利用空间位阻和氢溢流协同作用促进5-羟甲基糠醛选择性加氢制备5-甲基糠醛

化学工业生产中，用氢气为还原剂，通过选择性加氢可以制备多种重要化学品。5-羟甲基糠醛是重要的生物质基平台化合物，而5-甲基糠醛是用途广泛的化学品。由5-羟甲基糠醛加氢得到5-甲基糠醛是一条非常理想的路径，但是选择性活化C-OH非常困难。本文设计并制备了Pt@PVP/Nb₂O₅(PVP: 聚乙烯吡咯烷酮)催化剂，该催化体系巧妙地结合了位阻效应、氢溢流和催化剂界面的电子效应，系统研究了该催化剂对5-羟甲基糠醛选择性加氢制备5-甲基糠醛催化性能，在最优条件下，5-甲基糠醛的选择性可达92%。利用密度泛函理论计算研究了5-羟甲基糠醛选择性加氢制备5-甲基糠醛反应路径。     

新型功能碳材料的高压截获

高性能功能材料在诸多领域具有广泛的应用前景,是人们一直关注的研究热点。高压可以有效地改变物质的原子间距和成键方式,是获得新型功能材料的重要途径。在碳材料的高压研究中,许多有趣的功能碳材料,如光学透明碳、高强度弹性碳和超硬非晶碳等,已经通过不同的碳前驱体合成。本文简要介绍了作者近年来在低维碳基纳米复合材料高压研究中取得的进展,基于设计的不同低维碳前驱体,高压下截获了具有超硬特性、新型压致共价聚合及发光增强的碳材料。     

Structural and phase characteristics of the diamond/matrix interfacial zone in high-resistant diamond composites

The structural-phase state of the contact zone and the factors that influence on the strength of diamond retention in the diamond carbide composites were determined. Composites were obtained by the new hybrid technology that eliminates the reheating of the metalized coating. The elaborated technology combines the thermal diffusion metallization of a diamond and the sintering by the scheme of self-dosed impregnation in a one-stage technological cycle. By the methods of electron microscopy, X-ray diffraction analysis, and Raman spectroscopy the structural and phase characteristics of the interphase boundary were investigated. The improvement of chemical and mechanical adhesion between the diamond and carbide matrix was obtained. It was shown that the specific productivity of the samples with a metalized diamond component is 39% higher than those without metallization.     

Pt Nanoparticle‐modified Carbon Fiber Microelectrode for Selective Electrochemical Sensing of Hydrogen Peroxide

We report a simple approach to the production of carbon fiber‐based amperometric microbiosensors for selective detection of hydrogen peroxide (H₂O₂), which was achieved by electrometallization of carbon fiber microelectrodes (CFMs) by electrodeposition of Pt nanoparticles. The Pt‐carbon hybrid sensing interface provided a sensitivity of 7711±587 μA ? mM^?1 ? cm^?2, a detection limit of 0.53±0.16 μM (S/N=3), a linear range of 0.8 μM–8.6 mM, and a response time of <2 sec. The morphologies of the Pt nanoparticle‐modified CFMs were characterized by scanning electron microscopy. To achieve selectivity, permseletive layers, polyphenylenediamine (PPD) and Nafion, were deposited resulting in exclusion of the anionic and cationic interferents, ascorbic acid and dopamine, respectively, at their physiologically relevant concentrations. The resultant sensors displayed a sensitivity to hydrogen peroxide of 1381±72 μA ? mM^?1 ? cm^?2, and a detection limit of 0.86±0.19 μM (S/N=3). This simple and rapid metallization method converts carbon fiber microelectrodes, which are readily accessible, to microscale Pt electrodes in 2 min, providing a platform for oxidase‐based amperometric biosensors with improved spatial resolution over more commonly used platinum electrode array microprobes.     

A hydrogen pump: Transfer of four hydrogens from a cyclohexane ring to a triple bond during a menthofuran/bromoacetylene adduct rearrangement

The cycloadducts of menthofuran with acylbromoacetylenes, (3-bromo-1,6-dimethyl-5,6,7,8-tetrahydro-2H-2,4a-epoxynaphthalen-4-yl)(aryl)methanones, rearrange (CHCl₃, reflux, 1 h) to 2-(2-acylethyl)benzofurans (along with the expected 2-bromo-3-hydroxy-4,7-dimethyl-5,6,7,8-tetrahydronaphthalene-1-yl)(aryl)methanones) via 2-acylethynylmenthofurans, thus indicating the exceptionally mild and rapid transfer of four hydrogens from a cyclohexane ring to a triple bond through the furan moiety in the key intermediate 2-acylethynylmenthofuran.     

New strategy for reversal tolerant anode for automotive polymer electrolyte fuel cell

New approach for the reversal tolerant anode for polymer electrolyte membrane fuel cell is suggested by using the multifunctional IrRu alloy catalyst having concurrent superior activities towards hydrogen oxidation reaction and oxygen evolution reaction to mitigate the degradation of anode under the fuel starvation condition.     

卟啉基非金属纳米片用于可见光光催化制氢

本文基于密度泛函理论预测了一种用于可见光范围光催化制氢的新型二维非金属纳米材料，该材料可以由HTAP分子脱氢聚合得到，具有良好的结构稳定性，且带隙为2.12 eV，可以实现可见光区域的光捕获. 材料的带边能级位置恰好包裹水的氧化还原电位，有利于实现全光解水. 电子的迁移率略高于空穴的迁移率，有利于光生载流子的分离. 光生电子可以提供足够的驱动力使得析氢反应自发进行.     

Current status of automotive fuel cells for sustainable transport

Automotive proton-exchange membrane fuel cells (PEMFCs) have finally reached a state of technological readiness where several major automotive companies are commercially leasing and selling fuel cell electric vehicles, including Toyota, Honda, and Hyundai. These now claim vehicle speed and acceleration, refueling time, driving range, and durability that rival conventional internal combustion engines and in most cases outperform battery electric vehicles. The residual challenges and areas of improvement which remain for PEMFCs are performance at high current density, durability, and cost. These are expected to be resolved over the coming decade while hydrogen infrastructure needs to become widely available. Here, we briefly discuss the status of automotive PEMFCs, misconceptions about the barriers that platinum usage creates, and the remaining hurdles for the technology to become broadly accepted and implemented.     

Experimental studies on the effect of ultrasonic treatment and hydrogen donors on residual oil characteristics

Residual oil, the residue after the distillation of crude oil, imposes deleterious effects on refinery due to its high viscosity and asphaltene content. In this context, ultrasonic technology has been widely applied in refining processes given its high efficiency and minimal environmental impacts. To guide the selection of operation parameters, in this work, we probed the effect of treatment duration, power, and hydrogen donor on the characteristics of residual oil under ultrasonic treatments. Underlying mechanisms of ultrasonic treatments, in the absence and presence of hydrogen donors, were verified through systematically analyzing viscosity, component conversion, molecular weight, hydrogen distribution, and functional groups of residual oil. While viscosity reductions under low-power density treatment are caused by colloidal system disaggregation, high-power density treatment can bring in both chemical bond cleavage and colloidal system disaggregation. In addition, adding hydrogen donor can effectively prevent radical recombination, and thus increases the yield of saturate. These results provide fundamental understandings on the effects of ultrasonic treatments.     

丹酚酸A 对H2O2 所致大鼠脑微血管内皮细胞氧化损伤保护的实验研究

目的 观察丹酚酸A 对H2O2所致大鼠脑微血管内皮细胞（RCMECs）氧化损伤的保护作用，并探讨其可能的作用机 制。方法 分离并培养大鼠脑微血管内皮细胞，用H2 O2 损伤的方法建立氧自由基损伤模型。采用丹酚酸A 进行干预后，分别测定细胞培养液中乳酸脱氢酶（LDH）活性、血栓素B2（TXB2）水平、6- 酮基前列腺素1α（6-keto-PGF1α）的含量，以及细胞内和培养液中脂质过氧化产物丙二醛（MDA）含量和超氧化物歧化酶（SOD）的活性。结果 H2O2致RCMECs 氧化损伤后，细胞LDH 释放水平、TXB2和MDA 的含量均明显增加，同时6-keto-PGF1α 含量和SOD 活性显著下降；而丹酚酸A 预处理后能呈浓度依赖性的降低RCMECs 氧化损伤后LDH 水平、TXB2含量和细胞内外的MDA 含量，提高受损细胞6-keto-PGF1α 的表达和细胞内外SOD 活性。结论 丹酚酸A 对H2O2所致RCMECs 氧化损伤具有保护作用，其机制可能与其抗氧化作用有关。