Highly Active Electrocatalyst Derived from ZIF-8 Decorated with Iron(III) and Cobalt(III) Porphyrin Toward Efficient Oxygen Reduction in Both Alkaline and Acidic Media

Zeolite imidazole frameworks 8(ZIF-8) and modified ones after pyrolysis are highly promising toward oxygen reduction reaction(ORR). Especially, the compositional modification of ZIF-8 is crucial to the enhancement of ORR performance, yet limited to the substitution of skeletal Zn(II) with other cations or simple physical adsorption of cations. Herein, we report the decoration of ZIF-8 with ORR active hemin(FeP) and Co(III) protoporphyrin(CoP) via the coordination between the peripheral carboxylic group of FeP and CoP with skeletal Zn(II). This allows well control over the quantity of loaded FeP and CoP, critical to the synthesis of advanced electrocatalysts. Subsequent pyrolysis of FeP and CoP co-decorated ZIF-8 leads to highly active ORR electrocatalysts with a half-wave potential(E_1/2) of 0. 913 V(vs. RHE) in 0.1 mol/L KOH aq. and an E_1/2 of 0.803 V(vs. RHE) in 0.1 mol/L HClO₄ aq. Moreover, our electrocatalyst shows much more improved and comparable durability in alkaline and acidic media, respectively, during 3000 cycles of cyclic voltammetry(CV) scanning relative to commercial Pt/C.     

From borophosphate to fluoroborophosphate: a rational design of fluorine-induced birefringence enhancement

The introduction of oxofluoride anion into anionic group assists to tune optical properties owing to the change of coordination,electronegativity,and according anionic framework.Here,we proposed a rational design of new compounds by fluorine-driven structure and optical property evolution.A new borophosphate Ba_2BP_3O_(11)with the monoclinic space group P2_1/c has been synthesized in the sealed system.Ba_2BP_3O_(11)exhibits a rare P–O–P bridge formation,which is the first example in alkaline-earth metal borophosphates.By further substituting[BO_4]~(3-)with[BO_3F]~(4-),the first alkaline-earth metal/lead fluoroborophosphates M_2BP_2O_8F (M=Ba and Pb) with the same space group were designed.Since the scissors effect of fluorine,in M_2BP_2O_8F (M=Ba and Pb),a BO_3F tetrahedron corner-sharing with three PO_4tetrahedra forms 1D chains along the b-axial direction,which are filled by MO_n(M=Ba/Pb,n=5,6,8) distorted polyhedra.The first principles calculation shows that the borophosphate Ba_2BP_3O_(11)has a birefringence about 0.013@1,064 nm,while the fluoroborophosphates M_2BP_2O_8F (M=Ba and Pb) have the values of 0.035 and 0.043@1,064 nm,respectively.Such an apparent enhancement in birefringence is derived from synergies of the oxyfluoride and cation.The introduction of fluorine-containing heteroanionic groups provides a feasible strategy to design novel promising optical materials.     

基于窄内径多孔层毛细管开管柱的纳流高效液相色谱用于N-衍生化氨基酸对映体的分离

窄内径多孔层毛细管开管柱（NPLOT柱）在生命科学领域,特别是单细胞分析领域具有较好的应用前景。本研究采用原位热引发聚合法来制备窄内径奎尼丁类手性固定相多孔层开管柱,在6 μ m i.d.的毛细管中制备有机聚合物多孔层,考察了不同热聚合时间（3、6和9 h）对NPLOT柱形貌的影响,热聚3 h和6 h制备的NPLOT柱形貌均一,多孔层厚度分别为103±51 nm和210±51 nm。将热聚合3 h制备的NPLOT柱用于纳流高效液相色谱分离N-衍生化氨基酸对映体,在2 min内即可实现基本分离,消耗的样品量仅为皮升级别。该研究将为单细胞分析提供研究手段。     

普瑞巴林的合成研究进展

普瑞巴林为Pfizer公司上市的新型γ-氨基丁酸(GABA)受体拮抗剂,临床用于治疗癫痫、焦虑和由脊髓损伤、外伤或多发性硬化症等引起的中枢神经疼痛,应用较为广泛,近年来文献报道合成方法较多.对普瑞巴林的合成方法进行了总结和概述,其中重点介绍了动力学拆分、去对称化反应、不对称氢化和不对称Michael加成等不对称合成方法.     

基于镜像酶正交酶切的蛋白质复合物规模化精准分析新方法

蛋白质主要以复合物的形式参与各项生命活动.化学交联质谱(CXMS)技术作为近年来新兴的蛋白质复合物解析技术,不仅可实现蛋白质复合物规模化解析,而且普遍适用于任意相对分子质量和纯度的蛋白质复合物样品,因此已成为X-射线晶体衍射技术、冷冻电镜技术等蛋白质复合物解析经典技术的重要补充.目前,CXMS主要采用胰蛋白酶将交联后的...     

GO-PtNi hybrid nanoenzyme mimics for the colorimetric detection of hydrogen peroxide

GO-PtNi nanocomposites with intrinsic peroxidase-like activity were obtained through one-pot synthesis. The hybrid nanomaterial was characterized by transmission electron microscopy (TEM) and X-ray powder diffraction (XRD). The peroxidase-like activity of GO-PtNi nanocomposites was found to be dependent on pH, temperature, the concentration of enzyme and substrates. The optimal conditions for the catalytic activity of GO-PtNi nanocomposites were determined. Based on these findings, a simple and sensitive colorimetric method for the detection of H₂O₂ by using GO-PtNi nanocomposites and 3,3′,5,5′-tetramethylbenzidine (TMB) was developed. The linear range was from 0.08 to 1.5 mM with a detection limit of 5 μM.     

Synthesis and characterization of a novel binuclear iron phthalocyanine/reduced graphene oxide nanocomposite for non-precious electrocatalyst for oxygen reduction

Binuclear iron phthalocyanine/reduced graphene oxide(bi-Fe Pc/RGO) nanocomposite with good electrocatalytic activity for ORR in alkaline medium was prepared in one step. High angle annular dark field image scanning transmission electron microscopy(HAADF-STEM) and energy dispersive X-ray spectroscopy element mapping results show bi-Fe Pc was uniformly distributed on RGO. An obvious cathodic peak located at about-0.23 V(vs. SCE) in CV and an onset potential of-0.004 V(vs. SCE) in LSV indicate the as-prepared bi-Fe Pc/RGO nanocomposite possesses high activity which is closed to Pt/C for ORR. The ORR on bi-Fe Pc/RGO nanocomposite follows four-electron transfer pathway in alkaline medium. Compared with Pt/C, there is only a slight decrease(about 0.02 V vs. SCE) for bi-Fe Pc/RGO nanocomposite when the methanol exists. The excellent activity and methanol tolerance in alkaline solutions proves that bi-Fe Pc/RGO nanocomposite could be considered as a promising cathode catalyst for alkaline fuel cells.     

1,4-二咔唑基苯微米结构的可控制备及光波导性质

采用液相组装法通过改变组装条件制备了高结晶性、 宽度为2 μm、 长度为10~40 μm的1,4-二咔唑基苯一维微米线(BeCzMW). X射线衍射和选区电子衍射结果表明, BeCz分子沿着晶体[100]方向生长. 通过扫描近场光学显微镜进一步发现, BeCzMW被紫外激光激发后产生的荧光被限域在一维结构中, 并沿着一维方向进行传导. BeCzMW在420 nm处的光学损耗系数R=0.0628 dB/μm, 表明BeCzMW具有良好的光波导性能.     

Mn3−xFexO4 Hollow Nanostructures for High-Performance Asymmetric Supercapacitor Applications

Design of hollow nanostructure and controllable phase of mixed metal oxides for improving performance in supercapacitor applications is highly desirable. Here we demonstrate the rational design and synthesis of Mn_3−xFe_xO₄ hollow nanostructures for supercapacitor applications. Owing to high porosity and the specific surface area that provides more active sites for electrochemical reactions, the electrochemical performance of Mn_3−xFe_xO₄ hollow nanostructure substantially enhanced comparing with pristine Mn₃O₄. Particularly, in 1.0 M KOH electrolyte, Mn_0.16Fe_2.84O₄ with a typical diameter of 20 nm exhibits excellent specific capacitance of 2675, 2320, 1662, 987 F g⁻¹ at current densities of 1, 2, 5, 10 A g⁻¹, respectively, which is significantly superior to those of other transition metal oxides. Besides, an asymmetric supercapacitor is assembled by using Mn_0.16Fe_2.84O₄ and activated carbon as a positive and a negative electrode, respectively. Electrochemical results indicate a high energy density of 42 Wh kg⁻¹ at a power density of 0.75 kW kg⁻¹, which makes this hollow nanostructure a highly promising electrode for achieving high-performance next-generation supercapacitors.