General Formation of Macro-/Mesoporous Nanoshells from Interfacial Assembly of Irregular Mesostructured Nanounits

Mesoporous core–shell nanostructures with controllable ultra-large open channels in their nanoshells are of great interest. However, soft template-directed cooperative assembly to mesoporous nanoshells with highly accessible pores larger than 30 nm, or even above 50 nm into macroporous range, remains a significant challenge. Herein we report a general approach for precisely tailored coating of hierarchically macro-/mesoporous polymer and carbon shells, possessing highly accessible radial channels with extremely wide pore size distribution from ca. 10 nm to ca. 200 nm, on diverse functional materials. This strategy creates opportunities to tailor the interfacial assembly of irregular mesostructured nanounits on core materials and generate various core–shell nanomaterials with controllable pore architectures. The obtained Fe,N-doped macro-/mesoporous carbon nanoshells show enhanced electrochemical performance for the oxygen reduction reaction in alkaline condition.     

A Highly Lewis Acidic Strontium ansa-Arene Complex for Lewis Acid Catalysis and Isobutylene Polymerization

The potential of a dicationic strontium ansa-arene complex for Lewis acid catalysis has been explored. The key to its synthesis was a simple salt metathesis from SrI₂ and 2 Ag[Al(OR^F)₄], giving the base-free strontium-perfluoroalkoxyaluminate Sr[Al(OR^F)₄]₂ (OR^F=OC(CF₃)₃). Addition of an ansa-arene yielded the highly Lewis acidic, dicationic strontium ansa-arene complex. In preliminary experiments, the complex was successfully applied as a catalyst in CO₂-reduction to CH₄ and a surprisingly controlled isobutylene polymerization reaction.     

Synthesis and characterization of VO–vanillin complex immobilized on MCM-41 and its facile catalytic application in the sulfoxidation reaction,and synthesis of 2,3-dihydroquinazolin-4(1H)-ones and disulfides in green media

In this work, a vanillin complex is immobilized onto MCM-41 and characterized by FT-IR, X-ray diffraction, scanning electron microscopy, energy dispersive spectroscopy, thermogravimetric analysis, and BET techniques. This supported Schiff base complex was found to be an efficient and recoverable catalyst for the chemoselective oxidation of sulfides into sulfoxides and thiols into their corresponding disulfides (using hydrogen peroxide as a green oxidant) and also a suitable catalyst for the preparation of 2,3-dihydroquinazolin-4(1H)-one derivatives in water at 90°C. Using this protocol, we show that a variety of disulfides, sulfoxides, and 2,3-dihydroquinazolin-4(1H)-one derivatives can be synthesized in green conditions. The catalyst can be recovered and recycled for further reactions without appreciable loss of catalytic performance.     

Theoretical studies of photovoltaic properties of five new silol dithiophene based D2-A-D1-A-D2 donors

Organic solar cell of silol dithiophene based D₂-A-D₁-A-D₂/PC₇₁BM (D: donor part; A: acceptor part; 1 and 2 denote different units) possesses promising power conversion efficiency. Researchers have studied D₂-A-D₁-A-D₂ molecules carefully, including the effects of the different number of terminal thiophenes, the different central moiety (D₁), and the length of the alkyl chain. However, there are few investigations, especially theoretical studies, on the influences of different A (acceptor) units on the properties of D₂-A-D₁-A-D₂ molecule. In the present work, we have designed and modeled five new D₂-A-D₁-A-D₂ (D₂ = bithiophene and D₁ = silol dithiophene) donors by changing A units (A = diketopyrrolopyrrole, naphtho[1,2-c:5,6-c′]bis[1,2,5]thiadiazole, 5-fluoro-2,1,3-benzoselenadiazole, benzobisthiadiazole, and thiazolo[5,4-d]thiazole). We have applied density functional theory (DFT) and time-dependent DFT to predict their ground-state electronic structures and the UV–vis spectra, and the open circuit voltages (Vocs) of organic solar cells of D₂-A-D₁-A-D₂/PC₇₁BM. Based on the calculated results, we find that bithiophene thiazolo[5,4-d]thiazole siloldithiophene (BTTS) (D₂ = bithiophene, A = thiazolo[5,4-d]thiazole, D₁ = silol dithiophene) possesses the highest lowest unoccupied molecular orbital (−2.60 eV) and the lowest highest occupied molecular orbital (−5.33 eV) energies, and the strongest absorption in the visible region. Besides, the solar cell of BTTS/PC₇₁BM has the highest Voc of 1.02 V. These results indicate that it may be a promising donor. In contrast, bithiophene benzobisthiadiazole siloldithiophene (BBBS) (A = benzobisthiadiazole) has low absorption strength in the visible region, which indicates that it may not be a suitable donor material.     

A DFT study on mechanisms of CO2 coupling with propargylic alcohols using alkali carbonates

The mechanisms of CO₂ coupling with the propargylic alcohol using alkali carbonates M₂CO₃ (M = Li, Na, K, Cs) have been investigated by means of density functional theory calculations. The calculations reveal that the target product tetronic acid (TA) is yielded through two stages: (a) the formation of the α-alkylidene cyclic carbonate (αACC) intermediate via Cs₂CO₃-mediated carboxylative cyclization of the propargylic alcohol with CO₂, and (b) the conversion of the αACC intermediate with Cs₂CO₃ to produce the cesium salt of the TA. Since the overall kinetic barriers for the two stages are comparable and affordable, the excellent chemoselectivity to the TA should be primarily originated from the high thermodynamic stability of the cesium salt of the TA. Moreover, relative to the TA, the possibility to yield the by-product acyclic carbonate can be excluded due to the both kinetics and thermodynamic inferiority. This result is different from the organic base-mediated reaction. Alternatively, our calculations predict that CsHCO₃ together generated with the cesium salt of the TA might also be an available mediating reagent for the incorporation of CO₂ with the propargylic alcohol. Compared to other alkali carbonates M₂CO₃ (M = Li, Na, K), the stronger basicity of Cs₂CO₃ and the lower ionic potential of cesium ion can raise the effective concentration of the αACC intermediate, and thus the conversion of the αACC intermediate into the cesium salt of the TA can be achieved with high yield.     

新型非对称二苯并[b,f][1,5]二氮杂环辛四烯的合成

以两种不同取代的2-氨基二苯甲酮为原料,氯苯为溶剂,BF3-Et2O为脱水剂,通过分子间脱水一步环化缩合制备非对称二苯并[b,f][1,5]二氮杂环辛四烯衍生物。运用HPLC监控反应过程,优化合成工艺,得到最佳反应条件为:等物质的量的两种不同取代2-氨基二苯甲酮和BF3-Et2O,在氯苯中回流反应12 h。化合物4a^4c为新化合物,其结构经1H NMR,13C NMR和MS(ESI)表征。     

Effect of Support on Catalytic Performance of Photothermal Fischer-Tropsch Synthesis to Produce Lower Olefins over Fe5C2-based Catalysts

Photothermal Fischer-Tropsch synthesis(FTS) has been extensively studied, but few reports were focused on systematically exploring the influence of support on catalytic performance. Herein, a series of Fe₅C₂-based catalysts with different supports was fabricated via a one-step wet-chemical method for photothermal conversion of syngas to lower olefins. Under light irradiation, the optimized Fe₅C₂/α-Al₂O₃ catalyst demonstrated remarkable photothermal FTS activity, delivering selectivity to lower olefins of 50.3% with a CO conversion rate of 52.5%. Characterization studies using X-ray diffraction and Mössbauer spectroscopy analysis revealed that the active catalyst mainly contained Fe₅C₂ nanoparticles on α-Al₂O₃ support. It was found that the weak interaction between active phase and α-Al₂O₃ could promote the formation of Fe₅C₂, which contributed to the high selectivity to lower olefins.