绿藻来源光脱羧酶McFAP的挖掘及其中短链脂肪酸选择性脱羧机制研究（英文）

利用脂肪酸脱羧制备烃类生物燃料是开发可再生能源的有效途径.相比于传统化学法,生物酶法具备高效、能耗低及环境友好等优势,更具有工业应用前景.光脱羧酶(FAP)是一类专一性强,催化效率高,催化过程无需额外添加昂贵辅因子,仅需利用蓝光即可将脂肪酸转化为烷(烯)烃的光驱动酶,在烃类生物燃料的高效可持续生物合成领域具有应用潜力.目前已报道的有偏好催化C12-C20链长脂肪酸的光脱羧酶,但其底物选择性机制尚未被深入探究.本文挖掘了来源于绿藻Micractinium conductrix的光脱羧酶Mc FAP,并开展了异源表达及制备、酶学性质表征、催化特性及底物选择性机制等研究.利用全基因合成技术获得了来源于绿藻Micractiniumconductrix假定的光脱羧酶基因序列mcfap,同时构建了N端缺失突变体Mc FAP-S (缺失1-550位氨基酸).在大肠杆菌中实现了Mc FAP-S的异源表达.重组的Mc FAP-S对链长为6-18的饱和直链脂肪酸均有脱羧活性,偏好中链脂肪酸,最适底物为正辛酸(C8:0)(转化率>99%).相同条件下, Mc FAP全细胞催化软脂酸(C16:0)脱羧的...     

生物质平台化合物电催化制备高值燃料与化学品研究进展

生物质是一类丰富的可再生碳基资源,有望代替传统化石资源生产燃料和化学品,受到了广泛关注和研究.近年来,电催化作为一种绿色高效的转化策略,成为生物质催化转化的重要研究方向之一,具有巨大的应用前景.本文总结了生物质平台化合物电催化制备高附加值燃料与化学品的研究进展,根据反应类型重点介绍了电催化氧化、还原和偶联反应,对催化反应过程和机理进行了阐述,并对电催化生物炼制的前景进行了展望.     

光电解水制氢耦合生物质醇/醛氧化的研究进展

生物质醇/醛是一类重要的生物基平台化合物, 通过催化氧化重整可将其进一步转化为高值含氧化学品或燃料. 太阳能驱动的光电催化技术是实现生物质醇/醛氧化最为绿色高效的途径之一. 与传统光电解水制氢相比, 利用生物质醇/醛氧化来替代阳极析氧过程不仅可以提高阳极产物的附加值, 同时可以提升太阳能到氢能的转化效率. 因此, 光电解水制氢耦合生物质醇/醛氧化对绿氢提效降本和高值化学品合成具有重要意义. 本文综合评述了光电解水制氢耦合生物质醇/醛的氧化反应机理, 总结了目前光电催化技术在生物质醇/醛氧化方面的研究进展, 最后对该领域所面临的机遇和挑战进行了展望.     

第二代生物柴油制备的多相催化剂的结构设计及研究进展

生物柴油是一种重要的可再生清洁能源, 特别是经催化加氢脱氧等系列过程制备的第二代生物柴油, 在成分上与石油基燃料相似, 有望成为一种替代传统化石燃料的绿色能源. 在合成第二代生物柴油的研究中, 设计与制备兼具高活性与高稳定性的加氢脱氧多相催化剂是关键问题. 近年来, 研究者对于催化剂的种类与应用进行了探索, 并取得了一定的进展. 详细分析了加氢脱氧制备第二代生物柴油反应原料及反应参数、反应器对生产路径和产能的影响, 并对反应机理进行了介绍; 进一步从双金属位点、金属-酸性位点及金属-空位协同作用三个方面对催化剂结构设计进行了讨论和分析; 最后, 对第二代生物柴油领域的未来发展趋势进行了展望.     

脂肪酸糖酯类表面活性剂的合成及应用

脂肪酸糖酯是一类绿色、安全、可生物降解的非离子型表面活性剂,因其具有良好的乳化能力和杀菌性能以及对皮肤刺激性低等诸多优点而被广泛应用于食品、医药、化妆品和农业领域。本文对脂肪酸糖酯的合成及应用进行了综述,从而为深入研究并开发脂肪酸糖酯类表面活性剂提供参考。     

《精细化学品催化合成技术(下册):催化合成反应与技术》

《精细化学品催化合成技术》分上、下两册,上册(第1~6章)为"绿色催化技术",下册(第7~14章)为"催化合成反应与技术"。本册(下册)在上册叙述精细化学品合成的绿色催化技术基础上详细介绍了各种类型催化剂参与的各种类型有机合成反应。包括在多孔本体和负载金属催化剂上使用氢气的有机化合物催化加氢和催化加氢裂解反应;在酸碱催化剂上进行精细化学品催化合成反应;使用分子氧和过氧化物作为氧源的催化氧化反应;使用手性辅助试剂催化合成手性化     

催化转移氢化制生物质基2,5-呋喃二甲醇研究进展

生物质基2,5-呋喃二甲醇（BHMF）可从廉价易得的糖类出发,经催化转化-选择性氢化制取,并作为一种用途广泛的化工中间体及燃料前体,尤其在改善传统聚酯性能以及合成绿色可降解的生物基聚酯新材料方面具有独特优势。BHMF制取过程中,传统的氢化方式消耗了大量高品位能源氢气,且高压氢气存在安全隐患并导致基础设施投入多。本工作立足于催化转移氢化的优势,综述了甲酸、醇类及其他类型氢供体通过催化转移氢化的方式选择性加氢制取BHMF的研究进展;并针对催化转移氢化过程中不同类型氢供体、催化剂和反应工艺的特点及存在的问题,分析了反应条件、强化手段等对BHMF选择性和收率的影响以及反应体系的优劣。在此基础上,提出了转移氢化制取BHMF新型催化体系的研究方向,并对清洁高效、本质安全BHMF制取工艺的发展进行了展望,为生物质转化中特定催化体系的研发提供科学参考。     

富勒烯材料的催化作用研究进展

介绍了富勒烯材料（富勒烯和富勒烯衍生物）的催化作用研究进展,特别是催化有机反应方面,包括催化氢转移和硅氢化反应、烷烃裂解反应、氢氘互换反应、耦合和烷基转移反应等.这种新材料还可以催化产生单线态氧（1O2）的化学反应、催化非金属固氮反应、催化石墨合成金刚石的反应,同时还可催化高能燃料的燃烧过程,具有广泛的应用前景.     

十二酸的α-氯代反应中的催化剂研究

α-氯代脂肪酸是一类可用于直接从脂肪酸合成α-氨基酸和甜菜碱类两性表面活性剂等精细化学品的重要中间体。本文从烯酮式反应机理出发,以α-氯代十二酸(α-CDA)的合成为模型,对酰氯化试剂(对甲苯磺酰氯、十二酰氯、氯磺酸等)和质子酸催化剂(如H型离子交换树脂、氯磺酸、对甲苯磺酸、醋酸等)进行组合和选择,并与文献报道的特殊添加剂乙酐比较,研究不同催化体系在酸催化合成α-氯代脂肪酸时的催化作用。氯磺酸既有磺酸基团提供强质子酸,又有磺酰氯基团作为酰氯化试剂,因而是催化十二酸的α-氯代反应的适宜催化剂。当w(氯磺酸)∶w(十二酸)=2%,搅拌转速1000r/min,氯气流量40L/h,反应温度为120℃时,反应3h后α-CDA产率达到96.4%。     

生物质转化合成新能源化学品乙酰丙酸酯

生物质是唯一可替代化石资源获取液态燃料和化学品的可再生资源,近年来由生物质转化合成乙酰丙酸酯引起了研究者们越来越广泛的关注。乙酰丙酸酯是一类重要的化学中间体和新能源化学品,具有高的反应特性和广泛的工业应用价值。目前开发的从生物质资源出发转化合成乙酰丙酸酯的潜在合成途径可概括为4种:直接酸催化醇解法、经乙酰丙酸酯化、经5-氯甲基糠醛醇解和经糠醇醇解。本文分别介绍了这4种转化合成途径的化学反应过程及最新研究进展,从反应合成工艺、催化体系、经济可行性等方面评述了各自的特点与发展趋势,并分析了目前工业规模转化生物质合成乙酰丙酸酯仍面临的一些科学难点。最后,对今后该领域的研究前景进行了展望。     

Light‐Driven Enzymatic Decarboxylation of Fatty Acids

The photoenzymatic decarboxylation of fatty acids to alkanes is proposed as an alternative approach for the synthesis of biodiesel. By using a recently discovered photodecarboxylase from Chlorella variabilis NC64A (CvFAP) we demonstrate the irreversible preparation of alkanes from fatty acids and triglycerides. Several fatty acids and their triglycerides are converted by CvFAP in near‐quantitative yield and exclusive selectivity upon illumination with blue light. Very promising turnover numbers of up to 8000 were achieved in this proof‐of‐concept study.     

绿色化学关键技术在精细化工中的应用

绿色化学理念及技术的创新发展,能够更好与精细化工的各环节结合,提升效率、降低消耗、节约成本、增强竞争力,符合我国低碳发展方向,满足行业的可持续发展需求。本文主要介绍近年来绿色化学技术在精细化工领域的发展现状和应用前景,探讨了生物催化/发酵技术、非贵金属或无金属催化技术、微通道反应技术、新能源驱动的化学反应技术、新型高效分离技术、生产过程的人工智能和自动化等绿色化学关键技术在精细化工研制中的应用实例,为推动绿色化学技术的综合利用和可持续发展提供参考和借鉴。     

Fructose dehydration to 5HMF in a green self-catalysed DES composed of N,N-diethylethanolammonium chloride and p-toluenesulfonic acid monohydrate (p-TSA)

Due to the increasing concerns about the availability and accessibility of fossil fuel reserves, and the subsequent effect of using them on climate change, production of green energy has recently become a hot area of interest in the research field. As a renewable energy source, biomass conversion to biofuels has shown a great potential towards green fuel production; particularly fructose conversion to 5-hydroxymethylfurfural (5HMF) as a building block material and source of green fuels and other high value chemicals.Herein, we investigate fructose dehydration to 5-hydroxymethylfurfural (5HMF) as a green fuel precursor, using a green self-catalysed environmentally friendly Deep Eutectic Solvent (DES), composed of inexpensive N,N-diethylethanolammonium chloride as organic salt and p-toluenesulfonic acid monohydrate (p-TSA) as a hydrogen bond donor (HBD) and novel medium for the fructose dehydration reaction.The advantage of using this DES is its ability to act as a solvent and catalyst simultaneously. It has shown to actively catalyse the dehydration reaction of fructose under moderate reaction conditions with a high 5HMF yield of 84.8% at a reaction temperature of 80 °C, reaction time of 1 h, DES mixing ratio of 1:0.5 salt to p-TSA (w/w), and initial fructose ratio of 5.     

复合金属氧化物催化剂用于甘油氧化制丙烯酸的研究进展

随着化石燃料的短缺及其利用所产生的环境问题,可再生生物质资源逐渐成为生产燃料以及化学品的重要来源。近年来,甘油作为生物柴油生产的主要副产物受到了人们的广泛关注,利用其生产高附加值产品以及开发相关的转化技术也成为了国内外学者研究的热点。在诸多转化技术中,甘油选择性氧化制丙烯酸展现出了广阔的发展前景,对该反应尤其是催化剂开展研究具有重要的经济意义和社会意义。文中综述了用于甘油选择性氧化制丙烯酸复合金属氧化物催化剂的研究现状,介绍了当前用于该反应的催化体系类型以及对甘油氧化制丙烯酸催化反应机理的认识,分析并提出了存在的问题以及对未来的展望。     

Advances in direct production of value-added chemicals via syngas conversion

Syngas conversion to fuels and chemicals is one of the most challenging subjects in the field of C1 chemistry. It is considered as an attractive alternative non-petroleum-based production route. The direct synthesis of olefins and alcohols as high value-added chemicals from syngas has drawn particular attention due to its process simplicity, low energy consumption and clean utilization of carbon resource, which conforms to the principles of green carbon science. This review describes the recent advances for the direct production of lower olefins and higher alcohols via syngas conversion. Recent progress in the development of new catalyst systems for enhanced catalytic performance is highlighted. We also give recommendations regarding major challenges for further research in syngas conversion to various chemicals.     

The thermodynamics analysis and experimental validation for complicated systems in CO_2 hydrogenation process

Catalytic conversion of CO_2 into chemicals and fuels is an alternative to alleviate climate change and ocean acidification.The catalytic reduction of CO_2 by H_2 can lead to the formation of various products:carbon monoxide,carboxylic acids,aldehydes,alcohols and hydrocarbons.In this paper,a comprehensive thermodynamics analysis of CO_2 hydrogenation is conducted using the Gibbs free energy minimization method.The results show that CO_2 reduction to CO needs a high temperature and H_2/CO_2 ratio to achieve a high CO_2 conversion.However,synthesis of methanol from CO_2 needs a relatively high pressure and low temperature to minimize the reverse water-gas shift reaction.Direct CO_2 hydrogenation to formic acid or formaldehyde is thermodynamically limited.On the contrary,production of CH_4 from CO_2 hydrogenation is the thermodynamically easiest reaction with nearly 100%CH4 yield at moderate conditions.In addition,complex reactions with more than one product are also calculated in this work.Among the considered carboxylic acids(HCOOH,CH_3COOH and C_2H_5COOH),propionic acid dominates in the product stream(selectivity above 90%).The same trend can also be found in the hydrogenation of CO_2 to aldehydes and alcohols with the major product of propionaldehyde and butanol,respectively.In the process of CO_2 hydrogenation to alkenes,low temperature,high pressure,and high H_2 partial pressure favor the CO_2 conversion.C_4H_6 is the most thermodynamically favorable among all considered alkynes under different temperatures and pressures.The thermodynamic calculations are validated with experimental results,suggesting that the Gibbs free energy minimization method is effective for thermodynamically understanding the reaction network involved in the CO_2 hydrogenation process,which is helpful for the development of high-performance catalysts.     

金团簇电催化二氧化碳还原反应的研究进展

二氧化碳电还原反应(CO₂RR)在改善能源利用方式、 实现可持续碳循环以及生产高附加值液体燃料和化学品等方面具有广阔的应用前景, 近年来受到广泛关注. 有机配体保护的金团簇具有确定的晶体结构, 其不同的尺寸、 配体及组成可以有效调控氧化还原电位, 作为一种独特的模型催化剂, 为探索原子水平的CO₂RR反应机理提供了新机遇. 本文综合评述了纯金团簇和异金属原子掺杂的金团簇催化CO₂RR的研究进展, 包括金团簇的电荷、 尺寸、 配体以及掺杂对CO₂RR性能的影响, 重点讨论了CO₂RR的反应机理, 总结了金团簇在CO₂RR中所面临的挑战, 并展望了金团簇在CO₂RR中未来的研究方向和发展前景.     

Photocatalytic non-oxidative coupling of methane: Recent progress and future

The importance of effectively converting methane to hydrogen and high value-added hydrocarbons chemicals is becoming more significant due to the huge resources of methane and increasing demands for chemicals. However, it is hard to convert methane into more useful hydrocarbons and hydrogen due to the enormous thermodynamic barrier, which often needs high energy and often results in catalyst deactivation and unsatisfactory product selectivity. Recently, a growing number of researches focusing on photocatalytic methane conversion under mild conditions have attracted much attention, demonstrating that photocatalytic non-oxidative coupling of methane (PNOCM) is a prospective and green method for methane conversion under mild conditions. Herein, we provide a review of the recent advance, remaining challenges, and prospects in PNOCM. Moreover, this review provides considerable guidance for rational design of efficient and stable photocatalysts towards PNOCM by theory predictions and experiment results. We hope this review can attract more attention to the important research field of energy conversion.     

钙钛矿材料在固体氧化物燃料电池燃料重整中的应用

固体氧化物燃料电池（solid oxide fuel cell,SOFC）是通过电化学反应将化石燃料（煤、石油和天然气等）、生物质燃料或其它碳氢燃料中的化学能直接转换为电能的发电装置,能量转换效率更高、污染更低,被公认为21世纪高效绿色能源技术. 但直接以碳氢化合物为燃料时,镍基阳极中容易产生积碳,从而失去电化学催化活性. 在阳极外侧进行一次燃料的预重整是一种行之有效的解决办法,其中高效稳定的重整催化剂至关重要. 本文将结合本课题组的研究进展对钙钛矿催化剂在燃料重整中的应用进行概述,并提出自己相应的观点和展望.     

Light‐Driven Kinetic Resolution of α‐Functionalized Carboxylic Acids Enabled by an Engineered Fatty Acid Photodecarboxylase

Chiral α‐functionalized carboxylic acids are valuable precursors for a variety of medicines and natural products. Herein, we described an engineered fatty acid photodecarboxylase (CvFAP)‐catalyzed kinetic resolution of α‐amino acids and α‐hydroxy acids, which provides the unreacted R‐configured substrates with high yields and excellent stereoselectivity (ee up to 99 %). This efficient light‐driven process requires neither NADPH recycling nor prior preparation of esters, which were required in previous biocatalytic approaches. The structure‐guided engineering strategy is based on the scanning of large amino acids at hotspots to narrow the substrate binding tunnel. To the best of our knowledge, this is the first example of asymmetric catalysis by an engineered CvFAP.