Scalable synthesis of multi-shelled hollow N-doped carbon nanosheet arrays with confined Co/CoP heterostructures from MOFs for pH-universal hydrogen evolution reaction

Developing low-cost but efficient hydrogen evolution reaction(HER)electrocatalysts over whole pH values is a significant but daunting task for the large-scale application of electrochemical hydrogen production.Herein,we develop,for the first time,a scalable MOF-assisted strategy for the fabrication and microstructural optimization of multi-shelled hollow N-doped carbon nanosheet arrays with confined Co/CoP heterostructures on carbon cloth(Co/CoP@NC/CC)for boosting HER performances.The key to this strategy is the step-by-step epitaxial growth of unprecedented multilayer ZIF-L arrays on carbon cloth,which are subsequently pyrolyzed and controllably phosphorized to achieve the precise control over the shell number and nanoarchitectures of the Co/CoP@NC/CC.Impressively,the HER performances can be significantly enhanced by increasing hollow shell number,and the optimal triple-shelled hollow Co/CoP@NC/CC exhibits low overpotentials of 86,78 and 145 mV in acidic,alkaline and neutral media to deliver a current density of 10 mA cm^-2,respectively,ranking as one of the best Co-based HER electrocatalysts over whole pH values.Further DFT calculations suggest that the Co/CoP heterostructures can effectively boost the cleavage of H–OH to generate protons and optimize the adsorption energy of hydrogen(ΔG_H*),which,together with the large electrode/electrolyte interface and accelerated charge/mass transfer of multi-shelled hollow array structure as well as the good conductivity and dispersity,are responsible for the remarkably improved HER performances.This study not only provides a new toolbox for enriching the family of multi-shelled nanoarchitecture materials,but also points out a general and effective route to develop highly efficient self-supported electrode materials for energy-related applications and beyond.     

七-O-乙酰基-β-乳糖异硫氰酸酯的合成、表征及电化学研究

本文合成了并培养出了七-O-乙酰基—β—乳糖异硫氰酸酯的单晶，用X射线衍射分析了其晶体结构。结果表明，晶体为正交晶系，P2₁2₁2₁空间群，a＝1．23282(7)，b＝1．80012(10)，c＝1.85230(10) nm，α＝β＝γ＝90°，V＝4．1107(4) nm³，Z＝4。电化学实验观测到单链DNA和双链DNA对该化合物的峰电流均有明显降低作用，表明化合物与DNA发生了静电作用。     

Ligand Exchange Between Penta-Coordinated Phosphoryl Serine and Histidine Compounds

With the assistance of HPLC-ESI-MS/MS, the self-assembly products of serine and histidine penta-coordinated phosphorus compound were separated and identified. The expectative product was seryl-histidine dipeptide, but it was found that there was almost equimolar amount of histidyl-histidine dipeptide as well as seryl-histidine dipeptide. The mechanism was speculated that there was iigand exchange between penta-coordinated phosphoryl serine and histidine in the reaction process. As a result,two types of dipeptide were produced.     

担载液相催化剂的研究——Ⅳ.催化剂的原位红外光谱表征

本文利用原位红外光谱方法对铑基担载液相催化剂(SLPC)在接近于实际反应条件下进行了表征。结果表明,新鲜催化剂上,铑膦络合物主要以二聚物的形式存在,如Rh_2(CO)_2(PPh_3)_4而在合成气或反应气氛中,催化剂铑膦络合物以单核络合物HRh(CO)_2(PPh_3)_2的形式存在。文中还对SLPC在CO,H_2,C_2-H_4,空气和HCl中处理时铑络合物种的变化进行了原位观察。实验结果表明,SLPC上活性铑络合物与对应的均相过程完全一致,进一步证实了SLPC催化在微观上就是一个均相催化过程。     

实验室废液的回收及效果评价——以“铬废液回收及评价”为例

This paper introduces an experiment about waste liquid recovery and effect evaluation in laboratory. Through this experiment, the basic operations of crystal preparation, chemical analysis and instrumental analysis are further consolidated. At the same time, it allows students to experience a series of possible problems of condition selection and control in the process of waste liquid treatment. We hope to improve the students' ability to analyze and solve problems, enhance their interest in learning, and strengthen their humanistic education.     

羰基过渡金属异核原子簇(PPh3)2CuFe2Co(CO)8(μ3-S)和(PPh3)3AuFe2Co(CO)7(μ3-S)的合成与表征

本文利用高压法制备HFe₂Co(CO)₉(μ₃-S),作为原料,经脱质子化作用,再分别与(PPh₃)₂Cu(NO₃)和PPh₃AuCl反应,将Ph₃Cu-或Ph₃Au-联接到原始簇合物的中心骨架上,使簇核扩大,得到了组成为(PPh₃)₂CuFe₂Co(CO)₈(μ₃-S)和(PPh₃)₃AuFe₂Co(CO)₇(μ₃-S)的化合物.文中对此两个新化合物进行了IR,UV,¹H和³¹P NMR.元素分析、熔点测定等性质表征,并对(PPh₃)₂CuFe₂Co(CO)₇(μ₃-S)进行了单晶X-射线衍射分析.两个化合物具有类似的中心骨架,在Fe₂和Co原子三角形的上面和下面分别键联着Cu和S,或Au和S原子,构成了三角双锥结构.其中一个簇合物由二个三苯基膦和八个羰基配位,另一个则由三个三苯基膦和七个羰基配位.     

K3Na5(H2NCH2CH2NH3)2{(VO)12O6[B3O6(OH)]6}(H2O)•12H2O的合成与晶体结构

利用水热合成技术成功制备出一种新型多钒硼氧化合物， 用X射线单晶衍射分析技术对其晶体结构和分子结构进行了确定。结果表明在该化合物中多钒硼氧阴离子具有一个新颖的三明治结构。上下两个结构单元都是由六个VO₅四角锥交替地通过顺式和反式共边的方式连接起来构成的一个钒氧三角形结构。中间的结构单元是由BO₃平面三角形和BO₄四面体以共角的方式相互连接形成的一个折叠型的B₁₈O₃₆(OH)₆环。三明治结构中层与层之间通过桥氧相连。一个水分子处于它的核心位置上，与每个VO₅四角锥中的钒原子都保持几乎相等的距离。该化合物及其晶体中存在着丰富的化学结构和成键信息，同时也有作为氧化还原反应催化剂的潜能。     

NaCl-CsCl熔盐中Ce(Ⅲ)离子的阴极过程研究

以钨微盘为研究电极采用循环伏安法和方波伏安法研究了温度为873K的NaCl-CsCl熔盐中Ce3 离子的阴极行为.结果表明,摩尔比为1:2的NaCl-CsCl熔盐体系中Ce3 离子分两步还原,其电化学反应历程为:Ce3 e=Ce2 ,Ce2 2e-=Ce.进一步计算得到熔盐体系中Ce3 离子的扩散系数(D).     

硅氧聚合度对细胞毒性的影响

本文采用家兔肺泡巨噬细胞(AM)存活率和细胞过氧化脂质(LPO)值为测定指标,研究了硅氧的聚合度对其细胞毒性的影响。结果表明:各种聚合度的硅氧都有一定的细胞毒性,聚合度愈大,细胞毒性也愈大。胶体SiO_2的粒径增大,其细胞毒性降低。十硅酸盐及粒径小于5nm的硅溶胶的细胞毒性大于α-石英。聚合度小于6的低聚硅酸及其盐、粒径18nm以上的硅溶胶以及硅胶H的毒性皆小于α-石英。本实验细胞存活率降低和过氧化脂质值升高的趋势基本一致,这表明硅氧可能主要与细胞表面膜作用,膜上磷脂等表面活性物质被氧化和变性,从而导致细胞损伤。     

Novel expanded porphyrinoids with multiple-inner-ring-fusion and/or tunable aromaticity

Novel expanded porphyrinoids with advanced structure features have a wide range of benefits (such as multi-metal coordination and facile tunable aromaticity) not offered by their normal porphyrin analogues. Considering research efforts have been devoted to address their limited synthetic accessibility issue. This review highlights some of these recent synthetic progresses towards these novel expanded porphyrinoids.