Incorporating Rare‐Earth Terbium(III) Ions into Cs2AgInCl6:Bi Nanocrystals toward Tunable Photoluminescence

The incorporation of impurity ions or doping is a promising method for controlling the electronic and optical properties and the structural stability of halide perovskite nanocrystals (NCs). Herein, we establish relationships between rare‐earth ions doping and intrinsic emission of lead‐free double perovskite Cs₂AgInCl₆ NCs to impart and tune the optical performances in the visible light region. Tb³⁺ ions were incorporated into Cs₂AgInCl₆ NCs and occupied In³⁺ sites as verified by both crystallographic analyses and first‐principles calculations. Trace amounts of Bi doping endowed the characteristic emission (⁵D₄→⁷F_6‐3) of Tb³⁺ ions with a new excitation peak at 368 nm rather than the single characteristic excitation at 290 nm of Tb³⁺. By controlling Tb³⁺ ions concentration, the emission colors of Bi‐doped Cs₂Ag(In_1?xTb_x)Cl₆ NCs could be continuously tuned from green to orange, through the efficient energy‐transfer channel from self‐trapped excitons to Tb³⁺ ions. Our study provides the salient features of the material design of lead‐free perovskite NCs and to expand their luminescence applications.     

Templated‐Assembly of CsPbBr3 Perovskite Nanocrystals into 2D Photonic Supercrystals with Amplified Spontaneous Emission

Perovskite nanocrystals (NCs) have revolutionized optoelectronic devices because of their versatile optical properties. However, controlling and extending these functionalities often requires a light‐management strategy involving additional processing steps. Herein, we introduce a simple approach to shape perovskite nanocrystals (NC) into photonic architectures that provide light management by directly shaping the active material. Pre‐patterned polydimethylsiloxane (PDMS) templates are used for the template‐induced self‐assembly of 10 nm CsPbBr₃ perovskite NC colloids into large area (1 cm²) 2D photonic crystals with tunable lattice spacing, ranging from 400 nm up to several microns. The photonic crystal arrangement facilitates efficient light coupling to the nanocrystal layer, thereby increasing the electric field intensity within the perovskite film. As a result, CsPbBr₃ 2D photonic crystals show amplified spontaneous emission (ASE) under lower optical excitation fluences in the near‐IR, in contrast to equivalent flat NC films prepared using the same colloidal ink. This improvement is attributed to the enhanced multi‐photon absorption caused by light trapping in the photonic crystal.     

Engineering Sensitized Photon Upconversion Efficiency via Nanocrystal Wavefunction and Molecular Geometry

Triplet energy transfer from inorganic nanocrystals to molecular acceptors has attracted strong attention for high‐efficiency photon upconversion. Here we study this problem using CsPbBr₃ and CdSe nanocrystals as triplet donors and carboxylated anthracene isomers as acceptors. We find that the position of the carboxyl anchoring group on the molecule dictates the donor‐acceptor coupling to be either through‐bond or through‐space, while the relative strength of the two coupling pathways is controlled by the wavefunction leakage of nanocrystals that can be quantitatively tuned by nanocrystal sizes or shell thicknesses. By simultaneously engineering molecular geometry and nanocrystal wavefunction, energy transfer and photon upconversion efficiencies of a nanocrystal/molecule system can be improved by orders of magnitude.     

Reducing Agents for Improving the Stability of Sn‐based Perovskite Solar Cells

Organic‐inorganic hybrid perovskite solar cells (PSCs) have aroused tremendous research interest for their high efficiency, low cost and solution processability. However, the involvement of toxic lead in state‐of‐art perovskites hinders their market prospects. As an alternative, Sn‐based perovskites exhibit similar semiconductor characteristics and can potentially achieve comparable photovoltaic performance in comparison with their lead‐based counterparts. The main challenge of developing Sn‐based PCSs lies in the intrinsic poor stability of Sn²⁺, which could be oxidized and converted to Sn⁴⁺. Notably, introduction of SnX₂ (X=Cl, Br, I) additive becomes indispensable in the fabrication process, which highlights the importance of incorporating a reducing agent to improve the device stability. Additionally, efforts are made to utilize other reducing agents with different functions for the further enhancement of device performance. Currently, Sn‐based PSCs could attain a record efficiency over 10% with great stability. In this review, we present the recent progress on reducing agents for improving the stability of Sn‐based PSCs, and we hope to shed light on the challenges and opportunities of this research field.     

Beyond Perovskite Solar Cells: Tellurium Iodide as a Promising Light‐Absorbing Material for Solution‐Processed Photovoltaic Application

Searching new light‐absorbing materials to replace toxic lead halide in solar cells is very important and highly desirable. In this research, we firstly demonstrated that tellurium iodide (TeI₄) could be used as a light‐absorbing material in solar cells due to its suitable optical band gap and the active lone‐pair electron orbital in Te⁴⁺. The best power conversion efficiency (PCE=3.56%) was achieved with a concentration of 0.9 M TeI₄ in DMF:DMSO (4 : 1, v,v) without any heat treatment or antisolvent dripping. Our study indicates the promising potential of TeI₄ for photovoltaic and optoelectronic applications.     

Promotion of oxidative desulfurization performance of model fuel by 3DOM Ce-doped HPW/TiO2 material

Phosphotungstic acid (HPW) supported on Ce-doped three-dimensional ordered macroporous (3DOM) TiO₂ catalysts are studied in catalytic oxidation desulfurization (ODS) of model oil. The structural and textural of as-synthesized catalysts are characterized by N₂ adsorption, XRD, Raman spectroscopy, SEM-EDS, TEM, FT-IR, XPS, UV–Vis and ICP. These results upheld the existence of periodically arranged macroporous structure of catalyst, with Keggin-type of HPW dispersed homogeneously on TiO₂ matrix. Among these 3DOM Ce-doped HPW/TiO₂ materials, catalyst with 15 wt.% cerium dosage exhibits best ODS performance, which oxidized 99.8% of dibenzothiophene (DBT) into corresponding sulfone within 40 min. The excellent ODS performance of 3DOM Ce-doped HPW/TiO₂ catalyst is related to the common influence of more oxygen vacancies produced by electron transformation between Ce³⁺ and Ce⁴⁺. The chemisorbed oxygen on the surface catalyst will facilitate the selective oxidation of sulfides to sulfones. Moreover, the 3DOM structure of catalyst will further promote the mass transfer of reactants and products on the pore channel. The as-prepared catalyst shows excellent reusability in the ODS system, no obviously decrease in catalytic activity even after 6 runs.     

Cr掺杂对Nd0.7Sr0.3MnO3电磁性质的影响

我们对多晶样品Nd0.7Sr0.3Mn1-xCrxO3(x≤0.30)进行了X射线衍射谱、电阻温度关系和磁化强度测量.实验发现:随Cr掺杂量的增加,样品的电阻率变大,电阻峰温度和居里温度降低,这是由Cr的介入弱化了双交换作用所致;在x=0.10附近,电阻出现了双峰现象,在其M~T上没有发现与低温峰对应的磁性异常;在锰位磁矩与Cr含量的关系中发现,Cr掺杂对样品的磁性几乎无贡献;通过分析,我们用相分离的图象解释了有关的现象.     

磺酸功能化三维有序大孔材料的制备与催化性能研究

采用模板法, 用正硅酸乙酯和3-巯丙基-三甲氧基硅烷的混合溶胶, 在聚苯乙烯胶晶间隙中原位转化, 除去模板后用双氧水将巯基氧化成磺酸基, 首次成功地制备了大孔规整排列的3DOM SiO₂-SO₃H材料. 样品用SEM, EDS, FT-IR等方法进行了测试表征. 结果表明, 所得到材料的三维大孔结构规整性十分好, 大孔孔径大约250 nm, 并由大约80 nm的小孔相连; 磺酸基很好地嵌入孔壁基质中, 吡啶吸附测定显示了典型的质子酸特征, 而且酸中心随硫含量增加而增多. 对乙酸与正丁醇的酯化反应显示了良好的催化性能, 磺酸含量越大, 催化活性越高. 这一研究为开发新型高效的固体酸催化剂提供了很有意义的结果.