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

Interfacial high-valence Ni(IV)-enabled C-H activation for photoelectrochemical C-C bond cleavage of lignin to exclusively produce aromatic carboxylic acids

Recently, PhD student Mr. Pei-dong Wu supervised by Profs. Hu Li and Zhen Fang published a research article in Chemical Engineering Journal about photoelectrochemical C-C bond cleavage of lignin to exclusively produce aromatic carboxylic acids.

Sustainable upgrading of biomass to high-value chemicals is greatly dependent on catalytic C-C/C-O bond cleavage of high selectivity. Here, an oxidation-enhanced photoelectrochemical protocol was developed to be capable of breaking different types of C-C bonds for efficiently producing aromatic carboxylic acids (85.0-99.8% yields) from lignin. Ni local electronic state of the prepared F-Fe₂O₃-Co:NiO_xH_y with excellent durability could be modulated, and high-valence Ni(Ⅳ) reactive species played a key role in the oxidative C-C bond scission of various lignin models. In-situ characterization and control experiments indicated that photocatalytic radical and electrocatalytic interface facilitated C-H/O-H delocalization, contributing significantly to the enhanced oxidation process. In addition, quantum calculations elaborated that photo-excited holes and Ni(Ⅳ) are key reactive species for enhancive electrocatalytic cleavage of different C-C bonds in lignin to exclusively furnish aromatic carboxylic acids. This research provides a renewable funnel strategy for using solar energy to produce high-value mono-functional products from biomass.

Related results were accepted in Chemical Engineering Journal:

PD Wu, LY Li, Hu Li *, Zhen Fang *, Interfacial high-valence Ni(IV)-enabled C-H activation for photoelectrochemical C-C bond cleavage of lignin to exclusively produce aromatic carboxylic acids, 2024, 490, 151722. https://doi.org/10.1016/j.cej.2024.151722.

A “funnel” type strategy for photoelectrochemical lignin high value utilization. 用于光电化学木质素高值化利用的“漏斗”型策略。

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Chemical Engineering Journal发表论文:

界面高价镍（IV）C-H活化促光电化学C-C键裂解木质素专一生产芳香族羧酸

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Chemical Engineering Journal (Q1; Impact factor: 15.1)上发表了一篇关于光电化学C-C键裂解木质素专一生产芳香族羧酸的论文。

生物质向高价值化学品的可持续升级在很大程度上依赖于C-C/C-O键的高选择性催化裂解。在此，我们开发了一种氧化增强型光电化学方案，该方案能够断裂不同类型的C-C键，从而高效地从木质素中生产出芳香族羧酸（产率为 85.0%-99.8%）。所制备的F-Fe₂O₃-Co:NiO_xH_y光电极具有优异的耐久性，其Ni局部电子态可被调控，高价态Ni（Ⅳ）活性物种在各种木质素模型的C-C键氧化裂解过程中发挥了关键作用。原位表征和对照实验表明，光催化自由基和电催化界面促进了C-H/O-H质子脱出，对氧化过程的增强起了重要作用。此外，DFT计算表明，光激发空穴和Ni（Ⅳ）是增强电催化木质素衍生物C-C键裂解的关键活性物种，使其可完全转换为芳香族羧酸。这项研究为利用太阳能从生物质中生产高价值单功能产品提供了一种可再生“漏斗”策略。

详情可见：

PD Wu, LY Li, Hu Li *, Zhen Fang *, Interfacial high-valence Ni(IV)-enabled C-H activation for photoelectrochemical C-C bond cleavage of lignin to exclusively produce aromatic carboxylic acids, 2024, 490, 151722. https://doi.org/10.1016/j.cej.2024.151722.

Prof. Fang and Dr. Xu visiting Tampere University in Finland

As invited by Prof. Chao He via the “Climate Neutrality and Energy Systems Society” (CNESS) platform at Tampere University in Finland, Prof. Zhen Fang and Dr. Lujiang Xu at Nanjing Agricultural University visited Finland on April 23-27, 2024. Prof. Fang and Dr. Xu had extensive discussions with Profs. He and Jukka Konttinen on biomass utilizations particularly in the fields of thermal conversions in both groups and planned to collaborate in research and students training, particularly focused on joint application of Jiangsu/China-Finland projects as well as exchange of graduate students and faculty staff.

Introduction Research in Biomass group at Nanjing Agricultural University

During the visiting, a joint Sino-Finnish CNESS seminar on Biomass Conversion Technology (https://research.tuni.fi/cness/news/ddd /) was held. Prof. Fang and Dr. Xu gave invited presentations entitled “Hydrothermal Conversion of Waste Materials” and “Production of Value-added Compounds from Biomass and Wastes via Catalytic Pyrolysis Process”, respectively.

Presentation by Prof. Fang

Presentation by Dr. Xu

Through this visiting, both sides have reached an agreement to jointly apply for Sino-Finish projects granted by both governments and companies to exchange and collaborate in energy area in both countries for carbon-neutral society to achieve the United Nations Sustainable Development Goals or UN SDGs by 2030. Both sides also agreed to find financial sources for exchanging students and faculty visiting.

This visiting promoted academic exchange and education and stimulated cooperative activities in sustainable development of renewable biomass resources. It also helps to inspire young scientists and students to work together in developing new ways to use biomass and to address many issues in energy and resources all over the world.

Discussion after presentation

方真院士和徐禄江老师对芬兰坦佩雷大学进行学术访问

应芬兰坦佩雷大学“气候中和能源系统与社会研究CNESS”平台Chao He 教授邀请, 2024年4月23-27日，南京农业大学生物质研究组方真院士和徐禄江老师对坦佩雷大学进行学术访问和交流。访问期间，方真院士和徐禄江老师与坦佩雷大学He教授和Jukka Konttinen教授就双方研究组科研情况以及双方后续合作展开充分交流。

在坦佩雷大学交流期间，同期还举行中芬CNESS 生物质转化技术论坛(https://research.tuni.fi/cness/news/ddd/，线上和线下会议)，方真院士和徐禄江老师分别应邀作“Hydrothermal Conversion of Waste Materials” 和 Production of Value-added Compounds from Biomass and Wastes via Catalytic Pyrolysis Process 学术报告，并与坦佩雷大学师生进行充分学术交流。

Dr. Xu, Profs. Konttinen, Fang and He

通过此次访问，双方达成协议，将共同申请两国政府和企业资助的中芬合作项目，在两国能源领域开展交流与合作，促进碳中和社会，在2030年前实现联合国可持续发展目标或联合国可持续发展目标。双方还同意为交换学生和教师访问寻找资金来源。

这次访问促进了学术交流和教育，促进了可再生生物质资源可持续发展方面的合作活动。它还有助于激励年轻的科学家和学生共同开发利用生物质的新方法，并解决世界各地能源和资源方面的许多问题。

Lab tour

Insight into the synergistic influence of nitrogen-doped biochar and NH₃ on selective production of 4-vinyl phenol from biomass catalytic pyrolysis by coupling catalyst in-situ regeneration

Recently, Master student Miss Wen-juan Guo supervised by Dr. Wei Chen and Prof. Zhen Fang published a research article entitled “Insight into the synergistic influence of nitrogen-doped biochar and NH₃ on selective production of 4-vinyl phenol from biomass catalytic pyrolysis by coupling catalyst in-situ regeneration” in Industrial Crops and Products.

A new catalytic pyrolysis system of biomass was proposed. Nitrogen-doped biochar catalyst was used to pyrolyze bamboo to produce valuable 4-vinyl phenol (2500 yuan/kg) under NH₃ atmosphere, and in-situ regeneration of the catalyst was realized. NH3 and nitrogen-doped biochar catalyst could significantly increase bio-oil yield (up to 68 wt.%) and phenols content (80%). The selectivity and absolute yield of 4-vinyl phenol were up to 28% and 5.85 wt.%, respectively. N/O-containing groups in the catalyst and free radicals from NH₃ promoted the break of ester bonds and β-O-4 bonds, and converted phenols intermediates to 4-vinyl phenol. Meanwhile, NH3 also acted as activator and nitrogen dopant, which realized the in-situ regeneration of the catalyst. The regeneration rate of nitrogen content and SBET of the catalyst was up to 84.5%-150% and 72.9%-85.4%, respectively. In addition, the nitrogen-doped biochar catalyst also showed good stability and reusability, and the yield of 4-vinyl phenol was still as high as 5.85-6.05 wt.% after repeated use of BC10 catalyst for 3 times. This was also the first time to explore the formation path of 4-vinyl phenol and the in-situ regeneration mechanism of the catalyst, based on the synergistic effect of NH₃ and the nitrogen-doped biochar catalyst. It proposed a new direction for the high value utilization of biomass resources.

Related results were accepted in Industrial Crops and Products：

W Guo, Y Wang, W Chen*, GX  Xu, G Zhu, GXie, LXu, Zhen Fang, Q Zhang, H Yang. Insight into the synergistic influence of nitrogen-doped biochar and NH3 on selective production of 4-vinyl phenol from biomass catalytic pyrolysis by coupling catalyst in-situ regeneration. Industrial Crops and Products (IF = 5.9) (2024) 214, 118520. https://doi.org/10.1016/j.indcrop.2024.118520

Selective production of 4-vinyl phenol from biomass catalytic pyrolysis by coupling catalyst in-situ regeneration原位再生掺氮生物炭催化剂催化热解生产4-乙烯基苯酚

NH₃气氛下基于掺氮生物炭催化剂原位再生的生物质催化热解选择性生产4-乙烯基苯酚

最近，硕士生郭文娟在陈伟副教授和方真教授的指导下，在国际学术期刊Industrial Crops and Products (Q1, IF = 5.9) 发表了一篇题为“Insight into the synergistic influence of nitrogen-doped biochar and NH3 on selective production of 4-vinyl phenol from biomass catalytic pyrolysis by coupling catalyst in-situ regeneration”的研究性论文。

该研究提出了一种新的生物质催化热解体系，在NH₃气氛下采用掺氮生物炭催化剂对竹子进行热解，制备得到了高价值的4-乙烯基苯酚(2500元/kg)，与此同时实现了催化剂的原位再生。NH₃和掺氮生物炭催化剂可显著提高生物油收率(68 wt.%)和酚类化合物含量(80%)。4-乙烯基苯酚的选择性和绝对含量分别高达28%和5.85 wt.%。催化剂中的含N/O官能团和来自NH3的NH*和NH2*自由基促进了酯键和β-O-4键的断裂，将酚类中间体转化为4-乙烯基苯酚。同时，NH₃还作为活化剂和氮掺杂剂，实现了掺氮生物炭催化剂的原位再生，催化剂氮含量和SBET的再生率分别为84.5%-150%和72.9%-85.4%。此外，催化剂也表现出良好的稳定性和可重复使用性，在BC10催化剂重复使用3次后，4-乙烯基苯酚的产率仍高达5.85-6.05wt.%。这项研究也是首次基于NH₃与掺氮生物炭催化剂的协同作用探究4-乙烯基苯酚的形成路径和催化剂的原位再生机理，为生物质资源的高值化利用指明了新的方向。

结果发表在Industrial Crops and Products：

W Guo, Y Wang, W Chen*, GX  Xu, G Zhu, GXie, LXu, Zhen Fang, Q Zhang, H Yang. Insight into the synergistic influence of nitrogen-doped biochar and NH3 on selective production of 4-vinyl phenol from biomass catalytic pyrolysis by coupling catalyst in-situ regeneration. Industrial Crops and Products (IF = 5.9) (2024) 214, 118520. https://doi.org/10.1016/j.indcrop.2024.118520

Red mud supported Ni-Cu bimetallic material for hydrothermal production of hydrogen from biomass

Recently, master student Mr. Gong-xun Xu supervised by Prof. Zhen Fang, collaborated with Dr. S Nanda (Dalhousie University), Profs. AK Dalai (University of Saskatchewan) and Prof. JA Kozinski (Lakehead University published a research article in Industrial Crops & Products about Red mud supported Ni-Cu bimetallic material for hydrothermal production of hydrogen from biomass.

Exploring efficient and reliable catalysts to achieve gasification of biomass waste is a promising research endeavour. In this study solid waste red mud (RM, an inexpensive and efficient support) loaded Ni-Cu metals (Ni-Cu/RM) was used to catalyze hydrothermal gasification of cotton stalk at 340-400 ℃ and 16-30 MPa. In the presence of Ni-Cu/RM catalyst, 21.88 mmol/g H₂ yield with 79.89% carbon balance was achieved, increased by 22.8 times under the optimized conditions (380 ℃ for 5 min) based on orthogonal experiments. Under the optimal conditions, H₂ yield with neat Ni and Ni/RM loaded on RM is 0.96 and 12.94 mmol/g, respectively due to the specific surface area soaring by 72.0 times from 0.7 to 50.5 m²/g. With Ni-Cu/RM bimetallic catalyst, H₂ yield jumped from 3.41 to 21.88 mmol/g, 6.7 times higher than that neat Ni, or reached 84% with Ni-Cu/Al₂O₃ if Al₂O₃ was as support. It is further found that Cu promoted the dispersion of Ni on red mud with surface area rising from 50.47 to 73.42 m²/g together with forming Ni-Cu alloy (alkalinity of Ni-Cu/RM rose to 285.65 from 172.21 μmol/g for Ni/RM) enhanced H₂ generation. When temperature grew from 340 ℃ (subcritical) to 400 ℃ (supercritical region), H₂ yield improved by 3 times from 9.21 to 28.50 mmol/g. Red mud is an ideal candidate for replacing the commercial support Al₂O₃.

Results were published in Industrial Crops and Products：

GX Xu, S Nanda , JJ Guo, YQ Song, JA Kozinski, AK Dalai, Zhen Fang*, Red Mud Supported Ni-Cu Bimetallic Material for Hydrothermal Production of Hydrogen from Biomass, Industrial Crops and Products (IF 6.4), 212 (2024), 118370. https://doi.org/10.1016/j.indcrop.2024.118370.

Red mud supported Ni-Cu bimetallic material for hydrothermal production of hydrogen from biomass赤泥负载Ni-Cu双金属材料用于生物质水热制氢

赤泥负载Ni-Cu双金属材料用于生物质水热制氢

最近，硕士徐功迅在方真教授的指导下，与加拿大Dalhousie大学助理教授S Nanda博士、Saskatchewan大学 AK Dalai院士和加拿大Lakehead 大学工学院院长JA Kozinski院士在在国际学术期刊Industrial Crops and Products (Q1, IF = 5.9) 发表了一篇题为“赤泥负载Ni-Cu双金属材料用于生物质水热制氢”的研究性论文。

探索高效可靠的催化剂来实现生物质废弃物的气化是一项有前途的研究工作。该研究以负载Ni-Cu金属(Ni-Cu/RM)的固体废赤泥(RM)为载体，在340 ~ 400 ℃、16 ~ 30 MPa条件下催化棉秆水热气化。在Ni-Cu/RM催化剂作用下，优化条件下(380℃、5 min)的H₂产率提高22.8倍，达到21.88 mmol/g，碳平衡79.89%。在最优条件下，纯Ni和Ni/RM负载在RM上的H₂产率分别为0.96和12.94 mmol/g，比表面积从0.7提高到50.5 m²/g，提高了72.0倍。采用Ni-Cu/RM双金属催化剂时，H₂产率从3.41提高到21.88 mmol/g，是纯Ni催化剂的6.7倍；在以Al₂O₃为载体时，H₂产率达到84%。Cu促进了Ni在赤泥上的分散，表面积从50.47增加到73.42 m²/g，并形成了Ni-Cu合金(Ni/RM的Ni-Cu/RM的碱度从172.21提高到285.65μmol/g)，促进了H₂的生成。当温度从340℃(亚临界)升高到400℃(超临界)时，H₂产率从9.21提高到28.50mmol/g，提高了3倍。赤泥是替代Al₂O₃的理想载体。

结果发表在Industrial Crops and Products：

GX Xu, S Nanda , JJ Guo, YQ Song, JA Kozinski, AK Dalai, Zhen Fang*, Red Mud Supported Ni-Cu Bimetallic Material for Hydrothermal Production of Hydrogen from Biomass, Industrial Crops and Products (IF 6.4), 212 (2024), 118370. https://doi.org/10.1016/j.indcrop.2024.118370.

Realizing the Co-valorization of Waste Cooking Oil into High-quality Biofuel and Carbon Nanotube Precursor via Catalytic Pyrolysis Process

Recently, Master student Mr. Guo-qiang Zhu supervised by Associate Prof. Lu-jiang Xu published a research article in Chemical Engineering Journal about realizing the co-valorization of waste cooking oil into high-quality biofuel and carbon nanotube precursor via catalytic pyrolysis process.

Valorizing renewable precursors into high-quality biofuel and functional carbon nanomaterials can considerably improve the economic viability. Here, we propose a process for integrated production of high-quality biofuel and carbon nanotubes from waste cooking oil via catalytic pyrolysis coupling with CVD technology. The natural biochar catalyst demonstrates excellent deoxygenation performance and good stability in catalytic pyrolysis process. The AAEMs content in biochar catalysts from various sources has a strong correlation with the selectivity of esters and hydrocarbons in bio-oil. The biofuel obtained under optimal conditions exhibited potential as a precursor for jet fuel. The combined CVD process successfully convert pyrolysis gas into multi-wall carbon nanotubes with yield of 2.13%. The technical-economic analysis demonstrated the feasibility of the integrated production process, projecting profitability and substantial total profit over a ten-year period. Overall, this study improves the economic viability of the waste cooking oil pyrolysis process and can support its wider commercial application.

Related results were published in Chemical Engineering Journal：

GQ Zhu, MX Zhu, EZ Wang, CX Gong, YR Wang, WJ Guo, GL Xie, W Chen, C He, LJ Xu*, H Li, Y Zhang, Zhen Fang, Natural Biochar Catalyst: Realizing the Co-Valorization of Waste Cooking Oil into High-Quality Biofuel and Carbon Nanotube Precursor via Catalytic Pyrolysis Process, Chemical Engineering Journal (IF 16.7), 486 (2024), 150195. https://doi.org/10.1016/j.cej.2024.150195.

Co-valorization of waste cooking oil into high-quality biofuel and carbon nanotube precursor via catalytic pyrolysis process催化热解工艺实现餐厨废油共价制备优质生物燃料和碳纳米管前驱体

催化热解工艺实现废食用油转化为优质生物燃料和碳纳米管前驱体

最近，硕士生祝国强在徐禄江副教授的指导下，在国际学术期刊Chemical Engineering Journal (Q1, IF=15.1) 发表了一篇关于原生生物炭热解催化废弃油脂联产高品质液体燃料和碳纳米管前驱体的研究性论文。

以废弃油脂为原料联产高品质液体燃料和功能性碳纳米材料可显著提高经济可行性。因此，本文提出了一种利用秸秆基生物炭催化热解耦合气相沉积技术联产生产高质量生物燃料和碳纳米管工艺。原生生物炭在催化热解过程中表现出优异的脱氧性能和良好的稳定性。不同来源的生物炭催化剂中碱金属含量与热解油中酯类和烃类的选择性呈一阶线性相关。在最佳条件下获得的生物燃料表现出作为航空燃料前体的潜力。气相沉积技术成功实现将热解气转化为多壁碳纳米管，收率为2.13%。技术经济评价证明了联产的可行性，并预测了10年期间的盈利能力。本研究提高了废弃油脂热解工艺的经济可行性，为其更广泛的商业应用提供了参考。

结果发表在Chemical Engineering Journal：

GQ Zhu, MX Zhu, EZ Wang, CX Gong, YR Wang, WJ Guo, GL Xie, W Chen, C He, LJ Xu*, H Li, Y Zhang, Zhen Fang, Natural Biochar Catalyst: Realizing the Co-Valorization of Waste Cooking Oil into High-Quality Biofuel and Carbon Nanotube Precursor via Catalytic Pyrolysis Process, Chemical Engineering Journal (IF 16.7), 486 (2024), 150195. https://doi.org/10.1016/j.cej.2024.150195.