Proton‑Prompted Ligand Exchange to Achieve High‑Efficiency CsPbI_(3) Quantum Dot Light‑Emitting Diodes

CsPbI_(3)perovskite quantum dots(QDs)are ideal materials for the next generation of red light-emitting diodes.However,the low phase stability of CsPbI_(3)QDs and long-chain insulating capping ligands hinder the improvement of device performance.Traditional in-situ ligand replacement and ligand exchange after synthesis were often difficult to control.Here,we proposed a new ligand exchange strategy using a proton-prompted insitu exchange of short 5-aminopentanoic acid ligands with long-chain oleic acid and oleylamine ligands to obtain stable small-size CsPbI_(3)QDs.This exchange strategy maintained the size and morphology of CsPbI_(3)QDs and improved the optical properties and the conductivity of CsPbI_(3)QDs films.As a result,high-efficiency red QD-based light-emitting diodes with an emission wavelength of 645 nm demonstrated a record maximum external quantum efficiency of 24.45%and an operational half-life of 10.79 h.

Photothermal Catalytic Selective Oxidation of Isobutane to Methacrylic Acid over Keggin-Type Heteropolyacid

Thermal and photothermal catalytic selec-tive oxidation of isobutane to methacrylic acid(MAA)are comparatively studied over a keggin-type Cs2.9Cu0.34V0.49PMo12O40 het-eropolyacid acid.An introduction of light was observed to enhance both the i-C4H10 conversion and the MAA selectivity,and consequently the MAA formate rate,particularly at low temperatures.Characterization re-sults show that oxidation of methacrolein(MAL)to MAA is the rate-limiting step while UV light illumination promotes the oxidation ofσ-bonded MAL with OH groups toσ-bonded MAA on the catalyst surface.These results demonstrate a synergistic effect of thermal cataly-sis and photocatalysis in selective oxidation of isobutane to MAA,which suggests photother-mal catalysis as a promising strategy to catalyze the selective oxidation of higher hydrocar-bons at relative mild reaction conditions.

Two-photon absorption of FAPbBr_(3) perovskite nanocrystals

Perovskite nanocrystals(NCs) with high two-photon absorption(TPA) cross-section are of great interest due to their potential applications in three-dimensional optical data storage and multiphoton fluorescence microscopy. Among various perovskite materials, FAPbBr_(3) NCs show a better development prospect due to their excellent stability. However, there are few reports on their nonlinear optical properties. In this work, the nonlinear optical behavior of FAPbBr_(3) NCs is studied.The methods of multiphoton absorption photoluminescence saturation and open aperture Z-scan technique were applied to determine the TPA cross-section of FAPbBr_(3)NCs, which was around 2.76 × 10^(-45)cm^(4)·s·photon^(-1) at 800 nm. In addition,temperature-dependent photoluminescence induced by TPA was investigated, and the small longitudinal optical phonon energy and electron–phonon coupling strength was obtained, which confirm the weak Pb–Br interaction. Meanwhile, it is found that the exciton binding energy in FAPbBr_(3) NCs was 69.668 me V, which may be ascribed to the strong hydrogen bond interaction. It is expected that our findings will promote the application of FAPbBr_(3) NCs in optoelectronic devices.

Analysis on the Heavy Rain Weather Process in Most Areas of China from July 26 to 30, 2022

To analyze a new heavy rain case over China during the year 2022, by using the data from NCC-CMA and NCEP, a heavy rain weather process in most areas of China from July 26 to 30, 2022 was analyzed. Synoptic methods were used in this research and results show that under the influence of low vortex and wind shear, the abundant water vapor supply brought by the southeast airflow in the lower level and the lifting of the Taihang Mountain, heavy rain weather occurred in the northern part of Henan, China. In the west of Liaoning and Jilin, the rainfall process had the characteristics of frontal rainfall and the stable precipitation resulted in heavy rain weather. To sum up, the rainfall process was mainly affected by the upper-level trough, low-level wind shear and low-level jet.

Activation and surface reactions of CO and H2 on ZnO powders and nanoplates under CO hydrogenation reaction conditions

Activation and surface reactions of CO and H2 on ZnO powders and nanoplates under CO hydrogenation reaction conditions were(quasi) in situ studied using temperature programmed surface reaction spectra, diffuse reflectance Fourier transform infrared spectroscopy, inelastic neutron scattering spectroscopy and electron paramagnetic resonance. CO undergoes disproportion reaction to produce gaseous CO2 and surface carbon adatoms, and adsorbs to form surface formate species. H2 adsorption forms dominant irreversibly-adsorbed surface hydroxyl groups and interstitial H species and very minor surface Zn-H species. Surface formate species and hydroxyl groups react to produce CO2 and H2, while surface carbon adatoms are hydrogenated by surface Zn-H species sequentially to produce CH(a), CH2(a), CH3(a)and eventually gaseous CH4. The ZnO nanoplates, exposing a higher fraction of Zn-ZnO(0001) and OZnO(000–1) polar facets, are more active than the ZnO powders to catalyze CO hydrogenation to CH4.These results provide fundamental understanding of the reaction mechanisms and structural effects of CO hydrogenation reaction catalyzed by ZnO-based catalysts.

手性等离子体核壳纳米结构的设计及应用

手性描述了一个物体不能与其镜像重叠的几何性质,自19世纪以来一直是化学和生物学中的一个关键概念。随着纳米技术的发展,手性等离子体纳米材料凭借其特殊的手性光学性质和良好的生物相容性已经成为科学家们的研究重点和手性功能材料开发的热点。然而,较弱的手性响应信号限制了其应用和发展。将手性等离子体纳米材料和核壳结构结合得到的手性等离子体核壳纳米结构是一种放大手性响应信号的有效策略。核壳纳米结构整合了内外两种材料的性质,互相补充各自的不足,能够进一步改善材料的物理化学性质,提升材料在各个领域的性能。本文依据手性分子的空间分布对手性等离子体核壳纳米结构的设计策略进行了总结,并综述了其在超灵敏传感和手性催化领域的应用,分析了目前尚存在的问题和可能的解决方式,对其未来的发展作了进一步展望。

Directional emissions from perovskite nanocrystals thin film enabled by metasurface integration through one step spin-coating process

Advances in thin film light-emitting devices have fueled the rapid growth of a new class of solid-state lighting devices,featuring low fabrication cost,high quantum efficiency,broadband spectrum coverage,etc.In contrast to the conventional inorganic semiconductors that rely on lattice matched high crystalline quality substrate,solution processable thin films eliminate the dependence on the substrate,which is highly desired for the ease and versatility of integrations with foreign medium.By taking this advantage,this work developed an ultracompact solution to control the directionality of thin film emitters using integrated dielectric metasurface through one step spin-coating process.As a proof of concept,directional emissions from perovskite nanocrystal thin film,including collimated light emissions and two-dimensional beam steering,are experimentally demonstrated.Notably,our approach,where light emitters were integrated on the back side of substrate after the fabrication of metasurface,judiciously avoids any potential degradation of material optical quality caused by the multi-step nanofabrication.Therefore,it can serve as a generalized scheme to engage the advantageous properties of dielectric metasurface,including the compactness,high efficiency,beam controllability with the emerging thin film light-emitting diodes(LEDs),which is applicable to a wide range of solution processable materials,including organic light-emitting diodes,quantum-dot light emitting diodes,polymer LEDs,and perovskite LEDs,opening up new pathways to develop low-cost and ultra-compact solid state light sources with versatile beams characteristics.

Self-assembling nanoarchitectonics of low dimensional semiconductors for circularly polarized luminescence

Recently,the development of materials with circularly polarized luminescence(CPL)has attracted numerous attentions owing to their potential applications in various fields.Among diverse mechanisms for the origin of chiroptical properties in low dimensional semiconductors(LDS),the self-assembly approach provides a powerful technique for acquisition of strong chiroptical activity.Benefiting from this approach,LDS could be endowed with CPL in which the dissymmetry factor,a vital parameter for evaluating the performance of CPL,could be greatly improved.In this review,state-of-the-art of selfassembled LDS will be summarized.The current challenges and perspectives in this emerging field are also presented.This review could not only provide insights of the fundamentals of self-assembled chirality,but also shine light for designing CPL-active functional nanomaterials toward their applications based on novel optoelectronic devices.

大分子网络体系中的反常扩散动力学机制

生物大分子网络是多种生物软质体系共同的结构基础之一.深入理解纳米尺度的粒子在大分子网络中的扩散动力学对于阐明众多生命现象背后的物理机制以及设计和制造具有优异性能的生物医用功能材料有重要意义.纳米粒子在大分子网络中的运动可能会受到其周围网络链的显著影响.从物理角度看,各种生物或合成聚合物链之间的主要区别在于其本征物理性质,这些性质可以显著改变纳米粒子所经历自由能势垒的高低与分布,进而决定纳米粒子的扩散动力学行为.本文从网络链的柔顺性、网格拓扑特征以及网络的动态共价连接三个方面的本征物理性质出发,综述了本课题组近年来针对该问题基于高分子凝聚态物理理论的研究进展,特别是对这些现象背后的熵机制进行了理论解释.最后对大分子网络中粒子扩散的未来发展方向进行了展望.

Over 16% efficiency all-polymer solar cells by sequential deposition

All-polymer solar cells(all-PSCs) have received extensive attention due to their excellent mechanical robustness and performance stability. However, the power conversion efficiency(PCE) of all-PSCs still lags behind those of organic solar cells(OSCs)based on non-fullerene small molecule acceptors. Herein, we report highly efficient all-PSCs via sequential deposition(SD) with donor and acceptor layers coated sequentially to optimize the film microstructure. Compared with the bulk heterojunction(BHJ)all-PSCs, an optimized morphology with vertical component distribution was achieved for the SD-processed all-PSCs due to the synergistic effect of swelling of polymer films and using additive. Such strategy involves using chlorobenzene as the first layer processing-solvent for polymer donor, chloroform as the second processing-solvent for polymer acceptor with trace 1-chloronaphthalene, efficiently promoting exciton dissociation and charge extraction and reducing trap-assisted recombination.Consequently, over 16% all-PSCs fabricated via SD method was realized for the first time, which is much higher than that(15.2%) of its BHJ counterpart and also among the highest PCEs in all-PSCs. We have further demonstrated the generality of this approach in various all-polymer systems. This work indicates that the SD method can yield excellent all-PSCs and provides a facile approach to fabricating high-performance all-PSCs.

Influence of mixed organic cations on the nonlinear optical properties of lead tri-iodide perovskites

Metal halide perovskite materials have been widely studied recently due to their excellent optoelectronic properties.Among these materials,organic-inorganic hybrid perovskites have attracted much attention because of their relatively soft framework,which makes them more suitable for nonlinear optical(NLO)applications.However,there is rare physical mechanism study on the coexistence of two-photon absorption(TPA)and saturable absorption(SA)in organic-inorganic hybrid perovskite materials.To clarify this issue,the NLO properties of mixed cation perovskite MA1-xFAxPbI3[MA=CH3NH3,FA=CH(NH2)2,x=0,0.2,0.4,0.6,and 0.8]thin films are investigated in this paper.Based on the nonlinear transmittance and femtosecond-transient absorption spectrum measurements,it is found that the MA1-xFAxPbI3 materials exhibit NLO behavior dependent on excitation intensity.The TPA coefficient of MA1-xFAxPbI3 decreases with the increase of formamidinium(FA)content,while the relevant saturable intensity increases.In addition,it is revealed that the linear absorption process from valence band 2 to valance band 1 still exists even under a very low excitation intensity.With the increase of excitation intensity,the light transmittance at 1300 nm decreases first and then increases sharply,which also supports the explanation for the coexistence of TPA and SA.It is expected that our findings will promote the application of perovskite materials in nonlinear optoelectronic devices.

Optical characteristics of self-trapped excitons in 2D (iso-BA)_(2)PbI_(4) perovskite crystals

Organic–inorganic halide metal perovskites are an exciting class of two-dimensional(2D) materials that have sparked renewed interest for next-generation optoelectronics. In particular, the self-trapped excitons(STEs)in 2D perovskite with excellent optical properties suggest great potential in display and narrowband detection.A prerequisite of understanding STEs’ properties is correct identification of the underlying interaction that leads to STEs. Here, the optical properties of STEs in(iso-BA)_(2)PbI_(4) are characterized through laser spectroscopy at various temperatures and excitation intensities. It is found that STEs are related to the octahedral distortion caused by strong electron–phonon interaction. Trapping and detrapping between STEs and free excitons(FEs) are clearly observed. With the increase in temperature, STEs and FEs will gain enough energy and migrate to each other. Moreover, by characterizing the thickness-dependent and two-photon excitation emission, it is confirmed that STEs exist inside the material because of their weak absorption. Our findings are of great significance for not only the fundamental understanding of STEs, but also the design and optimization of 2D-perovskite-based electronic and optoelectronic devices.

Entropy-driven self-assembly of tethered Janus nanoparticles on a sphere

Understanding the effect of curvature and topological frustration on self-assembly yields insight into the mechanistic details of the ordering of identical subunits in curved spaces,such as the assembly of viral capsids,growth of solid domains on vesicles,and the self-assembly of molecular monolayers.However,the self-assembly of nanoparticles with anisotropic surface topology and compartmentalization on curved surfaces remains elusive.By combining large-scale molecular simulations as well as theoretical analysis,we demonstrate here that the interplay among anisotropy,curvature,and chain conformation induces tethered Janus nanoparticles to self-assemble into diverse novel structures on a sphere,including binary nanocluster(C_(B)),trinary nanocluster(C_(T)),nanoribbon(R_(N))and hexagon with centered reverse(HR),which are mapped on a phase diagram related to the length asymmetry of tethered chains and Janus balance of the nanoparticles.The dynamical mechanism for the formation of these structure states is analyzed by examining the detailed kinetic pathways as well as free energy.We also show that the centered-reverse state is more prone to emerging around the topological defects,indicating the defect-enhanced entropy effect on a curved surface.Finally,the analytical model that rationalizes the regimes of these structure states is developed and fits simulations reasonably well,resulting in a mechanistic interpretation based on the order through entropy.Our findings shed light on curvature engineering as a versatile strategy to tailor the superstructures formed by anisotropic building blocks toward unique properties.