Biomass Group, Nanjing Agricultural University, PO Box 68, 40 Dianjiangtai Road, Nanjing 210031

航空燃料合成Lanthanide catalyst for synthesis of jet fuel intermediates

Recently, master student Miss Lu-ping Li supervised by Dr. Xiao Kong and Prof. Zhen Fang published a research article in Molecular Catalysis about the synthesis of jet fuel intermediates.

Jet fuel precursors (4-(2-furyl)-3-buten-2-one (FAc) and 1,5-di-2-furanyl-1,4-pentadien-3-one (F₂Ac)) can be produced from aldol condensation between furfural and acetone over basic catalysts. However, there is still a need to develop efficient alkaline catalysts and understand the role of alkaline sites. In this work, La₂O₂CO₃-Al₂O₃ catalyst was successfully prepared by coprecipitation and the effect of preparation conditions on the properties and catalytic performance was investigated. Experiments showed that La₂O₂CO₃ and La₂O₃ were formed after calcination, and the activity was greatly improved by the introduction of La₂O₂CO₃. At higher coprecipitation pH, rod-shaped La₂O₂CO₃ was formed, exposing basic La³⁺-O^2- sites for good performance in aldol condensation reactions. The catalytic performance of La₂O₂CO₃-Al₂O₃ in aldol condensation of furfural with acetone was also evaluated and compared with that of Al₂O₃, La₂O₃, La₂O₃-Al₂O₃, La(OH)₃/Al₂O₃ and La₂O₂CO₃/Al₂O₃. A total conversion of furfural can be realized with F₂Ac yield of 67.8% at a furfural/acetone ratio of 1/1 and 90 ^oC, with a FAc yield of 25.8% at the same time. The deactivation mechanism of the La₂O₂CO₃-Al₂O₃ catalyst was also studied.

Liquid fuel precursors can be produced by furfural-acetone aldol condensation over La₂O₂CO₃-Al₂O₃ catalyst with C13 yield of 67.8%（通过糠醛和丙酮之间的羟醛缩合在La₂O₂CO₃-Al₂O₃催化剂上制备液体燃料中间体，C13产率为67.8%）

Related results were published in Molecular Catalysis:

Lu-ping Li, Zhen Fang*, Xiao Kong*, Wen-Jie Cong, Molecular Catalysis, 515, 111893 (2021). https://doi.org/10.1016/j.mcat.2021.111893.

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镧系催化剂合成航空燃料中间体

最近，硕士生李路平（女）在方真老师和孔晓博士的指导下，在国际学术期刊Molecular Catalysis（IF5.062，Q2）上发表关于镧系催化剂用于合成航空燃料中间体的研究文章。

通过糠醛和丙酮的羟醛缩合可以在碱性催化剂上获得航空燃料前体呋喃加合物4-（2-呋喃基）-3-丁烯-2-酮（FAc）和1,5-二-2-呋喃基-1,4-戊二烯-3-酮（F₂Ac）。然而，仍然需要开发有效的碱性催化剂并了解碱性位点的作用。本工作采用共沉淀法成功制备了La₂O₂CO₃-Al₂O₃催化剂，并研究了制备条件对其结构和催化性能的影响。实验表明，经煅烧后形成La₂O₂CO₃和La₂O₃，而La₂O₂CO₃极大的提高了催化活性。在较高的共沉淀pH值下可以形成棒状的La₂O₂CO₃，并暴露出更多的La³⁺-O^2-碱性位点，在羟醛缩合反应中表现出良好的性能。之后，在糠醛与丙酮的羟醛缩合实验中评价了La₂O₂CO₃-Al₂O₃的催化性能，并与Al₂O₃、La₂O₃、La₂O₃-Al₂O₃、La(OH)₃/Al₂O₃和La₂O₂CO₃/Al₂O₃的进行了催化性能的比较。在糠醛/丙酮比为1/1和90 ^oC下，糠醛的总转化率为67.8%，同时FAc产率为25.8%。最后研究了La₂O₂CO₃-Al₂O₃催化剂的失活机理。详情可见：

Lu-ping Li, Zhen Fang*, Xiao Kong*, Wen-Jie Cong, Molecular Catalysis, 515, 111893 (2021). https://doi.org/10.1016/j.mcat.2021.111893.

水热胺化Hydrothermal amination of biomass to nitrogenous chemicals

Recently, Profs. Hu Li (Guizhou University) and Zhen Fang, published a review (Critical review, 2021 Green Chemistry Hot Articles) paper in Green Chemistry about hydrothermal amination of biomass to nitrogenous chemicals.

Biomass is the most abundant and low-cost renewable source for the production of value-added nitrogen-containing compounds. However, a large amount of water exists in natural biomass and relevant bio-derivatives, which often need to be removed prior to conducting valorization processes. Direct use of wet biomass and bio-derivatives as feedstocks definitely avoids energy consumption of drying processes, in which water acts as a reactive medium and is friendly to the environment and reaction devices. Hydrothermal amination of wet biomass feedstocks is thus an attractive technical strategy for producing nitrogen-containing compounds. This review summarizes state-of-the-art technologies in hydrothermal amination of natural biomass, bio-polymeric derivatives, and bio-based platform molecules with or without nitrogenous species into organonitrogen chemicals. Efforts are made to shed light on conversion routes and economic/environmental impacts of biomass hydrothermal amination. Challenges and perspectives on the large-scale production of biomass-derived nitrogenous compounds are also put forward.

Conversion routes, processing strategies, state-of-the-art technical advances, challenges and perspectives in hydrothermal amination of N-rich biomass sources and N-free biomass feedstocks to nitrogenous chemicals.（水热胺化富氮和无氮生物质原料为含氮化学品的转化路线、加工策略、最新技术进展、挑战和前景。）.

Related results were published in Green Chemistry:

HG Wu, H Li,* Zhen Fang*, Hydrothermal Amination of Biomass to Nitrogenous Chemicals, Green Chemistry, 23, 6675-6697, (2021) (Critical review, 2021 Green Chemistry Hot Articles)), https://doi.org/10.1039/D1GC02505H

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李虎和方真教授在国际学术期刊Green Chemistry发表学术论文:

水热胺化生物质制备含氮化合物

最近，国际学术期刊Green Chemistry以Critical review形式，发表了生物质水热胺化制备含氮化合物的综述。

生物质是生产高附加值含氮化合物最丰富、成本最低的可再生资源。然而，天然生物质和相关衍生物中存在大量水，通常需要在进行高值化过程之前将其去除。直接使用湿生物质和生物衍生物作为原料避免了干燥过程的能耗，在干燥过程中，水作为反应介质，对环境和反应装置友好。因此，湿生物质原料的水热胺化是生产含氮化合物的一种有吸引力的技术策略。本文综述了将天然生物质、生物聚合物衍生物和含氮或不含氮的生物基平台分子水热胺化为有机氮化学品的最新技术。努力阐明生物质水热胺化的转化路线和经济/环境影响。并对生物质含氮化合物的大规模生产提出了挑战和展望。

详情可见：

Related results were published in Green Chemistry:

HG Wu, H Li,* Zhen Fang*, Hydrothermal Amination of Biomass to Nitrogenous Chemicals, Green Chemistry, 23, 6675-6697, (2021) (Critical review, 2021 Green Chemistry Hot Articles), https://doi.org/10.1039/D1GC02505H

博士答辩Miss Wen-jie Cong successfully defended her doctoral dissertation

Started from 2:30 pm September 1, 2021, Miss Wen-jie Cong supervised by Prof. Zhen Fang, successfully defended her dissertation at B404 Huixian Building, Pukou Campus of Nanjing Agricultural University. The defending committee was composed of Prof. Jian-chun Jiang (Chair) from Institute of Chemical Industry of Forest Products, Chinese Academy of Forestry, Prof. Zhao-ping Zhong from Southeast University as well as Profs Chang-ying Ji, Wei-min Ding and Chun-xia He from Nanjing Agricultural University.

Miss Wen-jie Cong presented her research results for doctoral dissertation in 30 min, the committee members raised relevant questions. Miss Cong studied the production of biodiesel and hydrogen from waste oil with solid bases from spent bleaching clay and metal-organic framework with dissertation entitled “solid bases derived from spent bleaching clay and nickel metal-organic framework for biodiesel and hydrogen production”. Her work realized full utilization of solid waste (spent bleaching clay) for high efficient production of biodiesel with waste oil, and built a green processing for co-production of biodiesel and hydrogen with nickel MOF-based alkali. She co-authored 7 papers and first-authored 2 papers. After discussion, the panel agreed that Miss Cong had successfully completed her research and course requirements on agricultural bio-environment and energy engineering, voted by secret ballot and decided to confer Doctor of Philosophy in Engineering to Miss Cong subjected to the approval by the Academic Degrees Committees of the college and university.

Congratulations!

She published 2 first-authored papers:

1. Cong W-J, Wang Y-T, Li H, Fang Z*, et al. Direct production of biodiesel from waste oils with a strong solid base from alkalized industrial clay ash. Applied Energy (IF= 9.746, Q1). 2020;264:114735.
2. Cong W-J, Nanda S, Li H, Fang Z*, et al. Metal–organic framework-based functional catalytic materials for biodiesel production: a review. Green Chemistry (IF= 10.182, Q1). 2021;23:2595-2618.

丛文杰同学顺利通过博士论文答辩

2021年9月1日下午2:30 pm，天空晴朗，万里无云，南京农业大学生物能源组2017级博士研究生丛文杰（女）同学（导师方真老师）毕业答辩会在南京农业大学浦口校区汇贤楼B404举行。中国工程院院士、中国林业科学研究院林产化工研究所研究员蒋剑春担任答辩评审委员会主席，东南大学能源与环境学院二级教授仲兆平，南京农业大学的姬长英教授，何春霞教授和丁为民教授共五位专家担任评审委员。

答辩会上，丛文杰同学对其在校期间的学术论文进行汇报，同时答辩委员会主席和各位评委提出了相关问题。根据丛文杰同学的问题回答以及学位论文的评阅，评委会经过评审决议，一致认为丛文杰同学顺利完成了农业生物环境与能源方面的研究和学习要求。丛文杰同学在毕业论文《利用废白土和镍基金属有机框架材料制备催化剂生产生物柴油和氢气的研究》中以废白土和镍基金属有机框架为基础合成了一系列固体碱，用以催化废弃油脂制备生物柴油和氢气，实现了固废废白土的全利用，建立了镍基MOF固体碱催化废弃油脂联产生物柴油和氢气的绿色加工工艺。丛文杰同学在校期间工作认真，以第一作者身份共发表学术论文2篇。经评委会无记名投票表决，一致同意通过博士学位论文答辩，建议授予工学博士学位。

祝贺丛文杰同学！