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

One-step production of biodiesel from Jatropha oils with high acid value by magnetic acid-base amphoteric nanoparticles

Alkaline oxides concerted with acidic -COOFe structure, for the one-pot esterification and transesterification of high AV Jatropha oils without saponification. Zn₈@Fe-C₄₀₀ achieved nearly 100% Jatropha biodiesel yield at 160 ^oC within 4 h, and was used for at least 10 cycles with biodiesel yield of >94.3% at AV of 6.3 mg KOH/g.（磁性酸碱两性催化剂通过两步法合成：羧甲基纤维素钠和Fe³⁺螯合生成的酸性结构-COOFe将碱性氧化物包埋在催化剂的内部，煅烧步骤将部分的-COOFe结构还原成Fe₃O₄，为催化剂引入磁性。合成的Zn₈@Fe-C₄₀₀可以催化酸值为6.3 mg KOH/g的小桐子油获得100.0%的生物柴油产率，循环使用10次小桐子生物柴油的产率仍然大于94.3%）

Recently, Miss Yi-Tong Wang (PhD student from Xishuangbanna Tropical Botanical Garden, Chinese Academy of Sciences) supervised by Prof. Zhen FANG has synthesized magnetic acid-base amphoteric nanoparticles. Alkaline oxides (ZnFe₂O₄, ferrihydrite, zincite, maghemite and magnetite) concerted with acidic -COOFe structure, benefited the one-pot esterification and transesterification of Jatropha oils with high acid value to produce biodiesel without additional pretreatment. The strong magnetism of catalyst helped catalyst separation for recycle in biodiesel production. Jatropha biodiesel yield of 100% at 160 ^oC within 4 h, with methanol/oil molar ratio of 40/1 and catalyst dosage of 7 wt% was achieved, while the catalyst can be cycled for at least 10 times with biodiesel yield > 94.3% at acid value of 6.3 mg KOH/g. No obvious saponification was observed during the reactions and storage.

The results were published:

YT Wang, Zhen Fang*, XX Yang, YT Yang, J Luo, K Xu, GR Bao. One-step production of biodiesel from Jatropha oils with high acid value at low temperature by magnetic acid-base amphoteric nanoparticles, Chemical Engineering Journal, 348, 929-939 (2018).

https://www.sciencedirect.com/science/article/pii/S1385894718308283

———————————————————————-

磁性酸碱两性纳米粒子催化高酸值的小桐子油在低温下一步法制备生物柴油

最近，王一同（女）同学（中国科学院西双版纳热带植物园博士研究生）在方老师的指导下，通过两步法合成了磁性酸碱两性催化剂，并应用于小桐子生物柴油的制备。

该研究通过简易的两步法合成高活性的磁性酸碱两性纳米颗粒，用于高酸值不可食用的小桐子油联合酯化和转酯化反应，一步法制备小桐子生物柴油。在低温160 ^oC反应4 h可以获得100.0%的生物柴油产率，通过简单的磁性分离可以循环使用10次 (产率仍然大于94.3%)，展现了非常出色的工业应用能力。通过半年的常温储存，合成的小桐子生物柴油未发生皂化。

结果发表在Chemical Engineering Journal: Yi-Tong Wang, Zhen Fang*, Xing-Xia Yang, Ya-Ting Yang, Jia Luo, Kun Xu, Gui-Rong Bao. One-step production of biodiesel from Jatropha oils with high acid value at low temperature by magnetic acid-base amphoteric nanoparticles, Chemical Engineering Journal (IF6.7), 348, 929-939 (2018)。

Efficient catalytic transfer hydrogenation of biomass-based furfural to furfuryl alcohol with recycable Hf-phenylphosphonate nanohybrids

Recently, Dr. Hu Li supervised by Profs. Zhen FANG and RL Smith has synthesized an acid-base bifunctional nanohybrid phenylphosphonic acid (PhP) – hafnium (1:1.5) through assembly of PhP with HfCl4 for catalytic transfer hydrogenation of furfural (FUR) to furfuryl alcohol (FFA) using 2-propanol as both reaction solvent and hydrogen donor source. An FFA yield of 97.6% with formation rate of 9760 μmol g-1 h-1 at 99.2% FUR conversion was obtained with the reaction system at 120 °C for 2 h reaction time. Activation energy (Ea) was estimated to be 60.8 kJ/mol with respect to FUR concentration, which is comparable with or even lower than Ea values attained over metal catalysts. The pronounced catalytic activity of PhP-Hf (1:1.5) is attributed to its moderate acidity and relatively strong basicity. The PhP-Hf (1:1.5) catalyst was demonstrated to maintain its activity for five consecutive reuse cycles.

Related results were published:
H Li, Y Li, Zhen Fang*, RL Smith Jr., Efficient Catalytic Transfer Hydrogenation of Biomass-Based Furfural to Furfuryl Alcohol with Recycable Hf-Phenylphosphonate Nanohybrids, Catalysis Today, https://doi.org/10.1016/j.cattod.2018.04.056,  2018.

Mesoporous PhP-Hf(1:1.5) nanohybrid material bearing acidic and basic sites promotes catalytic transfer hydrogenation of furfural to furfuryl alcohol with 97.6% yields with 2-propanol as solvent and hydrogen donor source at 120 °C in 2 h reaction time.【介孔PhP-Hf（苯磷酸-铪）纳米MOF(金属有机框架材料)复合物同时具有酸性和碱性位点，促进了糠醛加氢催化转化为糠醇，120℃反应两小时，使用异丙醇作为反应溶剂和氢供体时，糠醇产率为97.6%。】

——————————————–

李虎博士在国际学术期刊Catalysis Today发表学术论文

可回收重复利用的苯基-铪纳米MOF复合物高效加氢催化糠醛转化为糠醇

最近，国际学术期刊Catalysis Today（影响因子4.7, Q1，第一署名单位为南京农业大学，第一作者为博士后李虎，通讯作者为方真教授），发表了生物燃料最新研究成果。

该研究团队通过组装苯磷酸（PhP）和四氯化铪而制成一种酸碱双官能团纳米杂化苯磷酸MOF（金属有机框架）催化剂，使用异丙醇作为反应溶剂和氢供体，用于加氢催化糠醛（FUR）转化为糠醇（FFA）。在120℃反应2小时的条件下，FUR的转化率为99.2%，FFA产率为97.6%，生成速率为9760μmol/gh。FUR转化的活化能（Ea）估计为60.8KJ/mol，与金属催化剂相比，其具有可与之媲美甚至更低的活化能。PhP-Hf（1:1.5; 苯磷酸-铪纳米MOF）显著的催化活性得益于其温和的酸性和相对强的碱性。PhP-Hf（1:1.5）催化剂可连续重复使用5次。

详情可见：
H Li, Y Li, Zhen Fang*, RL Smith Jr., Efficient Catalytic Transfer Hydrogenation of Biomass-Based Furfural to Furfuryl Alcohol with Recycable Hf-Phenylphosphonate Nanohybrids, Catalysis Today, https://doi.org/10.1016/j.cattod.2018.04.056,  2018.

These 3 books below are highly downloaded (以下3本由方老师等编著的专著为Springer高下载图书）:

1.Zhen Fang*, R. L. Smith, Jr., X. Qi (Editors), Production of Platform Chemicals from Sustainable Resources, Springer Book Series – Biofuels and Biorefineries, Springer-Verlag, Heidelberg Berlin, hardcover, 14 Chapters, ISBN 978-981-10-4171-6, 500 pages, 2017. (Among the top 25% most downloaded eBooks in 2017; 7k chapter downloads, Feb. 2018).

2.Zhen Fang*, R. L. Smith, Jr.(Editors), Production of Biofuels and Chemicals from Lignin, Springer Book Series – Biofuels and Biorefineries, Springer-Verlag, Heidelberg Berlin, hardcover, ISBN 978-981-10-1964-7, 2016. (Among the top 50% most downloaded eBooks in 2016; 12k chapter downloads, Feb. 2018).

3.Zhen Fang (Editor), Pretreatment Techniques for Biofuels and Biorefineries, Springer-Verlag, Berlin Heidelberg,  ISBN 978-3-642-32734-6, hardcover, 476 pages, 2013. (Among the top 25% most downloaded eBooks in 2013; 36k chapter downloads, Feb. 2018).

Prof. Zhen Fang Won “2018 Most Cited Chinese Researchers” in Energy by Elsevier, He also won the award in 2014, 2015, 2016 and 2017 [China ranks the first in total citation and citation of the influential research papers (Top10%) in engineering, 2013-2015].

方老师获爱思唯尔能源领域“2017年中国高被引学者”，他2014，2015和2016也进入“中国高被引学者”榜单。

Cellulase immobilized on mesoporous biochar synthesized by ionothermal carbonization of cellulose

Recently, Mr. Chang-hui Zhu (a PhD student from Guangzhou Institute of Energy Conversion, Chinese Academy of Sciences) supervised by Prof. Zhen FANG synthesized biochar via ionothermal carbonization and pyrolysis, and it was subsequent used to adsorb free cellulase physically for enzymatic hydrolysis.

In order to recover free cellulase, a mesoporous biochar was synthesized from cellulose by ionic thermal and pyrolysis methods for the adsorption of free cellulase. Kinetics analysis showed that the affinity of the immobilized cellulase to carboxymethyl cellulose was better than that of free cellulase. The immobilized cellulase at different pH and temperatures was more stable than those of free cellulase. It was used to hydrolyze pretreated cellulose with [Bmim]Cl with total reducing sugar yield of 99.9%. The immobilized cellulase activity can still retain 74.8% after 5 cycles. Lastly, the immobilized cellulase can improve sugar production from the pretreated corncob for potential practical applications.

Results were published in Cellulose: Chang-hui Zhu, Zhen Fang*, Tong-chao Su, and Qi-ying Liu, Cellulase Immobilized on Mesoporous Biochar Synthesized by Ionthermal Carbonization of Cellulose, Cellulose,  25(4), 2473-2485 (2018).

Mesoporous biochar was synthesized by ionothermal carbonization, and pyrolysis for the immobilization of cellulase to hydrolyze ionic liquid pretreated cellulose and corncob. During pretreated cellulose hydrolysis, total reducing sugar yield of 92.2 % was achieved with 74.8% enzyme activity remained after 5 cycles.（通过离子热和热解方法合成了介孔生物炭，该生物炭用于固定纤维素酶，固定化纤维素酶用于水解离子液体预处理的纤维素以及玉米芯。其中在预处理纤维素水解，总还原糖产率可达92.2%，固定化酶循环使用5次后，活性仍保留74.8%）。

最近，朱长辉同学（中国科学院广州能源研究所博士研究生）在方老师的指导下，通过离子热和热解法由纤维素合成生物炭以及后续物理吸附制备固定化纤维素酶，并将其应用于离子液体预处理纤维素/生物质的水解。
为了回收游离纤维素酶，通过离子热和热解两步法由纤维素合成一种介孔生物炭以用于吸附游离纤维素酶。动力学分析表明，固定化纤维素酶对羧甲基纤维素的亲和力优于游离纤维素酶。 不同pH和温度下的固定化纤维素酶比游离纤维素酶更稳定。该固定化酶具有较好的催化预处理纤维素水解的能力，总还原糖产率可达92.2%，固定化酶循环使用5次后，活性仍保留74.8%。最后，该固定化酶结合离子液体预处理技术，对水解生物质纤维素表现出一定的应用前景。
结果发表在Cellulose: Chang-hui Zhu, Zhen Fang*, Tong-chao Su, and Qi-ying Liu, Cellulase Immobilized on Mesoporous Biochar Synthesized by Ionthermal Carbonization of Cellulose, Cellulose 25(4), 2473-2485 (2018).