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源自木质素-金属有机框架复合材料的双金属硫化镍钴作为木质素二聚体氢解的高效多相催化剂。

Bimetallic nickel‑cobalt sulfide derived from lignin-MOFs hybrid as a high-efficiency heterogeneous catalyst for hydrogenolysis of lignin dimers.

作者信息

Xue Haonan, Xia Haihong, Li Hui, Ge Fei, Xu Wei, Yang Xiaohui, Zhou Minghao

机构信息

School of Chemistry and Chemical Engineering, Yangzhou University, Yangzhou 225002, China.

Institute of Chemical Industry of Forest Products, Chinese Academy of Forestry, Nanjing 210042, China.

出版信息

Int J Biol Macromol. 2025 Jan;287:138658. doi: 10.1016/j.ijbiomac.2024.138658. Epub 2024 Dec 10.

Abstract

Lignin represents a significant source of aromatic hydrocarbons in the natural world. The production of high-value chemicals from lignin has the great potential to effectively address the issue of fossil energy scarcity. In this study, complex sulfides of nickel‑cobalt bimetallic catalysts were prepared via hydrothermal synthesis and subsequently employed in the catalytic hydrogenolysis of CO bonds present in lignin. A series of complex sulfides NiS/CoS-CS-x-T derived from lignin-MOF (n = 0.5, 1, 1.5 and 2; x = 2, 4 and 6; T = 400, 500, 600 and 700 °C), were prepared under different conditions and subsequently employed in the catalytic hydrogenolysis of lignin model compounds. The optimal catalyst NiS/CoS-CS-4-500 exhibited the highest conversion rate of benzyl phenyl ether (BPE) (about 97.3 %), and the yields of toluene and phenol produced were 49.5 % and 43.6 %, respectively with isopropanol as the reaction solvent and no external H. The introduction of element sulfur in catalysts could effectively inhibit the further hydrogenation of generated aromatic chemicals. The catalysts were well characterized, and the results demonstrated that the catalysts exhibited high catalytic activity with an increased loading of active components. This study provided some novel findings for the construction of biomass-based catalysts and the production lignin-derived aromatic chemicals.

摘要

木质素是自然界中芳烃的重要来源。从木质素生产高价值化学品具有有效解决化石能源短缺问题的巨大潜力。在本研究中,通过水热合成制备了镍钴双金属催化剂的复合硫化物,随后将其用于木质素中存在的碳氧键的催化氢解。在不同条件下制备了一系列源自木质素-MOF的复合硫化物NiS/CoS-CS-x-T(n = 0.5、1、1.5和2;x = 2、4和6;T = 400、500、600和700°C),随后将其用于木质素模型化合物的催化氢解。最佳催化剂NiS/CoS-CS-4-500表现出最高的苄基苯基醚(BPE)转化率(约97.3%),以异丙醇为反应溶剂且无外部氢气时,生成的甲苯和苯酚产率分别为49.5%和43.6%。催化剂中元素硫的引入可有效抑制生成的芳烃化合物的进一步氢化。对催化剂进行了充分表征,结果表明随着活性组分负载量的增加,催化剂表现出高催化活性。本研究为构建生物质基催化剂和生产木质素衍生的芳烃化学品提供了一些新发现。

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