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

A US patent was awarded about synthesizing of 2,5-dimethylfuran

Recently, a US patent was awarded to Profs. Hu Li and Zhen Fang, entitled “Hydrophobic palladium/metal organic framework material, preparation method thereof, and application therefor for use in synthesizing 2,5-dimethylfuran” (US 11,584,729 B2, Filed: October 18, 2017, Date of Patent: February 21, 2023, Assignee: Nanjing Agricultural University, Inventors: Zhen Fang, Hu Li; https://patents.justia.com/patent/11584729).

A hydrophobic palladium/metal organic framework (MOF) material, which is a solid catalyst material obtained by taking a porous MOF as a carrier, introducing elementary palladium by means of an immersion-reduction method, and performing polydimethylsiloxane coating layer processing. A method which uses hydrophobic palladium/MOF material to selectively catalyze hexoses to prepare 2,5-dimethylfuran comprises: dissolving a hexose into an alcohol; using the hydrophobic palladium/MOF material as a catalyst and polymethylhydrosiloxane as a hydrogen donor, reacting at 70 to 130 °C. for 0.25 to 12 h under the action of an acidic additive; the concentration of the hexose in the alcohol is 0.2 to 10 wt %, and the total amount of Pd contained in the hydrophobic palladium/MOF material relative to a hexose is 0.1 to 5 mol %.

Hydrophobic palladium/metal organic framework material, preparation method thereof, and application therefor for use in synthesizing 2,5-dimethylfuran. (“疏水性钯/金属有机骨架材料，制备方法及其在合成2,5-二甲基呋喃中的应用”获美国专利)

李虎博士获美国授权发明专利

最近，方真教授和李虎博士获美国授权发明专利。方真，李虎 题为“疏水性钯/金属有机骨架材料，制备方法及其在合成2,5-二甲基呋喃中的应用”（US 11584729 B2，申请日期：2017年10月18日，专利日期：2023年2月21日，受让人：南京农业大学，发明人：方真、李虎；https://patents.justia.com/patent/11584729)。

一种疏水性钯/金属有机框架（MOF）材料，其是通过将多孔MOF作为载体，通过浸渍还原法引入元素钯，并进行聚二甲基硅氧烷涂层处理而获得的固体催化剂材料。一种使用疏水性钯/MOF材料选择性催化己糖制备2,5-二甲基呋喃的方法包括：将己糖溶解于醇中；使用疏水性钯/MOF材料作为催化剂，使用聚甲基氢硅氧烷作为氢供体，在酸性添加剂的作用下，在70至130 °C下反应0.25至12小时；醇中己糖的浓度为0.2至10wt%，并且疏水性钯/MOF材料中所含的Pd的总量相对于己糖为0.1至5mol%。

Non-quantum nanostructures-enabled hot carriers generation for enhancive photoelectrocatalytic oxidation of bio-alcohol in water coupled with hydrogen evolution

Recently, PhD student Mr Pei-dong Wu supervised by Profs. Hu Li and Zhen Fang published research article in Green Chem about photoelectrocatalytic oxidation of bio-alcohol in water coupled with hydrogen evolution.

Photoelectrochemical system is a promising way for biomass valorization but still in its infancy. Herein, a Mo-BVO-TiCoNO-CoFeO_xy photoanode with a nanowire structure was prepared for efficiently converting bio-based benzyl alcohol (BA) to benzoic acid (97.7% yield) for the first time, while coupling H₂ production of 136.8  μmol cm^-2. The nanowire structure enables a significant increase in the exposed active sites on the photoelectrode surface to enhance the BA oxidation capacity, whereas its large aspect ratio increases the visible light absorption and thermal effect (resulting from size effect) increases H₂ production at the counter electrode. DFT calculations and further experiments revealed that Co species of the CoFeO_xy layer functioned as stabilizers of photoelectrode property while Fe species acted as catalytic site providers in the BA oxidation.

Publication:

Pei-dong Wu, Lanyun Li, Keping Wang, Hu Li*, Zhen Fang*. Non-quantum nanostructures-enabled hot carriers generation for enhancive photoelectrocatalytic oxidation of bio-alcohol in water coupled with hydrogen evolution, Green Chem., 2023,

https://doi.org/10.1039/D3GC00226H

The use of photoelectrochemical system for the high value use of biomass-derived alcohols coupled with hydrogen production is a significant contribution to the “two-carbon”. The loading of a “two birds with one stone” CoFeO_xy layer on BVO substrate enabled rapid separation of photoexctied carriers while achieving a 97.7% yield of benzyl alcohol (BA) to benzoic acid (BEN). 使用光电化学（PEC）的方法将生物质衍生醇高值化利用耦合产氢，对于“双碳”目标的实现具有极大的促进意义。我们在钒酸铋基底上负载具有“一石二鸟”作用的CoFeO_xy外层实现光致载流子的快速分离，同时实现对苯甲醇（BA）到苯甲酸（BEN）97.7%的产率。

博士生吴培栋在李虎教授和方真教授的指导下，在国际学术期刊Green Chemistry发表研究性论文:

非量子纳米结构产生热载流子增强光电氧化生物质醇同时耦合产氢的能力

最近，博士生吴培栋在李虎教授和方真教授的指导下，在国际学术期刊Green Chemistry (Q1; Impact factor: 11)上发表了一篇关于光电化学氧化生物质醇到苯甲酸的研究性论文。

PEC氧化系统是一种很有前途的方法可以将生物质高值化利用，但仍处于起步阶段。在此基础上，我们制备了具有纳米线结构的Mo-BVO-TiCoNO-CoFeO_xy光阳极，首次将生物质衍生醇-苯甲醇(BA)高效转化为苯甲酸(收率97.7%)，同时偶联H₂产量为136.8  μmol cm^-2。纳米线结构使暴露在光电极表面的活性物显著增加，从而增强BA氧化能力，而其较大的纵横比增加了其可见光吸收，同时产生的热效应(由尺寸效应引起)增加了对电极H₂的产量。DFT计算和对照实验表明，CoFeO_xy层中的Co物种是光电极性能的稳定剂，Fe物种在BA氧化的过程中提供了催化位点。

详情可见：

Pei-dong Wu, Lanyun Li, Keping Wang, Hu Li*, Zhen Fang*. Non-quantum nanostructures-enabled hot carriers generation for enhancive photoelectrocatalytic oxidation of bio-alcohol in water coupled with hydrogen evolution, Green Chem., 2023,

https://doi.org/10.1039/D3GC00226H

Microwave-assisted one-step production of biodiesel from waste cooking oil by magnetic bifunctional SrO–ZnO/MOF catalyst

Recently, master student Mr. Jian Yang supervised by Prof. Zhen Fang published a research article in Journal of Cleaner Production about synthesizing bifunctional SrO–ZnO/MOF catalyst for biodiesel production from waste cooking oil.

Magnetic bifunctional SrO–ZnO/MOF catalyst supported on metal-organic framework (MOF) was synthesized for one-step biodiesel production from high acid value oils. The catalyst presented both basicity (2.84 mmol/g) and acidity (0.02 mmol/g) due to active components of Sr₃Fe₂O₆ and ZnO. MOF support increased catalyst specific surface by 3.7 times and provided Fe₃O₄ component for magnetic separation. The highest soybean biodiesel yield of 99.5% was obtained at 80 ℃ with 3 catalyst cycles. Microwave heating significantly reduced reaction time from 20 min to 5 min at 99.0% biodiesel yield and 80 ℃. The catalyst was highly active and resistant to free fatty acids with biodiesel yield of 90.0% from waste cooking oil (AV of 3.3 mg KOH/g) at longer reaction time of 30 min. SrO–ZnO/MOF has potential application in biodiesel industry.

Related results were accepted in Journal of Cleaner Production.

Jian Yang, Wen-Jie Cong, Zongyuan Zhu**, Zheng-diao Miao, Yi-Tong Wang***, Michael Nelles, Zhen Fang*. Microwave-assisted one-step production of biodiesel from waste cooking oil by magnetic bifunctional SrO–ZnO/MOF catalyst. Journal of Cleaner Production 395 (2023) 136182. https://doi.org/10.1016/j.jclepro.2023.136182

Acid/base SrO-ZnO/MOF catalyst for one-step biodiesel production from waste cooking oil in 30 min with microwave radiation. (双功能SrO-ZnO/MOF催化剂在微波辅助加热下30分钟从废弃食用油中一步生产生物柴油。)

微波辅助磁性双功能SrO–ZnO/MOF催化剂一步法从废弃食用油中制备生物柴油

最近，硕士生杨剑在方真教授的指导下，在国际学术期刊Journal of Cleaner Production （Q1, IF 11.072）发表一篇关于使用双功能磁性SrO–ZnO/MOF催化剂从废弃食用油中制备生物柴油的研究性论文。

合成了由金属有机骨架（MOF）负载的磁性双功能SrO–ZnO/MOF催化剂，用于高酸值油一步制备生物柴油。Sr₃Fe₂O₆和ZnO为催化剂提供碱度（2.84mmol/g）和酸度（0.02mmol/g）。MOF载体将催化剂比表面积提高了3.7倍，形成的Fe₃O₄赋予催化剂磁性。催化豆油制备生物柴油的产率在80 ℃下达到99.5%，通过简单的磁性分离催化剂可循环使用3次。微波加热显著缩短了反应时间，在相同的生物柴油产率（99.0%）下，传统油浴加热需要20 min，而微波加热将反应时间缩短3倍，仅用了5 min。该催化剂具有高度活性，并且对游离脂肪酸具有抗性，在80 ℃下反应30分钟，催化酸值为3.3 mg KOH/g的废弃食用油的生物柴油产率达到90.0%。SrO–ZnO/MOF催化剂在生物柴油工业中具有潜在应用。

结果发表在Journal of Cleaner Production

Jian Yang, Wen-Jie Cong, Zongyuan Zhu**, Zheng-diao Miao, Yi-Tong Wang***, Michael Nelles, Zhen Fang*. Microwave-assisted one-step production of biodiesel from waste cooking oil by magnetic bifunctional SrO–ZnO/MOF catalyst. Journal of Cleaner Production 395 (2023) 136182. https://doi.org/10.1016/j.jclepro.2023.136182

球磨碱盐耦合预处理: Effect of alkali salt-coupled ball milling pretreatment of wheat straw on improving enzymatic hydrolysis and energy efficiency

Effect of alkali salt-coupled ball milling pretreatment of wheat straw on improving enzymatic hydrolysis and energy efficiency

Recently, PhD student Miss Xiao-le Liu supervised by Prof. Zhen Fang published a research article in Fuel about alkali salt-coupled ball-milling pretreatment of wheat straw for enzymatic hydrolysis.

Wheat straw was pretreated with a combination of ball milling (BM) and NaAlO₂ particles (NaAlO₂-BM) for enzymatic hydrolysis within a short hydrolysis period. The effects of energy consumption on modifications of physicochemical proprieties and energy efficiency were elucidated. NaAlO₂-BM pretreatment decreased particle size rapidly to tissue scale in 10 min with energy consumption reduced by 0.5 times compared to BM pretreatment. NaAlO₂-BM pretreated for 20 min achieved a glucose yield of 95.4% at a cellulase loading of 10 FPU/g dry substrate for 24 h enzymatic hydrolysis and provided the highest energy efficiency of 0.121 kg glucose/kWh, increasing by 1.1 times than BM pretreatment. Energy consumption showed a positive relationship with cellulose content while it negatively correlated with median particle size, cellulose crystallinity and energy efficiency. The combination of BM and NaAlO₂ particles was demonstrated to be a promising pretreatment approach for glucose production and improving energy efficiency during hydrolysis of lignocellulose.

Related results were published in Fuel:

Xiao-le Liu, Zhen Fang*, Xiao-fei Tian*, Zheng-diao Miao, Effect of alkali salt-coupled ball milling pretreatment of wheat straw on improving enzymatic hydrolysis and energy efficiency. Fuel 340 (2023) 127336. https://doi.org/10.1016/j.fuel.2022.127336

Wheat straw was ball milling pretreated with NaAlO₂ particles for 20 min with 95.4% glucose yield after 24 h enzymatic hydrolysis. It achieved the highest energy efficiency of 0.121 kg glucose/kWh.（球磨辅助NaAlO₂颗粒预处理小麦秸秆20分钟。酶水解24 h，预处理后的麦秸秆酶解率可达95.4%，最大能效为0.121千克葡萄糖/千瓦时）

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球磨碱盐耦合预处理麦秸秆对提高酶解和能效的影响

最近，博士生刘小乐（女）在方真教授的指导下，在国际学术期刊Fuel （Q1, IF 8.035）发表一篇关于球磨辅助NaAlO₂颗粒预处理小麦秸秆用于提高酶解和能效的研究性论文。

采用球磨和NaAlO₂颗粒耦合预处理麦秸秆，并阐述了能量消耗对物理化学性质改变和能量效率的影响。球磨耦合NaAlO₂颗粒预处理10分钟可使颗粒粒径迅速减小至组织规模，能耗比单独球磨预处理降低0.5倍。球磨耦合NaAlO₂颗粒预处理20分钟，纤维素酶添加量为10 FPU/g干基质，酶解24 h后的葡萄糖收率可达95.4%；其能量效率高达0.121 kg葡萄糖/千瓦时，是单独球磨预处理的1.1倍。能量消耗与纤维素含量呈正相关，与平均粒径、纤维素结晶度和能量效率呈负相关。

结果发表在Fuel

Xiao-le Liu, Zhen Fang*, Xiao-fei Tian*, Zheng-diao Miao, Effect of alkali salt-coupled ball milling pretreatment of wheat straw on improving enzymatic hydrolysis and energy efficiency. Fuel 340 (2023) 127336. https://doi.org/10.1016/j.fuel.2022.127336