二氧化碳高值利用合成苯氨基甲酸甲酯（英文）

苯氨基甲酸甲酯(MPC)是合成二苯甲烷二异氰酸酯(MDI)的关键原料。以二氧化碳(CO₂)及其等价物或衍生物作为碳源合成MPC代表了绿色和可持续的精细化学品合成方法。基于该领域研究,概述了基于CO₂转化合成苯氨基甲酸甲酯的研究方法进展。合成路线包括研究较多的CO₂等价物(尿素或苯基脲)醇解法,碳酸二甲酯(DMC)氨解法以及二苯基脲和DMC耦合反应法。另外,最理想的合成方法是近几年发展的苯胺、CO₂和甲醇三组分“一锅”反应法,以及使用脂肪胺类原料构建氨基甲酸烷基酯类化合物,其代表了最有前景的CO₂利用途径之一。详细探讨了反应机理和催化剂选择等问题。研究进展将为进一步提升绿色催化和可持续化学过程效率提供重要理论支持。     

金属-有机骨架衍生催化剂在二氧化碳加氢和费托合成反应中的应用

CO₂加氢和费托合成反应是C1化学中重要的研究领域,CO₂加氢制备高附加值化学品和燃料有助于降低大气中CO₂浓度,减轻化石燃料消耗的压力;费托合成反应是以非石油资源为原料生产液体燃料和化学品的重要路径。 开发新型、高效、稳定的催化剂是CO₂加氢和费托合成反应的关键点之一。 利用金属-有机骨架(Metal-Organic Frameworks,MOFs)材料的特点制备的MOFs衍生催化剂在CO₂加氢和费托合成反应中具有较好的应用前景。 本文综述了CO₂加氢和费托合成反应中MOFs衍生催化剂的制备方法,以及催化剂在各反应中的催化性能,并对目前所存在的问题以及今后的发展进行了总结和展望。     

二氧化碳与不饱和烃的还原羧化反应

过渡金属催化CO₂参与的不饱和烃还原羧化反应是合成羧酸及丙烯酸类化合物的重要途径, 具有重要的研究价值和工业应用潜力．过渡金属试剂与不饱和烃、CO₂生成稳定的金属杂环内酯或金属羧酸盐．还原剂能够与金属杂环内酯或金属羧酸盐发生转金属作用, 重新生成活泼催化剂, 从而实现催化剂的循环利用．本文总结了还原剂, 包括有机金属试剂、硅烷、硼烷、金属粉末、甲醇和氢气等在不饱和烃与CO₂的还原羧化反应中的应用, 并着重描述其反应特点和反应机理.     

共价有机框架材料在光催化CO2还原中的应用

全球范围内化石燃料的大量消耗导致了能源危机,同时其所排放的CO₂等温室气体使环境问题日渐突出。将CO₂等废气进一步转化为高附加值燃料是解决能源与环境问题的理想方案。利用取之不尽的太阳能作为能源实现光催化CO₂还原为能源化合物被认为是有效解决此问题的最佳途径之一。共价有机框架材料(COFs)是一类新型晶态多孔有机聚合物材料,具有结构稳定性、可设计性和结构多样化的特征,因此在光催化CO₂还原领域表现出了巨大潜力。本文概述了近年来COFs在光催化CO₂还原领域中的催化应用研究进展,包括引入不同金属离子提供活性位点、增加光敏性官能团提高其对可见光利用率等方法。最后对以COFs材料为光催化CO₂还原催化剂的研究进行了总结和展望,我们认为更进一步的新材料合成、修饰与催化机理研究仍是前景广阔的研究领域。     

酶法催化二氧化碳制备高附加值化学品研究进展

现代工业的发展不断消耗煤、石油、天然气等碳化石燃料,并产生了大量的温室气体CO₂,使人类面临能源和环境的双重挑战,开发绿色能源、控制CO₂对环境的影响迫在眉睫.CO₂是一种廉价的碳源,可通过化学法、光化学法、电化学法或酶法等转化为高附加值含碳化学品,实现CO₂的资源化循环利用,是解决全球碳排放所带来的能源和环境危机的双赢策略.受CO₂胞内天然生物转化的启发,酶法为CO₂的循环利用带来了新的机遇,相比于传统的化学及光、电化学法,可表现出绿色、高效、温和、高选择性等优点,有望为CO₂高值化利用带来新的契机.有鉴于此,本文从胞内CO₂生物转化机理出发,综述了国内外近年来多种单酶及多酶级联催化CO₂高值化利用的最新研究进展,并交叉论述了固定化酶催化体系的构建、酶定向进化和改造、酶催化过程调控等内容,总结了酶法转化目前存在的缺陷和不足,并提出了展望,以期为酶法催化CO₂高值化利用提供一定的参考和借鉴.     

金属有机框架材料的制备及在吸附分离CO2中的应用

金属有机框架（MOFs）材料是当今的研究热点之一,是一类颇有潜力成为适用于CO₂吸附和分离的重要材料。本文从MOFs的发展及其所具有的特点、MOFs用于CO₂的吸附与分离所取得的突破性进展以及MOFs的传统合成及绿色制备方法三个方面展开论述。主要论述了MOFs适用于CO₂吸附的原理,及其相对于传统的CO₂吸附材料所具有的特点和优势,亦阐述了MOFs修饰与调变的方法。列出了MOFs用于单组分CO₂吸附及CO₂/CH₄、CO₂/N₂吸附分离的结果。同时,针对传统MOFs制备方法不适宜大规模CO₂捕集材料的生产,特别论述了机械化学合成法和新兴的潮湿矿物风化法,其均具有绿色化、无溶剂、低能耗和简单等特点,是一类较有研究价值和应用潜力的技术。随着温室效应和不可再生石化燃料的消耗等环境和能源问题的日趋严峻,研究及开发适用于CO₂捕集与封存技术的MOFs新材料迫在眉睫,且任重而道远。     

单原子催化剂在电催化还原CO2领域的应用

温和条件下以CO₂为原料制备高附加值化学品, 是CO₂资源化利用的重要方法, 在众多CO₂转化方法中, 电催化CO₂还原(e-CO₂RR)具有绿色、 清洁及条件可控等优势, 可以促进碳中和, 实现可持续发展. 然而, 由于其缓慢的动力学和较低催化剂活性, CO₂电催化还原仍然存在低选择性, 低电流密度的问题. 单原子催化剂具有最大的原子利用率和明确定义的催化活性位点, 同时因其良好的配位结构和独特的电子结构极大地促进了CO₂电催化还原的动力学过程, 是CO₂电还原领域极具发展潜力的催化材料. 本文讨论了过渡金属和主族金属基单原子催化剂用于电催化CO₂还原的研究进展, 系统总结了杂原子配位, 双/单原子位点, 金属-载体相互作用, 空间限域和分子桥联等策略调控单原子的微环境进而优化催化的性能, 揭示了单原子催化剂在 e-CO₂RR领域内的突出优势和广阔的应用前景. 最后, 分析了单原子催化剂在CO₂电催化转化过程中面临的挑战, 并对其未来进行了展望.     

二氧化碳加氢制甲醇多相催化剂研究进展

化石燃料的利用为人类社会带来了前所未有的繁荣和发展. 然而, 化石燃料燃烧引起的过量的二氧化碳(CO₂)排放导致全球气候变化和海洋酸化; 而且作为一种有限的资源, 化石燃料的消耗将迫使人们寻找其它碳源以维持可持续的发展. 利用可再生能源获取电能分解水制得的绿色氢气(H₂)与捕集后的CO₂反应制成甲醇, 不仅能有效利用工业废气中多余的CO₂, 还能获取清洁、 可再生的甲醇化学品, 该过程的技术核心是开发高效稳定的CO₂加氢制甲醇催化剂. 本文综合评述了现有研究关注较多的多相催化CO₂加氢制甲醇催化剂的反应机理和构效关系, 总结了目前多相催化CO₂加氢制甲醇催化剂(Cu基催化剂、 贵金属与双金属催化剂、 氧化物催化剂以及其它新型催化剂)的设计与合成方面的研究进展, 最后对该领域所面临的机遇和挑战进行了展望.     

二氧化碳与二甲胺催化合成N,N-二甲基甲酰胺

二氧化碳(CO₂)是大气中主要温室气体之一,也是丰富、安全、可再生的碳一资源。将CO₂催化转化为高附加值化学品不仅能改善人类长期依赖化石资源的困境,还能有效减少CO₂排放,助力实现“碳达峰、碳中和”这一“双碳”目标。N,N-二甲基甲酰胺(DMF)是一种年产百万吨级的平台化合物,是优良的溶剂以及重要的化工中间体。因此,以CO₂作为羰源,通过高效催化体系的构建实现CO₂与二甲胺反应合成DMF具有重要意义。本文分别从还原剂、催化体系和反应机理等角度综述了这一领域近年来的研究进展。最后,对CO₂合成DMF催化过程中所面临的问题和未来的发展方向进行了探讨和展望。     

多孔骨架固定分子催化剂催化CO2加氢制备甲酸研究进展

近年来, 大气中CO₂含量急剧增加, 导致了严重的温室效应. 将CO₂作为C1资源转化为燃料或精细化学品引起了越来越多的关注. 开发高效、 稳定、 可回收利用的催化剂成为CO₂资源化利用的关键. 在众多的CO₂加氢催化剂中, 功能性多孔骨架材料固定型分子催化剂展示出优异的性能, 成为研究的热点之一. 功能性骨架材料, 如多孔有机聚合物(POPs)、 共价有机骨架(COFs)和金属有机骨架(MOFs), 具有比表面积大、 热稳定性高和可调性等特点, 在设计合成催化剂方面发挥着重要作用. 本文介绍了POPs/COFs/MOFs多孔骨架材料固定分子催化剂的开发及在催化CO₂合成甲酸领域的最新进展.     

2-取代苯并噻唑化合物的合成进展

2-取代苯并噻唑在生物医药、材料科学等领域的应用和研究使其合成方法受到了广泛的关注.在传统合成方法的研究基础之上,单质硫介导的氧化还原反应和饱和化合物的脱氢芳构化反应等新方法的发展,为苯并噻唑衍生物的合成提供更多可能.此外,近年来新型金属-有机骨架催化剂、组合离子液体/凝胶、超声以及微波辅助等的应用,极大地丰富了苯并噻唑衍生物的合成方式.综述了近年来2-取代苯并噻唑的合成方法.     

Benzothiazoles from Condensation of o-Aminothiophenoles with Carboxylic Acids and Their Derivatives: A Review

Nowadays, organic chemists are interested in the field of heterocyclic chemistry due to its use in the synthesis of a great variety of biologically active compounds. Heterocyclic compounds are widely found in nature and are essential for life. Among these, some natural nitrogen containing heterocyclic compounds have been used as chemotherapeutic agents. Their attachment to sugar molecules either as thioglycosides or as nucleosides analogues plays an important role in vital biological processes as well as in synthetic organic chemistry. Molecules containing benzothiazole (BT) nuclei are of this interesting class of compounds because some of them have been found to have a wide variety of biological activities. In this sense, we selected this topic to review and to then summarize the procedures related to the condensation reactions of o-aminothiophenoles (ATPs) as well as their disulfides with carboxylic acids, esters, orthoesters, acyl chlorides, amides, and nitriles. The condensation reactions with carbon dioxide (CO₂) are included. Conventional methods with the use of acid and metal catalysts as well as recent green techniques, such as microwave irradiation, the use of ionic liquids, and ultrasound (US) chemistry, which have proven to have many advantages, were found in the review.     

Utilisation of CO2 as a chemical feedstock: opportunities and challenges

The need to reduce the accumulation of CO(2) into the atmosphere requires new technologies able to reduce the CO(2) emission. The utilization of CO(2) as a building block may represent an interesting approach to synthetic methodologies less intensive in carbon and energy. In this paper the general properties of carbon dioxide and its interaction with metal centres is first considered. The potential of carbon dioxide as a raw material in the synthesis of chemicals such as carboxylates, carbonates, carbamates is then discussed. The utilization of CO(2) as source of carbon for the synthesis of fuels or other C(1) molecules such as formic acid and methanol is also described and the conditions for its implementation are outlined. A comparison of chemical and biotechnological conversion routes of CO(2) is made and the barriers to their exploitation are highlighted.     

Development and evaluation of porous materials for carbon dioxide separation and capture

The development of new microporous materials for adsorption separation processes is a rapidly growing field because of potential applications such as carbon capture and sequestration (CCS) and purification of clean-burning natural gas. In particular, new metal-organic frameworks (MOFs) and other porous coordination polymers are being generated at a rapid and growing pace. Herein, we address the question of how this large number of materials can be quickly evaluated for their practical application in carbon dioxide separation processes. Five adsorbent evaluation criteria from the chemical engineering literature are described and used to assess over 40 MOFs for their potential in CO(2) separation processes for natural gas purification, landfill gas separation, and capture of CO(2) from power-plant flue gas. Comparisons with other materials such as zeolites are made, and the relationships between MOF properties and CO(2) separation potential are investigated from the large data set. In addition, strategies for tailoring and designing MOFs to enhance CO(2) adsorption are briefly reviewed.     

碳纳米管的最新制备技术及生长机理

结合笔者的工作综述了碳纳米管的制备技术及生长机理的最新研究进展，重点介绍了近两年来碳纳米管制备的进展情况，包括传统制备方法的改进（电弧放电法、化学气相沉积法和激光蒸发法）、新型制备技术、特殊结构的碳纳米管制备；同时探讨了碳纳米管的各种生长机理；最后提出了碳纳米管制备技术和生长机理的发展方向。     

Fischer-Trospch Synthesis on Ordered Mesoporous Cobalt-Based Catalysts with Compact Multichannel Fixed-Bed Reactor Application: A Review

CO hydrogenation to hydrocarbons through Fischer–Tropsch synthesis (FTS) reaction is one of the promising chemical processes, which can convert alternative feedstocks such as natural gas or biomass into synthetic fuels. The FTS reaction has received many attentions due to a limited petroleum resource with an increased demand for using alternative carbon sources such as stranded gas or shale gas. Some proper synthetic methods of an effective FTS catalyst having a larger active metal surface area and a lower deactivation rate are the most important issues for a long-term operation. Therefore, some ordered mesoporous materials (OMM) have been widely investigated in the field of CO hydrogenation using some heterogeneous catalysts. The present brief review paper summarized the various preparation methods of the ordered mesoporous materials for the possible applications of FTS reaction with a lower deactivation rate and a higher catalytic performance. The applications of the ordered mesoporous cobalt oxides for FTS reaction are briefly introduced and the ways to improve a structural stability even under reductive CO hydrogenation conditions by using efficient pillaring materials as well as by preparing mixed metal oxides. A higher catalytic activity of the ordered mesoporous cobalt oxide was also verified in a multi-channel fixed-bed compact reactor having the intersected interlayers of micro-channel heat exchanger. The thermal stability of ordered mesoporous cobalt-based catalysts was mainly affected by a structural stability which can easily remove the heavy hydrocarbons from the inner surfaces.     

Modern Approaches to the Synthesis and Transformations of Practically Valuable Benzothiazole Derivatives

The review is devoted to modern trends in the chemistry of 2-amino and 2-mercapto substituted benzothiazoles covering the literature since 2015. The reviewed heterocycles belong to biologically active and industrially demanded compounds. Newly developed synthesis methods can be divided into conventional multistep processes and one-pot, atom economy procedures, realized using green chemistry principles and simple reagents. The easy functionalization of the 2-NH₂ and 2-SH groups and the benzene ring of the benzothiazole moiety allows considering them as highly reactive building blocks for organic and organoelement synthesis, including the synthesis of pharmacologically active heterocycles. The review provides a summary of findings, which may be useful for developing new drugs and materials and new synthetic approaches and patterns of reactivity.     

An efficient synthetic route to biologically relevant 2-phenylbenzothiazoles substituted on the benzothiazole ring

Certain 2-phenylbenzothiazoles containing substituents on the benzothiazole ring possess important biological properties, yet the majority of synthetic methods to 2-phenylbenzothiazoles described to date focus on their unsubstituted ring counterparts. Here we describe a new concise and efficient synthetic route to biologically relevant 2-phenylbenzothiazoles in high yield from the reaction of substituted 2-aminothiophenol disulfides and benzaldehydes, promoted by the inexpensive and non-toxic inorganic oxidant sodium metabisulfite in DMSO at 120 °C. Our new method is tolerant of a range of substituents on both the benzothiazole and phenyl ring, and affords efficient access to substituted 2-phenylbenzothiazoles without the need for column chromatography.     

二氧化碳在化学合成上的研究进展

二氧化碳合成化学在发展对环境友好的新合成工艺和利用ＣＯ２制备附加价值较高的化工产品等方面的研究取得了重要进展,它有助于减少ＣＯ２对大气中的排放量。     

Phenols as Novel Photocatalytic Platforms for Organic Synthesis

In recent years, organic chemists have devoted a great deal of effort towards the implementation of novel green photocatalytic synthetic protocols. To this end, the development of new effective, non-toxic, inexpensive photocatalysts, which are capable of driving value-added chemical transformations, is highly desirable. Interestingly, phenols fulfill all these requirements due to their outstanding physicochemical features, therefore emerging as promising metal-free photocatalytic platforms for organic synthesis. This Perspective aims at highlighting the most recent applications of phenols in organic photocatalysis. More specifically, phenolate anions, formed upon deprotonation of phenols, are photo-active organic intermediates that may absorb light within the visible region. Thus, when in the excited states, these anions may be used as reductants to generate reactive open shell species from suitable precursors under mild operative conditions. Alternatively, phenolate anions and suitable radical precursors can form electron donor-acceptor (EDA) complexes. Specifically, the photochemical activity of these molecular aggregates can be used to initiate organic radical reactions. Lastly, forward-looking opportunities within this research field have been discussed.