In this manuscript,we consider a non-autonomous dynamical system.Using the Carathéodory structure,we define a BS dimension on an arbitrary subset and obtain a Bowen’s equation that illustrates the relation of th...In this manuscript,we consider a non-autonomous dynamical system.Using the Carathéodory structure,we define a BS dimension on an arbitrary subset and obtain a Bowen’s equation that illustrates the relation of the BS dimension to the Pesin-Pitskel topological pressure given by Nazarian[24].Moreover,we establish a variational principle and an inverse variational principle for the BS dimension of non-autonomous dynamical systems.Finally,we also get an analogue of Billingsley’s theorem for the BS dimension of non-autonomous dynamical systems.展开更多
Owing to their global search capabilities and gradient-free operation,metaheuristic algorithms are widely applied to a wide range of optimization problems.However,their computational demands become prohibitive when ta...Owing to their global search capabilities and gradient-free operation,metaheuristic algorithms are widely applied to a wide range of optimization problems.However,their computational demands become prohibitive when tackling high-dimensional optimization challenges.To effectively address these challenges,this study introduces cooperative metaheuristics integrating dynamic dimension reduction(DR).Building upon particle swarm optimization(PSO)and differential evolution(DE),the proposed cooperative methods C-PSO and C-DE are developed.In the proposed methods,the modified principal components analysis(PCA)is utilized to reduce the dimension of design variables,thereby decreasing computational costs.The dynamic DR strategy implements periodic execution of modified PCA after a fixed number of iterations,resulting in the important dimensions being dynamically identified.Compared with the static one,the dynamic DR strategy can achieve precise identification of important dimensions,thereby enabling accelerated convergence toward optimal solutions.Furthermore,the influence of cumulative contribution rate thresholds on optimization problems with different dimensions is investigated.Metaheuristic algorithms(PSO,DE)and cooperative metaheuristics(C-PSO,C-DE)are examined by 15 benchmark functions and two engineering design problems(speed reducer and composite pressure vessel).Comparative results demonstrate that the cooperative methods achieve significantly superior performance compared to standard methods in both solution accuracy and computational efficiency.Compared to standard metaheuristic algorithms,cooperative metaheuristics achieve a reduction in computational cost of at least 40%.The cooperative metaheuristics can be effectively used to tackle both high-dimensional unconstrained and constrained optimization problems.展开更多
As a representative transition metal dichalcogenides(TMD),NiTe_(2)has an ultra-fast optical response,high carrier mobility,and excellent environmental stability.It has a broad application prospect in the fields of ene...As a representative transition metal dichalcogenides(TMD),NiTe_(2)has an ultra-fast optical response,high carrier mobility,and excellent environmental stability.It has a broad application prospect in the fields of ener-gy,biomedicine,optoelectronic devices,and so on.At present,there have been scant reports on the application of NiTe_(2)in the field of ultrafast photonics.In this work,NiTe_(2)was synthesized by chemical vapor deposition(CVD)and integrated with a tapered optical fiber to achieve mode-locking in an erbium-doped fiber laser(EDFL)and a thu-lium-doped fiber laser(TDFL).The mode-locked EDFL exhibited a pulse width of 678 fs and an output power of 3.92 mW.The pulse width of mode-locked TDFL was estimated to have a pulse width of 694 fs with an output power of 21.64 mW.These results demonstrate that NiTe_(2)is an effective saturable absorber material with potential applica-tions in the field of ultrafast optics.展开更多
Copper is a versatile material,commonly utilized in power transmission and electronic devices,but its relative high reactivity necessitates a long-lasting protective technique.Here,we report a method that combines pla...Copper is a versatile material,commonly utilized in power transmission and electronic devices,but its relative high reactivity necessitates a long-lasting protective technique.Here,we report a method that combines plasma-enhanced non-equilibrium magnetron sputtering physical vapor deposition(PEUMS-PVD)and anodization to construct a self-healing three-dimensional Ti/Al-doped TiO_(2)nanotubes/Ti_(3)AlC_(2)coating on the surface of Cu substrates.This novel strategy enhances the corrosion resistance of copper substrates in marine environments,with corrosion current densities of up to 4.5643×10^(−8)A/cm^(2).Among them,the doping of nano-aluminum particles makes the coating self-healing.The mechanistic analysis of the corrosion behaviors during early immersion experiments was conducted using electrochemical noise,and revealed that during the initial stages of coating immersion,uniform corrosion predominates,with a minor occurrence of localized corrosion.展开更多
We present a comprehensive study of the CO_(2)-CO interaction potential using a 9-dimensional(9D)potential energy surface(PES)constructed with the fundamental invariant-neural networks(FINN)method.The PES was generate...We present a comprehensive study of the CO_(2)-CO interaction potential using a 9-dimensional(9D)potential energy surface(PES)constructed with the fundamental invariant-neural networks(FINN)method.The PES was generated from 65330 CCSD(T)-F12a/aug-cc-pVTZ ab initio data points,with counterpoise correction,applied to eliminate basis set superposition error(BSSE).We performed quasi-classical trajectory simulations using this PES to investigate the rotational energy transfer dynamics.Our results reveal complex energy transfer mechanisms,with significant rotational excitation and relaxation dependent on collision energy and initial rotational states.The 9D PES provides a more accurate representation of the CO_(2)-CO system,offering new insights into molecular dynamics and interaction mechanisms.展开更多
Two-dimensional energetic materials(2DEMs),characterized by their exceptional interlayer sliding properties,are recognized as exemplar of low-sensitivity energetic materials.However,the diversity of available 2DEMs is...Two-dimensional energetic materials(2DEMs),characterized by their exceptional interlayer sliding properties,are recognized as exemplar of low-sensitivity energetic materials.However,the diversity of available 2DEMs is severely constrained by the absence of efficient methods for rapidly predicting crystal packing modes from molecular structures,impeding the high-throughput rational design of such materials.In this study,we employed quantified indicators,such as hydrogen bond dimension and maximum planar separation,to quickly screen 172DEM and 16 non-2DEM crystal structures from a crystal database.They were subsequently compared and analyzed,focusing on hydrogen bond donor-acceptor combinations,skeleton features,and intermolecular interactions.Our findings suggest that theπ-πpacking interaction energy is a key determinant in the formation of layered packing modes by planar energetic molecules,with its magnitude primarily influenced by the strongest dimericπ-πinteraction(π-π2max).Consequently,we have delineated a critical threshold forπ-π2max to discern layered packing modes and formulated a theoretical model for predictingπ-π2max,grounded in molecular electrostatic potential and dipole moment analysis.The predictive efficacy of this model was substantiated through external validation on a test set comprising 31 planar energetic molecular crystals,achieving an accuracy of 84%and a recall of 75%.Furthermore,the proposed model shows superior classification predictive performance compared to typical machine learning methods,such as random forest,on the external validation samples.This contribution introduces a novel methodology for the identification of crystal packing modes in 2DEMs,potentially accelerating the design and synthesis of high-energy,low-sensitivity 2DEMs.展开更多
Microwave absorption(MA)materials often face poor synergy between impedance matching and attenuation in the low-frequency range.Balancing permittivity and permeability through magnetic-dielectric synergy is a promisin...Microwave absorption(MA)materials often face poor synergy between impedance matching and attenuation in the low-frequency range.Balancing permittivity and permeability through magnetic-dielectric synergy is a promising strategy to address this issue.To realize the synergy,herein,Sn whiskers with an in situ oxide layer served as substrates for magnetic-loss-active CoNi nanosheet growth,forming a hierarchical CoNi@SnO_(2)@Sn(CNS)heterostructure.The CNS absorber achieves a minimum reflection loss(RL_(min))value of-62.29 dB with an effective absorption bandwidth(EAB)of 2.2 GHz,covering the entire C-band with 70%absorption at only 2.61 mm thickness.The nanosheet design of CoNi enhances magnetic anisotropy to promote natural resonance,while the conductive Sn core and abundant Sn/SnO_(2) and CoNi/SnO_(2) heterointerfaces facilitate conduction loss and dielectric polarization.When composited into a thermoplastic polyurethane(TPU)matrix,the resulting CNS/TPU-2 film(20 wt%CNS)exhibits an RL_(min) value of-61.04 dB and a 2.5 GHz EAB.Its in-plane and through-plane thermal conductivities reach 2.41 and 0.51 W m^(-1) K^(-1),representing 4.1 and 2.6 times those of pure TPU films,respectively,facilitating heat dissipation from protected devices.This work provides valuable insights into magnetic-dielectric synergy for low-frequency MA of 1D metal-based materials,offering promising potential for 5G communications and flexible electronics.展开更多
The preparation of electromagnetic(EM)wave absorption materials provided with the characteristics of thin matching thickness,broad bandwidth,and mighty absorption intensity is an efficient solution to current EM pollu...The preparation of electromagnetic(EM)wave absorption materials provided with the characteristics of thin matching thickness,broad bandwidth,and mighty absorption intensity is an efficient solution to current EM pollution.Herein,Graphene nanosheets(GN)were firstly fabricated via a facile high-energy ball milling method,subsequently high-purity 1T-MoS_(2) petals were uniformly anchored on the surface of GN to prepare 1T-MoS_(2)@GN nanocomposites.Plentiful multiple reflection and scattering of EM waves in a distinctive multidimensional structure formed by GN and 1T-MoS_(2),copious polarization loss consisting of interfacial polarization loss and dipolar polarization loss severally derived from multitudinous heterointerfaces and profuse electric dipoles in 1T-MoS_(2)@GN,and mighty conduction loss originated from plentiful induced current in 1T-MoS_(2)@GN generated via the migration of massive electrons,all of which endowed 1T-MoS_(2)@GN nanocomposites with exceptional EM wave absorption performances.The minimum reflection loss(RLmin)of 1T-MoS_(2)@GN reached–50.14 dB at a thickness of only 2.10 mm,and the effective absorption bandwidth(EAB)was up to 6.72 GHz at an ultra-thin matching thickness of 1.84 mm.Moreover,the radar scattering cross section(RCS)reduction value of 36.18 dB m2 at 0°could be achieved as well,which ulteriorly validated the tremendous potential of 1T-MoS_(2)@GN nanocomposites in practical applications.展开更多
Photocatalytic CO_(2)reduction into value-added chemicals holds significant promise for carbon-neutral recycling and solar-to-fuel conversion.Enhancing reaction efficiency by manipulating charge transfer is a key appr...Photocatalytic CO_(2)reduction into value-added chemicals holds significant promise for carbon-neutral recycling and solar-to-fuel conversion.Enhancing reaction efficiency by manipulating charge transfer is a key approach to unlocking this potential.In this work,we construct a two-dimensional/twodimensional(2D/2D)FeSe_(2)/protonated carbon nitride(FeSe_(2)/PCN)heterostructure to promote the interfacial charge transfer dynamics,leading to a four-fold improved conversion efficiency of photocatalytic CO_(2)reduction with near 100%CO selectivity.Combining in situ X-ray photoelectron spectroscopy,in situ soft X-ray absorption spectroscopy,and femtosecond transient absorption spectroscopy,it is revealed that FeSe_(2)acts as an electron acceptor upon photoexcitation,introducing an additional electron transfer pathway from PCN to FeSe_(2)that suppresses radiative recombination and promotes charge transfer.In situ X-ray absorption fine structure spectroscopy,in situ diffuse reflectance infrared Fourier transform spectroscopy,and density functional theory calculation further unravel that the electron-enriched FeSe_(2)functions as the active sites for CO_(2)activation and significantly reduces the energy barrier of key intermediate COOH*formation,which is the rate-determined step for CO generation.This work underscores the importance of regulating photocarrier relaxation pathways to achieve effective spatial charge separation for promoted photocatalytic CO_(2)reduction and demonstrates the powerful functions of in situ spectroscopies in in-depth understanding of the photocatalytic mechanism.展开更多
Background:Successful liver resection in oncologic surgery depends on safety,precision,and efficacy,all of which require a thorough understanding of liver anatomy.Contrast-enhanced computed tomography(CT)-generated th...Background:Successful liver resection in oncologic surgery depends on safety,precision,and efficacy,all of which require a thorough understanding of liver anatomy.Contrast-enhanced computed tomography(CT)-generated three-dimensional(3D)models have been proposed as a valuable tool to enhance this understanding.However,a systematic comparison of different display modalities across professional groups has not yet been performed.Methods:In this prospective,monocentric randomized trial,we compared high-resolution twodimensional(2D)CT images of liver malignancies with their corresponding standardized,non-colored 3D virtual and printed models in facilitating anatomical and spatial understanding as well as surgical decision-making.A total of 91 participants,including 40 surgeons,10 radiologists,and 41 students,evaluated six clinical cases(three centrally and three peripherally located liver malignancies).Each participant assessed one central and one peripheral case per display modality,presented in a random order.Results:Compared to 2D CT images,both 3D virtual and printed models significantly improved the identification of tumor location(P<0.001),enhanced the comprehension of spatial relationships with adjacent liver and portal veins(P<0.001 and P=0.019,respectively),and facilitated clinical decisionmaking(P<0.001).No significant difference was observed between virtual and printed models in terms of effectiveness.Within the different groups,surgeons and students,but not radiologists,more accurately identified tumor location and spatial relationships with adjacent liver and portal veins using 3D models.Subjectively,most surgeons and students preferred 3D printed models over virtual models and 2D CT images.Conclusions:This study demonstrated that standardized,non-colored 3D virtual and printed models equally help preoperative anatomical understanding and decision-making,particularly for surgeons and students.By isolating the influence of display modality,our findings clarify prior inconsistent results and support the integration of cost-effective 3D visualization by applying virtual models into surgical planning and education.Preference for printed models despite comparable efficacy highlights the importance of user-centered implementation strategies.展开更多
Two-dimensional(2D)noble transition-metal dichalcogenide materials(NTMDs)have garnered remarkable attention due to their intriguing properties exhibiting potential applications in nanoelectronics,optoelectronics,and p...Two-dimensional(2D)noble transition-metal dichalcogenide materials(NTMDs)have garnered remarkable attention due to their intriguing properties exhibiting potential applications in nanoelectronics,optoelectronics,and photonics.The electronic structure and physical properties of 2D NTMDs can be effectively modulated using alloy engineering strategy.Nevertheless,the precise growth of wafer-scale 2D NTMDs alloys remains a significant challenge.In this work,we have achieved the controllable preparation of wafer-scale(2-inch)2D PdS_(2x)Se_(2(1-x)) nanofilms(NFs)with fully tunable compositions on various substrates using pre-deposited Pd NFs assisted chemical vapor deposition technique.High-performance photodetectors based on the PdS_(2x)Se_(2(1-x))NFs were fabricated,which exhibit broadband photodetection performance from visible to near-infrared(NIR)wavelength range at room temperature.Significantly,the PdS0.9Se1.1-based photodetectors display a responsivity up to 0.192 A W^(-1) and a large specific detectivity of 5.5×1011 Jones for 850 nm light,enabling an excellent high-resolution NIR single-pixel imaging(SPI)without an additional filtering circuit.Our work paves a new route for the controlled synthesis of wafer-scale and high-quality 2D NTMDs alloy NFs,which is essential for designing advanced optoelectronic devices.展开更多
With high surface-to-volume ratio,the abundant surface states and high carrier concentration are challenging the nearinfrared photodetection behaviors of narrow band gap semiconductors nanowires.In this study,the narr...With high surface-to-volume ratio,the abundant surface states and high carrier concentration are challenging the nearinfrared photodetection behaviors of narrow band gap semiconductors nanowires.In this study,the narrow band gap semiconductor of Bi_(2)O_(2)Se nanosheets(NSs)is adopted to construct mixed-dimensional heterojunctions with GaSb nanowires(NWs)for demonstrating the impressive self-powered NIR photodetection.Benefiting from the built-in electric field of~140 meV,the as-constructed NW/NS mixeddimensional heterojunction self-powered photodetector shows the low dark current of 0.07 pA,high I_(light)/I_(dark)ratio of 82 and fast response times of<2/2 ms at room temperature.The self-powered photodetector performance can be further enhanced by fabricating the NW array/NS mixed-dimensional heterojunction by using a contact printing technique.The excellent photodetection performance promises the asconstructed NW/NS mixed-dimensional heterojunction self-powered photodetector in imaging and photocommunication.展开更多
The single-layer Ti_(3)C_(2)T_(x)/MXene has become a special electromagnetic wave absorber near the terahertz band because of its abundant surface groups and excellent conductivity.However,the macro-preparation of sin...The single-layer Ti_(3)C_(2)T_(x)/MXene has become a special electromagnetic wave absorber near the terahertz band because of its abundant surface groups and excellent conductivity.However,the macro-preparation of single-layer Ti_(3)C_(2)T_(x)/MXene shows significantly difficult to influence its application.The two-dimensional Ti_(3)C_(2)T_(x)is easily prepared to have high production,but its weak absorption ability due to high surface conductivity also restricts its application.To realize the strong electromagnetic wave absorption of two-dimensional Ti_(3)C_(2)T_(x)/MXene,a new strategy with magnetic FeNi nanoparticles decorating Ti_(3)C_(2)T_(x)/MXene composites(FeNi-Ti_(3)C_(2)T_(x))were proposed and the effective electromagnetic wave absorption features covering 170-220 GHz that means the absorption band width reach 50 GHz.With an absorber composite film thickness being only 0.6 mm,the absorptivity of the composite is enhanced with the increase of decorating FeNi nanoparticles and promote up to 75%when the FeNi nanoparticles loading content reaches 30 wt%.The improvement of absorption is attributed to the introduction of soft magnetic FeNi to adjust the high surface conductivity of MXene and improve the electromagnetic balance of the absorber.展开更多
Microplastics(MPs)are ubiquitous in the environment,continuously undergo aging processes and release toxic chemical substances.Understanding the environmental behaviors of MPs is critical to accurately evaluate their ...Microplastics(MPs)are ubiquitous in the environment,continuously undergo aging processes and release toxic chemical substances.Understanding the environmental behaviors of MPs is critical to accurately evaluate their long-term ecological risk.Generalized twodimensional correlation spectroscopy(2D-COS)is a powerful tool for MPs studies,which can dig more comprehensive information hiding in the conventional one-dimensional spectra,such as infrared(IR)and Raman spectra.The recent applications of 2D-COS in analyzing the behaviors and fates of MPs in the environment,including their aging processes,and interactions with natural organicmatter(NOM)or other chemical substances,were summarized systematically.The main requirements and limitations of current approaches for exploring these processes are discussed,and the corresponding strategies to address these limitations and drawbacks are proposed as well.Finally,new trends of 2D-COS are prospected for analyzing the properties and behaviors of MPs in both natural and artificial environmental processes.展开更多
We propose and investigate a novel stable two-dimensional(2D)AlO_(2)with anomalous stoichiometric ratios based on first-principles calculation.2D AlO_(2)has metallic properties.It possesses the rare in-plane and out-o...We propose and investigate a novel stable two-dimensional(2D)AlO_(2)with anomalous stoichiometric ratios based on first-principles calculation.2D AlO_(2)has metallic properties.It possesses the rare in-plane and out-of-plane negative Poisson's ratio(NPR)phenomenon,originating from its special sawtooth-like structure.The absolute value of the NPR decreases as the number of layers increases.The adsorption of volatile organic compounds(VOCs)including CH_(2)O,C_(2)H_(3)Cl and C_(6)H_(6)by AlO_(2)exhibit small adsorption distance,large adsorption energy,large charge transfer and significant density of states(DOS)changes,indicating the presence of strong interactions.The desorption time of each gas molecule on the AlO_(2)surface is also evaluated,and the results further suggest that the desorption of VOCs can be controlled by changing the temperature to achieve the recycling of AlO_(2).These interesting properties make 2D AlO_(2)a promising material for electronic,mechanical and sensing applications for VOCs.展开更多
The size effects were experimentally investigated and the underlying mechanism was analyzed.The results reveal that,as the specimen size increases,the interconnectivity of macropores slightly decreases.This in turn co...The size effects were experimentally investigated and the underlying mechanism was analyzed.The results reveal that,as the specimen size increases,the interconnectivity of macropores slightly decreases.This in turn constrains the diffusion of CO_(2) and moisture in the specimens,resulting in an increase in the discrepancy between the internal and external carbonation degrees.An increase in cement paste thickness simultaneously decreases the quantity,average size,and interconnectivity of macropores,lowering the diffusion efficacy of CO_(2) and moisture and exacerbating the overall heterogeneity in carbonation.Moreover,the gradual blockage of macropores leads to the emergence of localized ‘occluded zones’ with much lower carbonation degree.The reduction in aggregate size significantly alters the average diameter and connectivity of macropores,leading to notable change to overall non-uniformity.This study provides insight into improving the CO_(2) curing effect of pervious concrete products and developing uniform curing methods.展开更多
The electrochemical reduction of carbon monoxide (COER) to high-value multicarbon (C_(2+)) products is an emerging strategy for artificial carbon fixation and renewable energy storage. However, the slow kinetics of th...The electrochemical reduction of carbon monoxide (COER) to high-value multicarbon (C_(2+)) products is an emerging strategy for artificial carbon fixation and renewable energy storage. However, the slow kinetics of the C–C coupling reaction remains a significant obstacle in achieving both high activity and selectivity for C_(2+) production. In this study, we demonstrated the use of defect engineering to promote COER towards C_(2+) products by introducing single chlorine vacancy (SVCl) into two-dimensional (2D) non-noble transition metal dichlorides (TMCl_(2)). Density functional theory (DFT) calculations revealed that SVCl in TMCl_(2) exhibits low formation energies and high stability, ensuring its feasibility for synthesis and application in electrocatalysis. The introduction of three-coordinated, unsaturated metal sites substantially enhances the catalytic activity of TMCl_(2), facilitating effective CO activation. Notably, SVCl-engineered CoCl_(2) and NiCl_(2) nanosheets exhibit superior performance in COER, with SVCl@CoCl_(2) showing catalytic activity for ethanol and propanol production, and SVCl@NiCl_(2) favoring ethanol production due to a lower limiting potential and smaller kinetic barrier for C–C coupling. Consequently, defective 2D TMCl_(2) nanosheets represent a highly promising platform for converting CO into value-added C_(2+) products, warranting further experimental investigation into defect engineering for CO conversion.展开更多
Electrocatalytic reduction of NO(NORR) is an effective method for NH_(3) synthesis, due to low bonding energy of N–O bond. In this work, we have investigated many CrS_(2)based catalysts, including pristine CrS_(2),Cr...Electrocatalytic reduction of NO(NORR) is an effective method for NH_(3) synthesis, due to low bonding energy of N–O bond. In this work, we have investigated many CrS_(2)based catalysts, including pristine CrS_(2),CrS_(2)with one S vacancy(v-CrS_(2)), and Ti doped CrS_(2)(Ti@CrS_(2)). The results have shown that the pristine CrS_(2)exhibits inert character for NO activation. However, v-CrS_(2)and Ti@CrS_(2)can exhibit enhanced interaction with NO, due to increased charge transfer between NO and substrates(0.52–0.75 e) and enhanced adsorption energies of NO on the catalysts(-0.96~-1.64 e V), compared to the situation of CrS_(2)(0.065 e/-0.30 e V). From the free energy profiles of NO electro-reduction to NH3, we can see that the v-CrS_(2)and Ti@CrS_(2)all exhibit ultralow limiting potentials of-0.03~-0.47 V, following both*NOH and*NHO mechanisms. Therefore, introducing vacancy and doping are all promising modification strategies for NORR catalysts. The results have provided a new idea for the search of catalysts for efficient electrocatalytic reduction of NO.展开更多
Double-resonance Raman(DRR)scattering in two-di-mensional(2D)materials describes the intravalley or intervalley scattering of an electron or a hole excited by incident photons.Although the presence of defects can prov...Double-resonance Raman(DRR)scattering in two-di-mensional(2D)materials describes the intravalley or intervalley scattering of an electron or a hole excited by incident photons.Although the presence of defects can provide additional momentum and influence the scat-tering process involving one or two phonons,only the idealized defects without any structural details are considered in tra-ditional DRR theory.Here,the second-order DRR spectra of WSe_(2) monolayer with different types of defects are calculated involving the combinations of acoustic and optical phonons in the vicinity of K(K')and M points of the Brillouin zone.The electronic band structures are modified due to the presence of defects,and the band unfolding method is adopted to show the bending of valence and conduction bands for the defective WSe_(2) monolayers.The associ-ated phononic band structures also exhibit different changes in phonon dispersion curves,re-sulting in different DRR spectra corresponding to the different types of defects in the WSe_(2) monolayers.For example,the existence of W vacancy in the WSe_(2) monolayer would result in downshifts in vibrational frequencies and asymmetrical broadenings in linewidths for most combination modes due to the dramatic changes in contour shape of electronic valleys at K and K'.Moreover,the scattering from K to Q is found to be forbidden for the two Se vacan-cies because of the elevation of conduction band at the Q point.Our work highlights the role of defect structures in the intervalley scattering and may provide better understanding in the underlying physics of DRR process in 2D materials.展开更多
Three-dimensional(3D)covalent organic frameworks(COFs)have attracted extensive attention as photocatalysts for CO_(2)reduction reactions.Introducing metal atoms is essential for enhancing activity,but previous metal s...Three-dimensional(3D)covalent organic frameworks(COFs)have attracted extensive attention as photocatalysts for CO_(2)reduction reactions.Introducing metal atoms is essential for enhancing activity,but previous metal sites in 3D COFs predominantly exhibit symmetrical coordination,making them unsuitable for CO_(2)activation.Here,we design a 3D COF with 2,2'-pyridine linked around tetra-(4-anilyl)methane(TCM-Bpy-COF),where Co^(2+)is asymmetrically coordinated by bipyridine and acetates(TCMBpy-COF-CoAc).The TCM-Bpy-COF-CoAc exhibits outstanding photocatalytic CO_(2)reduction performance under weak visible light,achieving a CO evolution rate of 26,650μmol g^(-1)h^(-1)under 5 W of lightemitting-diode(LED)lamp and high apparent quantum efficiency.The performance far exceeds that of symmetrically coordinated bipyridine-Co-bipyridine TCM-Bpy-COF and surpasses most reported COF-based photocatalysts.In-situ spectral characterizations and theoretical calculations show that asymmetric N,O-coordination around the Co^(2+)center polarizes electron density and lowers reaction energy barriers of^(*)COOH intermediates,enhancing the conversion of CO_(2)to CO.This work inspires the design of 3D COF-based photocatalysts with highly catalytic efficiency.展开更多
基金supported by the NSFC(12461012)and the NSF of Chongqing(CSTB2024NSCQ-MSX1246).
文摘In this manuscript,we consider a non-autonomous dynamical system.Using the Carathéodory structure,we define a BS dimension on an arbitrary subset and obtain a Bowen’s equation that illustrates the relation of the BS dimension to the Pesin-Pitskel topological pressure given by Nazarian[24].Moreover,we establish a variational principle and an inverse variational principle for the BS dimension of non-autonomous dynamical systems.Finally,we also get an analogue of Billingsley’s theorem for the BS dimension of non-autonomous dynamical systems.
基金funded by National Natural Science Foundation of China(Nos.12402142,11832013 and 11572134)Natural Science Foundation of Hubei Province(No.2024AFB235)+1 种基金Hubei Provincial Department of Education Science and Technology Research Project(No.Q20221714)the Opening Foundation of Hubei Key Laboratory of Digital Textile Equipment(Nos.DTL2023019 and DTL2022012).
文摘Owing to their global search capabilities and gradient-free operation,metaheuristic algorithms are widely applied to a wide range of optimization problems.However,their computational demands become prohibitive when tackling high-dimensional optimization challenges.To effectively address these challenges,this study introduces cooperative metaheuristics integrating dynamic dimension reduction(DR).Building upon particle swarm optimization(PSO)and differential evolution(DE),the proposed cooperative methods C-PSO and C-DE are developed.In the proposed methods,the modified principal components analysis(PCA)is utilized to reduce the dimension of design variables,thereby decreasing computational costs.The dynamic DR strategy implements periodic execution of modified PCA after a fixed number of iterations,resulting in the important dimensions being dynamically identified.Compared with the static one,the dynamic DR strategy can achieve precise identification of important dimensions,thereby enabling accelerated convergence toward optimal solutions.Furthermore,the influence of cumulative contribution rate thresholds on optimization problems with different dimensions is investigated.Metaheuristic algorithms(PSO,DE)and cooperative metaheuristics(C-PSO,C-DE)are examined by 15 benchmark functions and two engineering design problems(speed reducer and composite pressure vessel).Comparative results demonstrate that the cooperative methods achieve significantly superior performance compared to standard methods in both solution accuracy and computational efficiency.Compared to standard metaheuristic algorithms,cooperative metaheuristics achieve a reduction in computational cost of at least 40%.The cooperative metaheuristics can be effectively used to tackle both high-dimensional unconstrained and constrained optimization problems.
基金Supported by Guangdong Basic and Applied Basic Research Fund,China(2024A1515012429)。
文摘As a representative transition metal dichalcogenides(TMD),NiTe_(2)has an ultra-fast optical response,high carrier mobility,and excellent environmental stability.It has a broad application prospect in the fields of ener-gy,biomedicine,optoelectronic devices,and so on.At present,there have been scant reports on the application of NiTe_(2)in the field of ultrafast photonics.In this work,NiTe_(2)was synthesized by chemical vapor deposition(CVD)and integrated with a tapered optical fiber to achieve mode-locking in an erbium-doped fiber laser(EDFL)and a thu-lium-doped fiber laser(TDFL).The mode-locked EDFL exhibited a pulse width of 678 fs and an output power of 3.92 mW.The pulse width of mode-locked TDFL was estimated to have a pulse width of 694 fs with an output power of 21.64 mW.These results demonstrate that NiTe_(2)is an effective saturable absorber material with potential applica-tions in the field of ultrafast optics.
基金Projects(42106051,42006046,U2106206) supported by the National Natural Science Foundation of ChinaProject(22373501D) supported by Hebei Provincial Key R&D Program,China。
文摘Copper is a versatile material,commonly utilized in power transmission and electronic devices,but its relative high reactivity necessitates a long-lasting protective technique.Here,we report a method that combines plasma-enhanced non-equilibrium magnetron sputtering physical vapor deposition(PEUMS-PVD)and anodization to construct a self-healing three-dimensional Ti/Al-doped TiO_(2)nanotubes/Ti_(3)AlC_(2)coating on the surface of Cu substrates.This novel strategy enhances the corrosion resistance of copper substrates in marine environments,with corrosion current densities of up to 4.5643×10^(−8)A/cm^(2).Among them,the doping of nano-aluminum particles makes the coating self-healing.The mechanistic analysis of the corrosion behaviors during early immersion experiments was conducted using electrochemical noise,and revealed that during the initial stages of coating immersion,uniform corrosion predominates,with a minor occurrence of localized corrosion.
基金financially supported by the National Natural Science Foundation of China(No.22173104)。
文摘We present a comprehensive study of the CO_(2)-CO interaction potential using a 9-dimensional(9D)potential energy surface(PES)constructed with the fundamental invariant-neural networks(FINN)method.The PES was generated from 65330 CCSD(T)-F12a/aug-cc-pVTZ ab initio data points,with counterpoise correction,applied to eliminate basis set superposition error(BSSE).We performed quasi-classical trajectory simulations using this PES to investigate the rotational energy transfer dynamics.Our results reveal complex energy transfer mechanisms,with significant rotational excitation and relaxation dependent on collision energy and initial rotational states.The 9D PES provides a more accurate representation of the CO_(2)-CO system,offering new insights into molecular dynamics and interaction mechanisms.
基金support from National Natural Science Foundation of China(Grant Nos.22275145,22305189and 21875184)Natural Science Foundation of Shaanxi Province(Grant Nos.2022JC-10 and 2024JC-YBQN-0112).
文摘Two-dimensional energetic materials(2DEMs),characterized by their exceptional interlayer sliding properties,are recognized as exemplar of low-sensitivity energetic materials.However,the diversity of available 2DEMs is severely constrained by the absence of efficient methods for rapidly predicting crystal packing modes from molecular structures,impeding the high-throughput rational design of such materials.In this study,we employed quantified indicators,such as hydrogen bond dimension and maximum planar separation,to quickly screen 172DEM and 16 non-2DEM crystal structures from a crystal database.They were subsequently compared and analyzed,focusing on hydrogen bond donor-acceptor combinations,skeleton features,and intermolecular interactions.Our findings suggest that theπ-πpacking interaction energy is a key determinant in the formation of layered packing modes by planar energetic molecules,with its magnitude primarily influenced by the strongest dimericπ-πinteraction(π-π2max).Consequently,we have delineated a critical threshold forπ-π2max to discern layered packing modes and formulated a theoretical model for predictingπ-π2max,grounded in molecular electrostatic potential and dipole moment analysis.The predictive efficacy of this model was substantiated through external validation on a test set comprising 31 planar energetic molecular crystals,achieving an accuracy of 84%and a recall of 75%.Furthermore,the proposed model shows superior classification predictive performance compared to typical machine learning methods,such as random forest,on the external validation samples.This contribution introduces a novel methodology for the identification of crystal packing modes in 2DEMs,potentially accelerating the design and synthesis of high-energy,low-sensitivity 2DEMs.
基金supported by the National Natural Science Foundation of China(52171033,52431003,U23A20574)the Fundamental Research Funds for the Central Universities(2242025K20004)the SEU Innovation Capability Enhancement Plan for Doctoral Students(CXJH_SEU 24148,CXJH_SEU 25036).
文摘Microwave absorption(MA)materials often face poor synergy between impedance matching and attenuation in the low-frequency range.Balancing permittivity and permeability through magnetic-dielectric synergy is a promising strategy to address this issue.To realize the synergy,herein,Sn whiskers with an in situ oxide layer served as substrates for magnetic-loss-active CoNi nanosheet growth,forming a hierarchical CoNi@SnO_(2)@Sn(CNS)heterostructure.The CNS absorber achieves a minimum reflection loss(RL_(min))value of-62.29 dB with an effective absorption bandwidth(EAB)of 2.2 GHz,covering the entire C-band with 70%absorption at only 2.61 mm thickness.The nanosheet design of CoNi enhances magnetic anisotropy to promote natural resonance,while the conductive Sn core and abundant Sn/SnO_(2) and CoNi/SnO_(2) heterointerfaces facilitate conduction loss and dielectric polarization.When composited into a thermoplastic polyurethane(TPU)matrix,the resulting CNS/TPU-2 film(20 wt%CNS)exhibits an RL_(min) value of-61.04 dB and a 2.5 GHz EAB.Its in-plane and through-plane thermal conductivities reach 2.41 and 0.51 W m^(-1) K^(-1),representing 4.1 and 2.6 times those of pure TPU films,respectively,facilitating heat dissipation from protected devices.This work provides valuable insights into magnetic-dielectric synergy for low-frequency MA of 1D metal-based materials,offering promising potential for 5G communications and flexible electronics.
基金supported by the PhD Start-up Fund of the Science and Technology Department of Liaoning Province(No.2022-BS-306)the General Cultivation Scientific Research Project of Bohai University(No.0522xn058)the PhD Research Startup Foundation of Bohai University(No.0521bs021).
文摘The preparation of electromagnetic(EM)wave absorption materials provided with the characteristics of thin matching thickness,broad bandwidth,and mighty absorption intensity is an efficient solution to current EM pollution.Herein,Graphene nanosheets(GN)were firstly fabricated via a facile high-energy ball milling method,subsequently high-purity 1T-MoS_(2) petals were uniformly anchored on the surface of GN to prepare 1T-MoS_(2)@GN nanocomposites.Plentiful multiple reflection and scattering of EM waves in a distinctive multidimensional structure formed by GN and 1T-MoS_(2),copious polarization loss consisting of interfacial polarization loss and dipolar polarization loss severally derived from multitudinous heterointerfaces and profuse electric dipoles in 1T-MoS_(2)@GN,and mighty conduction loss originated from plentiful induced current in 1T-MoS_(2)@GN generated via the migration of massive electrons,all of which endowed 1T-MoS_(2)@GN nanocomposites with exceptional EM wave absorption performances.The minimum reflection loss(RLmin)of 1T-MoS_(2)@GN reached–50.14 dB at a thickness of only 2.10 mm,and the effective absorption bandwidth(EAB)was up to 6.72 GHz at an ultra-thin matching thickness of 1.84 mm.Moreover,the radar scattering cross section(RCS)reduction value of 36.18 dB m2 at 0°could be achieved as well,which ulteriorly validated the tremendous potential of 1T-MoS_(2)@GN nanocomposites in practical applications.
基金supported by the National Natural Science Foundation of China(12241502,92045301)Fundamental Research Funds for the Central Universities(20720220010)+7 种基金USTC Research Funds of the Double First-Class Initiative(YD2310002012)the Launching Special Funds of Scientific Research for Introduced Talents from University of Science and Technology of China(KY2310000060)National Key Research and Development Program of China(2019YFA0405602)Anhui Provincial Natural Science Foundation(2408085QB049)the Instruments Center for Physical Science and USTC Center for Micro and Nanoscale Research and Fabrication,University of Science and Technology of Chinathe solid supports from the BL03U,BL10B,and BL12B beamlines of the National Synchrotron Radiation Laboratory(NSRL,Hefei)the Shanghai Synchrotron Radiation Facility(SSRF,Shanghai)of BL11B(https://cstr.cn/31124.02.SSRF.BL11B)and BL14W1(https://cstr.cn/31124.02.SSRF.BL14W1)beamlines for the assistance on XAFS measurementsAnhui Chuangpu Instruments Co.,Ltd.for the assistance in the test of Table XAFS。
文摘Photocatalytic CO_(2)reduction into value-added chemicals holds significant promise for carbon-neutral recycling and solar-to-fuel conversion.Enhancing reaction efficiency by manipulating charge transfer is a key approach to unlocking this potential.In this work,we construct a two-dimensional/twodimensional(2D/2D)FeSe_(2)/protonated carbon nitride(FeSe_(2)/PCN)heterostructure to promote the interfacial charge transfer dynamics,leading to a four-fold improved conversion efficiency of photocatalytic CO_(2)reduction with near 100%CO selectivity.Combining in situ X-ray photoelectron spectroscopy,in situ soft X-ray absorption spectroscopy,and femtosecond transient absorption spectroscopy,it is revealed that FeSe_(2)acts as an electron acceptor upon photoexcitation,introducing an additional electron transfer pathway from PCN to FeSe_(2)that suppresses radiative recombination and promotes charge transfer.In situ X-ray absorption fine structure spectroscopy,in situ diffuse reflectance infrared Fourier transform spectroscopy,and density functional theory calculation further unravel that the electron-enriched FeSe_(2)functions as the active sites for CO_(2)activation and significantly reduces the energy barrier of key intermediate COOH*formation,which is the rate-determined step for CO generation.This work underscores the importance of regulating photocarrier relaxation pathways to achieve effective spatial charge separation for promoted photocatalytic CO_(2)reduction and demonstrates the powerful functions of in situ spectroscopies in in-depth understanding of the photocatalytic mechanism.
文摘Background:Successful liver resection in oncologic surgery depends on safety,precision,and efficacy,all of which require a thorough understanding of liver anatomy.Contrast-enhanced computed tomography(CT)-generated three-dimensional(3D)models have been proposed as a valuable tool to enhance this understanding.However,a systematic comparison of different display modalities across professional groups has not yet been performed.Methods:In this prospective,monocentric randomized trial,we compared high-resolution twodimensional(2D)CT images of liver malignancies with their corresponding standardized,non-colored 3D virtual and printed models in facilitating anatomical and spatial understanding as well as surgical decision-making.A total of 91 participants,including 40 surgeons,10 radiologists,and 41 students,evaluated six clinical cases(three centrally and three peripherally located liver malignancies).Each participant assessed one central and one peripheral case per display modality,presented in a random order.Results:Compared to 2D CT images,both 3D virtual and printed models significantly improved the identification of tumor location(P<0.001),enhanced the comprehension of spatial relationships with adjacent liver and portal veins(P<0.001 and P=0.019,respectively),and facilitated clinical decisionmaking(P<0.001).No significant difference was observed between virtual and printed models in terms of effectiveness.Within the different groups,surgeons and students,but not radiologists,more accurately identified tumor location and spatial relationships with adjacent liver and portal veins using 3D models.Subjectively,most surgeons and students preferred 3D printed models over virtual models and 2D CT images.Conclusions:This study demonstrated that standardized,non-colored 3D virtual and printed models equally help preoperative anatomical understanding and decision-making,particularly for surgeons and students.By isolating the influence of display modality,our findings clarify prior inconsistent results and support the integration of cost-effective 3D visualization by applying virtual models into surgical planning and education.Preference for printed models despite comparable efficacy highlights the importance of user-centered implementation strategies.
基金supported by Open Research Fund of Songshan Lake Materials Laboratory(No.2023SLABFK08)Key Research and Development Program of Hunan Province(No.2022GK2007)+2 种基金Key Project from Department Education of Hunan Province(No.22A0123)National Natural Science Foundation of China(No.11974301)Graduate Student Research Innovation of Xi-angtan University(No.XDCX2024Y198).
文摘Two-dimensional(2D)noble transition-metal dichalcogenide materials(NTMDs)have garnered remarkable attention due to their intriguing properties exhibiting potential applications in nanoelectronics,optoelectronics,and photonics.The electronic structure and physical properties of 2D NTMDs can be effectively modulated using alloy engineering strategy.Nevertheless,the precise growth of wafer-scale 2D NTMDs alloys remains a significant challenge.In this work,we have achieved the controllable preparation of wafer-scale(2-inch)2D PdS_(2x)Se_(2(1-x)) nanofilms(NFs)with fully tunable compositions on various substrates using pre-deposited Pd NFs assisted chemical vapor deposition technique.High-performance photodetectors based on the PdS_(2x)Se_(2(1-x))NFs were fabricated,which exhibit broadband photodetection performance from visible to near-infrared(NIR)wavelength range at room temperature.Significantly,the PdS0.9Se1.1-based photodetectors display a responsivity up to 0.192 A W^(-1) and a large specific detectivity of 5.5×1011 Jones for 850 nm light,enabling an excellent high-resolution NIR single-pixel imaging(SPI)without an additional filtering circuit.Our work paves a new route for the controlled synthesis of wafer-scale and high-quality 2D NTMDs alloy NFs,which is essential for designing advanced optoelectronic devices.
基金the Natural Science Foundation of Shandong Province(Nos.ZR2022JQ05 and ZR2024MF010).
文摘With high surface-to-volume ratio,the abundant surface states and high carrier concentration are challenging the nearinfrared photodetection behaviors of narrow band gap semiconductors nanowires.In this study,the narrow band gap semiconductor of Bi_(2)O_(2)Se nanosheets(NSs)is adopted to construct mixed-dimensional heterojunctions with GaSb nanowires(NWs)for demonstrating the impressive self-powered NIR photodetection.Benefiting from the built-in electric field of~140 meV,the as-constructed NW/NS mixeddimensional heterojunction self-powered photodetector shows the low dark current of 0.07 pA,high I_(light)/I_(dark)ratio of 82 and fast response times of<2/2 ms at room temperature.The self-powered photodetector performance can be further enhanced by fabricating the NW array/NS mixed-dimensional heterojunction by using a contact printing technique.The excellent photodetection performance promises the asconstructed NW/NS mixed-dimensional heterojunction self-powered photodetector in imaging and photocommunication.
基金supported by the National Key R&D Program of China(Nos.2023YFF0718303 and 2022YFB3504804)the National Natural Science Foundation of China(Nos.51871219,52031014 and 52401255)the Science and Technology Project of Shenyang City(No.22-101-0-27).
文摘The single-layer Ti_(3)C_(2)T_(x)/MXene has become a special electromagnetic wave absorber near the terahertz band because of its abundant surface groups and excellent conductivity.However,the macro-preparation of single-layer Ti_(3)C_(2)T_(x)/MXene shows significantly difficult to influence its application.The two-dimensional Ti_(3)C_(2)T_(x)is easily prepared to have high production,but its weak absorption ability due to high surface conductivity also restricts its application.To realize the strong electromagnetic wave absorption of two-dimensional Ti_(3)C_(2)T_(x)/MXene,a new strategy with magnetic FeNi nanoparticles decorating Ti_(3)C_(2)T_(x)/MXene composites(FeNi-Ti_(3)C_(2)T_(x))were proposed and the effective electromagnetic wave absorption features covering 170-220 GHz that means the absorption band width reach 50 GHz.With an absorber composite film thickness being only 0.6 mm,the absorptivity of the composite is enhanced with the increase of decorating FeNi nanoparticles and promote up to 75%when the FeNi nanoparticles loading content reaches 30 wt%.The improvement of absorption is attributed to the introduction of soft magnetic FeNi to adjust the high surface conductivity of MXene and improve the electromagnetic balance of the absorber.
基金supported by the National Natural Science Foundation of China(Nos.52293444 and 22076209)the Key R&D Project of Ningxia(No.2021BEG02006).
文摘Microplastics(MPs)are ubiquitous in the environment,continuously undergo aging processes and release toxic chemical substances.Understanding the environmental behaviors of MPs is critical to accurately evaluate their long-term ecological risk.Generalized twodimensional correlation spectroscopy(2D-COS)is a powerful tool for MPs studies,which can dig more comprehensive information hiding in the conventional one-dimensional spectra,such as infrared(IR)and Raman spectra.The recent applications of 2D-COS in analyzing the behaviors and fates of MPs in the environment,including their aging processes,and interactions with natural organicmatter(NOM)or other chemical substances,were summarized systematically.The main requirements and limitations of current approaches for exploring these processes are discussed,and the corresponding strategies to address these limitations and drawbacks are proposed as well.Finally,new trends of 2D-COS are prospected for analyzing the properties and behaviors of MPs in both natural and artificial environmental processes.
基金financially supported by National Natural Science Foundation of China(No.22275149)Fundamental Research Funds for the Central Universities(No.SWU118105)the Next-Generation Advanced Energy Materials Program of BatteroTech Co.,Ltd.
文摘We propose and investigate a novel stable two-dimensional(2D)AlO_(2)with anomalous stoichiometric ratios based on first-principles calculation.2D AlO_(2)has metallic properties.It possesses the rare in-plane and out-of-plane negative Poisson's ratio(NPR)phenomenon,originating from its special sawtooth-like structure.The absolute value of the NPR decreases as the number of layers increases.The adsorption of volatile organic compounds(VOCs)including CH_(2)O,C_(2)H_(3)Cl and C_(6)H_(6)by AlO_(2)exhibit small adsorption distance,large adsorption energy,large charge transfer and significant density of states(DOS)changes,indicating the presence of strong interactions.The desorption time of each gas molecule on the AlO_(2)surface is also evaluated,and the results further suggest that the desorption of VOCs can be controlled by changing the temperature to achieve the recycling of AlO_(2).These interesting properties make 2D AlO_(2)a promising material for electronic,mechanical and sensing applications for VOCs.
基金Funded by the National Natural Science Foundation of China (No.22203066)the 6th Young Elite Scientist Sponsorship Program by China Association for Science and Technology (No.2020QNRC001)。
文摘The size effects were experimentally investigated and the underlying mechanism was analyzed.The results reveal that,as the specimen size increases,the interconnectivity of macropores slightly decreases.This in turn constrains the diffusion of CO_(2) and moisture in the specimens,resulting in an increase in the discrepancy between the internal and external carbonation degrees.An increase in cement paste thickness simultaneously decreases the quantity,average size,and interconnectivity of macropores,lowering the diffusion efficacy of CO_(2) and moisture and exacerbating the overall heterogeneity in carbonation.Moreover,the gradual blockage of macropores leads to the emergence of localized ‘occluded zones’ with much lower carbonation degree.The reduction in aggregate size significantly alters the average diameter and connectivity of macropores,leading to notable change to overall non-uniformity.This study provides insight into improving the CO_(2) curing effect of pervious concrete products and developing uniform curing methods.
基金financially supported by the International Partnership Program of the Chinese Academy of Sciences(No.172GJHZ2022010MI)the Natural Science Funds for Distinguished Young Scholars of Heilongjiang Province(No.JC2018004).
文摘The electrochemical reduction of carbon monoxide (COER) to high-value multicarbon (C_(2+)) products is an emerging strategy for artificial carbon fixation and renewable energy storage. However, the slow kinetics of the C–C coupling reaction remains a significant obstacle in achieving both high activity and selectivity for C_(2+) production. In this study, we demonstrated the use of defect engineering to promote COER towards C_(2+) products by introducing single chlorine vacancy (SVCl) into two-dimensional (2D) non-noble transition metal dichlorides (TMCl_(2)). Density functional theory (DFT) calculations revealed that SVCl in TMCl_(2) exhibits low formation energies and high stability, ensuring its feasibility for synthesis and application in electrocatalysis. The introduction of three-coordinated, unsaturated metal sites substantially enhances the catalytic activity of TMCl_(2), facilitating effective CO activation. Notably, SVCl-engineered CoCl_(2) and NiCl_(2) nanosheets exhibit superior performance in COER, with SVCl@CoCl_(2) showing catalytic activity for ethanol and propanol production, and SVCl@NiCl_(2) favoring ethanol production due to a lower limiting potential and smaller kinetic barrier for C–C coupling. Consequently, defective 2D TMCl_(2) nanosheets represent a highly promising platform for converting CO into value-added C_(2+) products, warranting further experimental investigation into defect engineering for CO conversion.
基金funded by the Natural Science Foundation of China (No. 21603109)the Henan Joint Fund of the National Natural Science Foundation of China (No. U1404216)+1 种基金the Scientific Research Program Funded by Shaanxi Provincial Education Department (No. 20JK0676)supported by Natural Science Basic Research Program of Shanxi (Nos. 2022JQ-108, 2022JQ096)。
文摘Electrocatalytic reduction of NO(NORR) is an effective method for NH_(3) synthesis, due to low bonding energy of N–O bond. In this work, we have investigated many CrS_(2)based catalysts, including pristine CrS_(2),CrS_(2)with one S vacancy(v-CrS_(2)), and Ti doped CrS_(2)(Ti@CrS_(2)). The results have shown that the pristine CrS_(2)exhibits inert character for NO activation. However, v-CrS_(2)and Ti@CrS_(2)can exhibit enhanced interaction with NO, due to increased charge transfer between NO and substrates(0.52–0.75 e) and enhanced adsorption energies of NO on the catalysts(-0.96~-1.64 e V), compared to the situation of CrS_(2)(0.065 e/-0.30 e V). From the free energy profiles of NO electro-reduction to NH3, we can see that the v-CrS_(2)and Ti@CrS_(2)all exhibit ultralow limiting potentials of-0.03~-0.47 V, following both*NOH and*NHO mechanisms. Therefore, introducing vacancy and doping are all promising modification strategies for NORR catalysts. The results have provided a new idea for the search of catalysts for efficient electrocatalytic reduction of NO.
基金supported by the National Natural Sci-ence Foundation of China(No.22174135,No.21790352)the National Key R&D Program of China(No.2021YFA1500500,No.2016YFA0200600)+4 种基金the Strategic Priority Research Program of Chinese Academy of Sciences(No.XDB36000000)Anhui Initiative in Quantum Information Technologies(No.AHY090100)CAS Project for Young Scientists in Basic Research(No.YSBR-054)Innovation Program for Quantum Science and Technology(No.2021ZD0303301)the Fundamental Research Funds for the Central Universities.
文摘Double-resonance Raman(DRR)scattering in two-di-mensional(2D)materials describes the intravalley or intervalley scattering of an electron or a hole excited by incident photons.Although the presence of defects can provide additional momentum and influence the scat-tering process involving one or two phonons,only the idealized defects without any structural details are considered in tra-ditional DRR theory.Here,the second-order DRR spectra of WSe_(2) monolayer with different types of defects are calculated involving the combinations of acoustic and optical phonons in the vicinity of K(K')and M points of the Brillouin zone.The electronic band structures are modified due to the presence of defects,and the band unfolding method is adopted to show the bending of valence and conduction bands for the defective WSe_(2) monolayers.The associ-ated phononic band structures also exhibit different changes in phonon dispersion curves,re-sulting in different DRR spectra corresponding to the different types of defects in the WSe_(2) monolayers.For example,the existence of W vacancy in the WSe_(2) monolayer would result in downshifts in vibrational frequencies and asymmetrical broadenings in linewidths for most combination modes due to the dramatic changes in contour shape of electronic valleys at K and K'.Moreover,the scattering from K to Q is found to be forbidden for the two Se vacan-cies because of the elevation of conduction band at the Q point.Our work highlights the role of defect structures in the intervalley scattering and may provide better understanding in the underlying physics of DRR process in 2D materials.
基金financial support from the National Natural Science Foundation of China(No.22072183)the Natural Science Foundation of Hunan Province,China(No.2022JJ30690)supported in part by the High Performance Computing Center of Central South University。
文摘Three-dimensional(3D)covalent organic frameworks(COFs)have attracted extensive attention as photocatalysts for CO_(2)reduction reactions.Introducing metal atoms is essential for enhancing activity,but previous metal sites in 3D COFs predominantly exhibit symmetrical coordination,making them unsuitable for CO_(2)activation.Here,we design a 3D COF with 2,2'-pyridine linked around tetra-(4-anilyl)methane(TCM-Bpy-COF),where Co^(2+)is asymmetrically coordinated by bipyridine and acetates(TCMBpy-COF-CoAc).The TCM-Bpy-COF-CoAc exhibits outstanding photocatalytic CO_(2)reduction performance under weak visible light,achieving a CO evolution rate of 26,650μmol g^(-1)h^(-1)under 5 W of lightemitting-diode(LED)lamp and high apparent quantum efficiency.The performance far exceeds that of symmetrically coordinated bipyridine-Co-bipyridine TCM-Bpy-COF and surpasses most reported COF-based photocatalysts.In-situ spectral characterizations and theoretical calculations show that asymmetric N,O-coordination around the Co^(2+)center polarizes electron density and lowers reaction energy barriers of^(*)COOH intermediates,enhancing the conversion of CO_(2)to CO.This work inspires the design of 3D COF-based photocatalysts with highly catalytic efficiency.
