介孔钯-硼合金纳米颗粒的制备和甲醇氧化电催化性能北大核心CSCD

合金化可以调节贵金属纳米材料的物理化学性质,从而显著提升它们的电催化性能。尽管合金化在过去的20多年里已取得诸多成果,但是如何充分发挥纳米合金的组分优势仍需深入的探究。本研究通过一步溶液相合成法实现了类金属硼(B)合金化的钯基介孔纳米催化剂材料的合成,同时探究了B原子的组分优势和介孔形貌的结构优势在碱性介质中电化学甲醇氧化反应(MOR)的协同作用。最优PdCuB介孔纳米催化剂表现出优异的电化学MOR活性和稳定性。机理研究表明,优异的催化活性源于B原子在Pd基介孔纳米催化剂中的积极协同作用;该协同作用通过电子效应(改变Pd的表面电子结构从而减弱CO基中间体的吸附)和双功能效应(促进OH_(2)的吸附从而氧化CO基中间体)在动力学上加速了有毒CO基中间体的去除(提高甲醇氧化的决速步骤)。同时,B原子的间隙插入和介孔结构抑制了物理奥斯特瓦尔德(Ostwald)熟化过程,显著增加了催化剂的稳定性。     

Visible-light-mediated external-reductant-free reductive cross coupling of benzylammonium salts with (hetero)aryl nitriles

Herein we report a novel visible-light-mediated external reductant-free reductive cross coupling for the construction of C sp~2–C sp~3 bonds. A variety of benzylammonium salts underwent selective coupling with(hetero)aryl nitriles to deliver important diarylmethanes under mild reaction conditions. Importantly, photocatalysts can be omitted for many cases, which might involve the electron donor acceptor(EDA) complex. Mechanistic studies indicated benzylic radicals might be involved as the key intermediates. Moreover, the in situ generated NMe_3 via cleavage of C–N bond in ammonium salts acts as the electron donor,thus avoiding the use of external-reductant.     

The effects of learning in production and group size on the lot-sizing problem

One of the lot-sizing problem extensions that received noticeable attention in the literature is the one that investigated the effects of learning in production. The studies along this line of research assumed learning to improve with the number of repetitions following a power form. There is evidence also that the group size, i.e., the number of workers learning in a group affects performance (time per unit). This note revisits the problem and modifies it by incorporating the group size, along with cumulative production, as a proxy for measuring performance. Numerical examples are provided to illustrate the behavior of the modified model. The results of the two models are also compared to draw some meaningful insights and conclusions. Although the results favor using a simple univariate learning curve, considering group size when modeling lot-sizing problems can significantly affect the unit production cost.     

Redox-Active Two-Dimensional Covalent Organic Frameworks (COFs) for Selective Reductive Separation of Valence-Variable,Redox-Sensitive and Long-Lived Radionuclides

We report the first example of 2D covalent organic framework nanosheets (Redox-COF1) for the selective reduction and in situ loading of valence-variable, redox-sensitive and long-lived radionuclides (abbreviated as VRL nuclides). Compared with sorbents based on chemical adsorption and physical adsorption, the redox adsorption mechanism of Redox-COF1 can effectively reduce the impact of functional group protonation under the usual high-acidity conditions in chemisorption, and raise the adsorption efficiency from the monotonous capture by pores in physisorption. The adsorption selectivity for UO₂²⁺ reaches up to unprecedented ca. 97 % at pH 3, more than for any analogous adsorbing material.     

First principles study on the structural,electronic and phonon properties of monolayer B2Si

Using first principles density functional theory, we predict a monolayer B₂Si structure with space group Pmm2 in the present work. This structure is confirmed to be dynamically stable. Based on the plane wave pseudopotential approach, the charge density, electron localization function, density of states, energy band, phonon property and thermal conductivity of Pmm2-B₂Si are systematically studied. It is interesting that the sp² hybridization and coordination bond of Si are found in Pmm2-B₂Si, which is the most important factor for its structural stability. The density of states and energy band analysis reveals that Pmm2-B₂Si is metallic because of the partial occupied Si 3pz and B 2pz states. Moreover, the acoustic-optical coupling is important for phonon transport in Pmm2-B₂Si, and the contribution of optical modes to the lattice thermal conductivity along the [100] and [010] directions is 13% and 12%, respectively. This study gives a fundamental understanding of the structural, electronic and phonon properties in Pmm2-B₂Si.     

A variational proximal alternating linearized minimization in a given metric for limited-angle CT image reconstruction

Due to the restriction of computed tomography (CT) scanning environment, the acquired projection data may be incomplete for exact CT reconstruction. Though some convex optimization methods, such as total variation minimization based method, can be used for incomplete data reconstruction, the edge of reconstruction image may be partly distorted for limited-angle CT reconstruction. To promote the quality of reconstruction image for limited-angle CT imaging, in this paper, a nonconvex and nonsmooth optimization model was investigated. To solve the model, a variational proximal alternating linearized minimization (VPALM) method based on proximal mapping in a given metric was proposed. The proposed method can avoid computing the inverse of a huge system matrix thus can be used to deal with the larger-scale inverse problems. What’s more, we show that each bounded sequence generated by VPALM globally converges to a critical point based on the Kurdyka–Lojasiewicz property. Real data experiments are used to demonstrate the viability and effectiveness of VPALM method, and the results show that the proposed method outperforms two classical CT reconstruction methods.     

Bio-safety assessment of carbon quantum dots,N-doped and folic acid modified carbon quantum dots: A systemic comparison

The carbon quantum dots(CQDs) and their functionalized materials are promising in biomedical field because of their unique properties;meanwhile,a growing concern has been raised about the potential toxicity of these modified materials in biosystem.In this study,we synthesized original CQDs and two common functionalized CQDs including N-doped CQDs(NCQDs) and folic acid-modified CQDs(FACQDs),and compared the toxicity and biocompatibility with each other in vitro and in vivo.L929,C6 and normal cell MDCK were selected to detect the adverse reaction of these materials in vitro.No acute toxicity or obvious changes were noted from in vitro cytotoxicity studies with the dose of these CQD materials increasing to a high concentration at 1 mg/mL.Among these materials,the FA-CQDs show a much lower toxicity.Moreover,in vivo toxicity studies were performed on the nude mice for 15 days.The experimental animals in 10 or 15 mg/kg groups were similar with animals treated by phosphate buffer solution(PBS) after 15 days.The results of the multifa rious biochemical parameters also suggest that the functionalized products of CQDs do not influence the biological indicators at feasible concentration.Our findings in vitro and in vivo through toxicity tests demonstrate that CQDs and their modified materials are safe for future biological applications.     

Synthesis of Glycoluril using Urea Phosphate

Russian Journal of Organic Chemistry - Glycolurils are building blocks for the synthesis of cucurbiturils that are important host materials for several applications. Glycolurils are prepared...