多级孔芳香骨架材料的合成及固载硫脲催化剂的研究

合成了一种多级孔芳香骨架材料(PAF-70); 使用由氨基修饰过的单体, 应用该合成策略得到了同样具有窄分布介孔的含有氨基活性位点的PAF材料, 并通过硫脲单体与其氨基活性位点的反应, 将硫脲基团引入PAF-70材料中, 获得了含有硫脲催化位点的材料(PAF-70-thiourea). 氮气吸附-脱附测试结果显示, PAF-70存在孔径分布较窄的介孔, 介孔孔径为3.8 nm, 与模拟计算值(约3.7 nm)吻合. 热重分析结果表明, PAF-70具有很高的热稳定性. PAF-70在大多数溶剂中可以稳定存在, 具有良好的化学稳定性. 将PAF-70-thiourea作为催化剂, 应用在N-溴代琥珀酰亚胺(NBS)氧化醇类的反应中, 其表现出较高的催化活性、 较高的稳定性和广泛的底物适用性. 与含有相同硫脲催化位点的金属有机框架(MOF)材料(IRMOF-3-thiourea)作为催化剂对比, 进一步证实PAFs材料非常适合作为催化有机反应的固载平台.     

Nanoporous NiO@SiO2 photo-catalyst prepared by ion-exchange method for fast elimination of reactive dyes from wastewater

Photo-catalytic elimination of organic contaminants plays a significant role in wastewater treatment. Developing a highly efficient photo-catalyst is one of the leading research topic. Herein, we reported the fabrication of a novel nanoporous NiO@SiO₂ photo-catalyst by a simple ion-exchange method to eliminate the reactive dyes. The synthesized NiO@SiO₂ catalyst exhibited fast photo-degradation and excellent adsorption capability and could efficiently remove Red FN-3GL dye from wastewater, due to a high loading of NiO and a large specific surface area, abundant electron-withdrawing groups, as well as narrow bandgap energy. In addition, the NiO@SiO₂ photo-catalyst also displayed a high capability to remove reactive dyes over a wide range of pH values (pH 3–9). The prominent adsorption and photo-degradation of dyes were strongly dependent on the surface charge of the catalyst and the generation of hydroxyl radicals (OH^?) by the catalyst, respectively. Furthermore, the NiO@SiO₂ photo-catalyst also exhibited excellent recyclability, thus demonstrating the feasibility of practical applications in industries. The strategy of covering the metal oxide to nanoporous silica is a promising method for developing active photo-catalysts and applying them in the wastewater treatments.     

Microwave-assisted hydrothermal synthesis of NiMoO4 nanorods for high-performance urea electrooxidation

A large surface area with high active site exposure is desired for the nano-scaled electrocatalysts fabrication.Herein,taking Ni Mo O₄nanorods for example,we demonstrated the advantages of the microwaveassisted hydrothermal synthesis method compared to the traditional hydrothermal approaches.Both monoclinic structured Ni Mo O₄in the nanorods morphology are found for these samples but it is more time-saving and efficient in the Ni-Mo synergism for the catalyst obtained by mi...     

Visible light-driven acridone catalysis for atom transfer radical polymerization

Acridone as a new kind of visible light photocatalyst has been developed to catalyze metal free atom transfer radical polymerization (ATRP). The photocatalyst possess low excited state potential as can undergo an oxidative quenching pathway to initiate ATRP of vinyl monomers. Kinetic study and light on/off reaction demonstrate the “living”/controlled nature of the polymerization by light. Block copolymers can be achieved by using PMMA as macroinitiator to reinitiate polymerization of other vinyl monomers, which shows highly preserved Br chain-end functionality in the synthesized polymers. Moreover, the polymerization can be conducted under air atmosphere as most photocatalysts need anaerobic condition, which may give inspiration of further application of this kind of photocatalyst.     

[Nb@Ge13/14]3−: New Family Members of Ge-Based Intermetalloid Clusters

During the past two decades, single-atom-centered medium-sized germanium clusters [M@Ge_n] (M=transition metals, n>12) have been extensively explored, both from theoretical perspectives and experimental gas-phase syntheses. However, the actual structural arrangements of the Ge₁₃ and Ge₁₄ endohedral cages are still ambiguous and have long remained an unresolved problem for experimental implementation. In this work, we successfully synthesize 13-/14-vertex Ge clusters [Nb@Ge₁₃]³⁻ ( 1 ) and [Nb@Ge₁₄]³⁻ ( 2 ), which are structurally characterized and exhibit unprecedented topologies, neither classical deltahedra nor 3-connected polyhedral structures. Theoretical analysis indicates that the major stabilization of the Ge backbones arises due to the substantial interaction of Ge 4p-AOs with the endohedral Nb 4d-AOs through three/four-center two-electron bonds with an enhanced electron density accumulated over the shortest Nb−Ge13 contact in 1 . Low occupancies of the direct two-center two-electron (2c–2e) Nb−Ge and Ge−Ge σ bonds point to a considerable degree of electron delocalization over the Ge cages revealing their electron deficiency.     

Substituent engineering in g-C3N4/COF heterojunctions for rapid charge separation and high photo-redox activity

Science China Chemistry - The heterojunction constructed of covalent organic frameworks (COFs) with adjustable structure and other photocatalysts has great potential in the field of photocatalysis....     

Fluorinated inverse opal carbon nitride combined with vanadium pentoxide as a Z-scheme photocatalyst with enhanced photocatalytic activity

In this work, Z-scheme V₂O₅ loaded fluorinated inverse opal carbon nitride (IO F-CN/V₂O₅) was synthesized as a product of ternary collaborative modification with heterostructure construction, element doping and inverse opal structure. The catalyst presented the highest photocatalytic activity and rate constant for degradation of typical organic pollutants Rhodamine B (RhB) and was also used for the efficient removal of antibiotics, represented by norfloxacin (NOR), sulfadiazine (SD) and levofloxacin (LVX). Characterizations confirmed its increased specific surface area, narrowed bandgap, and enhanced visible light utilization capacity. Further mechanism study including band structure study and electron paramagnetic resonance (EPR) proved the successful construction of Z-scheme heterojunction, which improved photo-generated charge carrier migration and provide sufficient free radicals for the degradation process. The combination of different modifications contributed to the synergetic improvement of removal efficiency towards different organic pollutants.     

Polymeric Carbon Nitride-based Single Atom Photocatalysts for CO2 Reduction to C1 Products

Photocatalytic CO₂ reduction to C₁ fuels is considered to be an important way for alleviating increasingly serious energy crisis and environmental pollution. Due to the environment-friendly, simple preparation, easy formation of highly-stable metal-nitrogen(M-N_x) coordination bonds, and suitable band structure, polymeric carbon nitride-based single-atom catalysts(C₃N₄-based SACs) are expected to become a potential for CO₂ reduction under visible-light irradiation. In this review, we summarize the recent advancement on C₃N₄-based SACs for photocatalytic CO₂ reduction to C₁ products, including the reaction mechanism for photocatalytic CO₂ reduction to C₁ products, the structure and synthesis methods of C₃N₄-based SACs and their applications toward photocatalytic CO₂ reduction reaction(CO₂RR) for C₁ production. The current challenges and future opportunities of C₃N₄-based SACs for photoreduction of CO₂ are also discussed.     

Photoelectrochemical oxygen atom transfer enabling efficient selective oxygenation

Photoelectrochemical(PEC)technique represents a promising approach to chemical transformation by harvesting sustainable solar energy.Despite the wide applications of PEC systems such as environmental remediation and solar energy conversion,the reported PEC reactions are dominated by the radical-based processes that are initiated by the single electron transfer between photo-induced carriers and adsorbed species on photoelectrode surface[1,2].For instance,hydroxyl radicals are often involved in the PEC oxidation reactions.As well known,it is a grand challenge to control the formation and evolution rates of radicals,which inevitably leads to the unsatisfactory product selectivity of PEC reactions.Naturally,such a circumstance brings about a question to the research community whether a different mechanism can be established to sustain efficient and selective oxygenation.Recently,based on their previous findings on PEC water oxidation[3,4],Zhao and coworkers[5]reported that many substrates can be oxidized in an oxygen atom transfer(OAT)pathway,a non-radical two electron process,to oxygenated products byα-Fe2O3 photoanodes.