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

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 Green Energy and Resource Transformation: from Nanomaterials to Bio-based Chemicals”：Int’l Sym. of High-level Talents was Successfully Held

On the morning of December 25, 2024, the “Green Energy and Resource Transformation: from Nanomaterials to Bio-based Chemicals”: International Symposium of High-level Talents was successfully held by the College of Engineering, Nanjing Agricultural University. At the invitation of Dr. Shuai Gao and Prof. Zhen Fang of the Biomass Group, Prof. Li Shuai from Fujian Agriculture and Forestry University, Senior Researcher Bing Song from the New Zealand Forest Research Institute (SCION), Prof. Richen Lin from the School of Energy and Environment, Southeast University, and Prof. Wenlei Zhu from the School of Environmental Science and Engineering, Nanjing University, attended the meeting and delivered presentations.

Prof. Shuai introduced his research on the reorganization of lignocellulosic biomass for the preparation of plastic-like materials. He elaborated on the chemical composition of lignin, cellulose, and hemicellulose, as well as their roles in biomass transformation processes. He shared his team’s research findings on the direct conversion of lignocellulosic biomass into plastic-like materials, including the preparation process and performance optimization of cellulose-reinforced lignin composites (CRL).

Dr. Song provided a detailed introduction to the application of γ-valerolactone (GVL) as a solvent, especially its various roles in biomass decomposition. Additionally, Dr. Song discussed the impact of GVL on the primary reactions of glucose. Through a series of experiments, he demonstrated how GVL can improve the efficiency of biomass decomposition and discussed the selectivity of GVL in the biomass conversion process.

Prof. Zhu shared his research achievements in the field of precise control of nanomaterials for electrocatalytic reduction of CO₂. He detailed how the morphology and structure of nanomaterials can be regulated to enhance the selectivity and efficiency of the CO₂ reduction reaction and explored the nanoconfinement coupling mechanism. Among his introductions, Prof. Zhu presented a self-developed self-pressurized nano-catalyst capsule that efficiently achieved CO₂ reduction, which broadened the students’ horizons.

Prof Lin introduced the technology of bioenergy conversion driven by green electricity, including hydrogen production through electrolysis, CO₂ conversion and utilization, and the high-value conversion of biomass. He emphasized the key role of biomass energy conversion in achieving carbon neutrality goals and shared the latest research progress in the design and optimization of bioenergy systems.

This event primarily focused on academic discussions and sharing around “Green Energy and Resource Transformation.” The activity enhanced academic exchanges and cooperation between Nanjing Agricultural University and domestic and international universities and research institutions. It also contributed the students’ understanding and knowledge of the forefront of biomass energy conversion, well inherited the spirit of scientific research, and promoted innovative thinking in biomass energy conversion technology and materials. Prof Fang of the Biomass Group host the meeting, all the young researchers of the research group attended the meeting.

“绿色能源与资源转化：从纳米材料到生物基化学品”暨海内外高层次人才学术研讨会成功举办

2024年12月25日上午，“绿色能源与资源转化：从纳米材料到生物基化学品”暨海内外高层次人才学术研讨会在南京农业大学工学院A106-108学术报告厅成功举办。应生物能源研究组高帅副教授和方真教授邀请，福建农林大学帅李教授、新西兰林业研究所（SCION）宋兵高级研究员、东南大学能源与环境学院林日琛教授、南京大学环境学院朱文磊教授出席会议并作报告。

福建农林大学的帅李教授向大家介绍了木质生物质重组制备仿塑材料的相关研究，阐述了木质素、纤维素和半纤维素的化学组成及其在生物质转化过程中的作用，分享了自己团队将木质生物质直接转换为可塑性材料的研究成果，包括纤维素增强木质素复合材料（CRL）的制备工艺和性能优化。

新西兰Scion研究所的宋兵高级研究员针对γ-戊内酯（GVL）作为溶剂进行了详细的应用介绍，特别是在生物质分解中的诸多作用，另外宋兵提到了GVL对葡萄糖初级反应的影响。通过一系列实验，宋兵展示了GVL如何提高生物质分解效率，并讨论了GVL在生物质转化过程中的选择性。

南京大学环境学院的朱文磊教授分享了他在纳米材料精确调控用于CO2电催化还原领域的研究成果。他详细介绍了如何通过纳米材料的形貌和结构调控来提高CO2还原反应的选择性和效率，并探讨了纳米限域偶联机制。其中朱文磊教授介绍了一种自研的自增压纳米催化剂胶囊，高效地实现了CO2的还原，让同学们大开眼界。

东南大学能源与环境学院的林日琛教授介绍了绿电驱动的生物能源转化技术，包括电解制氢、CO2转化与利用、以及生物质的高值化转化。他强调了生物质能源转化在实现碳中和目标中的关键作用，并分享了他在生物能源系统设计和优化方面的最新研究进展。

活动围绕“绿色能源与资源转化”进行学术研讨与分享。增进了南京农业大学与国内外高校和科研机构的学术交流与合作，同时增强了同学们对生物质能源转化前沿知识的理解与认识，很好地传承了科研精神，推动了生物质能源转化技术与材料等方面的创新思考。生物能源研究组方真院士主持会议，课题组全体青年教师出席会议。

Lower temperature pretreatment of wheat straw for high production of fermentable sugars using ball-milling combined with deep eutectic solvent

Recently, PhD student Miss Li Wang supervised by Prof. Zhen Fang published a research article in Renewable Energy about pretreatment of ball-milling combined with deep eutectic solvent to enhance yield of fermentable sugar of wheat straw.

Mechanochemical pretreatment based on ball-milling (BM) and DES was designed to deconstruct wheat straw at moderate temperatures (50–60 ℃) for enzymatic hydrolysis. High glucose and xylose yield of 99.71 % and 92.77 % were achieved for 72 h enzymatic hydrolysis after BM assisted with choline chloride/oxalic acid (CO) treatment. This ascribes to the synergy of ball-milling and DES resulting in the loosening and collapse of lignocellulosic structures, leading to the selective removal and modification of hemicellulose and lignin. Relative saccharification activity of glucose and xylose was increased by 294.82 % and 658.41 % pretreated with BM and CO sequentially as compared with raw wheat straw, because of reduced crystallinity and increased of surface area and reducing-end concentration of pretreated wheat straw. Energy efficiency of ternary DES (CEO) system was 1.33 times that for the binary DES (CO) system during sequential treatment of BM and DES. Relative saccharification activity and energy consumption (or energy efficiency) was fitted as quadratic functions. This green and effective pretreatment method provides new insights for the lignocellulosic deconstruction.

Related results were published in Renewable Energy:

L Wang, CX Gong, JJ Guo, Zhen Fang*. Lower Temperature Pretreatment of Wheat Straw for High Production of Fermentable Sugars Using Ball-Milling Combined with Deep Eutectic Solvent,  Renewable Energy (IF 9), 241 (2025), 122240. https://doi.org/10.1016/j.renene.2024.122240

High sugar yield (99.7% glucose and 92.8% xylose) of wheat straw was achieved by ball-milling combined with deep eutectic solvent pretreatment at lower temperature. （采用球磨法结合低共熔溶剂在较低温度下预处理，小麦秸秆的葡萄糖得率达到99.7%，木糖得率为92.8%）

球磨结合低共熔溶剂在温和温度下预处理小麦秸秆高产可发酵糖

近期，博士生王莉同学在方真教授的指导下，在国际学术期刊Renewable Energy (Q1，IF 9)发表了一篇关于球磨结合低共熔溶剂在温和温度下预处理小麦秸秆高产可发酵糖的研究性论文。

设计了基于球磨和低共熔溶剂的机械化学预处理方法，在50-60°C的中等温度下对小麦秸秆进行预处理。球磨辅助氯化胆碱/草酸处理后，葡萄糖和木糖的产率在酶解72 h时分别达到99.71%和92.77%。这归因于球磨和DES的协同作用，导致木质纤维素结构松动和崩溃，半纤维素和木质素被选择性去除和改性。葡萄糖和木糖的相对糖化活性提高了294.82%和658.41%，这与小麦秸秆的结晶度降低，表面积和还原端浓度增加有关。在球磨和低共熔溶剂的顺序处理过程中，三元低共熔溶剂（氯化胆碱/乙二醇/草酸）体系的能量效率是二元低共熔溶剂（氯化胆碱/草酸）体系的1.33倍，同时建立了相对糖化活性与能量消耗（或能量效率）的二次函数关系。这种绿色有效的预处理方法为木质纤维素的解构提供了新的思路。

结果发表在Renewable Energy：

L Wang, CX Gong, JJ Guo, Zhen Fang*. Lower Temperature Pretreatment of Wheat Straw for High Production of Fermentable Sugars Using Ball-Milling Combined with Deep Eutectic Solvent,  Renewable Energy (IF 9), 241 (2025), 122240. https://doi.org/10.1016/j.renene.2024.122240

Comprehensive insights into synergistic effects of cotton stalk and polyethylene in hydrothermal liquefaction process

Recently, PhD student Mr. Sheng-ren Li, supervised by Prof. Zhen Fang, published a research article on hydrothermal synergistic effects of cotton straw and polyethylene.

The synergistic effects of cotton stalks (CS) and polyethylene (PE) during the hydrothermal co-liquefaction process increased the bio-oil yield by 22.8%, with solid residue decreased by 6.1% and {gas + aqueous} products declined by 18.2%. GC-MS presented oxygen-containing compounds in oil decreased but hydrocarbons (HCs from 6.2 % to 66.8%) increased. TG analysis and FT-IR of solid residues revealed significant mutual promotion of the decomposition between CS and PE. The decomposition kinetics calculation demonstrated that co-treatment reduced the decomposition temperature by 33 ℃, increased the mass loss by 7.8 wt%, and lowered the decomposition activation energy by 6.8 % (from 240.0 to 225.7 KJ/mol). Moreover, co-liquefaction of PE with biomass components further revealed that cellulose in CS predominantly facilitated the depolymerization of PE, followed by hemicellulose. This effect could be attributed to the acid from hydrolysis of cellulose and hemicellulose as well as high [H]⁺/[OH]^– concentration in from hydrothermal water, which promoted the β-scission of PE. The synergistic reaction pathways were proposed: CS and PE mutually promoting decomposition, with PE-derived olefins and hydrogen undergoing Diels-Alder, alkylation, and hydrodeoxygenation (HDO) reactions with CS intermediates, thereby enhancing HCs yield and inhibiting carbonization rearrangement of intermediates. This work reveals the causes and reaction pathways underlying synergistic effects, offering comprehensive guidance on producing crude bio-oil.

Related results were accepted in Chemical Engineering Journal：

SR Li, GQ Zhu, C He, LJ Xu*, JA Kozinski, Zhen Fang*, Comprehensive insights into synergistic effects of cotton stalk and polyethylene in hydrothermal liquefaction process, Chemical Engineering Journal, 502 (2024), 157845. https://doi.org/10.1016/j.cej.2024.157845

Cellulose and hemicellulose predominantly facilitate the β-scission of PE, with the  derived hydrogens and olefins undergoing Diels-Alder, alkylation, and HDO reactions with lignocellulosic intermediates. (纤维素和半纤维素主要促进PE的β-scission,其衍生的氢和烯烃与木质纤维素中间体发生Diels-Alder 、烷基化和HDO反应) 。

棉花秸秆和聚乙烯在水热液化过程中协同效应的综合研究

近期，博士生李胜任在方真教授的指导下，在国际学术期刊Chemical Engineering Journal发表了一篇关于棉花秸秆与聚乙烯水热协同效应的研究性论文。

棉花秸秆(CS)和聚乙烯(PE)在水热共液化过程中的协同作用将生物油产率提高了22.8%，固体残渣减少了6.1 %，气+水产物减少了19.2%。气相色谱-质谱联用（GC-MS）分析表明，油中含氧化合物含量下降，而碳氢化合物(HC)含量从6.2%上升至66.8%。固体残留物的热重（TG）分析和傅里叶变换红外光谱（FT-IR）分析表明，CS和PE之间存在显著的相互促进作用。分解动力学计算表明，共处理使分解温度降低了33℃，质量损失增加了7.8 wt%，分解活化能降低了6.8%（从240.0降至225.7 KJ/mol）。此外，PE与生物质组分的共液化进一步表明，CS中的纤维素主要促进PE的解聚，其次是半纤维素。这可能是由于纤维素和半纤维素水解产生的酸以及热液中较高的[H]⁺/[OH]^–浓度促进了PE的β-scission。提出了CS和PE的协同反应途径：CS和PE相互促进分解，PE衍生烯烃和氢与CS中间体发生Diels-Alder、烷基化和加氢脱氧（HDO）反应，从而提高HC产率，抑制中间体的碳化重排。这项工作揭示了引发协同效应的原因和反应途径，为生物原油生产提供了综合指导。

结果发表在Chemical Engineering Journal：

SR Li, GQ Zhu, C He, LJ Xu*, JA Kozinski, Zhen Fang*, Comprehensive insights into synergistic effects of cotton stalk and polyethylene in hydrothermal liquefaction process, Chemical Engineering Journal, 502 (2024), 157845. https://doi.org/10.1016/j.cej.2024.157845

Regulating N-doped biochar with Fe-Mo heterojunctions as cathode in long-life zinc-air battery

Recently, PhD student Miss Xiao-ru Meng, supervised by Dr. Shuai Gao and Prof. Zhen Fang, published a research article on synthesizing cathode from soybean straw for zinc-air battery.

Carbonaceous electrode loaded nano Mo₂C-Fe₃N@NCF was synthesized by solvothermal and pyrolysis from soybean straw for high-performance zinc-air batteries (ZABs). The empowered ZAB achieved 1.51 V open-circuit voltage, 88.40 mW cm⁻² power density and over 1150 h cycle life. Density functional theory analysis indicates that charge transfer from Mo₂C-Fe₃N heterogeneous structure to N-doped biochar can significantly reduce the reaction barrier for oxygen reduction/evolution reactions, enhancing the adsorption of oxygen intermediates. Cellulose-derived carbon provides a large specific surface area, and N-doping enhances the conductivity of the resultant biochar, which both play a crucial role in the efficient loading of Fe and Mo active sites. This work inspires the design and application of interfacial engineering on low-cost biochar carriers.

Related results were published in Chemical Engineering Journal:

XR Meng, S Gao*, NX Liu, PD Wu, Zhen Fang*. Regulating N-doped biochar with Fe-Mo heterojunctions as cathode in long-life zinc-air battery, Chemical Engineering Journal, 500 (2024), 157463. https://doi.org/10.1016/j.cej.2024.157463

 Carbonaceous material with multilayer structure derived from soybean straw was developed for long-life zinc-air batteries一种由大豆秸秆衍生的多层结构碳质材料，用于长寿命锌空气电池。

以Fe-Mo异质结为阴极调控长寿命锌空气电池中的 N 掺杂生物炭

近期，博士生孟晓茹同学在高帅博士和方真教授的指导下，在国际学术期刊Chemical Engineering Journal发表了一篇关于生物炭制备高性能氧电催化剂的研究性论文。

碳质电极负载纳米Mo₂C-Fe ₃N@NCF 是通过大豆秸秆的溶剂热和热解合成的，用于高性能锌空气电池（ZABs）。可逆的ZAB实现了1.51 V开路电压，88.40 mW cm⁻²功率密度和超过1150小时的循环寿命。密度泛函理论分析表明，从Mo₂C-Fe₃N向N掺杂生物炭发生电荷转移，此非均相结构可以显著降低氧还原/析出反应的反应势垒，增强氧中间体的吸附。纤维素衍生的碳提供了较大的比表面积，而N掺杂增强了所得生物炭的电导率，这两者都在Fe和Mo活性位点的有效负载中起着至关重要的作用。这项工作启发了界面工程在低成本生物炭载体上的设计和应用。

结果发表在Chemical Engineering Journal:

XR Meng, S Gao*, NX Liu, PD Wu, Zhen Fang*, Regulating N-doped biochar with Fe-Mo heterojunctions as cathode in long-life zinc-air battery, Chemical Engineering Journal, 500 (2024), 157463. https://doi.org/10.1016/j.cej.2024.157463