Microwave-Assisted Confining Growth and Liquid Exfoliation of sp^(3)-Hybrid Carbon Nitride Nano/Micro-Crystals

As one promising carbon-based material,sp^(3)-hybrid carbon nitride has been predicted with various novel physicochemical properties.However,the synthesis of sp^(3)-hybrid carbon nitride is still limited by the nanaoscale,low crystallinity,complex source,and expensive instruments.Herein,we have presented a facile approach to the sp^(3)-hybrid carbon nitride nano/micro-crystals with microwave-assisted confining growth and liquid exfoliation.Actually,the carbon nitride nano/micro-crystals can spontaneously emerge and grow in the microwave-assisted polymerization of citric acid and urea,and the liquid exfoliation can break the bulk disorder polymer to retrieve the highly crystalline carbon nitride nano/micro-crystals.The obtained carbon nitride nano/micro-crystals present superior blue light absorption strength and surprising photoluminescence quantum yields of 57.96% in ethanol and 18.05%in solid state.The experimental characterizations and density functional theory calculations reveal that the interface-trapped localized exciton may contribute to the excellent intrinsic light emission capability of carbon nitride nano/micro-crystals and the interparticle staggered stacking will prevent the aggregation-caused-quenching partially.Finally,the carbon nitride nano/micro-crystals are demonstrated to be potentially useful as the phosphor medium in light-emitting-diode for interrupting blue light-induced eye damage.This work paves new light on the synthesis strategy of sp^(3)-hybrid carbon nitride materials and thus may push forward the development of multiple carbon nitride research.

氯自由基介导的光催化芳基醚C(sp^(3))−H氧化生成酯

饱和的碳氢键氧化是合成化学和化学工业中一类重要的化学反应.然而,饱和C(sp^(3))−H键离解能(BDEs)较高、极性较弱,导致了底物难以活化和催化转化效率较低等问题.在过去的几十年,C(sp^(3))−H键的定向活化转化取得了重要的进展.其中,关于C(sp^(3))−H键催化氧化的研究主要涉及一些键能低的、预活化的C−H键,包括苄基型、亚甲基型、脂肪族X−CH_(2)(X=O,N)和甲苯等,含有未活化C(sp^(3))−H键的复杂化合物的选择性氧化仍具有挑战性.例如,芳基醚C(sp^(3))−H键功能化通常采用计量的过氧化物氧化剂,或者通过单电子氧化和碱促进的去质子化进一步构建C−C/C−N键,产物选择性较低,也带来了一些不利的环境影响.因此,有必要开发高效、温和的芳基醚C(sp^(3))−H键选择氧化方法,并将其应用于有机合成和药物开发.近年来,光催化C(sp^(3))−H键氧化因其操作简便、氧化还原中性等优点,已发展成为一种有用且多样的催化研究工具.本文发展了一种利用氧气作为氧化剂,在可见光驱动下选择性地将芳基醚C(sp^(3))−H键氧化成为甲酸苯酯类产物的新方法.使用Mes-10-phenyl-Acr^(+)−BF_(4)^(-)光催化剂,高效活化多种氯源(如盐酸、无机氯盐和有机氯化物)得到氯自由基,由于其具有较高的氧化能力(+2.03 V vs.SCE)和对氢原子的亲和力,能够通过氢原子转移过程活化芳基醚C(sp^(3))−键,攫取氢自由基得到相应的烷基碳自由基(•CH_(2)OPh)中间体,进一步被分子氧选择氧化得到酯类目标产物.研究结果表明,多种链状芳基醚和不同取代(如给电子基和吸电子基)芳基醚均可发生氧化反应,高收率地合成了一系列官能团丰富的甲酸苯酯类化合物.本文方法具有反应条件温和、操作简单、官能团耐受性好以及可规模化放大等优点,并且少量的水对反应没有明显影响.机理实验研究结果表明,芳基醚C(sp^(3))−H键的断裂是反应过程的决速步骤.紫外可见吸收光谱结果表明,氯离子与催化剂之间的相互作用强于底物,并且自由基捕获实验证实反应体系中存在氯自由基和烷基碳自由基物种,表明反应经历自由基路径.此外,电子顺磁共振测试结果表明,反应过程中存在单线态氧物种,可能是激发态的光催化剂直接与氧气发生能量转移得到;同位素实验(18O)揭示了甲酸苯酯类化合物氧的来源.综上,本文实现了温和条件下光催化芳基醚C(sp^(3))−H键选择氧化反应,高收率合成了一系列甲酸苯酯类化合物.该方法避免了化学计量的过氧化物和碱等添加剂的使用以及底物的过度氧化,阐明了催化反应机制,为其他醚类化合物的C(sp^(3))−H键氧化功能化提供了新思路,为后续化学合成和药物开发提供了参考和启示.

银催化苄基C(sp^(3))—H键与炔丙基C(sp^(3))—H键的位点选择性胺化

探讨了一种合成环状氨基磺酸酯的新方法。采用AgClO4/三(2-吡啶基甲基)胺催化体系,催化苄基C(sp^(3))—H键与炔丙基C(sp^(3))—H键的分子内位点选择性胺化反应,以89%收率和9.2∶1位点选择性得到了环状氨基磺酸酯。反应具有条件温和、官能团耐受性好、原子经济性和步骤经济性高等优点,为碳氮的构建提供了一种选择策略。

Adsorption Regularity and Characteristics of sp^3-Hybridized Gas Molecules on Anatase TiO_2(101) Surface

We report the anatase titanium dioxide （101） surface adsorption of sp3-hybridized gas molecules, including NH3, 1-12 0 and CH4, using first-principles plane-wave ultrasoft pseudopotential based on the density functional theory. The results show that it is much easier for a surface with oxygen vacancies to adsorb gas molecules than it is for a surface without oxygen vacancies. The main factor affecting adsorption stability and energy is the polarizability of molecules, and adsorption is induced by surface oxygen vacancies of the negatively charged center. The analyses of state densities and charge population show that charge transfer occurs at the molecule surface upon adsorption and that the number of transferred charge reduces in the order of N, 0 and C. Moreover, the adsorption method is chemical adsorption, and adsorption stability decreases in the order of NH3, tt2 0 and CH4. Analyses of absorption and reflectance spectra reveal that after absorbed CH4 and H2 O, compared with the surface with oxygen vacancy, the optical properties of materials surface, including its absorption coefficients and reflectivity index, have slight changes, however, absorption coefficient and reflectivity would greatly increase after NH3 adsorption. These findings illustrate that anatase titanium dioxide （101） surface is extremely sensitive to NH3.

非晶碳膜中sp^2和sp^3相的检测方法

非晶碳薄膜由sp2和sp3杂化的碳原子组成。sp2和sp3碳原子的比例是决定非晶碳膜的结构和性能的重要参数。如何定量或定性地分析碳薄膜中sp2和sp3碳的含量一直是十分重要的问题。目前用来测定sp2和sp3碳及其比例的实验方法有13C核磁共振谱(NMR)、电子能量损失谱(EELS)、X射线光电子能谱(XPS)、椭圆偏振谱、拉曼光谱(Raman)、红外光谱(IR)等。综述了这些测定方法及其特点。

类金刚石薄膜sp^2-sp^3轨道杂化的第一性原理研究

以强σ键连接的sp2和sp3杂化碳饱和簇模型,即金刚石和石墨两相和团簇模型为研究对象,通过分子结构、电荷分布、能带结构、电子态密度和分子轨道的第一性原理计算和分析,研究了类金刚石薄膜中sp2-sp3轨道杂化的空间结构稳定性的成键特性等.结果表明,成键过程中由于微扰作用破坏了原子内部"吸引"与"排斥"的平衡关系,使电子云重新分布,而键能大小和电子云的重叠密切相关,因而两相共存对电荷分布和结构均有影响.能带结构分析发现sp2杂化C原子将π键引入,产生π和π*能带使带隙变窄,说明类金刚石薄膜的半导体本质.电子态密度计算结果中费米能级附近出现杂质峰,说明存在中间杂化和/或π态和σ态的转化.

非晶金刚石薄膜的sp^3键成分的XPS谱研究

把非晶金刚石薄膜的XPSC1s谱分解为中心在 2 84 .4± 0 .1eV和 2 85 .2± 0 .1eV的两个高斯特征峰 ,分别对应于碳薄膜中的sp2 C和sp3 C。用这两个高斯特征峰的面积除以C1s谱的总面积 ,得出非晶金刚石薄膜中sp2 C和sp3 C的比例。用上述方法对sp3 C比例不同的一组样品进行了分析计算 ,并与先前用紫外 -可见光吸收光谱和拉曼光谱对同一组样品分析得出的结果进行了比较 ,结果表明 :用XPS谱能简便而有效地定量确定非晶金刚石薄膜中sp2 C和sp3 C的比例 ,且这种方法适用于所有功能碳薄膜。

金刚石薄膜中SP^2／SP^3键价比拉曼光谱分析

金刚石薄膜中ＳＰ￣２／ＳＰ￣３键价比拉曼光谱分析张兵临Ｈ，Ｍ．Ｐｈｉｌｌｌｉｐｓ（郑州大学物理系郑州４５００５２）ＡｎａｌｙｓｉｓｏｆＳＰ￣２／ ＳＰ￣２／ＳＰ￣３ＢｏｎｄｉｎｇＲａｔｉｏｉｎＤｉａｍｏｎｄＴｈｉｎＦｉｌｍｓｂｙＲａｍａｎＳｐｅｃｔｒ...

sp^(3)-like defect structure of hetero graphene-carbon nanotubes for promoting carrier transfer and stability

Three-dimensional(3 D) hybrid of nanocarbons is a very promising way to the high-performance design of electrocatalysis materials.However,sp^(3)-like defect structure,a combination of high strength and conduction of graphene and carbon nanotubes(CNTs) is rarely reported.Herein,3 D neural-like hybrids of graphene(from reduced graphene oxide) and carbon nanotubes(CNTs) have been integrated via sp^(3)-like defect structure by a hydrothermal approach.The sp^(3)-like defect structure endows 3 D nanocarbon hybrids with an enhanced carrier transfer,high structural stability,and electrocatalytic durability.The neural-like structure is shown to demonstrate a cascade effect of charges and significant performances regarding bio-electrocatalysis and lithium-sulfur energy storage.The concept and mechanism of "sp^(3)-like defect structure" are proposed at an atomic/nanoscale to clarify the generation of rational structure as well as the cascade electron transfer.

Simultaneously Enhanced Activity and Selectivity for C(sp^(3))-H Bond Oxidation Under Visible Light by Nitrogen Doping

Selective oxidation of saturated C(sp^(3))-H bonds in hydrocarbon to target chemicals under mild conditions remains a signifi-cant but challenging task because of the chemical inertness and high dissociation energy of C(sp^(3))-H bonds.Semiconductor photocatalysis can induce the generation of holes and oxidative radicals,off ering an alternative way toward selective oxidation of hydrocarbons under ambient conditions.Herein,we constructed N-doped TiO_(2) nanotubes(N-TNTs)that exhibited remark-able activity and selectivity for toluene oxidation under visible light,delivering the conversion of toluene and selectivity of benzaldehyde of 32% and>99%,respectively.Further mechanistic studies demonstrated that the incorporation of nitrogen induced the generation of N-doping level above the O 2p valance band,directly contributing to the visible-light response of TiO_(2).Furthermore,hydroxyl radicals generated by photogenerated holes at the orbit of O 2p were found to be unselective for the oxidation of toluene,aff ording both benzaldehyde and benzoic acid.The incorporation of nitrogen was able to inhibit the generation of hydroxyl radicals,terminating the formation of benzoic acid.

通过醚的α-位C(sp^(3))—H键官能化合成醚类衍生物的研究进展

醚及其类衍生物是有机化合物中的重要组成部分,许多生物活性分子、药物和天然产物中也存在醚类结构。近年来通过醚类分子(包括环醚和非环醚)的α-位C(sp^(3))—H官能化来合成了多种不同类型的醚类衍生物已取得了令人瞩目的研究成果。本综述从醚α-位C(sp^(3))—H官能化所需的反应条件出发,对2017年到2020年来的研究成果进行了综述。

Photocatalyzed site‐selective C(sp^(3))‒H sulfonylation of toluene derivatives and cycloalkanes with inorganic sulfinates

The development of practical methods for the direct and selective C(sp^(3))‒H functionalization of hydrocarbons is an attractive topic in synthetic chemistry.Although the radical‐mediated hydrogen atom transfer(HAT)process has shown considerable potential in such reactions,it still faces fundamental problems associated with reactivity and selectivity.Herein,we report a convenient and economic approach to site‐selective C(sp^(3))‒H sulfonylation via photo‐induced HAT catalysis.Employing a conjugated polycyclic quinone as a direct HAT photocatalyst,commercially available inorganic sulfinates as the sulfonylation source,copper triflate as an inexpensive oxidant,a variety of toluene derivatives and cycloalkanes were converted into biologically and synthetically interesting sulfone products under mild conditions.The mechanistic studies reveal that the reaction sequence involves direct HAT‐induced radical formation and a subsequent copper‐mediated organometallic process for the C‒S bond formation.This method offers an appealing opportunity to furnish high value‐added products from abundant hydrocarbon starting materials and inexpensive reagents.

sp^(2)碳用于3D打印技术综述:材料、性能和应用

3D打印可以改变现有的生产方法,是第四次工程革命中的一项现代技术。它从成型原理上提出了分层制造、逐层叠加成型的新颖生产方法,从根本上简化了制造工艺,实现了大规模定制生产。然而,这一新技术仍存在许多问题。除了纯石墨烯外,sp^(2)碳具有好的亲水性,3D打印难度较小。sp^(2)碳还可在3D打印中的各种阶段应用。纯石墨烯的疏水性使其难以在水系介质中打印和加工。毛细管油墨的发展使得纯石墨烯的3D打印成为可能。本文综述了sp^(2)碳的3D打印技术的最新进展。首先简要概述了3D打印技术,随后概述了sp^(2)碳的3D打印及其在各种方面的应用。最后,讨论了这一新领域的发展前景和机遇。

α-C(sp^(3))-H Arylation of Cyclic Carbonyl Compounds

α-C(sp^(3))-H arylation is an important type of C-H functionalization.Various biologically significant natural products,chemi-cal intermediates,and drugs have been effectively prepared via C-H functionalization.Cyclic carbonyl compounds comprise of cyclic ketones,enones,lactones,and lactams.Theα-C(sp^(3))-H arylation of these compounds have been exhibited high efficiency in forming C(sp^(3))-C(sp^(2))bonds,played a crucial role in organic synthesis,and attracted majority of interests from organic and medicinal communities.This review focused on the most significant advances including methods,mechanism,and applications in total synthesis of natural products in the field ofα-C(sp^(3))-H arylations of cyclic carbonyl compounds in recent years.

甘氨酸衍生物C(sp^3)―H官能团化反应在喹啉类化合物合成中的应用

C(sp^3)―H键官能团化反应被认为是构建C―C键的最直接和高效的合成方法。近年来,通过甘氨酸衍生物C(sp^3)―H官能团化反应来合成喹啉类化合物的研究逐渐引起研究者的广泛关注。本文简要介绍了甘氨酸衍生物C(sp^3)―H官能团化反应研究现状,并总结了不同催化体系下此类反应在喹啉衍生物合成中的应用,目的在于通过对前沿科研内容的介绍,开拓大学生的知识视野,激发他们对于科学探索的兴趣。

电化学促进未活化C(sp^(3))—H官能团化研究进展

有机电合成以无痕电子代替传统的化学氧化剂或还原剂,具有绿色易放大等优势.未活化C(sp^(3))—H键的官能团化可以将目标官能团直接引入分子中进行修饰,避免预官能团化,兼具原子经济性和步骤经济性.随着有机电合成发展的日益成熟,电化学促进未活化C(sp^(3))—H官能团化成为了有机合成的研究热点之一.根据官能团类型对反应进行分类,总结了近年来涉及未活化C(sp^(3))—H官能化的研究成果,重点分析了反应优势、底物特点以及反应机理,最后展望了面临的挑战及未来的发展趋势.

Synthesis of biheteroaryls via 2-methyl quinoline C(sp^(3))-H functionalization under metal-free conditions

An acetic acid-promoted C(sp^(3))-H functionalization of 2-methyl quinoline,enaminoesters and elemental sulfur for the synthesis of 3,4,5-trisubstituted isothiazoles under metal-free conditions has been developed.This approach provides viable access to various 5-(quinolin-2-yl)isothiazoles in moderate to good yields with good functional group tolerance.Moreover,the success of the gram-scale reaction gives this reaction a great potential application.

基于甘氨酸衍生物α-C(sp^(3))—H官能团化的催化体系研究进展

α-氨基酸是组成蛋白质的基本结构单元,应用范围非常广泛,它不仅能用于许多生物活性分子的合成、药物化学和材料工业中,还可作为有机催化剂或配体用于各类化合物的不对称合成中.甘氨酸作为最普遍且具有潜手性的α-氨基酸,在有机合成领域是一类非常重要的合成砌块,利用甘氨酸衍生物或多肽的α-C(sp^(3))—H官能团化,高效构建结构多样性的非天然α-氨基酸或多肽引起了越来越多科研工作者的关注.对近五年来甘氨酸衍生物α-C(sp^(3))—H官能团化领域所取得的研究进展进行了综述,根据不同类型的催化体系进行了分类讨论,并对该领域所面临的挑战和机遇进行了展望和探讨.

Electro-reductive carboxylation of acyclic C(sp^(3))–C(sp^(3))bonds in aromatic hydrocarbons with CO_(2)

Despite the recent advances in the selective functionalization of C–C bonds in specific substrates,cleavage and functionalization of C–C bonds in acyclic substrates,such as ethane derivatives,remains challenging.In contrast to the well-developed functionalization of one carbon fragment after C–C bond cleavage,herein,we report a novel electro-reductive carboxylation of C(sp^(3))–C(sp^(3))bond in multi-aryl ethanes with carbon dioxide(CO_(2))by utilizing both carbon fragments.Thus,this reaction exhibits an atom-,step-economic approach for the synthesis of carboxylic acids,fulfilling principal aspirations of organic synthesis.Moreover,this method features mild reaction conditions,broad substrate scope,and good functional group tolerance.Symmetric and asymmetric substrates bearing primary,secondary,or tertiary C(sp^(3))–C(sp^(3))bonds are all amenable to this strategy,enabling one or two structurally different carboxylic acids to be facilely constructed at the same time.Mechanistic investigations indicate that carbanions might be the key intermediates in this reaction,which could be captured by CO_(2)efficiently.

Rhodium-catalyzed enantioselective in situ C(sp^(3))-H heteroarylation by a desymmetrization approach

A rhodium-catalyzed desymmetrization reaction for enantioselective methyl C-H arylation is achieved by utilizing an in situ arylating reagent via nucleophilic cyclization of o-aminoaryl alkyne.The reaction results in chiral indoles containing all-carbon quaternary stereocenters under atmospheric conditions,with a wide range of substrates exhibiting good enantioselectivity(44 examples).Mechnism and DFT studies show that the stereocontrol is reasonably achieved through the collaborative control of a large silicon substituted chiral ligand and C-H···π,LP···πinteractions between aryl rings of the carboxylate group and the substrate.Control experiments demonstrate that Rh-aryl bond formation via in situ nucleophilic cyclization is more critical for reaction efficiency than via C-H activation of the nucleophilic cyclization byproduct.