Ligand Design in Atomically Precise Copper Nanoclusters and Their Application in Electrocatalytic Reactions

Metal nanoclusters (MNCs) are compositionally well-defined and also structurally precise materials with unique molecule-like properties and discrete electronic energy levels. Atomically precise ligand-protected Cu nanoclusters (LP-CuNCs) are one category of typical MNCs that usually demonstrate unique geometric and electronic structures to serve as electrocatalysts. However, the synthesis, application, as well as structure-performance relationship of LP-CuNCs are not adequately studied. Significantly, the ligands are essential to the geometric structure, crystal structure, size, and electronic structure of LP-CuNCs, which determine their physiochemical properties and applications. In this review, significant progress in the ligand design of LP-CuNCs, and their application in electrocatalytic reactions is introduced. The general basics of ligand-protected MNCs (LP-MNCs) are first introduced and the functions of ligands are emphasized. Subsequently, a series of different ligands for LP-CuNCs including thiolates, phosphines, alkynyl, polymers, and biomolecules are highlighted. Thereafter, their applications in different electrocatalytic reactions are discussed. It is believed that this review will not only inspire the design and synthesis of novel LP-CuNCs, but also contribute to the extension of their applications in electrocatalytic reactions and the establishment of accurate structure-performance relationships.     

Aperture-Adjustable and Repairable Metal-Based MOFs Catalysis Membrane for Water Purification

Precise adjustment of the pore size, damage repair, and efficient cleaning is all challenges for the wider application of inorganic membranes. This study reports a simple strategy of combining dry-wet spinning and electrosynthesis to fabricate stainless-steel metal–organic framework composite membranes characterized by customizable pore sizes, targeted reparability, and high catalytic activity for membrane cleaning. The membrane pore size can be precisely customized in the range of 14–212 nm at nanoscale, and damaged membranes can be repaired by targeted treatment in 120 s. In addition, advanced oxidation processes can be used to quickly clean the membrane and achieve 98% flux recovery. The synergistic actions of the membrane matrix and the selective layer increase the adsorption energy of active sites to oxidant, shorten the electron transfer cycle, and enhance the overall catalytic performance. This study can provide a new direction for the development of advanced membranes for water purification and high-efficiency membrane cleaning methods.     

The first measurement of an absolute surface concentration of reaction intermediates in ethylene hydrogenation

The first measurement of a turnover rate with respect to surface intermediate concentration in a high pressure heterogeneous catalytic reaction is reported. By using infrared-visible sum frequency generation to study the hydrogenation of ethylene on Pt(111), it was found that the surface concentration of -bonded ethylene, the key reaction intermediate, represented approximately 4% of a monolayer. Thus the absolute turnover rate per surface adsorbed ethylene molecule is 25 times faster than the rate measured per platinum atom. To explain these results, we propose a model of weakly adsorbed ethylene intermediates reacting on atop sites.     

On the rate of heterogeneous catalytic reactions with ionic intermediates

A facile way to compute the rate law of a catalytic reaction with ionic intermediates is proposed, based on the theory of complex reactions. When the ionic nature of intermediates is taken into account it is necessary to add balance equations which correspond to the electroneutrality of the catalyst. Several mechanisms of the olefin hydrogenation were considered as examples.     

Atmospheric effects of friction,friction noise and wear with silicon and diamond. Part II. SEM tribometry of silicon in vacuum and hydrogen

Scanning electron microscope (SEM) tribometric data on polycrystalline silicon (poly-Si) vs. poly-Si, Si(100) vs. Si(100) and Si(111) vs. Si(111) interfaces, obtained in Torr and in 0.2 Torr partial pressure of hydrogen gas ( ) from room temperature to 850^°C, were performed under standard and much slower thermal ramping rates. The friction data were analyzed per the methodology described in part I of this paper series. The results indicate a highly beneficial friction- and wear-reducing regime within a relatively narrow thermal region. This desirable region coincides with some chemisorption of excited species of molecular hydrogen just before the mass thermal desorption of surface hydrides. These data represent the tribochemical equivalent of a method routinely used in electronics, whereby deep electron traps (dangling Si bonds) are passivated by baking in molecular hydrogen. The also exerts a moderating influence on the size of the friction noise at all test temperatures. However, the general level of friction beyond the beneficial thermal region is high. In parallel, the general wear rate of Si representative of the entire range of standard thermal ramping in both atmospheric environments is in the extremely high 10^-12m³/(N m) range. Operating strictly in the beneficial, low-friction thermal regime resulted in a several orders-of-magnitude reduction in the wear rate over those measured under standard thermal ramping conditions. Although the results confirm previous findings that Si is not a good material of construction for miniaturized moving mechanical assemblies (e.g., microbearings and gears), there seems to be some limited possibility of gas-phase lubrication of Si micromechanisms with rarefied hydrogen at surface temperatures between 100 and 300^°C. This revised version was published online in July 2006 with corrections to the Cover Date.     

催化分光光度法测定痕量亚硝酸根

本文基于亚硝酸根对溴酸钾氧化孔雀石绿而使其褪色的催化作用，建立了高灵敏度催化吸光光度法测定痕量亚硝酸根的新方法，测定范围为（０．０２６～０．３００）ｍｇ／Ｌ，用于几种蔬菜样品中亚硝酸根的测定，获得了满意结果．     

生物质气催化合成甲醇的实验研究

为了探索秸秆类生物质转化为燃料甲醇的工艺条件,采用热化学方法将玉米秸秆裂解为秸秆燃气,对该燃气进行优化实验,制备出秸秆合成气.在直流流动等温积分反应器中,使用国产C301铜基催化剂,对催化合成甲醇的反应压力、反应温度、秸秆合成气组成进行优化实验研究.结果表明:合成甲醇的最佳反应温度和反应压力分别为230℃和5 MPa,秸秆合成气适宜组成为10.49%CO,8.8%CO2,40.49%H2,0.95%CnHm,37.32%N2.     

Directed Evolution of Phi Class Glutathione Transferases Involved in Multiple-Herbicide Resistance of Grass Weeds and Crops

The extensive application of herbicides in crop cultivation has indisputably led to the emergence of weed populations characterized by multiple herbicide resistance (MHR). This phenomenon is associated with the enhanced metabolism and detoxifying ability of endogenous enzymes, such as phi class glutathione transferases (GSTFs). In the present work, a library of mutant GSTFs was created by in vitro directed evolution via DNA shuffling. Selected gstf genes from the weeds Alopecurus myosuroides and Lolium rigidum, and the cereal crops Triticum durum and Hordeum vulgare were recombined to forge a library of novel chimeric GSTFs. The library was activity screened and the best-performing enzyme variants were purified and characterized. The work allowed the identification of enzyme variants that exhibit an eight-fold improvement in their catalytic efficiency, higher thermal stability (8.3 °C) and three-times higher inhibition sensitivity towards the herbicide butachlor. The crystal structures of the best-performing enzyme variants were determined by X-ray crystallography. Structural analysis allowed the identification of specific structural elements that are responsible for k_cat regulation, thermal stability and inhibition potency. These improved novel enzymes hold the potential for utilization in biocatalysis and green biotechnology applications. The results of the present work contribute significantly to our knowledge of the structure and function of phi class plant GSTs and shed light on their involvement in the mechanisms of MHR.     

新型有机-无机杂化物(TB0.5Zr0.5H0.5PW)催化合成苯甲醛乙二醇缩醛反应

通过离子交换法制备了系列季铵盐锆盐共掺杂磷钨酸催化剂,利用SEM、FT-IR、XRD、XPS、TGA-DTG以及正丁胺电位法等技术手段对催化剂结构、酸度进行表征,并对其催化缩醛反应性能进行研究。考察了催化剂用量、醇醛摩尔比、带水剂量和反应时间对苯甲醛乙二醇缩醛产率的影响。研究表明,TB_0.5Zr_0.5H_0.5PW(TB为四丁基溴化铵)固体酸催化剂具有优异的催化性能,催化剂强的Bronsted酸性、Bronsted与Lewis酸中心间的协同效应及“假液相”特性是该催化剂具有高活性的原因。以TB_0.5Zr_0.5H_0.5PW为催化剂,经响应面优化所得苯甲醛乙二醇缩醛最佳制备工艺条件为：乙二醇与苯甲醛摩尔比1.5:1,TB_0.5Zr_0.5H_0.5PW用量为苯甲醛质量的1.9%,反应时间3 h,带水剂环己烷量12.6 mL,该条件下苯甲醛乙二醇缩醛产率为94.6%。TB_0.5Zr_0.5H_0.5PW固体酸催化剂在重复使用6次后仍然表现出优异的催化性能,表明该催化剂具有较好的工业应用前景。关键词：磷钨酸;季铵盐;缩醛反应;苯甲醛乙二醇缩醛;催化技术 中图分类号：TQ655 文献标识码： A 文章编号：1003-5214 (2020) 01-0000-00     

Recent Advances in Porphyrin-Based Systems for Electrochemical Oxygen Evolution Reaction

Oxygen evolution reaction (OER) plays a pivotal role in the development of renewable energy methods, such as water-splitting devices and the use of Zn–air batteries. First-row transition metal complexes are promising catalyst candidates due to their excellent electrocatalytic performance, rich abundance, and cheap price. Metalloporphyrins are a class of representative high-efficiency complex catalysts owing to their structural and functional characteristics. However, OER based on porphyrin systems previously have been paid little attention in comparison to the well-described oxygen reduction reaction (ORR), hydrogen evolution reaction, and CO₂ reduction reaction. Recently, porphyrin-based systems, including both small molecules and porous polymers for electrochemical OER, are emerging. Accordingly, this review summarizes the recent advances of porphyrin-based systems for electrochemical OER. Firstly, the electrochemical OER for water oxidation is discussed, which shows various methodologies to achieve catalysis from homogeneous to heterogeneous processes. Subsequently, the porphyrin-based catalytic systems for bifunctional oxygen electrocatalysis including both OER and ORR are demonstrated. Finally, the future development of porphyrin-based catalytic systems for electrochemical OER is briefly prospected.