设计p-n同质结构实现碳氮光催化剂的全解水性能

非金属氮化碳(CN)因其独特的光催化性能而备受关注.本文利用水热处理、高温烧结、高能球磨和烧结的方法成功制得一种具有混合结构的CN光催化剂.先以三聚氰胺为原料进行水热处理(180 ℃,24 h),过滤干燥后,转移到高纯氩气保护下的管式炉中,于550 ℃处理1 h得到CN材料.然后将CN用三聚氰胺和氟化铵水热180 ℃处...     

Activation and Conversion of Molecular Nitrogen to the Precursor of Ammonia on Silicon Substituted Cyclo[18]Carbon: a DFT Design

Recent synthesis of sp-hybridized cyclo[18]carbon allotrope has attracted immense curiosity. Since then, a generous amount of theoretical studies concerning aromaticity, adsorption, and spectra of the molecule have been performed. However, very few stuides have been carried out concerning its reactivities and catalytic behaviour. In this article, a DFT-based inquisition has been reported regarding the reactivity of Si substituted cyclo[18]carbon molecule towards molecular N₂. Results show that the Si substituted derivative is effective in producing adducts with molecular nitrogen. Charge calculations and IRC trapping methods indicate that only the Si center of C₁₇Si and its (HOMO-1) level participate in N₂ addition. The N-adduct so formed, is then found to spontaneously react with molecular H₂. The addition of two H₂ molecules to the activated nitrogen molecule to give respective amine derivatives have also been studied. The successful generation of the precursor of NH₃ by C₁₇Si lays a clear emphasis on its potentiality.     

Block Copolymer Micelles with Near Infrared Metal Phthalocyanine Dyes for Laser Induced Writing

A route has been developed to disperse metal‐containing phthalocyanine dyes in a non‐polar medium based on amphiphilic block copolymer micelles of poly[styrene‐block‐(4‐vinylpyridine)] (PS‐b‐P4VP) and poly[styrene‐block‐(acrylic acid)] (PS‐b‐PAA) copolymers. Polar P4VP and PAA efficiently encapsulate cobalt(II ), manganese(II ), and nickel(II ) phthalocyanine dyes by axial coordination of nitrogen and µ‐oxo bridged dimerization with the transition metals, respectively. Good dispersion of the dyes is confirmed by the linear enhancement of Q‐bands in UV–vis absorption spectra with dye concentration. A thin monolayered PS‐b‐P4VP micelle film that contained a nickel(II ) phthalocyanine dye which efficiently adsorbs a laser beam on a localized area to generate a local heat higher than the glass transition temperatures of both blocks. One‐dimensional laser writing on the dye‐containing film allows the fabrication of a few submicrometer wide line patterns in which the self‐assembled nanostructure of the block copolymer is modified by the directional heat arising from laser scanning.

     

Electronic Configuration Regulation by N-Doped MXenes Boosting Electrocatalytic Performance of Cobalt Phthalocyanine

The precise control of electronic configurations of catalytic sites via molecular engineering is significantly desirable for boosting electrocatalytic activity. We reported a new-type composite electrocatalyst with cobalt phthalocyanine supported on N-doped MXene nanosheets (N-MXene/CoPc) through a self-assembly process. Beneficial from the joint action of N sites participation and axial coordination, N-MXene/CoPc exhibits a high ORR activity with positive onset potential (E_onset=0.98 V vs. RHE) and half-wave potential (E_1/2=0.863 V), which is superior over the pristine CoPc (E_1/2=0.72 V) and the composite with undoped MXene as support (MXene/CoPc, E_1/2=0.771 V). Additionally, N-MXene/CoPc exhibits an excellent durability with only 8.5 % attenuation after 25000 s of continuous i-t test, while a more obvious decay 18.6 % for 20 wt.% Pt/C. This work not merely reported a robust ORR catalyst, but more provides a reasonable design strategy for nonnoble-metal catalysts through catalyst-support interactions.     

Design of smart nanodevices based on N-vinyl caprolactam nanogels for photosensitizers

Smart PVCL-based nanogels for photosensitizers were prepared following the thermo precipitation methodology. PVCL-based imprinted and non-imprinted NGs are reported with different percentages of N,N′-methylenebisacrylamide (BIS) as crosslinker agent. Zn(II)phthalocyanine (ZnPc) is employed as a model photosensitizer and incorporated as a template molecule for imprinted NGs or it loads post-synthesis for non-imprinted NGs. In order to analyze the chemical structure, NGs were characterized using infrared microscopy. Hydrodynamic diameter was determined by dynamic light scattering. The phase transition temperature was measured by UV–vis spectroscopy. The phase transition temperature and D_h values were regulated by the percentage of crosslinker and the presence of the photosensitizer as a template or post-synthesis load. In all cases, the yields were acceptable and the smart nanodevices were stable.     

Quantum chemical study of oxidation processes in Cu-phthalocyanine

Quantum chemical calculations reproduced quite well the experimental infrared spectra of CuPc and CuNO₃Pc · HNO₃. The agreement in the changes of line intensities during the oxidation supports the idea of ligand oxidation. This result is in agreement with the Mulliken population analysis.     

Synthesis of Isomeric Tb3+-Phthalocyanine Double-Decker Complexes Depending on the Difference in the Direction of Coordination Plane and Their Magnetic Properties

A C_4h symmetrically substituted phthalocyanine, 1,8,15,22-tertrakis(2,4-dimethylpent-3-oxy)phthalocyanine (H₂TdMPPc), was used to synthesize Tb³⁺-phthalocyanine double-decker complexes ([Tb(TdMPPc)₂]s). Because H₂TdMPPc has C_4h symmetry, S,S, R,R, and meso isomers of [Tb(TdMPPc)₂] were obtained depending on the difference in the direction of the coordination plane of two C_4h-type phthalocyanines with respect to a central Tb³⁺ ion. We investigated the physical properties of these [Tb(TdMPPc)₂] isomers, including their single-ion magnetic properties, and found that the spin-reversal energy barrier (U_eff) of the meso isomer was apparently higher than that of the enantiomers. Detailed crystal structural analyses indicated that the meso isomer has a more symmetrical structure than do the enantiomers, thereby suggesting that the higher U_eff of the meso isomer originated from the more highly symmetrical structure.     

Au(111)表面单个钴酞菁分子的去氢过程

利用低温超高真空扫描隧道显微镜对单个钴酞菁分子实现了选键化学反应.通过对吸附于Au(111)表面的单个钴酞菁分子外围H原子的"剪裁",并用实验图像和谱学方法,结合第一性原理理论计算研究了逐步去除钴酞菁分子8个外围H原子的过程.理论计算结果再现了实验中所观测到的分子空间构型的变化,并阐明了吸附体系中局域自旋的恢复和变化过程.