Effects of Coverage,Water, and Defects on Catechol/TiO2 Interface

Catechol adsorbed on TiO₂ is one of the simplest models to explore the relevant properties of dye-sensitized solar cells. However, the effects of water and defects on the electronic levels and the excitonic properties of the catechol/TiO₂ interface have been rarely explored. Here, we investigate four catechol/TiO₂ interfaces aiming to study the influence of coverage, water, and defects on the electronic levels and the excitonic properties of the catechol/TiO₂ interface through the first-principles many-body Green's function theory. We find that the adsorption of catechol on the rutile (110) surface increases the energies of both the TiO₂ valence band maximum and conduction band minimum by approximately 0.7 eV. The increasing coverage and the presence of water can reduce the optical absorption of charge-transfer excitons with maximum oscillator strength. Regarding the reduced hydroxylated TiO₂ substrate, the conduction band minimum decreases greatly, resulting in a sub-bandgap of 2.51 eV. The exciton distributions in the four investigated interfaces can spread across several unit cells, especially for the hydroxylated TiO₂ substrate. Although the hydroxylated TiO₂ substrate leads to a lower open-circuit voltage, it may increase the separation between photogenerated electrons and holes and may therefore be beneficial for improving the photovoltaic efficiency by controlling its concentration. Our results may provide guidance for the design of highly efficient solar cells in future.     

(-)-N-芳硫基樟脑内磺酰胺的合成及其与β-酮酯的反应

(1S)-(-)-2,10-樟脑内磺酰胺与原位生成的芳基硫氯反应,制得系列亲电性N-芳硫基樟脑内磺酰胺试剂（1a~1c）,并将其应用于与β-酮酯活泼氢的不对称亲电取代反应,合成了具有光学活性的α-芳硫基-β-酮酯衍生物。考察了试剂结构、底物酯基的体积及环大小、添加剂种类及用量,以及溶剂、温度等反应条件对手性诱导效率的影响。初步实验结果表明：以(1S)-(-)-N-对甲基苯硫基樟脑内磺酰胺（1a）为亲电试剂,六元环β-酮甲酯为底物,甲苯为溶剂,碳酸钾为碱,室温反应48 h,α-芳硫基-β-酮酯的收率可达91%,对映选择性达40%ee。     

In2BP3O12:Cr3+宽带近红外荧光粉的发光性能及应用研究※

近红外光谱技术在安防监控、食品检测、生物成像、农业等领域具有重要应用价值, 而开发出紧凑高效的近红外光源是其大规模商业应用的前提. 荧光粉转换型近红外发光二极管(light emitting diodes, LED)光源具有结构紧凑、成本低、使用寿命长、发射光谱可调等优点, 因此近些年受到广泛关注, 其关键就在于开发出能被蓝光有效激发的高性能近红外荧光粉. 本工作利用高温固相法制备了一种新型宽带近红外荧光粉In₂BP₃O₁₂:Cr³⁺, 在480 nm激发下, 荧光粉发射峰值位于950 nm, 光谱覆盖了750~1350 nm范围, 半峰宽达到210 nm. 采用该荧光粉与商用蓝光InGaN LED芯片封装, 获得了具有宽带发射的近红外LED光源, 在60 mA的驱动电流下, 近红外光辐射功率为5 mW. 当采用该光源照射人的手掌, 用近红外电感耦合器(charge coupled device, CCD)相机能够对手掌中的血管进行清晰的成像. 上述结果表明该近红外荧光粉可用于制备基于蓝光芯片的宽带近红外LED光源, 并在生物医学等领域具有潜在应用前景.     

双功能聚二甲基硅氧烷/铜纳米线复合薄膜的制备与性能

通过环境友好的葡萄糖模板法和改进的湿化学还原法制备了聚二甲基硅氧烷/铜纳米线(PDMS/CuNWs)复合薄膜, 其采用的“类夹心结构”有效解决了铜在空气中易氧化进而导致电导率大幅度下降的问题, 同时获得了具有优异电磁屏蔽和光热转化性能的双功能轻质柔性复合薄膜. CuNWs面密度为1.6 g/cm²的复合薄膜在重复弯折1000次后性能保持率最高可达99.07％; CuNWs面密度为2.4 g/cm²的复合薄膜在X波段下总电磁屏蔽效能达到30.1 dB, 屏蔽效率达到99.9％; 同时, 在2 W/cm²的近红外光照射下, 复合薄膜在仅加热15 s后其表面温度高达211.2 ℃, 具有十分快速的光热响应和转化效率.     

Optimizing the quasi-equilibrium state of hot carriers in all-inorganic lead halide perovskite nanocrystals through Mn doping: fundamental dynamics and device perspectives

Hot carrier (HC) cooling accounts for the significant energy loss in lead halide perovskite (LHP) solar cells. Here, we study HC relaxation dynamics in Mn-doped LHP CsPbI₃ nanocrystals (NCs), combining transient absorption spectroscopy and density functional theory (DFT) calculations. We demonstrate that Mn²⁺ doping (1) enlarges the longitudinal optical (LO)–acoustic phonon bandgap, (2) enhances the electron–LO phonon coupling strength, and (3) adds HC relaxation pathways via Mn orbitals within the bands. The spectroscopic study shows that the HC cooling process is decelerated after doping under band-edge excitation due to the dominant phonon bandgap enlargement. When the excitation photon energy is larger than the optical bandgap and the Mn²⁺ transition gap, the doping accelerates the cooling rate owing to the dominant effect of enhanced carrier–phonon coupling and relaxation pathways. We demonstrate that such a phenomenon is optimal for the application of hot carrier solar cells. The enhanced electron–LO phonon coupling and accelerated cooling of high-temperature hot carriers efficiently establish a high-temperature thermal quasi-equilibrium where the excessive energy of the hot carriers is transferred to heat the cold carriers. On the other hand, the enlarged phononic band-gap prevents further cooling of such a quasi-equilibrium, which facilitates the energy conversion process. Our results manifest a straightforward methodology to optimize the HC dynamics for hot carrier solar cells by element doping.

Mn doping modulates the hot carrier dynamics in all-inorganic lead halide perovskite nanocrystals according to the excitation energy.     

二甲基甲酰胺的变温付立叶变换红外光谱研究

DMF是一种具有优异性能的常用溶剂。根据FT-IR的高分辨率和高灵敏度的特点,研究了液体DMF的20-120℃的变温红外光谱,不同浓度的CCl₄溶液光谱和气体光谱。结果表明在液体DMF中存在着聚合分子,它们是以分子中醛基的C-H键与另一分子的羰基生成C-H…O式氢键而相互作用的。这种以C-H健与O所形成的氢键,已有报导的实例很少。     

热定型聚酯纤维内应力与晶格变形的关系

<正> 结晶学家认为低分子物结晶虽可能存在一定缺陷和变形,但一般都具有一定的晶胞参数。这一概念对于高分子物结晶已不再正确。Bosley认为成形、热处理、冷却速率和杂质的存在皆可引起晶格变形;Fakirov故意在PET中加入少量杂质,却未引起变形。至今,PET已累积了7组晶胞参数,8个计算所得的晶区密度显示了较大幅度的波动(见     

3D bioprinted cancer cells are more tolerant to serum starvation than 2D cells due to autophagy

Cancer is a global issue and a serious threat to human health, one approach to treatment is starvation therapy. Recently, three-dimensional (3D) bioprinted tumor tissue models have been developed; however, whether 3D bioprinted models are good for in vitro study of starvation therapy is unclear. In this study, we studied the state of cells with serum-free medium in both 3D bioprinted scaffold and 2D cell cultures and found that 3D bioprinted cancer cells (3D cells) were more tolerant to serum starvation than 2D cells in terms of cell viability, cell proliferation, and M2 macrophage polarization. Moreover, the ratio of LC3II/I, an index of autophagy, increased much more in 3D cells, and 3D cells showed more autophagosomes than 2D cells after serum starvation, which indicated that the autophagy levels were higher in 3D cells. These results suggested that 3D cells are more tolerant to serum starvation than 2D cells, and autophagy may play an important role in this process.     

Effect of Irradiation Absorbed Dose and Organic Solvent on the Grafting Rate of PVDF-g-PHEMA through Gamma-ray Irradiation in a Homogenous Solution

High Energy Chemistry - Modification of Polyvinylidene fluoride (PVDF) by radiation grafting is a research hotspot in recent years. In this study, the monomer 2-Hydroxyethyl methacrylate (HEMA) was...     

钙钛矿太阳能电池的商业化进展与挑战

钙钛矿太阳电池是一项颠覆性的光伏技术,具有能量转化效率高、生产成本低、制备工艺简单等优势。当前,钙钛矿太阳能电池的认证效率已达25.7%,但其面临着严重的商业化瓶颈,如稳定性差、模组效率相对低、铅毒性等,且这些问题相互关联。本文简述了钙钛矿太阳能电池的工作原理和器件结构,并归纳总结了在解决钙钛矿太阳能电池稳定性、封装和模组化等商业化瓶颈问题方面的主要研究进展。最后,本文提出了钙钛矿光伏商业化进程中值得关注的解决措施。