射频等离子制备石墨烯负载Co3O4催化剂及其析氧性能研究

氢能的引入能有效提升配电网的供电可靠性,而电解水制氢是实现低碳转型的关键技术,开发高效的电解水催化剂势在必行。过渡金属氧化物储量大、催化活性高,是具有广阔应用前景的析氧反应催化剂。本文通过射频等离子体处理制备石墨烯上负载Co₃O₄析氧催化剂,XRD、Raman和XPS测试结果显示,二维结构石墨烯的引入加速表面电子迁移,增大了反应面积。等离子体处理促进了纳米粒子在石墨烯上的负载,利用等离子体刻蚀作用在催化剂表面制造出大量碳结构缺陷和氧空位结构,改善了活性位点分布,有效调控Co₃O₄电子结构,提高析氧催化活性。电化学测试表明,本文中合成的Co₃O₄@rGO在电流密度为50 mA·cm^-2时的过电位为410 mV,动力学反应速率较快,表现出优于商业IrO₂的析氧催化活性。     

The influence of radiation-induced vacancy on the formation of thin-film of compound layer during a reactive diffusion process

A theoretical approach is developed that describes the formation of a thin-film of AB-compound layer under the influence of radiation-induced vacancy. The AB-compound layer is formed as a result of a chemical reaction between the atomic species of A and B immiscible layers. The two layers are irradiated with a beam of energetic particles and this process leads to several vacant lattice sites creation in both layers due to the displacement of lattice atoms by irradiating particles. A- and B-atoms diffuse via these lattice sites by means of a vacancy mechanism in considerable amount to reaction interfaces A/AB and AB/B. The reaction interfaces increase in thickness as a result of chemical transformation between the diffusing species and surface atoms (near both layers). The compound layer formation occurs in two stages. The first stage begins as an interfacial reaction controlled process, and the second as a diffusion controlled process. The critical thickness and time are determined at a transition point between the two stages. The influence of radiation-induced vacancy on layer thickness, speed of growth, and reaction rate is investigated under irradiation within the framework of the model presented here. The result obtained shows that the layer thickness, speed of growth, and reaction rate increase strongly as the defect generation rate rises in the irradiated layers. It also shows the feasibility of producing a compound layer (especially in near-noble metal silicide considered in this study) at a temperature below their normal formation temperature under the influence of radiation.     

Covalently Assembled Dipeptide Nanospheres as Intrinsic Photosensitizers for Efficient Photodynamic Therapy in Vitro

Monodispersed diphenylalanine‐based nanospheres with excellent biocompatibility are fabricated through a facile covalent reaction‐induced assembly. Interestingly, the nanospheres exhibit red autofluorescence. Most importantly, such assembled dipeptide nanospheres can serve as intrinsic photosensitizer to convert O₂ to singlet oxygen (¹O₂). Thus, photodynamic therapy in vitro can be achieved effectively. The versatile strategy could be extended to other biomolecules containing a primary amine group for the fabrication of potential intrinsic photosensitizers.     

Exploring the Reactivity of α‐Lithiated Aryl Benzyl Ethers: Inhibition of the [1,2]‐Wittig Rearrangement and the Mechanistic Proposal Revisited

By carefully controlling the reaction temperature, treatment of aryl benzyl ethers with tBuLi selectively leads to α‐lithiation, generating stable organolithiums that can be directly trapped with a variety of selected electrophiles, before they can undergo the expected [1,2]‐Wittig rearrangement. This rearrangement has been deeply studied, both experimentally and computationally, with aryl α‐lithiated benzyl ethers bearing different substituents at the aryl ring. The obtained results support the competence of a concerted anionic intramolecular addition/elimination sequence and a radical dissociation/recombination sequence for explaining the tendency of migration for aryl groups. The more favored rearrangements are found for substrates with electron‐poor aryl groups that favor the anionic pathway.     

Preliminary study on singlet oxygen production using CeF3:Tb3+@SiO2-PpIX

Luminescent properties and singlet oxygen production using CeF₃:Tb³⁺-based nanoparticles modified with SiO₂ and protoporphyrin IX (PpIX) were studied. CeF₃:Tb³⁺ nanopowder was prepared via sol–gel route, with subsequent surface coating by SiO₂ layer and the conjugation with photosensitive PpIX molecules. Radioluminescence spectra suggest an energy transfer from Ce³⁺ to Tb³⁺ ions and from Tb³⁺ to molecules of PpIX photosensitizer. The energy transfer was confirmed by photoluminescence decay curves. Singlet oxygen production was detected using a reaction of ¹O₂ with 3’-(p-aminophenyl) fluorescein (APF) chemical probe after X-Ray excitation. Qualitative changes in time resolved photoluminescence spectra in the region of 520 nm indicate ¹O₂ generation. Studied nanocomposites may be good candidates for the application in X-ray induced photodynamic therapy.     

Analytic equation of state for solids with multi-exponential potential based on analytic mean field potential approach and applied to the epsilon phase of solid oxygen

The thermodynamic properties of the ε phase of solid oxygen are studied by using the analytic mean field approach （AMFP）. Analytic expressions for the Helmholtz free energy, internal energy and equation of state of solid oxygen have been derived based on the multi-exponential potential. The formulism for the case of double-exponential （DE） model is applied to the ε phase of solid oxygen. Its four potential parameters are determined through fitting the experimental compression data of the ε phase of solid oxygen. Numerical results of the pressure dependence of the volume calculated by using the AMFP are in good agreement with the original experimental data. This suggests that the AMFP is a useful approach to study the thermodynamic properties of the ε phase of solid oxygen. Furthermore, we predict the variation of the volume, lattice parameters and intermolecular distances with pressure, and some thermodynamic quantities versus volume, at several higher temperatures.     

低轨道原子氧对2种侧链结构多烷基环戊烷真空摩擦学性能的影响

设计合成了2种侧链长度的多烷基环戊烷(MACs)润滑剂,利用多功能空间摩擦学试验系统考察了模拟低轨道原子氧辐照环境对其真空摩擦学性能的影响,同时采用黏度仪、凝胶色谱仪、精密分析天平、扫描电子显微镜(SEM)和傅立叶变换红外光谱仪(FT-IR)等表征了原子氧辐照前后2种MACs润滑剂的黏度、分子量、质量损失、化学结构和磨痕形貌.结果表明:所合成的2种侧链长度的MACs润滑剂在真空下对GCr15/GCr15球-盘摩擦副均具有良好润滑性能.原子氧辐照后,2种MACs润滑剂在真空中对上述摩擦副的摩擦系数均明显增大,摩擦副表面的磨损程度加剧.此外,原子氧辐照还导致润滑剂的黏度和数均分子量增大.红外分析结果显示:原子氧辐照过程中O原子插入了MACs的碳链之间破坏了MACs的化学健,同时与C原子结合生成了CO、C—O—C等新键,并导致润滑剂的酸值增大.原子氧辐照后,MACs中烃类的碳链长度仍大于4,因此仍然具有一定的润滑性能.质量损失结果比较发现具有较长支链的MACs润滑剂耐原子氧侵蚀性能较强,表明设计调控适当的支链长度是改善MACs耐原子氧性能的一条可能途径.     

电激励O2（1△g）发生器的理论模拟研究

 建立了基于分子反应动力学的氧等离子体化学反应模型，该模型包括了电子与氧分子，以及氧原子与氧分子的碰撞反应过程。利用反应动力学理论计算并讨论了电激励O₂(¹△)发生器的放电参数，发现电子能量应小于2.5eV。电子浓度对O₂(¹△)产率的影响不大，当放电压力与气体线流速一定时，存在最佳的电子平均能量。     

V-Ag-Ni系氧化物的表面氧性质与甲苯选择性氧化的催化性能

制备了一系列Ｖ，Ａｇ，Ｎｉ原子比不同的三元氧化物，应用ＴＰＤ－ＭＳ技术研究了样品表面氧的性质，并测定了甲苯选择性氧化生成苯甲醛的催化活性。实验结果表明，样品表面存在有多种吸附的氧物种。在脱附温度＜９００℃：当Ｎｉ含量对Ａｇ（或Ｖ）的原子比为０．２５或０．５０时，仅在低温处出现有表面的Ｏ＾－和Ｏ＾２＾－两种氧物种的脱附峰；当Ｎｉ含量对Ａｇ（或Ｖ）的原子比增高到＞０．７５时，除有表面的Ｏ＾－和Ｏ＾２＾