the point defect concentration and introduces abundant boundaries simultaneously,scattering the phonons at both the atomic scale and nanoscale.The thermal conductivity of Ag0.03Bi0.03Sn0.94S decreased to 0.535 W·m^(−1)·K^(−1)at room temperature and 0.388 W·m^(−1)·K^(−1)at 275°C,which is below the amorphous limit of 0.450 W·m^(−1)·K^(−1)for SnS.This strategy offers a simple way to enhance the doping limit and achieve ultralow thermal conductivity in solids below the amorphous limit without precise structural modification.
基金supported by the National Natural Science Foundation of China(6193101562071335)+1 种基金the Technological Innovation Project of Hubei Province of China(2019AAA061)the Natural Science F oundation of Hubei Province of China(2021CFA002)。
文摘In this paper,we study the accuracy of delay-Doppler parameter estimation of targets in a passive radar using orthogonal frequency division multiplexing(OFDM)signal.A coarse-fine joint estimation method is proposed to achieve better estimation accuracy of target parameters without excessive computational burden.Firstly,the modulation symbol domain(MSD)method is used to roughly estimate the delay and Doppler of targets.Then,to obtain high-precision Doppler estimation,the atomic norm(AN)based on the multiple measurement vectors(MMV)model(MMV-AN)is used to manifest the signal sparsity in the continuous Doppler domain.At the same time,a reference signal compensation(RSC)method is presented to obtain highprecision delay estimation.Simulation results based on the OFDM signal show that the coarse-fine joint estimation method based on AN-RSC can obtain a more accurate estimation of target parameters compared with other algorithms.In addition,the proposed method also possesses computational advantages compared with the joint parameter estimation.
文摘new coordination polymer {[Zn(CF3COO)2(C5H5ON)]·H2O}n was synthesized based on the reaction of zinc(Ⅱ) trifluoroacetate and 3-hydroxypyridine(C5H5ON) in methanol medium for the first time. The structure of the coordination polymer was confirmed by IR, 1H NMR, elemental analysis and thermal analysis. The crystal structure of the coordination polymer was also determined by X-ray single crystal diffraction. The crystal belongs to monoclinic system with space group P21/m, and crystallographic data of the coordination polymer are: a= 0.863 1(4) nm, b=0.717 7(3) nm, c=1.116 4(5) nm, α=γ=90°, β=107.542(6)°, V=0.659 4(5) nm3; Dc=2.037 g·cm-3; Z=2; F(000)=400; μ=1.969 mm-1. Zinc(Ⅱ) atom lies at the center of an octahedron formed by the coordination of zinc atom and six O atoms which come from four different trifluoroacetate ions and two different 3-hydroxypyridine molecules where each trifluoroacetate ion and 3-hydroxypyridine are coordinated to two different zinc ions to form coordination polymer. CCDC: 253909.
文摘A new binuclear copper(Ⅱ) complex, [Cu2(phen)2(H2O)2( μ2-C2O4)](NO3)2, has been synthesized and characterized by elemental analysis, IR and UV-Vis spectrum. Its crystal structure was determined by single crystal X-ray diffraction techniques. Crystal data: monoclinic, space group P21/c, a=0.712 21(8) nm, b=1.170 93(14) nm, c=1.783 7(2) nm, β=111.828(2)°, and V=1.380 8(3) nm3, Dc=1.769 Mg·m-3, Z=2, F(000)=744, R1=0.025 4, wR2=0.069 5, Gof=1.077, Δρ=328^-455 e·nm-3. The complex is packed by one centrosymmetry binuclear copper(Ⅱ) unit, oxalate dianion and NO3- anion. In the molecule structure of the title complex, two Cu(Ⅱ) ions are bridged by oxalate dianion and each Cu(Ⅱ) ions coordinates with two nitrogen atoms from 1,10-phenanthroline ligand and one oxygen atom from water to form a five-coordinate distorted square-pyramidal configuration. The hydrogen bonds are observed between coordinated water molecules and NO3- anions. The analysis of the crystal structure indicates that the complex has a two-dimensional stacking network structure, which is formed by intramolecular hydrogen bonds, intermolecular hydrogen bonds and stacking effect of aromatic ring. CCDC: 255345.
文摘The μ-oxygen-bis[tri(p-fluorobenzyl)tin] was synthesized. The structure were characterized by elementary analysis, IR and 1H NMR and the crystal structure were determined by X-ray single crystal diffraction. The crystal of the title compound belongs to rhombohedral with space group R, a=1.346 4(4), b=1.346 4(4), c=1.772 9(7) nm, α=90°, β=90°, γ=120°, Z=3, V=2.783 2(15) nm3, Dc=1.625 g·cm-3, μ(Mo Kα)=1.408 mm-1, S=1.088, F(000)=1 350, R1=0.027 5, wR2=0.065 9. In compound, the tin atom has a distorted tetrahedral coordination configuration. CCDC: 257079.
文摘Diorganotin(Ⅳ) compound [(p-CNC6H4CH2)2Sn(C9H7N3O3)(H2O)]2 was synthesized by the reaction of tri-p-cyanobenzyltin chloride with Schiff base ligand pyruvic acid isonicotinyl hydrazone. The compound was characterized by elemental analysis, IR, 1H NMR. The crystal structure was determined by X-ray single crystal diffraction. The crystal belongs to monoclinic space group C2/c, with a=3.143 1(3) nm, b=0.989 99(10) nm, c=1.785 68(18) nm, β=114.908 0(13)°, V=5.039 6(9) nm3, Z=4, μ=1.054 mm-1, Dc=1.513 Mg·m-3, F(000)=2 304, R=0.042 8, wR=0.090 3, GOF=0.997. In this compound, the Sn atom exists in a distorted octahedral coordination environment in which one water molecule, one tridentate pyruvic acid isonicotinyl hydrazone ligand, and two trans p-cyanobenzyl groups coordinate to each Sn center, the angle of the axial C10-Sn1-C18 is 166.1(2)°. Two molecules form a weak-bridged dimmer with weak interactions of Sn...O bonding and hydrogen bonds. CCDC: 270796.
