Sulfur-Modified Oxygen Vacancies in Iron–Cobalt Oxide Nanosheets: Enabling Extremely High Activity of the Oxygen Evolution Reaction to Achieve the Industrial Water Splitting Benchmark

The oxygen vacancies of defective iron–cobalt oxide (FeCoO_x-Vo) nanosheets are modified by the homogeneously distributed sulfur (S) atoms. S atoms can not only effectively stabilize oxygen vacancies (Vo), but also form the Co−S coordination with Co active site in the Vo, which can modulate the electronic structure of the active site, enabling FeCoO_x-Vo-S to exhibit much superior OER activity. FeCoO_x-Vo-S exhibits a mass activity of 2440.0 A g⁻¹ at 1.5 V vs. RHE in 1.0 m KOH, 25.4 times higher than that of RuO₂. The Tafel slope is as low as 21.0 mV dec⁻¹, indicative of its excellent charge transfer rate. When FeCoO_x-Vo-S (anode catalyst) is paired with the defective CoP₃/Ni₂P (cathode catalyst) for overall water splitting, current densities of as high as 249.0 mA cm⁻² and 406.0 mA cm⁻² at a cell voltage of 2.0 V and 2.3 V, respectively, can be achieved.     

Accelerating Crystallization of Open Organic Materials by Poly(ionic liquid)s

The capability to significantly shorten the synthetic period of a broad spectrum of open organic materials presents an enticing prospect for materials processing and applications. Herein we discovered 1,2,4-triazolium poly(ionic liquid)s (PILs) could serve as a universal additive to accelerate by at least one order of magnitude the growth rate of representative imine-linked crystalline open organics, including organic cages, covalent organic frameworks (COFs), and macrocycles. This phenomenon results from the active C5-protons in poly(1,2,4-triazolium)s that catalyze the formation of imine bonds, and the simultaneous salting-out effect (induced precipitation by decreasing solubility) that PILs exert on these crystallizing species.     

Quantum Dots for Display Applications

This article offers a materials-chemistry perspective for colloidal quantum dots (QDs) in the field of display, including QD-enhanced liquid-crystal-display (QD-LCD) and QD-based light-emitting-diodes (QLEDs) display. The rapid successes of QDs for display in the past five years are not accidental but have a deep root in both maturity of their synthetic chemistry and their unique chemical, optical, and optoelectronic properties. This article intends to discuss the natural match of QD emitters for display and chemical means to eventually bring about their full potential.     

A Non-Conjugated Polymer Acceptor for Efficient and Thermally Stable All-Polymer Solar Cells

A non-conjugated polymer acceptor PF1-TS4 was firstly synthesized by embedding a thioalkyl segment in the mainchain, which shows excellent photophysical properties on par with a fully conjugated polymer, with a low optical band gap of 1.58 eV and a high absorption coefficient >10⁵ cm⁻¹, a high LUMO level of −3.89 eV, and suitable crystallinity. Matched with the polymer donor PM6, the PF1-TS4-based all-PSC achieved a power conversion efficiency (PCE) of 8.63 %, which is ≈45 % higher than that of a device based on the small molecule acceptor counterpart IDIC16. Moreover, the PF1-TS4-based all-PSC has good thermal stability with ≈70 % of its initial PCE retained after being stored at 85 °C for 180 h, while the IDIC16-based device only retained ≈50 % of its initial PCE when stored at 85 °C for only 18 h. Our work provides a new strategy to develop efficient polymer acceptor materials by linkage of conjugated units with non-conjugated thioalkyl segments.     

Aggregation-Induced Emission Gold Clustoluminogens for Enhanced Low-Dose X-ray-Induced Photodynamic Therapy

The use of gold nanoparticles as radiosensitizers is an effective way to boost the killing efficacy of radiotherapy while drastically limiting the received dose and reducing the possible damage to normal tissues. Herein, we designed aggregation-induced emission gold clustoluminogens (AIE-Au) to achieve efficient low-dose X-ray-induced photodynamic therapy (X-PDT) with negligible side effects. The aggregates of glutathione-protected gold clusters (GCs) assembled through a cationic polymer enhanced the X-ray-excited luminescence by 5.2-fold. Under low-dose X-ray irradiation, AIE-Au strongly absorbed X-rays and efficiently generated hydroxyl radicals, which enhanced the radiotherapy effect. Additionally, X-ray-induced luminescence excited the conjugated photosensitizers, resulting in a PDT effect. The in vitro and in vivo experiments demonstrated that AIE-Au effectively triggered the generation of reactive oxygen species with an order-of-magnitude reduction in the X-ray dose, enabling highly effective cancer treatment.     

通过赝反伽伐尼反应实现金纳米粒子模块替换

通过可控的方式精确调控纳米粒子的结构仍是一个富有挑战性和鼓舞人心的课题.尽管单原子或两、三个金属原子的精细调控已经在金纳米粒子中实现,涉及三个以上金属原子的取代（模块取代）还没有报道.本工作报道了环己硫醇配体保护的Au₄₈（CHT）₂₆的合成及其通过赝反伽伐尼过程的模块取代.单晶结构揭示模块取代的产物与母体团簇共用一个相似的Au₃₁（CHT）₁₂主体,但剩余部分不同（Au₆（CHT）₁₁ vs.Au₁₆（CHT）₁₄）.一个有趣的发现是模块取代抑制了Au₄₈（CHT）₂₆的光热过程,却增强了它的发射,赋予了所合成团簇更好的双（多）功能应用潜力.光热效应的减弱和发射的增强也暗示了这两种作用能够彼此至少部分转化,对于研究这两种效应之间的相互影响也具有重要的启示.     

碳基介熵材料:理论与实验

富碳型材料,包括纯碳材料的各种同素异形体、碳基骨架的稠环芳香分子、聚合物、框架材料等,已成为当今材料领域最重要的研究领域之一.在这些研究当中,很大一部分工作都是研究材料本身的结构与性质,而忽略了这些材料之间的内在联系.课本中的很多概念,如同分异构体、同素异形体和拓扑缺陷,已经无法用于深入理解种类和数量繁多的富碳型材料之间的构效关系.这就使得通过改变已知材料的有限结构来调控材料的性质变得工作重复而繁重,且基础理解受限于研究个体上.作者将从材料"熵"的概念入手,尝试理解富碳型材料之间熵的相对高低,并建议基于"介熵"的认识开发新型富碳型材料、开发新型介熵富碳型材料的全新性质.基于对具体的不同的新型富碳型材料的讨论,将"介熵"这一概念引入到同素异形体、同分异构体以及广泛存在于碳材料中的拓扑缺陷的理解上.类似富碳型材料的关系不再模糊地停留在几何结构层面上,为今后介熵富碳型材料及其他介熵材料的开发提供参考.     

凝聚态化学研究中的动力学振动光谱理论与技术

化学变化的本质是化学键的形成与断裂。凝聚态化学的主要特征是分子内的物理与化学过程与周围环境之间的动态相互作用和动力学耦合,不仅会影响化学键形成与断裂的化学反应平衡与反应速率,还会改变化学反应的走向。动力学振动光谱技术是探测凝聚态体相中与表面上各种微观分子细节最为有力的当代谱学表征技术之一。与脉冲核磁技术类似,科学家们使用一组精心设计的激光脉冲在凝聚态体系中激发复杂的光学响应,所产生的信号中包含了比传统吸收光谱丰富得多的反应机理、分子与溶液结构、分子运动、电荷与能量传递等微观信息。近年来,各种动力学振动光谱被运用于凝聚态化学的各个领域,尤其是在溶液态和表界面态领域,获得了一系列突破性进展,并且处于不断发展的过程之中。在本文中,我们将回顾及展望动力学振动光谱技术的基本概念、实验方法和理论框架,以及它们在凝聚态及表面态化学中的重要应用。     

Spectroscopic Properties,Conformation and Structure of Difluorothiophosphoryl Isocyanate in the Gaseous and Solid Phase

Difluorothiophosphoryl isocyanate, F₂P(S)NCO was characterized with UV/vis, NMR, IR (gas and Ar-matrix), and Raman (liquid) spectroscopy. Its molecular structure was also established by means of gas electron diffraction (GED) and single crystal X-ray diffraction (XRD) in the gas phase and solid state, respectively. The analysis of the spectroscopic data and molecular structures is complemented by extensive quantum-chemical calculations. Theoretically, the C_s symmetric syn-conformer is predicted to be the most stable conformation. Rotation about the P−N bond requires about 9 kJ mol⁻¹ and the predicted existence of an anti-conformer is dependent on the quantum-chemical method used. This syn-orientation of the isocyanate group is the only one found in the gas phase and contained likewise in the crystal. The overall molecular structure is very similar in gas and solid, despite in the solid state the molecules arrange through intramolecular O⋅⋅⋅F contacts into layers, which are further interconnected by S⋅⋅⋅N, S⋅⋅⋅C and C⋅⋅⋅F contacts. Additionally, the photodecomposition of F₂P(S)NCO to form CO, F₂P(S)N, and F₂PNCO is observed in the solid Ar-matrix.     

Aggregation‐Induced Emission Gold Clustoluminogens for Enhanced Low‐Dose X‐ray‐Induced Photodynamic Therapy

The use of gold nanoparticles as radiosensitizers is an effective way to boost the killing efficacy of radiotherapy while drastically limiting the received dose and reducing the possible damage to normal tissues. Herein, we designed aggregation‐induced emission gold clustoluminogens (AIE‐Au) to achieve efficient low‐dose X‐ray‐induced photodynamic therapy (X‐PDT) with negligible side effects. The aggregates of glutathione‐protected gold clusters (GCs) assembled through a cationic polymer enhanced the X‐ray‐excited luminescence by 5.2‐fold. Under low‐dose X‐ray irradiation, AIE‐Au strongly absorbed X‐rays and efficiently generated hydroxyl radicals, which enhanced the radiotherapy effect. Additionally, X‐ray‐induced luminescence excited the conjugated photosensitizers, resulting in a PDT effect. The in vitro and in vivo experiments demonstrated that AIE‐Au effectively triggered the generation of reactive oxygen species with an order‐of‐magnitude reduction in the X‐ray dose, enabling highly effective cancer treatment.