二维光催化材料

正二维纳米材料是一类性能独特且有良好前景的光催化材料。二维材料表面原子排列通常与块体材料不同,对表面性质和界面电荷转移有显著影响,展现出独特的表/界面特性。近年来,各类二维纳米材料合成方法和表面改性策略的快速发展,在光催化性能提升和能源环境领域应用等方面发挥了重要作用。本专刊邀请了从事光催化研究的学者,分享了他们在二维光催化材料方面的最新研究成果。     

二硫化钨纳米材料的应用研究现状

近年来,二硫化钨作为具有类石墨烯结构的二维材料,由于具有优异的电学、光学和催化性能得到了广泛研究.本文介绍了二硫化钨纳米材料的结构性质,并综述了二硫化钨纳米材料在润滑材料、催化领域、能量储存、光电器件和微波吸收领域的应用研究现状,最后总结了二硫化钨纳米材料研究中存在的问题,并展望了其发展前景.     

二维磁性纳米材料的可控合成及磁性调控

自旋电子学的研究重点在于同时利用电子的电荷和自旋两个自由度对信息进行处理和存储,其具有运行速度快、存储密度高和能耗低等优势。毫无疑问,发展二维磁性纳米材料的可控合成方法及磁性调控策略,对于新型自旋电子学器件的构筑具有重要的科学意义和应用价值。然而,目前得到的二维磁性纳米材料的种类十分有限,而且合成方法及磁性调控手段相对单一,极大地限制了该领域的发展。本文首先根据磁性的来源,对二维磁性纳米材料进行了分类,介绍了诱导产生的磁性和具有本征磁性的二维纳米材料,然后详细地归纳了二维磁性纳米材料常见的合成方法,如机械剥离法、电化学剥离法、化学气相沉积法以及液相合成方法等。此外,着重总结了二维材料磁性的主要调控手段,最后展望了该领域遇到的瓶颈、未来的研究重点及应用前景。     

超薄二维MOF纳米材料的制备和应用

超薄二维金属有机框架材料(MOF)纳米材料是MOF材料中的一类,不同于传统体相MOF材料,超薄片状结构赋予了它高比表面积、丰富的配位不饱和的金属位点等独特性质,能够有效改善MOF在催化、分离和传感等领域中的性能。本文综述了近年来国内外在超薄二维MOF纳米材料的构建及制备方法的研究进展,其中包括自上而下法、自下而上法以及独立于二者的二维氧化物模板牺牲法等。同时,本文详细讨论了超薄二维MOF纳米材料在气体吸附与气体分离、催化、能量储存和传感平台等领域的应用前景,并对未来超薄二维MOF纳米材料的研究面临的挑战和机遇做了进一步的分析。     

碳纳米材料及其在多相催化中的应用

碳纳米材料（包括零维、一维、二维碳纳米材料以及碳纳米孔材料）是一类新型的催化剂或催化剂载体材料,在氧化脱氢、选择加氢、合成氨、氨分解制氢以及燃料电池等多相催化领域具有广阔的应用前景。本文综述了近年来新型碳纳米材料在多相催化领域中的应用研究进展,介绍了这类催化材料的制备方法,重点阐述了碳载体的微/介观结构、掺杂、电子性质、表面性质、限域效应等对所担载的催化活性组分的分散,对反应物的扩散以及对催化反应的活性和选择性等方面的影响。     

二维纳米材料热传导行为及其界面调控※

二维纳米材料具有独特的二维无限拓展超薄结构, 其声子输运受到维度限制, 从而赋予了二维纳米材料新奇的热传导性质, 是研究微纳尺度热传导的理想材料平台. 界面工程可以引发二维纳米材料中声子振动模式的改变和声子振动的耦合, 导致材料的热传导行为改变, 为实际应用中微纳器件的散热、极端环境的热防护等提供了可能的解决方案. 详细介绍了在经典二维纳米材料中热传导的不同机制及新奇特性, 阐述了界面工程对二维纳米材料热传导的影响, 并进一步展望了原子分子级别界面调控在二维材料热传导领域的研究前景.     

新型二维纳米材料在电化学领域的应用与发展

以石墨烯为代表的新型二维纳米材料具有独特的结构和优异的电子特性,在电化学各领域具有巨大的应用潜力。 本综述总结了新型二维纳米材料在电化学各领域(能源存储、能源转化和电化学传感)的研究现状和存在的问题。 展望了二维纳米材料在电化学领域的发展趋势。     

二维层状离子型纳米材料在化妆品领域的应用进展

二维层状离子型纳米材料具有独特的结构和界面性能,使其在透皮吸收、防晒、活性物的靶向传递、构建稳定的纳米微胶囊等功效中显示出极大的优势,在化妆品行业中具有良好的市场前景。 该类化合物根据层板电荷不同可分为阳离子型粘土材料和阴离子型水滑石类材料。 基于近年来国内外对二者的研究报道和实验研究成果,本文综述了二维离子型纳米材料的特点、性能及其在化妆品领域的应用历史和发展现状,并进一步展望了该类材料在化妆品领域中的应用前景。     

气敏新材料MXenes在呼出气体传感器中的应用

电子鼻结合人工智能对呼出气进行检测、分析和识别已成为非侵入性医疗检测领域的研究热点。然而,目前已报道的气体传感材料尚不能同时满足高灵敏度、高选择性和稳定的室温检测,阻碍了气体传感器在医疗健康领域的应用及发展,寻找合适的传感材料具有重要的意义和挑战。新型二维层状纳米材料MXenes具有种类多、比表面积大、导电性能强、表面含有丰富的官能团以及能带宽度可调等优异性能,是高灵敏、低能耗气体传感器的明星候选材料。本综述针对MXenes基材料的特殊结构,总结梳理了MXenes基材料在气体传感中的最新研究成果,聚焦于MXenes材料的气体传感机理和改性方法,对MXenes材料用于气体传感依然存在的问题和挑战进行深入探讨。     

MXene在电化学传感器中的应用

过渡金属碳化物或氮化物(MXene)作为一种新型的二维层状材料,由于具有良好的导电性、水中分散性、高的生物相容性和稳定性等,在电化学传感领域具有巨大的应用潜力。将MXene与其他纳米材料复合,可以扬长避短,在性能上实现优势协同和功能互补,有效提高电化学传感器的灵敏度和选择性。本文按照检测物的种类进行分类,综述了基于MXene材料构建的电化学传感平台在生物标记物和环境污染物检测中的应用,并讨论了MXene材料在电化学传感领域未来研究发展和应用中所面临的挑战。     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.     

A carbanion induced synthesis of highly congested pyrazole and imidazole containing heterocycles

An efficient approach to the synthesis of highly congested di, penta and hexacyclic pyrazoles as well as imidazole fragment containing novel heterocyclic molecule has been developed through a carbanion induced transformation of suitably functionalized 2H-pyran-2-ones, benzo[h]chromene and thiochromeno[4,3-b]pyrans. Due to the presence of fluorescence, we report their prime application metal sensor as off/on switching in ferric ions.     

Synthesis of pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles by Curtius reaction in Morita-Baylis-Hillman derivatives

Synthesis of substituted pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles from the Morita-Baylis-Hillman derivatives of acrylates via saponification followed by Curtius reaction is described.     

正丁胺对激光染料荧光谱影响的研究

用正丁胺作为碳源,采用射频辉光放电制备碳膜,选用激光染料R6G和聚乙二醇混合液作为蒸气源,采用单源热蒸发,在蒸发室与染料同时沉积得到混合膜,用拉曼光谱和红外光谱分析了碳膜的结构和键合方式,分析表明:碳膜中存在胺基团和氢原子.混合膜的荧光谱测量结果表明,认为正丁胺对染料荧光谱的影响是因为胺基和氢原子的存在.     

Selective synthesis of 4,5-dihydroimidazo- and imidazo[1,5-a]quinoxalines via modified Pictet–Spengler reaction

An efficient tandem approach for the selective synthesis of 4,5-dihydroimidazo[1,5-a]quinoxalines 6a–g and imidazo[1,5-a]quinoxalines 7a–h by the reaction of 2-imidazolyl anilines 4a–c with aryl aldehydes 5a–k under mild reaction conditions is described. Introduction of electron releasing alkyl groups in substrates 4a–b was found to be instrumental for the success of the reaction.     

Understanding the Diels-Alder reactivity of 1,2-azaborine analogues

The Diels-Alder reactivity of 1,2-heteroborines (H₄C₄B(H)X, X?=?NH, PH, AsH; O, S, Se) has been computationally explored by means of Density Functional Theory (DFT) calculations. The influence of the HB?=?X fragment on the reactivity of the system has been quantitatively analyzed in detail by means of the so-called Activation Strain Model (ASM) of reactivity. It is found that the interaction between these species and the dienophile is significantly stronger than that computed for their all-carbon isoelectronic counterpart, benzene. In addition, the strain energy plays a key role in the observed reactivity trends. The role of the aromaticity strength of these heteroarenes on the reactivity is also assessed.