TiO2晶面依赖的Ir-TiOx相互作用对Ir/TiO2催化剂巴豆醛选择性加氢性能的影响

α,β-不饱和醇是一类重要的精细化学品,主要通过α,β-不饱和醛选择性加氢获得.由于α,β-不饱和醛分子中含有共轭的C=C键和C=O键,且后者键能更大,在热力学和动力学上均不利于C=O键的选择性加氢生成α,β-不饱和醇.因此,提高α,β-不饱和醛中C=O的加氢选择性是催化领域中一项挑战性的课题.巴豆醛属于典型的α,β-不饱和醛,研究其选择性加氢生成巴豆醇具有广泛的代表意义;Ir负载在具有还原性载体(如TiO2)上时,表现出很好的C=O加氢选择性,因此,成为近年来的研究热点.由于暴露不同晶面的TiO2具有不同的形貌和电子结构,因此研究Ir-TiO2相互作用的晶面依赖性及其对巴豆醛选择性加氢反应的影响具有重要意义.本文以分别暴露{101}、{100}和{001}晶面的锐钛矿TiO2纳米晶为载体,制备了负载型Ir/TiO2催化剂,系统研究了催化剂经过不同的预处理过程(在不同温度下H2还原和O2再氧化)后对巴豆醛的气相选择性加氢的性能.利用高分辨透射电镜、原位X射线光电子能谱和原位漫反射红外光谱及氨程序升温脱附等技术研究发现,预处理条件显著改变了Ir-TiOx的相互作用,包括Ir金属的几何、电子性质及催化剂表面酸性.这种相互作用与TiO2的暴露晶面密切相关,从而改变了不同Ir/TiO2催化剂上不同加氢反应行为.研究结果表明,经300℃预还原的Ir/TiO2-{101}催化剂催化性能最好,在80℃下初始反应速率为166.1 μmol g-Ir-1 s-1,巴豆醇的生成转化频率为0.022 s-1.与其他催化剂相比,Ir/TiO2-{101}催化剂表面Ir0浓度最高,表面酸度适中,因此表现出最佳的催化性能.同时Ir-TiOx界面在反应中的协同作用,对H2和巴豆醛分子中C=O键的吸附和活化起到了关键作用.然而当催化剂经过400℃的H2预还原后,由于产生了强的金属-载体相互作用使得TiOx对Ir粒子进行了包裹从而导致Ir-TiOx界面缺失,因而催化剂催化巴豆醛加氢性能降低.本文为理解金属-载体相互作用对巴豆醛选择性加氢反应的影响提供了新的见解,并为设计高性能α,β-不饱和醛选择性加氢催化剂提供了理论依据.     

微流控纸芯片在环境分析检测中的应用

近年来,微流控纸芯片由于低成本、便携化、检测快等优点,在需要快速检测的环境分析领域中展现出了巨大的应用前景。该综述从微流控纸芯片在环境分析中的应用角度,总结归纳了微流控纸芯片在环境分析中的最新研究进展,并展望了其在未来的发展趋势与挑战。论文内容引用150余篇源于科学引文索引(SCI)与中文核心期刊中的相关论文。该综述包括微流控纸芯片在环境检测中的优势与制造方法介绍;电化学法、荧光法、比色法、表面增强拉曼法、集成传感法等基于纸芯片的先进分析方法介绍;根据环境分析目标物种类,如重金属离子、营养盐、农药、微生物、抗生素以及其他污染物等,对纸芯片的最新应用现状进行了举例评述;基于微流控纸芯片的环境分析研究的未来发展趋势和前景展望。通过综述近期相关研究,表明微流控纸芯片从提出至今虽然只有十几年的发展历程,但其在环境分析研究中的发展却十分迅速。微流控纸芯片可以根据不同的环境条件和检测要求灵活选择制作与分析方法,实现最佳的检测效果。但是微流控纸芯片也面临一些挑战,如纸张机械强度不足、流体控制程度不佳等问题。这些问题指出了微流控纸芯片在环境检测领域的发展趋势,相信随着不断深入的研究,纸芯片将会在未来的环境分析中发挥更大作用。     

Sarcaglarols A—D,Lindenane−Monoterpene Heterodimers from Sarcandra glabra Based on Molecular Networks

Sarcaglarols A—D ( 1 — 4 ), two pairs of lindenane?monoterpene heterodimers fused by a 1,2‐dioxane moiety, were discovered and isolated from the leaves of Sarcandra glabra guided by MS/MS molecular networking‐based strategy. Their planar structures, absolute configurations of basic skeleton and flexible polyhydric side chain were established by analysis of HRESIMS, NMR spectroscopic data, ECD spectrum, and the X‐ray diffraction study of isopropylidene derivatives. An intermolecular [2+2+2] cycloaddition may play a key role in the biosynthesis pathway of the 1,2‐dioxane moiety fused lindenane?monoterpene heterodimer skeleton, which can be recognized as the biogenetic precursors of our previous reported lindenane?normonoterpene conjugates. In addition, compounds 1 , 3 and 4 exhibited moderate inhibitory effects of lipid accumulation in free fatty acid‐exposed L02 cells.     

Recent advances in the development of colorimetric analysis and testing based on aggregation-induced nanozymes

Colorimetric sensing strategies as a powerful point-of-care testing(POCT) tool have attracted significant interest in various chem/biosensing applications.Taking the excellent bare-eye-detectable signaling feature,nanozymes-based colorimetric sensors enable more potential applications and have been a new forefront in the colorimetric POCT analysis toward different target analytes.However,the low catalytic activity of nanozymes in most cases limits their practical application.Recent efforts demonstrate that the aggregation-induced nanozymes provide a general means to modulate nanozymes activity and enhance colorimetric sensing performances of some nanozymes-based colorimetric sensors.But there are few reports are explored to discuss and review such aggregation-induced nanozymes and their colorimetric sensing applications.To highlight the advances and progress in aggregation-induced nanozymes based colorimetric assays,we herein summary the fundamentals,classify and applications of this newlydeveloping field,focusing on the aggregation-induced activity enhancement of nanozymes(AIAEnanozymes) with a significant "signal-on" feature and aggregation-induced activity inhibition of nanozymes(AIAI-nanozymes) with a dramatical "signal-of" characteristics.Finally,we also propose the current challenges and the future prospects on both AIAE-nanozymes and AIAI-nanozymes.     

全无机卤化铅钙钛矿的结构、热力学稳定性和电子性质

有机-无机杂化卤化铅钙钛矿因具有独特的电子和光学特性,已经成为光电领域最有前途的材料。但是,有机-无机钙钛矿材料及器件稳定性差,限制了其实际应用。与杂化钙钛矿相比,全无机卤化物钙钛矿CsPbX₃(X=Cl,Br,I)显示出更强的热稳定性。全无机卤化物钙钛矿CsPbX₃具有多个晶型,在不同的温度下呈不同相结构。目前,关于CsPbX₃的结构和物理性质仍存在争议。本文我们针对三个晶相α-,β-和γ-CsPbX₃的结构,热力学稳定性和电子性质进行了全面的理论研究。第一性原理计算表明,从高温α相到低温β相,然后再到γ相的相变伴随着PbX₆八面体的畸变。零温形成能计算表明,γ相最稳定,这与实验中γ相为低温稳定相的结论一致。电子性质计算表明,所有CsPbX₃钙钛矿都表现出直接带隙性质,并且带隙值从α相到β相再到γ相逐渐增加。这是由于相变发生时,Pb-X成键强度逐渐减弱,使价带顶能量降低,进而带隙增加。在所有相中,α相结构中较强的Pb-X相互作用,导致了较强的带边色散,使其具有较小的载流子有效质量。     

An interlocked coordination cage based on aromatic amide ligands

An interlocked M_4 L_8 coordination cage was synthesized by coordination-driven self-assembly of palladium(Ⅱ) ions with aromatic amide bidentate ligands.The reaction of the ligand and the metal at 2:1 ratio led to the monomeric M_2 L_4 cage as the kinetic product,while the thermodynamic product M_4 L_8 cage was obtained by prolongating the reaction.This conve rsion and the interlocked structure was clearly revealed by using ~1 H NMR,mass spectrometry and X-ray crystallography.The driving force of interlocking was mainly attributed to the interactions(hydrogen bonding,aromatic stacking and electrostatic interaction) arising from the aptitude of flexibility of the amide ligand.     

Copper-cobalt-nickel oxide nanowire arrays on copper foams as self-standing anode materials for lithium ion batteries

Numerous scientists are in the pursuit of energy storage materials with high energy and high power density by assembly of electrochemically active materials into conductive scaffolds, owing to the emerging need for next-generation energy storage devices. In this architectures, the active materials bonded to the conductive scaffold can provide a robust and free-standing structure, which is crucial to the fabrication of materials with high gravimetric capacity. Thus, hierarchical copper-cobalt-nickel ternary oxide (CuCoNi-oxide) nanowire arrays grown from copper foam were successfully fabricated as free-standing anode materials for lithium ion batteries (LIBs). CuCoNi-oxide nanowire arrays could provide more active sites owing to the hyperbranched structure, leading to a better specific capacity of 1191 mAh/g, cycle performance of 73% retention in comparison to CuO nanowire structure, which exhibited a specific capacity of 1029 mAh/g and capacity retention of 43%, respectively.     

Three-dimensional porous photo-thermal fiber felt with salt-resistant property for high efficient solar distillation

The urgent need for fresh water resource is a public issue facing the world. Solar distillation for seawater desalination is a promising freshwater production method. Interfacial solar evaporation systems based on 2D photo-thermal membranes have been widely studied, but salt pollution is one of the main challenges for solar distillation. In order to solve this problem, a hydrophilic three-dimensional (3D) porous photo-thermal fiber felt (PFF) was obtained by one-step method, through a simple polydopamine (PDA) coating method with hydrophobic graphite felt as a substrate. The PFF had a good evaporation rate of 1.48 kg m^?2 h^-1 and its corresponding light-vapor conversion efficiency reached 87.4%. In addition, the PFF exhibited an excellent salt-resistant ability when applied to photo-thermal evaporation of high-salinity seawater with 10 wt% NaCl, owing to its intrinsic 3D macroporous structure for the migration circulation of salt ions. The development of the PFF offers a new route for the exploration of salt-resistant photo-thermal materials and is promising for the practical application of solar distillation.     

Dinitrile compound containing ethylene oxide moiety with enhanced solubility of lithium salts as electrolyte solvent for high-voltage lithium-ion batteries

A dinitrile compound containing ethylene oxide moiety (4,7-dioxa-1,10-decanedinitrile, NEON) is synthesized as an electrolyte solvent for high-voltage lithium-ion batteries. The introduction of ethylene oxide moiety into the conventional aprotic aliphatic dinitrile compounds improves the solubility of lithium hexafluorophosphate (LiPF₆) used commercially in the lithium-ion battery industry. The electrochemical performances of the NEON-based electrolyte (0.8 M LiPF₆?+?0.2 M lithium oxalyldifluoroborate in NEON:EC:DEC, v:v:v?=?1:1:1) are evaluated in graphite/Li, LiCoO₂/Li, and LiCoO₂/graphite cells. Half-cell tests show that the electrolyte exhibits significantly improved compatibility with graphite by the addition of vinylene carbonate and lithium oxalyldifluoroborate and excellent cycling stability with a capacity retention of 97 % after 50 cycles at a cutoff voltage of 4.4 V in LiCoO₂/Li cell. A comparative experiment in LiCoO₂/graphite full cells shows that the electrolyte (NEON:EC:DEC, v:v:v?=?1:1:1) exhibits improved cycling stability at 4.4 V compared with the electrolyte without NEON (EC:DEC, v:v?=?1:1), demonstrating that NEON has a great potential as an electrolyte solvent for the high-voltage application in lithium-ion batteries.