Biomass Group, Nanjing Agricultural University

Springer book “Production of Platform Chemicals from Sustainable Resources” was published

Recently, Springer has published a book entitled “Production of Platform Chemicals from Sustainable Resources” edited by Profs. Zhen Fang, Richard L. Smith Jr. and Xinhua Qi, Springer, Hardcover ISBN978-981-10-4171-6, 475 pages, 2017 (http://www.springer.com/cn/book/9789811041716).

With increasing concerns on environmental pollution and global warming that resulted from traditional fossil resource applications, much progress has been made in the past few years in developing catalytic reaction systems and chemistries for the conversion of various biomass resources into platform chemicals. This text provides state-of-the-art reviews, current research, prospects, and challenges of production of platform chemicals such as C6 sugars, 5-hydroxymethylfurfural, furfural, γ-valerolactone, xylitol, 2,5-furandicarboxylic acid, levulinic acid, ethanol, and others from sustainable biomass resources with processes that include heterogeneous catalysis, ionic liquid, hydrothermal/solvothermal, electrochemical, and fermentation methods. Reaction mechanism, methods for product separation and purification, and process integration are introduced. The application of these chemicals and their derivatives for synthesizing commodity chemicals via various routes is also covered.

This book contains 14 chapters contributed by leading experts in the field. The text is arranged into five key areas:

Part I: Production of Sugars (Chap. 1)

Part II: Production of Aldehydes (Chaps. 2, 3, and 4)

Part III: Production of Acids (Chaps. 5, 6, 7, and 8)

Part IV: Production of Alcohols (Chaps. 9, 10, 11 and 12)

Part V: Production of Lactones and Amino Acids (Chaps. 13 and 14)

The text should be of interest to students, researchers, academicians, and industrialists who are working in the areas of renewable energy, environmental and chemical sciences, engineering, resource development, biomass processing, sustainability, materials, biofuels, and chemical industries.

This book is the seventh book of the Springer series entitled, “Biofuels and Biorefineries” (Prof. Zhen Fang is serving as Editor-in-Chief), and the fourteenth English book edited/authored by Prof. Zhen Fang since 2009.

Biofuels and Biorefineries：

http://www.springer.com/series/11687?detailsPage=titles

斯普林格新书《可持续资源生产平台化学品》出版

由方真老师，日本东北大学Richard L. Smith Jr.教授和农业部环境保护科研监测所漆新华教授主编的新书Production of Platform Chemicals from Sustainable Resources》，最近由斯普林格公司出版发行。（精装，475页， ISBN 978-981-10-4171-6, 2017）(http://www.springer.com/cn/book/9789811041716)。

由于传统化石资源大量应用, 人们对环境污染和全球变暖日益关注。在过去的几年中，利用催化反应系统和化学、生物方法，将各种生物质资源转化为平台化学品方面取得了很大的进展。

本书回顾了, 最新研究、前景和生产平台化学品的挑战。这些平台化学品包括C6糖类、5-羟甲基糠醛、糠醛、伽马-戊内酯、木糖醇、 2,5-呋喃二甲酸、乙酰丙酸、乙醇和其他来自可持续生物质资源合成的化学品。合成的方法和过程, 包括非均相催化、离子液体、水热/溶剂热、电化学和发酵方法等。本书还介绍了反应机理、产物分离、纯化方法和工艺集成。

最后，本书涵盖了这些化学品及其衍生物合成为商品化学品的各种途径。

本书包含14章，由来自世界各地该领域的顶尖专家撰写，每章均被同行评审和编辑以提高文本的质量、研究范围和覆盖的主题。该书包括五个关键领域：

第一部分：生产糖类（第1章）

第二部分：生产醛类（第2-4章）

第三部分：产酸类（第5-8章）

第四部分：生产醇类（第9-12章）

第五部分：内酯和氨基酸的生产（第13和章）

本书在可再生能源、环境与化学科学、工程、资源开发、生物质加工、可持续性、材料、生物燃料和化学工业等领域提供了全面的信息。它为生物化学和能源领域的学生，研究人员，学者和实业家提供了宝贵的学术资源。

该书是斯普林格系列丛书“生物燃料和生物炼制- Biofuels and Biorefineries”（方真老师担任该丛书总编辑）出版的第七本专著，也是方真老师自2009年以来，编著出版的第十四部英语专著

生物燃料和生物炼制丛书：

http://www.springer.com/series/11687?detailsPage=titles。

方真老师2007年初全职回国后， 自2009以来出版的十五部英文专著：

Springer Book Series – Biofuels and Biorefineries: Titles

1.Production of Biofuels and Chemicals with Ionic Liquids, 2013, edited by Zhen Fang, R. L. Smith, Jr., X. Qi 

2.Near-critical and Supercritical Water and Their Applications for Biorefineries, 2014, edited by Zhen Fang, C Xu

Prof. Zhen FANG was invited to the editorial board of “The Journal of Supercritical Fluids”

Recently, Prof. Zhen FANG joined the editorial board of The Journal of Supercritical Fluids as invited by Editor-in-Chief Prof. Erdogan Kiran, Publishers Dr. Angela Welch and Mr. Ian Salusbury. Initially the appointment will be for a period of 4 years. As an editorial board member, Prof. Fang will help maintain and improve the journal standards by monitoring the editorial policy of the journal in terms of scope and the level and quality of papers published.
The Journal of Supercritical Fluids (Impact factor 2.99, Elsevier, https://www.journals.elsevier.com/the-journal-of-supercritical-fluids/) is an international journal devoted to the fundamental and applied aspects of supercritical fluids and processes. Its aim is to provide a focused platform for academic and industrial researchers to report their findings and to have ready access to the advances in this rapidly growing field. Its coverage is multidisciplinary and includes both basic and applied topics.

In addition, Prof. Fang is also serving as:
1.Editor-in-Chief, Springer Book Series – Biofuels and Biorefineries
（http://www.springer.com/series/11687?detailsPage=titles）
2.Associate Editor, Biotechnology for Biofuels (IF 5.3)（http://www.biotechnologyforbiofuels.com/about/edboard）
Editorial (advisory) board members,
3.Biofuels, Bioproducts and Biorefining -Biofpr (IF 3.69), （http://onlinelibrary.wiley.com/journal/10.1002/(ISSN)1932-1031/homepage/EditorialBoard.html）
4.Energy, Sustainability and Society-a Springer open journal (http://www.energsustainsoc.com/about/edboard)
5.Energy and Policy Research (Taylor & Francis)(http://www.tandfonline.com/toc/uetp21/current)

方真老师应邀担任《The Journal of Supercritical Fluids》编委

最近,  应主编 Erdogan Kiran教授, 出版商Angela Welch博士和 Ian Salusbury先生邀请，方真老师担任《The Journal of Supercritical Fluids》【《超临界流体学报》】编委。最初的任命将为期4年。作为编辑委员会成员, 方老师将负责监测刊物的编辑政策，发表论文的范围、水平和质量, 帮助维护和改进期刊标准。《The Journal of Supercritical Fluids》 (影响因子 2.99, 化工Q1区，https://www.journals.elsevier.com/the-journal-of-supercritical-fluids/) ，是爱思唯尔（ELSEVIER）主办的国际期刊, 专门涉及超临界流体和过程的基本原理和应用。其目的是为学术和工业界研究人员提供一个重点的平台, 报告他们的研究结果, 并准备好进入这一迅速发展的领域的进展。它的覆盖面是多学科的并且包括基础的和应用的专题。

此外, 方老师还担任其他国际著名学术期刊（四大巨头：Springer，ELSEVIER, WILEY和Taylor&Francis Group）出版社所属的丛书和期刊的总编辑和编委:
1.总编辑, 斯普林格系列丛书-生物燃料和生物炼制 Springer Book Series – Biofuels and Biorefinerie（http://www.springer.com/series/11687?detailsPage=titles）
2.副主编，生物燃料技术 Biotechnology for Biofuels (影响因子： 5.2)（http://www.biotechnologyforbiofuels.com/about/edboard, Springer)
3.顾问编委, 生物燃料, 生物制品和生物炼制 Biofuels, Bioproducts and Biorefining -Biofpr (影响因子： 3.69)（http://onlinelibrary.wiley.com/journal/10.1002/(ISSN)1932-1031/homepage/EditorialBoard.html, Wiley)
4.顾问编委, 能源、可持续性与社会-斯普林格开放期刊, Energy, Sustainability and Society, a Springer open Journal (http://www.energsustainsoc.com/about/edboard)
5.编委, 能源和政策研究 (泰勒和弗朗西斯) Energy and Policy Research (http://www.tandfonline.com/toc/uetp21/current, Taylor & Francis)

Hydrophobic Pd nanocatalysts for one-pot and high-yield production of liquid furanic biofuels at low temperatures

Efficient production of furanic/aromatic hydrocarbons (>95% yields) from biomass derivatives is achieved via a single-step process under mild conditions (25-130 ºC) by using readily available polymethylhydrosiloxane as liquid H-donor over hydrophonic Pd nanoparticles on MOFs.【以聚甲基氢硅氧烷为氢源，在低温条件下 (25-130 ºC)，利用疏水纳米钯Pd催化糖类（羰基和羟基化物），一锅高效(> 95% 产量)合成呋喃液体燃料】

 Recently, Dr. Hu Li supervised by Prof. Zhen FANG has developed a single-step catalytic process for direct conversion of various saccharides to produce furanic biofuels such as 2,5-dimethylfuran and 2-methylfuran with high yields (> 95%) at 110-130 ºC. The negatively charged hydride (H-) of readily available polymethylhydrosiloxane (PMHS) acting as green H-donor over hydrophobic Pd nanoparticles did not obstruct upstream reactions (e.g., hydrolysis, isomerization and dehydration) for the in situ formation of furanic aldehydes/alcohols from sugars, and could selectively facilitate the subsequent hydrodeoxygenation of carbonyl and hydroxyl groups other than the furanic ring in one pot, as clarified by deuterium-labeling study. Importantly, the unreduced Pd(II) catalysts also exhibited comparable performance in the selective hydrodeoxygenation reaction. Moreover, the catalytic strategy was extended to various carboxides for quantitative production of corresponding furanic/aromatic hydrocarbons at room temperature that were more pronounced than previously reported results, and the optimal Pd/MIL-53(Al) coated with polydimethylsiloxane (Pd/MIL-53(Al)-P) was highly stable with little deactivation and Pd leaching for at least five consecutive cycles.
Related results were published:
1.H Li, W Zhao, Zhen Fang*, Hydrophobic Pd Nanocatalysts for One-Pot and High-Yield Production of Liquid Furanic Biofuels at Low Temperatures, Applied Catalysis B: Environmental, 215, 18–27 (2017).
2.H Li, W Zhao, A Riisager, S Saravanamurugan*, Z Wang, Zhen Fang*, S Yang*, Pd-catalyzed in-situ domino process for mild and quantitative production of 2,5-dimethylfuran directly from carbohydrates,  Green Chemistry, 19, 2101–2106 (2017).
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高效低温从糖和羰基化物一步直接合成呋喃液体燃料

最近，国际学术期刊Applied Catalysis B: Environmental（影响因子9.4，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）及Green Chemistry 【影响因子9.2，第一作者为李虎博士，通讯作者为杨松教授（贵州大学），Saravanamurugan博士（印度）和方真教授】，发表了生物燃料最新研究成果。
该研究团队开发了一个单步催化过程, 以聚甲基氢硅氧烷polymethylhydrosiloxane (PMHS)为氢源，在低温条件下 (25-130 ºC)，利用疏水纳米钯（Pd）催化糖类（羰基和羟基化物），单步高效(> 95% 产量)合成呋喃液体燃料。
他们发现PMHS（带负电荷的高分子氢化物），作为绿色氢源，以纳米钯为催化剂，在原位加氢糖类合成呋喃醛/醇时，不会阻碍其上游的反应 (例如, 水解, 异构化和脱水)。通过同位素氘标记研究证明，该反应系统可以一锅法，有选择地促进羰基和羟基化物的加氢脱氧。更重要的是, 未还原的Pd(II)纳米催化剂在选择性加氢脱氧反应中也表现出相当的性能。此外, 当该催化反应系统扩展到利用各种羰基化物时, 可在室温下，定量生产相应的呋喃/芳烃。用聚二甲基硅氧烷涂层的疏水Pd催化剂具有极高的稳定性, 且在至少连续五个周期中几乎没有失活和Pd浸出。

详情可见：
1.H Li, W Zhao, Zhen Fang*, Hydrophobic Pd Nanocatalysts for One-Pot and High-Yield Production of Liquid Furanic Biofuels at Low Temperatures, Applied Catalysis B: Environmental, 215, 18–27 (2017).
2.H Li, W Zhao, A Riisager, S Saravanamurugan*, Z Wang, Zhen Fang*, S Yang*, Pd-catalyzed in-situ domino process for mild and quantitative production of 2,5-dimethylfuran directly from carbohydrates,  Green Chemistry, 19, 2101–2106 (2017).

Biodiesel production from high acid value oils with a highly active and stable bifunctional magnetic acid

Carbonaceous bifunctional magnetic solid acid catalyst with high acid content was synthesized by four-step method. It efficiently catalyzed the esterification of oleic acid, transesterification of soybean oil and pretreatment of Jatropha oil with easy separation for 10 cycles. （双功能磁性固体酸催化剂通过四步法合成和活化，用于酯化油酸，转酯化豆油和预处理小桐子油制备生物柴油，只需简单的磁性分离步骤可循环使用10次）。

Recently, Miss Yi-Tong Wang (PhD student from Xishuangbanna Tropical Botanical Garden, Chinese Academy of Sciences) supervised by Prof. Zhen FANG has synthesized carbonaceous bifunctional magnetic solid acid catalyst with both Brønsted and Lewis sites to efficiently catalyze the esterification of oleic acid with 97% biodiesel yield, transesterification of mixed soybean oil with high acid value (AV) with 95% biodiesel yield and pretreat Jatropha oil with AV reduced from 17.2 to 0.7 mg KOH/g. Biodiesel yield > 90% at 90 oC for 4 h reaction time was obtained for ten cycles by easy magnetic separation which showed potential practical applications in the field of green production of biodiesel.
The results were published:
YT Wang, Zhen Fang*, XX Yang, Biodiesel Production from High Acid Value Oils with a Highly Active and Stable Bifunctional Magnetic Acid, Applied Energy, 204, 702–714(2017).

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高活性和稳定性的磁性固体酸催化剂催化高酸值的油脂制备生物柴油

最近，王一同同学（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，通过四步法合成了双功能磁性固体酸催化剂，并应用于生物柴油制备。

为了降低生物柴油制备工艺的能耗，通过四步法合成一种同时具有路易斯酸位点和布朗斯特酸位点的磁性固体酸。合成的磁性固体酸具有优秀的催化能力，可以酯化油酸获得97%生物柴油产率，转酯化高酸值的豆油获得95%生物柴油产率，预处理酸值为17.2 mg KOH/g的小桐子原油使其酸值降为0.7 mg KOH/g。合成的双功能磁性固体酸拥有较好的稳定性，通过简单的磁性分离可以循环使用10次，展示了出色的商业化应用前景。

结果发表在Applied energy: Yi-Tong Wang, Zhen Fang*, Xing-Xia Yang, Biodiesel Production from High Acid Value Oils with a Highly Active and Stable Bifunctional Magnetic Acid, Applied Energy, 204, 702–714(2017).

One-Pot Hydrolysis of cellulose and hemicellulose in Lignocellulosic Biomass Pretreated by NaOH-Freeze

Biomass wastes were NaOH-freeze pretreated for one-pot hydrolysis with yields increased by >214% for cellulose, >59% for hemicellulose, respectively. （对生物质废弃物进行一锅法水解，NaOH 冷冻预处理后，纤维素水解率增加>214%，半纤维素水解率增加>59%。）

  Recently, Miss Tongchao Su (PhD student from China University of Science and Technology) supervised by Prof. Zhen FANG hydrolyzed cellulose and hemicellulose in lignocelluloses in one-pot. In their work, in order to achieve one-pot hydrolysis of cellulose and hemicellulose in lignocellulosic biomass, freeze pretreatment with 0−5 wt % NaOH (3 wt% was chosen as the best concentration) and subsequent microwave-assisted dilute sulfuric acid hydrolysis were applied to tropical plant wastes. Single factor optimization of hydrolysis of the pretreated bagasse was studied, and the best conditions (140 °C, 30 s, substrate/solvent ratio of 1/60 and 0.4 M H2SO4) were further applied to Jatropha and Plukenetia hulls. Under the best conditions, yields of sugars from cellulose (glucose) and hemicellulose (xylose, mannose, and arabinose) in the pretreated bagasse were 84.0% and 92.7%, enhanced by 273.4% and 59.3% as compared with untreated sample, respectively. For the pretreated Jatropha and Plukenetia hulls, yields of glucose and hemicellulose sugars were 85.7% and 93.3% (increased by 225.9% and 75.4%),  and 85.0% and 92.9% (increased by 214.8% and 81.4%), respectively.
The results were published:
TC Su, Zhen Fang*, One-pot microwave-assisted hydrolysis of cellulose and hemicellulose in selected tropical plant wastes by NaOH-freeze pretreatment, ACS Sustainable Chemistry & Engineering, 5(6), 5166–5174 (2017).

一锅法水解 经NaOH 冷冻预处理后的生物质中纤维素和半纤维素

  最近，苏同超同学（中国科学技术大学生命学院博士研究生）在方老师的指导下，对木质纤维素中的纤维素和半纤维素进行了一锅水解的研究。
为了实现木质纤维素生物质中的纤维素和半纤维素的同时水解，首先对生物质用0−5 wt% NaOH（3wt%被选为最佳浓度）冷冻预处理，随后进行微波稀酸水解。
对预处理后的甘蔗渣水解条件的优化进行了单因素实验研究，并利用所得的最佳条件（140 °C，30秒，生物质/溶剂比为1／60和0.4 M H2SO4）进一步用于小桐子和星油藤壳的水解。在最佳条件下，和未经处理的样品相比，预处理后的甘蔗渣纤维素糖产量（葡萄糖）和半纤维素（木糖、甘露糖、阿拉伯糖）糖产量，分别为84%和92.7%，提高了273.4%和59.3%。对预处理后的小桐子和星油藤壳，产生葡萄糖和半纤维素糖分别为85.7%和93.3%（分别增加225.9%、75.4%），85%和92.9%（分别增加了214.8%和81.4%）。
结果发表在ACS Sustainable Chemistry & Engineering: TC Su, Zhen Fang*, One-pot microwave-assisted hydrolysis of cellulose and hemicellulose in selected tropical plant wastes by NaOH-freeze pretreatment, ACS Sustainable Chemistry & Engineering, 5(6), 5166–5174 (2017).

方真教授会见加拿大约克大学JA Kozinski院士

方真教授访问加拿大约克大学和麦基尔大学

应加拿大约克大学JA Kozinski教授（加拿大工程院院士）邀请，方真教授2017年6月14-21日对加拿大进行了访问。他参观了约克大学工学院机械系和土木工程系，访问了约克大学能源实验室（多伦多）并讨论双方合作研究和共同申请项目等问题。

同时，方真教授还顺访了位于蒙特利尔市的麦基尔大学，会见了化学系Ian Butler教授，材料工程系Roderick I. L. GUTHRIE教授（加拿大皇家科学院院士）和土木工程系的Yixin Shao教授, 探讨进一步合作问题。另外，方真教授参观了化学系CJ Li教授（加拿大皇家科学院院士，Green Chem副主编）实验室，对他们在绿色化学方面的成果和研究产生了浓厚的兴趣。

Prof. Zhen Fang visited York and McGill in Canada

From June 14 to 21, 2017, Prof. Zhen Fang visited York and McGill in Canada. At York, he met Prof. Kozinski (The Founding Engineering Dean) and toured the Departments of Mechanical and Civil engineering, visited the York University Energy Laboratory and discussed issues such as collaborative research and joint application for projects.

Later, Prof. Fang visited McGill University in Montreal, where he met Profs. Ian Butler (Chemistry Department), Roderick I. L. Guthrie (Materials Engineering Department) and Yixin Shao (Civil Engineering Department) to explore further cooperation. In addition, Prof. Fang visited Prof CJ Li’s Lab (Prof. Li is associate editor of Green Chem) in Chemistry Department, and found a strong interest in the achievements and research in the field of green and sustainable chemistry made at McGill.

李兴康顺利通过2017年博士学位论文答辩

2017年5月22日，由昆明理工大学、云南师范大学等5位专家组成的答辩委员会听取了博士毕业生李兴康的论文<<有机溶剂预处理甘蔗渣及酶水解的研究>>报告和答辩。经答辩委员会讨论和无记名投票表决，一致同意李兴康同学通过学位论文答辩，建议按有关规定授予理学博士学位。在此毕业之际，向李兴康同学表示祝贺。

英国爱丁堡大学郑莹教授一行访问我院

Synthesis of Magnetic Carbonaceous Solid Acid and Base from Jatropha Hulls for the Production of Jatropha Biodiesel

Jatropha seeds were extracted oil for biodiesel production and the hulls were carbonized to load active sites as magnetic carbonaceous solid acid and base catalysts. Crude Jatropha oil was esterified to decrease its acid value to 1.3 from 17.2 mg KOH/g by the solid acid, and subsequently transesterified to biodiesel (96.7% yield) catalyzed by the solid base. After 3 cycles and magnetically separated, the deactivated base was catalyzed the hydrothermal gasification of biodiesel by-product (crude glycerol) with gasification rate of 81% and 82% H₂ purity.

    Recently, biomass group synthesized magnetic carbonaceous solid acid (C-SO₃H@Fe/JHC) and base (Na₂SiO₃@Ni/JRC) catalysts by loading active groups on the carbonaceous supporters derived from Jatropha-hull hydrolysate and hydrolysis residue. Characterization of their morphology, magnetic saturation, functional groups and total acid/base contents were performed by various techniques. Additional acidic functional groups that formed with Jatropha-hull hydrolysate contributed to the high acidity of C-SO₃H@Fe/JHC catalyst for the pretreatment (esterification) of crude Jatropha oil with high acid values (AV). The AV of esterified Jatropha oil dropped down from 17.2 to 1.3 mg KOH/g, achieving a high biodiesel yield of 96.7% after subsequent transesterification reaction with Na₂SiO₃@Ni/JRC base that was cycled at least 3 times with little loss of catalysis activity. Both solid acid and base catalysts were easily recovered by magnetic force with average recovery yields of 90.3 wt% and 86.7%, respectively. After washed by ethanol, the catalysts were cycled for 10 times. The AV of esterified oil and biodiesel yield using the recycled catalysts remained below 2.0 mg KOH/g and above 85%, respectively. The existence of catalyst ions and residual methanol contributed to high H₂ yield (81.0%) and high purity (81.7%) in the hydrothermal gasification of glycerol by-product using the deactivated solid base.

The results were published:

F Zhang, XF Tian, Zhen Fang*, M Shah, YT Wang, W Jiang, M Yao, Catalytic Production of Jatropha Biodiesel and Hydrogen with Magnetic Carbonaceous Acid and Base Synthesized from Jatropha Hulls,  Energy Conversion and Management, 142, 107–116  (2017).

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小桐子壳合成磁性固体酸和碱催化剂及用以生产小桐子生物柴油和氢气

最近,生物能源组通过对小桐子壳水解液和水解残渣合成的磁性碳载体加载活性基团，合成磁性炭质固体酸 (C-SO₃H@Fe/JHC)和碱(Na₂SiO₃@Ni/JRC)催化剂。通过各种测试技术对其形态、磁性饱和度、功能基团和总酸/碱含量进行表征。小桐子壳水解液形成的酸性官能团有助于其负载的催化剂（C-SO₃H@Fe/JHC）具备更高的酸密度，用于预处理(酯化)高酸值小桐子油, 酸值从17.2 降为 1.3 mg KOH/g。预处理后的小桐子油，在由小桐子壳水解残渣合成的碱性催化剂(Na₂SiO₃@Ni/JRC)作用下，通过脂交换反应，生物柴油产率可高达96.7%,该碱性催化剂可循环至少三次, 催化活性损失很少。固体酸和碱催化剂均可通过磁铁轻易地回收, 平均回收率为 90.3 wt% 和86.7%。用乙醇洗涤后, 催化剂可循环十次。使用回收的催化剂，预处理油的酸值低于2.0 mg KOH/g，生物柴油的产率高达85%以上。催化剂离子和残留的甲醇可用于进一步提高，用失活固体碱催化水热气化甘油副产品的氢气产量 (81.0%) 和纯度 (81.7%)。

结果发表在Energy Conversion and Management : F Zhang, XF Tian, Zhen Fang*, M Shah, YT Wang, W Jiang, M Yao, Catalytic Production of Jatropha Biodiesel and Hydrogen with Magnetic Carbonaceous Acid and Base Synthesized from Jatropha Hulls,  Energy Conversion and Management, 142, 107–116  (2017)。

Orderly layered Zr-benzylphosphonate nanohybrids for efficient transfer hydrogenation

Zirconium-xylylenediphosphonate nanohybrids, a class of unconventional metal-organic frameworks (UMOFs), are simply synthesized to have unique properties and are highly active for prodcuing biofules and chemicals via catalytic transfer hydrogenation

Catalytic transfer hydrogenation (CTH) is a sustainable and selective way to increase the hydrogen content of unsaturated molecules for producing either biofuels or valuable chemicals. Dr. Hu Li, a postdoctoral student, supervised by Profs. Song Yang (Guizhou university) and Zhen Fang prepared a series of mesoporous and orderly layered nanohybrids for the first time via simple and template-free assembly of zirconium with different xylylenediphosphonates. It was found that m-PhPZr nanoparticles (ca. 20-50 nm) with mesopores centered at 7.9 nm, and high molar ratio of Lewis acid to base sites (1:0.7) exhibited superior performance in CTH of ketones and biomass-derived aldehydes to corresponding alcohols with almost quantitative yields under mild conditions (as low as 82 ºC), especially in CTH of ethyl levulinate to the biofuel additive γ-valerolactone (up to 98% yield). It also showed high activity in one-pot production of biodiesel (with 89% yield) from high acid value oil, and in 5-hydroxymethylfurfural production (with 56% yield) via isomerization and dehydration of glucose. The catalyst is stable with little Zr leaching and deactivation after 5 cycles. Lewis acidic (Zr) and basic (PO3) centers of the heterogeneous catalyst were revealed to play a synergistic role in CTH of carbonyl compounds, e.g., ethyl levulinate to γ-valerolactone. Isotopic labeling experiments further indicated the occurrence of direct hydrogen transfer rather than metal hydride route.

The study was published:
H Li, Zhen Fang*, J He, S Yang, Orderly Layered Zr-Benzylphosphonate Nanohybrids for Efficient Acid/Base-Mediated Bifunctional/Cascade Catalysis, ChemSusChem, 10, 681–686  (2017).

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介孔金属-有机膦酸层片材料的制备及其用于转移加氢合成生物燃料

催化转移加氢 （CTH; Catalytic transfer hydrogenation） 是一种可持续、选择性的方法来增加用于生产生物燃料或有价值的化学物质的不饱和分子中氢含量。生物能源组博士后李虎在杨松教授（贵州大学）和方真教授的指导下，通过简单、无模板的组装方法，用锆和不同的苯膦酸，合成了一系列的介孔和有序层状的纳米杂化材料。实验结果表明，m-PhPZr 纳米颗粒 (约 20-50  nm) 具有 7.9 nm介孔中心和高摩尔比的路易斯酸/碱 (1/0.7)， 展现出在催化转移加氢酮和醛类生物质平台分子为相应的醇的优越性能，给出几乎定量的产率，反应温度温和（低至 82 º C），特别是在催化乙酰丙酸乙酯生成生物燃料γ-内酯具有高的活性（高达 98%的产率）。该催化剂，可从高酸值油脂中，一步法生产生物柴油 （产率为 89%），通过异构化和脱水葡萄糖生产5-羟甲基糠醛（产率为 56%）。催化剂表现出良好的稳定性，可以重复使用五次。在催化转移加氢羰基化合物（如乙酰丙酸乙酯合成 γ-戊内酯）时，刘易斯酸性 (Zr) 和碱(PO3) 中心发挥协同作用。同位素标记实验进一步预示着发生直接氢转移，而不是金属氢化物路线。

详情可见：
H Li, Zhen Fang*, J He, S Yang, Orderly Layered Zr-Benzylphosphonate Nanohybrids for Efficient Acid/Base-Mediated Bifunctional/Cascade Catalysis, ChemSusChem, 10, 681–686  (2017).