Phosphoric Acid-assisted Pretreatment Strategy for the Rational Synthesis of Lignin-derived Hierarchical Porous Carbon Toward High-performance Supercapacitors

In this article, a facile two-step activation method, coupled with phosphoric acid (H₃PO₄)-assisted pretreatment and followed KOH activation, was reported for constructing hierarchical porous carbon (HPC) materials derived from lignin. The introduction of H₃PO₄, cross-linked with lignin sources generated phosphate (and/or polyphosphate) ester groups throughout the lignin structure, which endowed the pre-activated intermediate char (IC) with a hierarchical porous structure. Such phosphate esters contributed to the multi-scale pore structure within the pre-activated IC, which was beneficial for the uniform distribution and impregnation of subsequent KOH activators, thus leading to the formation of HPC materials. The as-prepared HPC exhibited a large specific surface area (SSA) of 1345.1 m²/g, which ensures the accessibility of the ion diffusion pathways. The supercapacitors integrated with HPC delivered a high specific capacitance of 241 F/g (in a three-electrode system) and outstanding rate capability with an 80.9% capacitance retention from 0.5 A/g to an ultra-high current density of 50 A/g.     

Ni-P/HZSM-5催化木质素降解制备酚类化学品

采用Ni-P复合改性HZSM-5催化剂催化木质素降解制备高附加值的单酚类化学品，探讨了催化剂种类、金属负载量、反应温度、反应时间以及溶剂种类对木质素催化降解制备酚类化合物的影响。同时采用X射线衍射仪（XRD）、比表面积和孔径分析仪（BET）、化学吸附仪（NH₃-TPD）、热重分析仪（TG）以及气相色谱质谱联用仪（GC/MS）对催化剂以及液相产物进行分析表征，同时探讨其催化失活以及再生机制。结果表明：Ni、P高度分散在HZSM-5催化剂的表面，Ni的添加有效地弱化了C－C键，致使β-O-4和α-O-4发生断裂，有效地提高了木质素加氢解聚的活性，减少了焦炭的生成，但催化剂的再生水热稳定性较差，重复使用性较低。当采用甲醇为供氢试剂，在反应温度为220℃，氢气压力为2MPa，反应时间为8h，催化剂负载量为10%，NaOH为共催化剂时，其木质素的转化率为98.6%，酚类化合物的含量达到74.97%。产物以苯酚、愈创木酚和紫丁香酚为主，低温促进了紫丁香酚的产生。     

Conversion of aqueous extracts from thermochemical treatment of bagasse into functional emulsifiers

Synthetic emulsifiers in food industries are being replaced with a customer-friendly food ingredient that is derived from biomass using sustainable green technologies. After hydrothermal liquefaction treatment, raw bagasse (21%), pith (26%), and rind portions (25%) were obtained with reduced ash contents. As aqueous extracts, with oligosaccharides and lignin residues, it was used in the preparation of oil-in-water emulsions with 5% soybean oil. Results showed that the emulsions stabilised the oil droplets with particle size between 11 and 17 µm by steric repulsion with raw bagasse-stabilised emulsion showing a better stability at 25 °C (31 days). It was demonstrated that raw bagasse extracts, without alteration, maybe a potential unconventional source for food-grade emulsifiers by integrating a versatile thermochemical conversion of waste without the use of chemicals.     

木质素化学降解及其在聚合物材料中应用的研究进展

木质素是自然界储量丰富的可再生天然酚类高分子，可替代传统化石资源应用于聚合物材料合成。木质素分子结构中的大分子刚性骨架可赋予材料独特的力学性能和热稳定性。但木质素化学组成和分子结构复杂、反应活性低，限制了在聚合物材料领域的应用。化学降解是一种高效、高选择性且应用广泛的降解方法，经化学降解处理得到的木质素低聚物具有活性官能团多、反应活性高、溶解性好等优点，有利于拓展木质素在聚合物材料领域的高附加值应用。重点综述了近年来国内外有关木质素化学降解及其降解产物应用于聚合物材料的研究进展。     

Optimizing the lignin based synthesis of flexible polyurethane foams employing reactive liquefying agents

The present work is focused on the optimization of a green process based on the employment of by‐products obtained from wood treatments as raw materials for producing flexible polyurethane foams. More specifically, lignin was employed in flexible polyurethane foams in order to partially replace the usual fossil polyols; therefore glycerol (GLY) and glycerin polyglycidyl ether (EJ 300) were used as the polyol fraction for lignin liquefaction. Polypropylene glycol triol was used as a chain extender in different ratios with liquefaction solvents, and polymeric diphenylmethane diisocyanate as an isocyanate fraction. Liquefaction of lignin was performed by microwave irradiation, thus reducing the processing time and energy required compared to present industrial production processes. All the foams were produced in controlled expansion through the adoption of a ‘one‐shot’ approach, using water as a blowing agent and with an isocyanate index (NCO/OH) of less than 100 to improve the flexibility of the foam. This approach allowed for the substitution of up to 12% of common petro derived polyol with commercial soda lignin. Finally, the foams were characterized, presenting properties that could be modulated as a function of lignin content, GLY/EJ 300 ratio and isocyanate index. The qualities of the foams were compatible with existing materials used for furniture and for the interiors of car seats and couches. © 2015 Society of Chemical Industry     

羟甲基化木质素/纤维素气凝胶粒子的制备、表征及吸附性能

以羟甲基化木质素和纤维素为原料，NaOH/尿素水溶液为溶解体系，采用冷冻干燥法制备羟甲基化木质素/纤维素气凝胶粒子。采用扫描电子显微镜（SEM）、傅里叶变换红外光谱（FT-IR）仪、X射线衍射（XRD）仪、比表面积及孔径分析仪等对其结构进行了表征。研究结果表明：羟甲基化木质素分子通过氢键作用附着在纤维素骨架上，气凝胶内部仍保持三维网状结构，羟甲基化木质素的引入使得气凝胶表面出现明显收缩，网状结构的致密度随着羟甲基化木质素用量提高而逐渐降低；同时气凝胶粒子具有纤维素Ⅱ型红外吸收峰和XRD衍射峰；粒子表现出Ⅱ型吸附/脱附等温线，孔径均在15 nm以下，且随着羟甲基化木质素用量不断提高，比表面积、孔容均有所减小，HKL-4的比表面积为105.3m²/g，孔容为0.336 6cm³/g，孔径为13.67nm。吸附性能分析表明在25℃下吸附5 h，HKL-4气凝胶粒子对金胺O、亚甲基蓝和罗丹明B的吸附量分别为33.06、96.06和43.26mg/g，对亚甲基蓝的饱和吸附量可达208.7 mg/g，吸附过程更符合Langmuir等温吸附模型，主要为单分子层吸附。     

AHP/碱木质素聚氨酯泡沫的阻燃性能

对精制后的碱木质素进行羟甲基化改性,再利用改性后的羟甲基化碱木质素部分替代聚醚多元醇,采用一步发泡法与聚合MDI制备了羟甲基化木质素基聚氨酯泡沫材料。将次磷酸铝(AHP)作为阻燃剂添加到泡沫中制备了阻燃碱木质素聚氨酯泡沫,通过极限氧指数(LOI)测试分析了羟甲基化木质素基阻燃聚氨酯泡沫的阻燃性能。利用热重分析(TG)和扫描电子显微镜(SEM)分别研究制得泡沫的热降解行为、成炭性能和残炭形貌。实验结果表明,当羟甲基化碱木质素替代聚醚多元醇的量为60%,次磷酸铝的添加量为30%时,碱木质素聚氨酯泡沫材料的极限氧指数(LOI)值达到了27.5%。因此,羟甲基化碱木质素和次磷酸铝使泡沫在燃烧时能更好的形成炭层,从而有效地隔绝空气,降低热传递,提高了材料的阻燃性能。