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林产化学与工业 ›› 2021, Vol. 41 ›› Issue (6): 10-18.doi: 10.3969/j.issn.0253-2417.2021.06.002

• 重点研发专栏 • 上一篇    下一篇

木质素制备燃料电池阴极电催化炭材料研究(Ⅱ)——改性酶解木质素炭的化学结构演变

金凯楠1, 左宋林1,*(), 桂有才1, 申保收2,3,*(), 王珊珊1, 胡欣1   

  1. 1. 南京林业大学 化学工程学院, 江苏 南京 210037
    2. 陕西省地表系统与环境承载力重点实验室, 陕西 西安 710127
    3. 西北大学 城市与环境学院/地表系统与灾害研究院, 陕西 西安 710127
  • 收稿日期:2021-07-14 出版日期:2021-12-28 发布日期:2021-12-31
  • 通讯作者: 左宋林,申保收 E-mail:zslnl@njfu.edu.cn;bsshen@nwu.edu.cn
  • 作者简介:申保收, 副教授, 硕士生导师, 研究领域为环境及储能材料与环境水化学, E-mail: bsshen@nwu.edu.cn
    左宋林, 教授, 博士生导师, 研究领域为生物质热化学转化与炭材料, E-mail: zslnl@njfu.edu.cn
    金凯楠(1996-), 男, 江苏南京人, 硕士生, 从事木质素的改性与应用研究
  • 基金资助:
    国家重点研发计划资助项目(2019YFB1503804);江苏省自然科学基金青年项目(BK20170928)

Studies on Lignin-based Carbon Materials as Electrocatalysts of Fuel Cells Cathode Ⅱ: Evolution of Chemical Structure of Lignin Derived Chars

Kainan JIN1, Songlin ZUO1,*(), Youcai GUI1, Baoshou SHEN2,3,*(), Shanshan WANG1, Xin HU1   

  1. 1. College of Chemical Engineering, Nanjing Forestry University, Nanjing 210037, China
    2. Shaanxi Key Laboratory of Earth Surface System and Environmental Carrying Capacity, Xi'an 710127, China
    3. College of Urban and Environmental Sciences/Institute of Earth Surface System and Hazards, Northwest University, Xi'an 710127, China
  • Received:2021-07-14 Online:2021-12-28 Published:2021-12-31
  • Contact: Songlin ZUO,Baoshou SHEN E-mail:zslnl@njfu.edu.cn;bsshen@nwu.edu.cn

摘要:

采用尿素和三聚氰胺改性酶解木质素,研究了改性前后木质素炭化制备的木质素基炭的化学结构演变过程。采用傅里叶变换红外光谱和X射线光电子能谱分析了不同炭化温度(300~900 ℃)对3种木质素基炭化学结构的影响,全面分析了炭的含氧和含氮化学官能团变化规律,研究结果显示:不管是未改性还是改性的酶解木质素,600~700 ℃是炭表面含氧和含氮基团发生显著变化的炭化温度区域。在600 ℃之前,3种木质素基炭主要含有羧基、羰基和羟基等含氧基团;高于600 ℃时得到的炭则主要含有羟基和羰基等含氧基团,且羟基官能团最多。经尿素和三聚氰胺改性后,600 ℃下木质素基炭含有的绝大部分含氮基团是吡啶氮和吡咯氮;达到700 ℃以后,升高炭化温度导致吡咯氮转化为季氮,季氮含量明显提高,木质素基炭含有的含氮基团则以吡啶氮、吡咯氮和季氮为主。

关键词: 木质素, 炭材料, 电催化, 尿素, 三聚氰胺, 化学结构

Abstract:

This paper investigated the evolution of chemical structure of the chars prepared by carbonization of enzymatic hydrolysis lignin and the urea-modified and melamine-modified lignin. Fourier transform infrared spectra and X-ray photoelectron spectra were collected for these carbonized lignin in the temperature range of 300-900 ℃. Based on these spectra, a comprehensive analysis was conducted in order to elucidate the evolution in chemical functional groups and the oxygen and nitrogen-containing groups involved in these lignin-derived chars. The results showed that, 600-700 ℃ is an important carbonization temperature range where the remarkable evolution of the oxygen-containing and nitrogen-containing groups happens, independent of the lignin modification by urea or melamine. Below 600 ℃, carboxyl, carbonyl and hydroxyl predominate in the oxygen-containing groups of the carbonized lignin; above 600 ℃, the hydroxyls and carbonyls are dominant, of which hydroxyls are the most. For the urea-modified and melamine-modified lignin, the pyridine-like and pyrrole-like groups are the predominant nitrogen-containing groups in the carbonized lignin before 600 ℃. Above 700 ℃, with the increase in the carbonization temperature, pyrrole-like groups were gradually transformed into quaternary species and, as a result, the species of the pyridine-like, pyrrole-like, quaternary nitrogen become a predominant nitrogen groups in the carbonized lignin chars.

Key words: lignin, carbon materials, electrocatalysis, urea, melamine, chemical structure

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