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

Inclusion of Zn into Metallic Ni Enables Selective and Effective Synthesis of 2,5-Dimethylfuran

Recently, Dr. X. Kong supervised by Profs. Y Zhu (Chinese Academy of Sciences) and Zhen Fang developed  a highly selective Ni-based alloy catalyst for furanic fuel production from 5-hydroxymethylfurfuran. The NiZn alloy catalyst was formed through Zn inclusion to Ni by controllable reduction of the NiZnAl hydrotalcite-derived NiO–ZnO–Al₂O₃ mixed oxide. The combination of temperature-programmed reduction (TPR), in situ X-ray diffraction (XRD), CO-adsorbed infrared spectroscopy (CO-IR), and X-ray photoelectron spectroscopy (XPS) revealed that the surface of the NiZn catalyst was composed of β₁-NiZn while the bulk was composed of α-NiZn. Moreover, the surface Ni atoms were geometrically isolated by Zn atoms and modulated to be electron-rich. Finally, the rate of C═O/C—O hydrogenolysis over C═C/C-C hydrogenation for NiZn alloy catalyst was approximately three times higher than that of monometallic Ni catalyst. A 93.6% yield of DMF was obtained over NiZn alloy catalyst. The greatly improved DMF yield was thus attributed to the electron modification and isolation of Ni atoms due to the formation of NiZn alloy.

Related results were published:

X. Kong, Y. Zhu, H. Zheng, Y. Zhu, Zhen Fang*, Inclusion of Zn into Metallic Ni Enables Selective and Effective Synthesis of 2,5-Dimethylfuran from Bioderived 5-Hydroxymethylfurfural, ACS Sustainable Chemistry & Engineering 5 (2017) 11280-11289.

High yield of DMF (93.6%) was obtained from hydrogenolysis of HMF, which is an important process for sustainable fuel production from biomass.【通过调变金属Ni的电子状态和结构状态，实现了Ni基催化剂高选择性催化5-羟甲基糠醛加氢制呋喃燃料的过程】

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高选择性Ni基催化剂催化5-羟甲基糠醛制呋喃液体燃料

最近，国际学术期刊ACS Sustainable Chemistry & Engineering（影响因子5.9，第一署名单位为南京农业大学，第一作者为孔晓，通讯作者为中科院山西煤化所朱玉雷研究员和方真教授），发表了生物能源组催化转化生物质平台分子制生物液体燃料最新研究成果。阐明了NiZn合金化对Ni加氢催化性能的调变。
孔晓博士通过在Ni催化剂上引入金属Zn，形成了NiZn合金催化剂。该催化剂表面由β1-NiZn组成，体相为α-NiZn。合金化过程使得催化剂表面得到调变，金属Zn向金属Ni转移电子，使Ni电子状态发生变化；同时Zn很好的稀释Ni原子，进而减弱呋喃环在Ni上的吸附，最后催化剂表现出较高的5-羟甲基糠醛选择性加氢选择性。

孔晓博士还在斯普林格出版社出版的专著《Production of Biofuels and Chemicals with Bifunctional Catalysts》上应邀撰写书的一章节，详细介绍了非均相催化剂的表征方法和基本原理，以及用固体酸、金属和金属酸双功能催化剂促进纤维素转化。

详情可见：
1. X. Kong, Y. Zhu, H. Zheng, Y. Zhu*, Zhen Fang*, Inclusion of Zn into Metallic Ni Enables Selective and Effective Synthesis of 2,5-Dimethylfuran from Bioderived 5-Hydroxymethylfurfural, ACS Sustainable Chemistry & Engineering 5 (2017) 11280-11289.
2. X Kong, Y Zhu, H Li, Zhen Fang*, RL Smith, Jr, Introduction to Characterization Methods for Heterogeneous Catalysts and Their Application to Cellulose Conversion Mechanisms, Editors: Zhen Fang, RL Smith Jr, H. Li, Production of Biofuels and Chemicals with Bifunctional Catalysts, Springer Book Series – Biofuels and Biorefineries, Publisher: Springer-Verlag, Heidelberg Berlin, ISBN 978-981-10-5136-4, Chapter 2, 2017.
3. H Li, X Kong, Zhen Fang*, RL Smith, Jr, Fundamentals of Bifunctional Catalysis for Transforming Biomass-Related Compounds into Chemicals and Biofuels, Editors: Zhen Fang*, RL Smith Jr, H. Li, Production of Biofuels and Chemicals with Bifunctional Catalysts, Springer Book Series – Biofuels and Biorefineries, Publisher: Springer-Verlag, Heidelberg Berlin, ISBN 978-981-10-5136-4, Chapter 1, 2017.

Production of Liquefied Oil Palm Empty Fruit Bunch Based Polyols via Microwave Heating

Recently, Mr. UA Amran (a PhD student from Universiti Kebangsaan Malaysia, Malaysia) supervised by Profs. S Zakaria and Zhen Fang produced polyols from oil palm wastes using microwave.

Optimization of microwave-assisted liquefaction of oil palm empty fruit bunch fiber (EFB) and cellulose (EFBC) in ethylene glycol (EG) was carried out to produce polyols. The liquefaction residues and hydroxyl numbers of the resultant polyols from respective sources were studied and compared. EFB produced a minimum residue of 3.22% at the optimal parameters of 160 °C and 15 min. Meanwhile, optimum liquefaction of EFBC produced 1.03% residue at 175 °C and 40 min. The maximum hydroxyl numbers of both EFB (749.22 mg KOH/g) and EFBC (639.91 mg KOH/g) polyols were obtained at optimum conditions. FTIR analysis revealed the degradation mechanism of cellulose and lignin in EFB at different temperatures. Lignin was found to be liquefied easily at lower temperatures (130 and 145 °C). However, most of the cellulose began to be liquefied at the optimum temperature (160 °C) and severely degraded at higher temperatures (175 and 190 °C).

Related results were published:
1. UA Amran, S Zakaria*, CH Chia, Zhen Fang*, MZ Masli, Production of Liquefied Oil Palm Empty Fruit Bunch (EFB) Based Polyols via Microwave Heating, Energy & Fuels, 31(10), 10975–10982 (2017).

通过微波加热，液化棕榈油果的空壳生产多元醇

生物能源组与Universiti Kebangsaan Malaysia联合培养的博士生UA Amran先生在导师S Zakaria和方真教授指导下，利用微波反应系统液化棕榈油果的空壳生产多元醇。相关研究结果以“Production of Liquefied Oil Palm Empty Fruit Bunch (EFB) Based Polyols via Microwave Heating”,为题发表在国际专业期刊Energy & Fuels, 31(10), 10975–10982 (2017)。

“Production of Biofuels and Chemicals with Bifunctional Catalysts” (Hardcover ISBN978-981-10-5136-4) edited by Profs. Zhen Fang and Richard L. Smith Jr., and Dr. Hu Li is published by Springer:

http://www.springer.com/cn/book/9789811051364

Catalytic processes in multiple steps are typically required in the selective conversion of biomass derivatives into value-added chemicals and biofuels. Much effort has been made in the past decades toward the integration of different types of catalytic transformations with a bifunctional catalyst to improve reaction efficiency, enhance product selectivity, and promote specific reaction pathways. This book provides state-of-the-art reviews, current research, prospects, and challenges of production of platform chemicals (e.g., hexose, 5-hydroxymethylfurfural, 2,5-furandicarboxylic acid, furfural, and levulinic acid) and liquid biofuels (e.g.,biodiesel, 2,5-dimethylfuran, 2-methylfuran, and γ-valerolactone) from sustainable biomass resources with cooperative catalytic processes that include heterogeneous bifunctional chemocatalysis (acid-base, Bronsted-Lewis acid, and metal-acid) and combined bio-/chemo-catalytic routes. Fundamentals of bifunctional catalysis and catalysts, characterization reaction mechanism/pathways, methods for heterogeneous catalysts, the impact of catalyst design on the reactivity, and catalytic process integration are introduced. The application of biomass-derived compounds for the synthesis of commodity chemicals and liquid transportation fuels via various catalytic routes is also covered.

This book is the eighth book of the series entitled “Biofuels and Biorefineries,” and it contains 12 chapters contributed by leading experts in the field.

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

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斯普林格新书《双功能催化剂生产生物燃料和化学品》出版

    由方真老师，日本东北大学Richard L. Smith Jr.教授和李虎博士主编的新书《Production of Biofuels and Chemicals with Bifunctional Catalysts》，最近由斯普林格公司出版发行。（精装，390页， Hardcover ISBN 978-981-10-5136-4, 2017）(http://www.springer.com/cn/book/9789811051364)。

    本书（12章）提供了生产生物燃料和化学品的最新评论、研究现状、前景和挑战。如生产呋喃生物燃料、生物柴油、羧酸、多元醇和从木质纤维素生物质生产别的生物燃料等、糠醛、合成气和用双功能催化剂合成戊内酯。包括用催化，并结合生物和化学催化过程。

    催化材料的双功能特性不仅仅是使用多功能固体材料作为活化剂的概念，而且在这样一种方式下设计材料，催化材料具有协同作用的特点，促进一连串的转换，性能大大优于简单混合单功能催化剂的转化。本书是为催化、能源、化工和生物质转化领域的研究人员、学者和实业家设计的参考书。读者会发现章节中包含实用和重要的丰富信息，用化学催化和生物技术评估各种生物燃料和化学品的生产和应用。

   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）出版的第八本专著，也是方真老师自2009年以来，编著出版的第十五部英语专著。