Copper Nanoparticles In鄄Situ Anchored on Nitrogen鄄Doped Carbon for High鄄Efficiency Oxygen Reduction Reaction Electrocatalyst北大核心CSCD

Compared with noble metal platinum (Pt)-based catalysts, inexpensive non-noble metal electrocatalysts have attracted extensive attention for oxygen reduction reaction (ORR). Herein, chitosan as a kind of biomass resource rich in nitrogen and carbon was used to prepare nitrogen-doped carbon (N-C) and N-C in-situ anchored by copper nanoparticles (Cu/N-C). The as-obtained N-C and Cu/N-C nanoparticles were successfully used as non-noble eletrocatalysts tested for ORR. Compared with the N-C, the Cu/N-C showed the high surface area of 607.3 m2窑g-1 with the mean pore size of 2.5 nm and the pore volume of 0.40 cm3窑g-1. The most positive Gibbs free energy change was the rate determining step for ORR process with the 4e mechanism, where the value of the Cu (111)/N-C(-0.39 eV) was lower than that of the N-C(-0.26 eV). The Cu/N-C exhibited superior onset and half-wave potentials (0.96 V and 0.84 V, respectively) in alkaline media (0.1 mol窑L-1 KOH), all of which are much better than those measured for N-C and commercial Pt/C. Furthermore, the Cu/N-C showed superior methanol crossover avoidance and oxygen reduction stability. © 2021 Authors. All rights reserved.     

Mo的引入方式对CeO2脱硝性能的影响

固定源排放的氮氧化物(NOx)导致了严重的环境污染问题,NH3选择性催化还原(NH3-SCR)被认为是目前控制NOx排放的最有效技术,已广泛应用于电力行业的烟气排放治理.然而,我国非电行业的NOx减排仍然面临着重大挑战,因为其排放的废气温度通常低于300oC,且含有一定量的SO2,传统的钒基SCR催化剂因活性温度(300～400oC)较高而无法有效发挥作用.因此,亟待开发新型的高效低温SCR催化剂.铈基催化剂由于氧化铈(CeO2)的优异储氧能力(OSC)和良好的氧化还原能力而显示出较好的低温(80～300oC)脱硝性能,如Mn-Ce,W-Ce,Ta-Ce,Cu-Ce和Nb-Ce等.但这些铈基催化剂易被烟气中的SO2毒化而导致催化活性降低.因此,提高铈基SCR催化剂抗硫中毒能力是其产业化应用的关键.已有研究发现,通过构筑结构保护层或添加另一种金属来保护活性组分是提高SCR催化剂抗硫性能的一种可行策略.氧化钼(MoO3)通常被用做传统V2O5/TiO2催化剂的促进剂以提高其水热稳定性和表面酸性.研究表明,在V/Ti催化剂中引入钼物种不仅可以提高其SCR活性,而且提高了V/Ti催化剂的抗SO2性能,这是由于VMo/Ti表面较少的V–O–V键削弱了对SO2的氧化作用.Tang等开发了一种Fe2O3/MoO3纳米片催化剂,显示出比纯Fe2O3更好的抗SO2能力,主要是由于层状结构的MoO3能阻止NH4+在硫酸氢铵中的沉积.目前关于Mo的引入方式即催化剂的制备方法对铈基催化剂物化性能和NH3-SCR催化性能(特别是抗SO2能力)的影响的研究还比较少.本文分别采用浸渍法和沉淀法在CeO2中引入钼物种,制备了Mo-CeO2和MoCe-cp催化剂来探究制备方法对MoCe催化剂的脱硝性能及抗SO2中毒能力的影响.结果表明,引入Mo可以显著地提高CeO2的低温脱硝性能,其中Mo-CeO2催化剂在150 oC即可达到80％以上的脱硝效率,同时抗SO2中毒性能也得到了显著提高.对催化剂结构、氧化还原能力、表面酸度和反应物分子的吸附脱附性质进行了表征,并与MoCe催化剂脱硝性能和抗硫性能相关联.结果表明,Mo-CeO2和MoCe-cp催化剂的物理化学性质和脱硝性能有明显区别.首先,Mo-CeO2中的钼物种主要存在于CeO2表面,而MoCe-cp中的钼物种主要存在于CeO2体相,其为Mo-CeO2表面带来大量的Br?nsted酸位并抑制了硝酸盐的吸附,促使NH3-SCR反应按照Eley-Rideal机理进行,进而表现出优于MoCe-cp的低温活性.其次,Mo-CeO2表面更多的Mo物种抑制了SO2的吸附,从而使Mo-CeO2表现出更好的抗SO2性能.本文为具有实际应用前景的铈基NH3-SCR催化剂的设计提供了参考.     

Preparation and adsorption property of novel inverse-opal hierarchical porous N-doped carbon microspheres

The design of pore structure is the key factor for the performance of porous carbon spheres.In this wo rk,novel micron-sized colloidal crystal microspheres consisting of fibrous silica(F-SiO_2) nanoparticles are firstly prepared by water-evapo ration-induced self-assembly of F-SiO_2 nanoparticles in the droplets of an inverse emulsion system to be used as sacrificial templates.Acrylonitrile(AN) was infiltrated in the voids of the F-SiO_2 colloidal crystal microspheres,and in-situ induced by ~(60)Co y-ray to polymerize into polyacrylonitrile(PAN).After the PAN-infiltrated F-SiO_2 colloidal crystal microspheres were carbonized and etched with HF solution,novel micron-sized inverse-opal N-doped carbon(IO-NC) microspheres consisting of hollow carbon nanoparticles with a hierarchical macro/meso-porous inner surface were obtained.The IO-NC microspheres have a specific surface area as high as 266.4 m~2/g and a molar ratio of C/N of 5.They have a good dispersibility in water,and show a high adsorption capacity towards rhodamine B(RhB) up to 137.28 mg/(g microsphe re).This work offers a way to obtain novel micron-sized hierarchical macro/meso-porous N-doped carbon microspheres,which opens a new idea to prepare high-performance hierarchical porous carbon materials.     

毛细管电泳法高效筛选8-氧代鸟嘌呤DNA糖基化酶的核酸适配体

8-氧代鸟嘌呤DNA糖基化酶(OGG1)是人体中重要的功能蛋白,在修复DNA氧化性损伤过程中起关键作用。氧化应激等引起的氧化损伤易导致炎症反应的发生,对OGG1的抑制可以一定程度上起到缓解作用;对癌细胞OGG1的抑制有望作为癌症治疗的新方法。目前的研究多集中于小分子对OGG1功能的影响和调控,而OGG1的适配体筛选尚未见报道。作为功能配体,适配体具有合成简单、高亲和力及高特异性等优点。该文筛选了OGG1的核酸适配体,结合毛细管电泳高效快速的优点建立了两种基于毛细管电泳-指数富集进化(CE-SELEX)技术的筛选方法:同步竞争法和多轮筛选法。同步竞争法利用单链结合蛋白(SSB)与核酸库中单链核酸的强结合能力,与目标蛋白OGG1组成竞争体系,并通过增加SSB浓度来增加竞争筛选压力,以去除与OGG1弱结合的核酸序列,一步筛选即可获得与OGG1强结合的核酸序列。多轮筛选法在相同孵育条件和电泳条件下,经3轮筛选获得OGG1的核酸适配体。比较两种筛选方法的筛选结果,筛选结果中频次最高的3条候选核酸适配体序列一致,其解离常数(K_D)值在1.71~2.64 μmol/L之间。分子对接分析结果表明候选适配体1(Apt 1)可能与OGG1中具有修复氧化性损伤功能的活性口袋结合。通过对两种筛选方法的对比,证明同步竞争法更加快速高效,对其他蛋白核酸适配体筛选方法的选择具有一定的指导意义。得到的适配体有望用于OGG1功能调控,以抑制其修复功能。     

In situ synthesis of CdS/ZnS composite nanoparticles from ZIF-8 for visible light disposal of Cr(VI)

Journal of Sol-Gel Science and Technology - Zeolitic Imidazolate Framework (ZIF-8) micropolyhedra were employed as a raw material for the synthesis of fine cadmium sulfide/zinc sulfide (CdS/ZnS)...     

Metal Sulfide Nanoparticle Synthesis with Ionic Liquids – State of the Art and Future Perspectives

Metal sulfides are among the most promising materials for a wide variety of technologically relevant applications ranging from energy to environment and beyond. Incidentally, ionic liquids (ILs) have been among the top research subjects for the same applications and also for inorganic materials synthesis. As a result, the exploitation of the peculiar properties of ILs for metal sulfide synthesis could provide attractive new avenues for the generation of new, highly specific metal sulfides for numerous applications. This article therefore describes current developments in metal sulfide nanoparticle synthesis as exemplified by a number of highlight examples. Moreover, the article demonstrates how ILs have been used in metal sulfide synthesis and discusses the benefits of using ILs over more traditional approaches. Finally, the article demonstrates some technological challenges and how ILs could be used to further advance the production and specific property engineering of metal sulfide nanomaterials, again based on a number of selected examples.     

Bioactive Trichothecenes Produced by the Myrothecium sp. QB‐1

Three new simple trichothecenes, 15‐acetyltrichoverrol B ( 3 ), 13′‐acetyltrichoverrin B ( 5 ), and 6′‐dehydroxytrichoverrin B ( 6 ), along with five known trichothecenes trichodermadienediol B ( 1 ), trichoverrol B ( 2 ), trichoverrin B ( 4 ), and roridins A ( 7 ) and D ( 8 ), have been isolated from the liquid culture of Myrothecium roridum (strain no. QB‐1). The structures of the new compounds were established by comprehensive analysis of 1D‐ and 2D‐NMR data. All the compounds were evaluated for antifungal activity, only compounds 7 and 8 showed significant antifungal activity against the tested fungi (MIC ranged from 10 to 5 μg/ml).     

Determination of Sunset Yellow using a carbon paste electrode modified with a nanostructured resorcinol-formaldehyde resin

This article describes an electrochemical sensor for the dye additive Sunset Yellow (SY). It consists of a carbon paste electrode modified with nanostructured resorcinol-formaldehyde (RF) resin. The RF resin warrants strong signal enhancement and a strongly increased oxidation peak currents of SY at 0.66 V (vs. SCE). The effects of pH value, amount of RF polymer, accumulation potential and time were optimized. The sensor has a linear response to SY in the 0.3 to 125 nM concentration range, and the limit of detection is 0.09 nM after a 2-min accumulation time. The electrode was applied to the analysis of samples of wastewater and drinks, and the results are consistent with those obtained by HPLC.

Nanostructured resorcinol-formaldehyde (RF) resin was prepared and used as a material for electrochemical determination of Sunset Yellow.

     

铑催化苯醌磺酰化反应合成磺酰基醌类衍生物

报道了一种过渡金属铑催化的醌类与磺酰氯化合物的偶联反应,实现了醌类的磺酰化反应.在温和的反应条件下,以较高的产率成功合成了一系列具有生物活性的磺酰基醌类化合物,此反应不仅对苯醌具有较好的适应性,对于萘醌底物也能取得较高的产率,并提出了初步的反应机理.     

自下而上法制备金-介孔二氧化硅复合纳米管用作还原4-硝基苯酚的催化剂

采用自下而上方法制备了金-介孔二氧化硅复合纳米管,其中金纳米粒子作为催化剂嵌在介孔二氧化硅纳米管管壁内侧。金纳米颗粒的团聚、脱落和晶粒尺寸生长都可以被有效限制,而且催化剂负载量和尺寸大小均可实现简单控制。管壁中的介孔孔道、纳米管末端开口以及一维中空管道可以协同促进反应物扩散,从而提高4-硝基苯酚还原反应活性。循环实验证明这种复合纳米管催化剂具有良好的可重复使用性,而且在反应过程中未出现金纳米粒子脱落或团聚现象。