单源MOF衍生具有三维有序大孔结构的氮掺杂碳包覆铁-氮合金复合材料用于高效氧还原

氧还原反应在一些能源转换系统如金属-空气电池中起着至关重要的作用.目前贵金属基材料(Pt/C)被认为是最有效的氧还原电催化剂,然而价格昂贵和储量有限等因素限制了它的商业化应用,因此探索高效的非贵金属氧还原电催化剂具有重要的意义.近年来,负载过渡金属铁的多孔碳催化剂由于独特的结构和优异的氧还原催化活性成为替代铂基催化剂最有潜力的候选者.该类材料的合成通常采用直接煅烧含有氮源、碳源和铁盐的混合前驱体的制备方法,但是热解时材料的多孔结构以及活性位点的均匀分布很难得到有效的控制.近年来,金属有机框架(MOFs)由于其多孔结构和组成可控等优点而经常被用作自牺牲模板来制备负载铁基纳米材料的多孔碳催化剂,并表现出优异的电催化活性.目前以MOF为前驱体制备高活性的载铁氮掺杂碳复合材料通常需要引入额外的氮源或铁源,因此选择氮含量丰富的铁基MOF材料作为单源前驱体制备载铁氮掺杂多孔碳复合材料具有重要的意义.除此之外,具有多级孔隙率的催化剂可以改善反应时的传质过程,同时有序交联的网络结构能够提供连续的电子传输.本文报道了一种简单可控的制备具有三维有序大孔结构的载铁氮掺杂多孔碳复合催化剂的合成方法,该材料表现出优异的电催化氧气还原性能和优异的催化稳定性.首先,以氮含量丰富的双氰胺和吡嗪配体所构筑的Fe-MOF作为前驱体,利用具有均一尺寸的聚苯乙烯微球作为造孔剂,合成得到了具有三维有序大孔结构的Fe-MOF前驱体,然后通过高温煅烧该单源前驱体制备得到具有三维有序大孔结构的氮掺杂多孔碳包覆铁-氮合金的复合型催化剂(3DOM Fe/Fe-NA@NC).扫描电镜和透射电镜结果表明,材料内形成了有序交联的大孔结构;氮气吸附测试表明,刻蚀之后材料的比表面积明显增加,结合分级多孔特性可以共同促进催化反应的传质过程.粉末X射线衍射结果证实了多孔碳材料中铁和铁-氮合金物种的成功合成.电化学测试结果表明,在0.1 M KOH电解液中,3DOM Fe/Fe-NA@NC-800催化剂表现出优于Pt/C的氧还原活性,其半波电位(E_1/2)为0.88 V,大于商业Pt/C的半波电位(E_1/2=0.85 V).同时,3DOM Fe/Fe-NA@NC-800表现出更加优异的稳定性,经过20000 s测试后,其电流保持率为94%,而Pt/C只保持了78%.关于活性位点探究的对比实验证明在所制备的复合材料中,铁物种作为高效的活性位点参与了电催化氧还原反应,与氮掺杂多孔碳之间的协同作用共同主导了3DOM Fe/Fe-NA@NC优异的氧还原活性.得益于其优异的氧还原活性,将其作为阴极活性材料组装为锌-空气电池进一步探究了其在实际应用中的可行性.本结果拓宽了高效的铁基催化剂的类型,同时也为制备封装非贵金属的多孔碳基催化剂提供了实验指导和理论依据.     

Electrocatalytic Hydrogen Evolution of the Cobalt Triaryl Corroles Bearing Hydroxyl Groups

Three isomeric A₂B-type new cobalt triaryl corroles bearing hydroxyphenyl substituents have been prepared and well characterized. Their activity and stability in the electrocatalytic hydrogen evolution reaction (HER) have been investigated. The results showed that the hydroxyl position of the phenyl group had significant influence on electrocatalytic HER. The ortho-hydroxyphenyl substituted cobalt corrole ( 1 ) core displays the best HER activity using TsOH proton source, and the turnover frequency (TOF) and catalytic efficiency (C.E) reach 318.68 s⁻¹ and 1.13, respectively. Moreover, a turnover number (TON) of 1447.39 and Faraday efficiency (FE) of 98.7 % have been observed in aqueous medium. The catalytic pathway is via EECEC, EECC or ECEC pathways depending on the acidity of acid proton source (E: electron transfer step, C: chemical step, in this case protonation). The catalytic HER performance of these cobalt corroles follows an order of o-hydroxyl > p-hydroxyl > m-hydroxyl isomer, showing the o- and p-hydroxyl of the phenyl groups are more efficient in accelerating proton relay.     

Near unity quantum yield of light-driven redox mediator reduction and efficient H2 generation using colloidal nanorod heterostructures

The advancement of direct solar-to-fuel conversion technologies requires the development of efficient catalysts as well as efficient materials and novel approaches for light harvesting and charge separation. We report a novel system for unprecedentedly efficient (with near-unity quantum yield) light-driven reduction of methylviologen (MV(2+)), a common redox mediator, using colloidal quasi-type II CdSe/CdS dot-in-rod nanorods as a light absorber and charge separator and mercaptopropionic acid as a sacrificial electron donor. In the presence of Pt nanoparticles, this system can efficiently convert sunlight into H(2), providing a versatile redox mediator-based approach for solar-to-fuel conversion. Compared to related CdSe seed and CdSe/CdS core/shell quantum dots and CdS nanorods, the quantum yields are significantly higher in the CdSe/CdS dot-in-rod structures. Comparison of charge separation, recombination and hole filling rates in these complexes showed that the dot-in-rod structure enables ultrafast electron transfer to methylviologen, fast hole removal by sacrificial electron donor and slow charge recombination, leading to the high quantum yield for MV(2+) photoreduction. Our finding demonstrates that by controlling the composition, size and shape of quantum-confined nanoheterostructures, the electron and hole wave functions can be tailored to produce efficient light harvesting and charge separation materials.     

Size-controllable synthesis of spherical ZnO nanoparticles: Size- and concentration-dependent resonant light scattering

A new and simple direct precipitation method assisted with ultrasonic agitation was proposed for the preparation of spherical ZnO nanoparticles. The size of the ZnO nanoparticles, 10 nm to 85 nm, was tuned through controlling the calcination temperature and changing the ratio of the reactants. The resonant light scattering (RLS) of the ZnO nanoparticles dispersed/suspended in aqueous solution of Triton X-100 was studied under room temperature. It was found that the ZnO nanoparticles of different size or concentration all have a characteristic RLS peak at 387 nm. Under optimal conditions, the RLS intensity was proportional to the ZnO concentration in the range of 7.3 × 10^?8–1 × 10^?4 mol L^?1, while the cubic root of the RLS intensity was found to be proportional to the size of ZnO nanoparticles. Further, the quantitative relationship of the size of the ZnO nanoparticles versus the calcination temperature was derived, and this could be used to forecast/control the nano-size in the nano-ZnO preparation.     

Two‐Dimensional Layered Heterostructures Synthesized from Core–Shell Nanowires

Controlled stacking of different two‐dimensional (2D) atomic layers will greatly expand the family of 2D materials and broaden their applications. A novel approach for synthesizing MoS₂/WS₂ heterostructures by chemical vapor deposition has been developed. The successful synthesis of pristine MoS₂/WS₂ heterostructures is attributed to using core–shell WO_3?x/MoO_3?x nanowires as a precursor, which naturally ensures the sequential growth of MoS₂ and WS₂. The obtained heterostructures exhibited high crystallinity, strong interlayer interaction, and high mobility, suggesting their promising applications in nanoelectronics. The stacking orientations of the two layers were also explored from both experimental and theoretical aspects. It is elucidated that the rational design of precursors can accurately control the growth of high‐quality 2D heterostructures. Moreover, this simple approach opens up a new way for creating various novel 2D heterostructures by using a large variety of heteronanomaterials as precursors.     

淀粉基聚合物胶束用作药物载体

两亲性聚合物能通过亲疏水作用自组装为核-壳结构,而这独特的优势已使其成为在肿瘤靶向药物缓释方面具有很好发展前景的药物载体.淀粉原材料来源丰富,价格低廉,同时具有良好的生物相容性和生物可降解性,故基于淀粉的两亲性聚合物胶束正引起越来越多研究者极大的关注.作为药物载体,淀粉基聚合物胶束不仅可以提高药物的水溶性、延长药物在体内的循环时间、降低副作用和通过增强渗透与滞留(EPR)效应提高药物在靶向部位的优先累积,还可以在淀粉骨架上引入一些刺激响应型的官能团实现胶束快速靶向释药的功能.因此,淀粉基聚合物胶束在用作药物载体方面有着广阔的发展潜力.本文结合本课题组目前的研究工作和近几年的相关报道对淀粉基聚合物胶束作为药物载体的最新研究进展做简要综述.     

Luminescence Properties of Ca2Ga2SiO7:RE Phosphors for UV White‐Light‐Emitting Diodes

A series of Eu²⁺‐, Ce³⁺‐, and Tb³⁺‐doped Ca₂Ga₂SiO₇ phosphors is synthesized by using a high‐temperature solid‐state reaction. The powder X‐ray diffraction and structure refinement data indicate that our prepared phosphors are single phased and the phosphor crystalizes in a tetrahedral system with the ${P\bar 42m}$ (113) space group. The Eu²⁺‐ and Ce³⁺‐doped phosphors both have broad excitation bands, which match well with the UV light‐emitting diodes chips. Under irradiation of λ=350 nm, Ca₂Ga₂SiO₇:Eu²⁺ and Ca₂Ga₂SiO₇:Ce³⁺, Li⁺ have green and blue emissions, respectively. Luminescence of Ca₂Ga₂SiO₇:Tb³⁺, Li⁺ phosphor varies with the different Tb³⁺ contents. The thermal stability and energy‐migration mechanism of Ca₂Ga₂SiO₇:Eu²⁺ are also studied. The investigation results indicate that the prepared Ca₂Ga₂SiO₇:Eu²⁺ and Ca₂Ga₂SiO₇:Ce³⁺, Li⁺ samples show potential as green and blue phosphors, respectively, for UV‐excited white‐light‐emitting diodes.     

Trichodermatides A-D, novel polyketides from the marine-derived fungus Trichoderma reesei

Four new polyketide derivatives, Trichodermatides A-D (1-4) were isolated from the marine-derived fungus Trichoderma reesei. Trichodermatide A (1) is an unprecedented example of a polyketide with a ketal-containing pentacyclic skeleton. The chemical structures and absolute configurations of compounds 1-4 were elucidated by extensive spectroscopic methods, especially 2D NMR and CD spectral analysis, and supported by their proposed biosynthesis pathway. The cytotoxicity of 1-4 was evaluated against A375-S2 human melanoma cell line.     

Molar heat capacity and thermodynamic properties of 1,2-cyclohexane dicarboxylic anhydride [C8H10O3]

The molar heat capacity C _p,m of 1,2-cyclohexane dicarboxylic anhydride was measured in the temperature range from T=80 to 390 K with a small sample automated adiabatic calorimeter. The melting point T _m, the molar enthalpy Δ_fus H _m and the entropy Δ_fus S _m of fusion for the compound were determined to be 303.80 K, 14.71 kJ mol⁻¹ and 48.43 J K⁻¹ mol⁻¹, respectively. The thermodynamic functions [H _T-H _273.15] and [S _T-S _273.15] were derived in the temperature range from T=80 to 385 K with temperature interval of 5 K. The thermal stability of the compound was investigated by differential scanning calorimeter (DSC) and thermogravimetry (TG), when the process of the mass-loss was due to the evaporation, instead of its thermal decomposition.     

Large third-order optical nonlinear effects of gold nanoparticles with unusual fluorescence enhancement

The third-order nonlinear optical properties of two solutions of gold nanoparticles protected by carbazolyldiacetylene derivatives were investigated using the Z-scan technique. Both gold nanoparticle colloid solutions in toluene show unusual fluorescent enhancement and large third-order nonlinear optical properties including nonlinear absorption and refractive effects. When extending the pi-conjugated length of the ligands, the third-order nonlinear properties of composite materials based on gold nanoparticles were enhanced accordingly.