磺化四(1,4-二噻英)四氮杂卟啉铁的合成及初步表征

用氯磺酸作磺化剂,在四（1,4-二噻英）四氮杂卟啉铁配合物外围功能基对-二噻英环上发生直接取代反应,合成了水溶性良好的多取代磺化（1,4-二噻英）四氮杂卟啉铁配合物（简写为FeSPz（dtn）4）.并对磺化产物进行UV-Vis,IR,1HNMR和XPS等结构表征.     

碘催化下苯硫酚和环己酮及其衍生物合成2-芳硫基苯酚类化合物的研究

2-芳硫基苯酚及其衍生物可以用作GlyT-1抑制剂。笔者发展了一种2-芳基硫醚苯酚的合成新方法，反应过程中以氧气作为氢的接受剂，以环己酮作为苯酚基来源，不需要任何金属参与，使用催化量的碘提高了反应产率，环己酮作为苯酚基来源。     

Carbon-nitrogen/graphene composite as metal-free electrocatalyst for the oxygen reduction reaction

Sheet-like carbon-nitrogen (CNx)/graphene composites with a high content of nitrogen (x≤0.15) was prepared by the carbonization of polypyrrole (PPy)/reduced-graphene-oxide (rGO) composite at 600-800°C. We used rGO instead of graphene oxide (GO) sheets as a template and a substrate to immobilize PPy since the PPy/GO composite agglomerates easily because of the dehydration of excess oxygen-containing groups on the GO sheets during the drying process. The dried PPy/rGO intermediate and its derived CNx/graphene products retain their high dispersion and loose-powder features. The as-prepared CNx/graphene composites have a total nitrogen content of about 10 at% and their nitrogen state is mainly of pyridinic and graphitic type. CNx/graphene composites exhibit excellent performance for the oxygen reduction reaction (ORR) in terms of electrocatalytic activity, stability and immunity towards methanol crossover and CO poisoning, suggesting their potential as metal-free electrocatalysts for the ORR.     

Carbon-nitrogen/graphene composite as metal-free electrocatalyst for the oxygen reduction reaction

Sheet-like carbon-nitrogen (CNx)/graphene composites with a high content of nitrogen (x≤0.15) was prepared by the carbonization of polypyrrole (PPy)/reduced-graphene-oxide (rGO) composite at 600-800°C. We used rGO instead of graphene oxide (GO) sheets as a template and a substrate to immobilize PPy since the PPy/GO composite agglomerates easily because of the dehydration of excess oxygen-containing groups on the GO sheets during the drying process. The dried PPy/rGO intermediate and its derived CNx/graphene...     

Encumbering the intramolecular π donation by using a bridge: A strategy for designing metal-free compounds to hydrogen activation

On the basis of the FLP (frustrated Lewis pair) principle, a new strategy has been proposed to construct the “frustration” in designing metal-free hydrogen activation compounds, by using FMO (frontier molecular orbital) analyses and quantum mechanics calculations. Unlike the known FLPs which use bulky substituents to prevent them from forming stable Lewis acid/base complexes, the new approach encumbers the intramolecular π donation from the electron donor to the acceptor (e.g. in BH₂NH₂) by using a CH₂ bridge (giving BH₂CH₂NH₂). The strategy is simple and effective. Its effectiveness is demonstrated by the small hydrogen activation energy (12.0 kcal/mol) of the model molecule (BH₂CH₂NH₂), which is significantly less than the 42.7 kcal/mol of BH₂NH₂ and also less than the 18.5 kcal/mol of BH₂PH₂ whose derivative, R₂PB(C₆F₅)₂, has been experimentally shown to be able to activate hydrogen. We also exemplified how to use the strategy to design experimentally more realizable molecules. The example shows promises as a hydrogen activation agent. The strategy can be used to design metal-free catalysts for direct hydrogenation.     

基于室温条件及无金属催化的多组分反应构建4-氨基-2-烷基-6-苯基-5-腈基嘧啶分子骨架

以硫脲、苯甲醛、丙二腈和溴代脂肪烃为原料,在无金属催化及室温条件下,建立了可以较高产率制备4-氨基-2-烷基-6-苯基-5-腈基嘧啶等嘧啶环系列化合物的4组分合成新方法,所得的合成新方法具有良好的普适性以及进一步推广应用的潜力.     

四氮杂卟啉铁(II)催化降解水中有机污染物

详细介绍了利用一种新的铁四氮杂卟啉作为催化剂活化氧降解水中染料如酸性品红、甲基橙、罗丹明 B( Rh B)和有毒有机分子对硝基苯甲酸 ( NBA)的初步研究结果 .用紫外可见光谱 ( U V- Vis)、高效液相色谱 ( HPL C)和红外光谱 ( FRIR)检测表明 :铁四氮杂卟啉 / H2 O2 体系有很好的氧化性 ,能使酸性品红、甲基橙褪色 ,但氧化效率下降较快 .发现了铁四氮杂卟啉 / O2 体系有很好的氧化性能且效率高 ,此体系能使有毒有机分子对硝基苯甲酸 NBA氧化开环 ,氧化率达 85 % ,在酸性、中性和碱性环境中都具有一定的氧化性 .7h内 ,在中性和酸性水中罗丹明 B降解近2 0 % ,尤其在碱性水中的降解达 5 2 % .     

利用循环伏安法研究氢-四氮杂卟啉的电势-pH图

将阳离子氢-四氮杂卟啉在碳电极表面吸附修饰后,浸入由CH3COOH,H3BO3和H3PO4组成并用0.2 mol/LNaOH溶液调节其pH值为2~12的缓冲溶液中,测得了其循环伏安图并得到了电势-pH图.根据电势-pH图中斜率的变化和氢-四氮杂卟啉的化学结构,得出在电势-pH图中各区域可能形成化合物的型态.