铁（Ⅲ）－5－硝基－邻菲啰啉配合物光还原作用的研究

无色的铁（Ⅲ）－５－硝基－邻菲 啉配合物在紫外光照射下发生光还原反应，生成红色的铁（Ⅱ）－５－硝基－邻菲 啉。实验证明，各种羧酸及表面活性剂均能影响上述反应，并对其机理作初步探讨。

Fabrication of highly dispersed platinum-deposited porous g-C_3N_4 by a simple in situ photoreduction strategy and their excellent visible light photocatalytic activity toward aqueous 4-fluorophenol degradation

A series of highly dispersed platinum‐deposited porous g‐C3N4 (Pt/pg‐C3N4) were successfully fabricated by a simple in situ photoreduction strategy using chloroplatinic acid and porous g‐C3N4 as precursors. Porous g‐C3N4 was fabricated by a pretreatment strategy using melamine as a raw material.The morphology, porosity, phase, chemical structure, and optical and electronic properties ofas‐prepared Pt/pg‐C3N4 were characterized. The photocatalytic activity of as‐prepared Pt/pg‐C3N4was preliminarily evaluated by the degradation of aqueous azo dyes methyl orange under visible light irradiation. The as‐prepared Pt/pg‐C3N4 were further applied to the degradation and mineralization of aqueous 4‐fluorophenol. The recyclability of Pt/pg‐C3N4 was evaluated under four consecutive photocatalytic runs.

Surface Modification of Cu-Cr Complex by NIR and MIR Laser

Irradiated by infrared laser, the surface reducibility and adsorbability of Cu-Cr complex could be improved, owing to the interaction of photo-fragmentation and laser texturing. Analyzed by the binding energy spectra and the auger spectra, the valence states of chromium ion and copper ion were+3 and+1 after radiation respectively, which still had the reducibility to release electrons. In contrast with the near-infrared(NIR)1 064 nm and mid-infrared(MIR) 10 600 nm laser at the same average output power of 15 W, the reduced metal percentage in the Cu-Cr complex was obviously distinguished at the depth from nanometer to micron. After chemical plating, the average coating thickness and mean-square deviation of the NIR sample were 11.61 μm and 0.30 for copper layer, and 2.69 μm and 0.08 for nickel layer. The results were much better than those of the MIR sample.

Buffer anion effects on water oxidation catalysis: The case of Cu(Ⅲ) complex

Water oxidation is the bottleneck of artificial photosynthesis.Since the first ruthenium-based molecular water oxidation catalyst,the blue dimer,was reported by Meyer’ s group in 1982,catalysts based on transition metals have been widely employed to explore the mechanism of water oxidation.Because the oxidation of water requires harsh oxidative conditions,the stability of transition complexes under the relevant catalytic conditions has always been a challenge.In this work,we report the redox properties of a CuⅢ complex(TAML-CuⅢ] with a redox-active macrocyclic ligand(TAML) and its reactivity toward catalytic water oxidation.TAML-CuⅢ displayed a completely different electrochemical behavior from that of the TAML-CoⅢ complex previously reported by our group.TAML-CuⅢ can only be oxidized by one-electron oxidation of the ligand to form TAML·+-CuⅢand cannot achieve water activation through the ligand-centered proton-coupled electron transfer that takes place in the case of TAML-CoⅢ.The generated TAML·+-CuⅢ intermediate can undergo further oxidation and ligand hydrolysis with the assistance of borate anions,triggering the formation of a heterogeneous B/CuOx nanocatalyst Therefore,the choice of the buffer solution has a significant influence on the electrochemical behavior and stability of molecular water oxidation catalysts.

Hexanuclear ring cobalt complex for photochemical CO_(2) to CO conversion

Photosynthesis in nature has been deemed as the most significant biochemical reaction,which maintains a relatively stable content of O_(2) and CO_(2) in the atmosphere.Herein,for a deeper comprehension of natural photosynthesis,an artificial photosynthesis model reaction of photochemical CO_(2) to CO conversion(CO_(2)+2 H^(+)+2e^(-)→CO+H_(2)O)catalyzed by a homogeneous hexanuclear ring cobalt complex{K_(2)[CoO_(3)PCH_(2)N(CH_(2)CO_(2))_(2)]}_(6)(Co6 complex)is developed.Using the[Ru(bpy)_(3)]^(2+)as a photosensitizer and TEOA as a sacrificial electron donor,an optimal turnover frequency of 503.3 h^(‒1) and an apparent quantum efficiency of 0.81%are obtained.The good photocatalytic CO_(2) reduction performance is attributed to the efficient electron transfer between Co6 complex and[Ru(bpy)_(3)]^(2+),which boosts the photogenerated carriers separation of the photosensitizer.It is confirmed by the j‐V curves,light‐assisted UV‐vis curves,steady‐state photoluminescence spectra and real‐time laser flash photolysis experiments.In addition,the proposed catalytic mechanism for CO_(2) reduction reaction catalyzed by the Co6 complex is explored by the potassium thiocyanate poison experiment,Pourbaix diagram and density functional theory calculations.

Photophysical and photochemical processes of riboflavin (vitamin B_2) by means of the transient absorption spectra in aqueous solution

Using time-resolved techniques of 337 and 248 nm laser flash photolysis, the photo physical and photochemical processes of riboflavin (RF, vitamin B2) were studied in detail in aqueous solution. The excited triplet state of riboflavin (3RF*) was produced with 337 nm laser, while under 248 nm irradiation, both3RF* and hydrated electron (eaq) formed from photoionization could be detected. Photobiological implications have been inferred on the basis of reactivity of3RF* including energy transfer, electron transfer and hydrogen abstraction. The RF·+ was generated by oxidation of SO4 ·-radical with the aim of confirming the results of photolysis.

Biothiol-specific fluorescent probes with aggregation-induced emission characteristics

Biothiols are important species in physiological processes such as regulating protein structures, redox homeostasis and cell signalling. Alternation in the biothiol levels is associated with various pathological processes, therefore non-invasive fluorescent probes with high specificity to biothiols are highly desirable research utilities. Meanwhile, fluorescent probes with aggregationinduced emission properties(AIEgens) possess unique photophysical properties that allow modulation of the sensing process through controlling the aggregation-disaggregation or the intramolecular rotational motions of the fluorophores. Herein we review the recent progress in the development of biothiol-specific AIEgens. In particular, the molecular design principles to target different types of biothiols and the corresponding sensing mechanisms are discussed, along with the potential of the future design and development of multi-functional bioprobes.