拓展光催化材料光谱响应的研究进展

光催化技术在解决能源短缺和环境污染问题方面有重要的应用前景,引起了人们的广泛关注。宽光谱响应和高量子效率是实现光催化材料大规模应用的前提。本文介绍了近年来紫外、可见和近红外光催化方面的最新进展,阐述了拓展光响应范围和促进载流子分离的有效途径,总结了光催化材料发展所面临的问题,并对其发展趋势进行了展望。     

Radical C−H Trifluoromethoxylation of (Hetero)arenes with Bis(trifluoromethyl)peroxide

Trifluoromethoxylated (hetero)arenes are of great interest for several disciplines, especially in agro- and medicinal chemistry. Radical C−H trifluoromethoxylation of (hetero)arenes represents an attractive approach to prepare such compounds, but the high cost and low atom economy of existing ^. OCF₃ radical sources make them unsuitable for the large-scale synthesis of trifluoromethoxylated building blocks. Herein, we introduce bis(trifluoromethyl)peroxide (BTMP, CF₃OOCF₃) as a practical and efficient trifluoromethoxylating reagent that is easily accessible from inexpensive bulk chemicals. Using either visible light photoredox or TEMPO catalysis, trifluoromethoxylated arenes could be prepared in good yields under mild conditions directly from unactivated aromatics. Moreover, TEMPO catalysis allowed for the one-step synthesis of valuable pyridine derivatives, which have been previously prepared via multi-step approaches.     

Fundamental Characterization,Photophysics and Photocatalysis of a Base Metal Iron(II)-Cobalt(III) Dyad

A new base metal iron-cobalt dyad has been obtained by connection between a heteroleptic tetra-NHC iron(II) photosensitizer combining a 2,6-bis[3-(2,6-diisopropylphenyl)imidazol-2-ylidene]pyridine with 2,6-bis(3-methyl-imidazol-2-ylidene)-4,4′-bipyridine ligand, and a cobaloxime catalyst. This novel iron(II)-cobalt(III) assembly has been extensively characterized by ground- and excited-state methods like X-ray crystallography, X-ray absorption spectroscopy, (spectro-)electrochemistry, and steady-state and time-resolved optical absorption spectroscopy, with a particular focus on the stability of the molecular assembly in solution and determination of the excited-state landscape. NMR and UV/Vis spectroscopy reveal dissociation of the dyad in acetonitrile at concentrations below 1 mM and high photostability. Transient absorption spectroscopy after excitation into the metal-to-ligand charge transfer absorption band suggests a relaxation cascade originating from hot singlet and triplet MLCT states, leading to the population of the ³MLCT state that exhibits the longest lifetime. Finally, decay into the ground state involves a ³MC state. Attachment of cobaloxime to the iron photosensitizer increases the ³MLCT lifetime at the iron centre. Together with the directing effect of the linker, this potentially makes the dyad more active in photocatalytic proton reduction experiments than the analogous two-component system, consisting of the iron photosensitizer and Co(dmgH)₂(py)Cl. This work thus sheds new light on the functionality of base metal dyads, which are important for more efficient and sustainable future proton reduction systems.     

A Molecular Photosensitizer in a Porous Block Copolymer Matrix-Implications for the Design of Photocatalytically Active Membranes

Recently, porous photocatalytically active block copolymer membranes were introduced, based on heterogenized molecular catalysts. Here, we report the integration of the photosensitizer, i. e., the light absorbing unit in an intermolecular photocatalytic system into block copolymer membranes in a covalent manner. We study the resulting structure and evaluate the orientational mobility of the photosensitizer as integral part of the photocatalytic system in such membranes. To this end we utilize transient absorption anisotropy, highlighting the temporal reorientation of the transition dipole moment probed in a femtosecond pump-probe experiment. Our findings indicate that the photosensitizer is rigidly bound to the polymer membrane and shows a large heterogeneity of absolute anisotropy values as a function of location probed within the matrix. This reflects the sample inhomogeneity arising from different protonation states of the photosensitizer and different intermolecular interactions of the photosensitizers within the block copolymer membrane scaffold.     

p区金属氧化物Ga2O3和Sb2O3光催化降解盐酸四环素性能差异

对沉淀法合成的p区金属氧化物Ga₂O₃和Sb₂O₃紫外光光催化降解盐酸四环素的性能进行了研究,讨论了制备条件对光催化性能的影响。最佳制备条件下得到的Ga₂O₃-900和Sb₂O₃-500样品光催化性能存在巨大差异,通过X射线粉末衍射、傅里叶红外光谱、N2吸附-脱附测试、荧光光谱、拉曼光谱、电化学分析及活性物种捕获实验等对样品进行分析,研究二者光催化降解盐酸四环素的机理,揭示影响光催化性能差异的本质因素。结果表明,Ga₂O₃和Sb₂O₃光催化性能差异主要归结于二者不同的电子和晶体结构、表面所含羟基数量及光催化降解机理。     

结晶氮化碳的制备与改性策略

石墨相氮化碳(g-C_3N_4)是最具代表性的二维有机聚合物半导体材料,其具有可见光响应性能、稳定化学结构和优良的生物相容性等优点,在环境和能源领域有非常广阔的应用前景。但是,普通g-C_3N_4材料的热聚合不完全,其体相和表面的缺陷多,因此光生载流子易复合,光催化活性不高。近年来,高活性结晶氮化碳(CCN)的研究得到了国内外学者的广泛关注。本文总结了目前CCN制备及其改性方法:5种代表性制备方法,包括传统熔盐法、预热熔盐法、固态盐法、溶剂法和质子化法;4种代表性CCN的改性方法,包括缺陷引入、形貌控制、单原子修饰和材料复合。文章重点介绍了 CCN制备原理、结构特征与光催化性能。最后,对CCN的制备与改性方法进行了评价,并对其研究方向进行了展望。     

NiFe2O4对刚果红的光催化降解性能研究

采用水热法合成了尖晶石型NiFe₂O₄,并利用X射线粉末衍射仪对其物相进行了表征,利用紫外-可见分光光度计对其光催化降解刚果红的性能进行了研究。以刚果红为光催化降解底物,探究了刚果红初始浓度、催化剂用量、溶液pH、不同光源等因素对NiFe₂O₄光催化降解刚果红活性的影响。结果表明,当刚果红溶液浓度为20 mg/L、催化剂NiFe₂O₄的用量为0.065 g、pH 2~10、在太阳光下照射480 min时,刚果红的降解率高达99%以上,催化剂性能稳定,适合处理刚果红类有机污染物。     

混合熔盐法低温合成Sm2Ti2S2O5及其光催化分解水产氢

以TiO2、TiS2及Sm2O3为前驱体,分别加入LiCl-KCl与LiCl-CsCl的最低共熔混合物作为熔盐,在较低温度下成功合成了Sm2Ti2S2O5(STSO)颗粒。通过对比不同温度下所制备产物的X射线衍射图,首次表明STSO的热力学结晶温度在520℃左右,远低于之前报道的650℃的最低合成温度。扫描电子显微镜照片显示,采用2种混合熔盐制备的STSO都呈片状形貌;同一合成温度下,采用LiCl-CsCl熔盐制备的STSO的厚度小于LiCl-KCl所得产物。采用出射光波长大于420 nm的氙灯作为光源,在含有Na2S-Na2SO3空穴牺牲剂的溶液中,所制备的STSO颗粒表现出最高35μmol·h-1的光催化分解水产氢活性以及20 h以上的产氢稳定性。     

Visible‐Light Sensitization of Vinyl Azides by Transition‐Metal Photocatalysis

Irradiation of vinyl and aryl azides with visible light in the presence of Ru photocatalysts results in the formation of reactive nitrenes, which can undergo a variety of C? N bond‐forming reactions. The ability to use low‐energy visible light instead of UV in the photochemical activation of azides avoids competitive photodecomposition processes that have long been a significant limitation on the synthetic use of these reactions.     

Metal Oxide‐Coated Three‐Dimensional Graphene Prepared by the Use of Metal–Organic Frameworks as Precursors

A simple method for the preparation of metal‐oxide‐coated three‐dimensional (3D) graphene composites was developed. The metal–organic frameworks (MOFs) that served as the precursors of the metal oxides were first synthesized on the 3D graphene networks (3DGNs). The desired metal oxide/3DGN composites were then obtained by a two‐step annealing process. As a proof‐of‐concept application, the obtained ZnO/3DGN and Fe₂O₃/3DGN materials were used in a photocatalytic reaction and a lithium‐ion battery, respectively. We believe this method could be extended to the synthesis of other metal oxide/3DGN composites with 3D structures simply through the appropriate choice of specific MOFs as precursors.