催化学报 ›› 2020, Vol. 41 ›› Issue (8): 1217-1229.DOI: 10.1016/S1872-2067(20)63534-3

• 论文 • 上一篇    下一篇

生物质基双功能氮掺杂多孔碳在对硝基苯酚还原和苯乙烯氧化中的应用

刘江永a, 李金兴a, 叶荣飞a, 晏晓东b, 王理霞a, 菅盘铭a   

  1. a 扬州大学化学化工学院, 江苏扬州 225002;
    b 江南大学化学与材料工程学院, 江苏无锡 214122
  • 收稿日期:2019-11-20 修回日期:2019-12-28 出版日期:2020-08-18 发布日期:2020-08-08
  • 通讯作者: 刘江永
  • 基金资助:
    江苏省高等学校自然科学研究项目(17KJB530011);江苏省博士后科研资助计划项目(2019K093);江苏高校优势学科建设工程资助项目(PAPD).

Versatile bifunctional nitrogen-doped porous carbon derived from biomass in catalytic reduction of 4-nitrophenol and oxidation of styrene

Jiangyong Liua, Jinxing Lia, Rongfei Yea, Xiaodong Yanb, Lixia Wanga, Panming Jiana   

  1. a School of Chemistry and Chemical Engineering, Yangzhou University, Yangzhou 225002, Jiangsu, China;
    b School of Chemical and Material Engineering, Jiangnan University, Wuxi 214122, Jiangsu, China
  • Received:2019-11-20 Revised:2019-12-28 Online:2020-08-18 Published:2020-08-08
  • Supported by:
    This work was supported by the Natural Science Foundation of the Jiangsu Higher Education Institutions of China (17KJB530011), the Jiangsu Planned Projects for Postdoctoral Research Funds (2019K093), and the Priority Academic Program Development of Jiangsu Higher Education Institutions (PAPD).

摘要: 大多数催化过程需以金属甚至贵金属作为活性位点,尽管金属基催化剂在很多情况下可以展现出较好的催化性能,但其实际应用受到价格较高、储量有限、组分流失和金属位点烧结等因素的限制.在非金属催化剂中,碳材料由于具有来源丰富、稳定性好以及可调控性强等特点而得到了广泛应用.研究表明,将具有供电子或吸电子特征的异质原子如氮、硼、硫和磷等掺入碳结构中是一种可行的策略,可通过电子结构调控产生缺陷来提高催化性能.其中,氮原子与碳原子的原子半径相近,可有效改善碳的化学惰性,是一种理想的掺杂原子.基于这些认识,各类氮掺杂碳材料,如碳纳米管、碳纳米球、石墨烯、介孔碳、碳纤维等已经被开发出来且显示出令人满意的催化效果.然而,传统氮掺杂碳材料的制备还存在反应条件苛刻、需要使用各类有毒试剂以及制备过程复杂等缺点.近年来,以廉价易得的生物质为原料,通过简单绿色方法合成氮掺杂碳材料,并进一步探索其在更多催化领域如有机催化中的应用得到了广泛关注.
对硝基苯酚的催化还原反应和苯乙烯的催化氧化反应一般需要金属催化剂.其中,对硝基苯酚是化学工业中常见的难降解污染物,可对环境和人类健康造成严重威胁.在所有减轻其污染和危害的方法中,从环境和工业角度出发,将其催化还原成对氨基苯酚是最经济的方法.苯乙烯的氧化反应可用于生产各类高附加值化学品,例如环氧苯乙烷是合成增塑剂、香料和药品等的重要中间体.对于这两个反应,开发高效的生物质基碳氮掺杂碳材料作为非金属催化剂仍具有挑战性.
本文以价廉易得的萝卜为原料,通过耦合氮掺杂、碳化和氢氧化钾活化过程,采用简单的一步法制备得到了一系列氮掺杂多孔碳(NKC),发现其在对硝基苯酚还原反应和苯乙烯氧化反应中均表现出良好的催化性能.NKC系列催化剂的比表面积、孔体积和N掺杂含量分别为918.9-3062.7m2 g-1,1.01-2.04cm3 g-1和1.29-15.3at%.综合表征结果和催化反应结果发现,催化性能与结构参数并不直接相关,而是与催化剂中石墨化氮的含量呈正相关关系.在NKC系列催化剂中,NKC-3-800对于这两个反应的催化反应效果最佳,其催化效果可达到或超过已报道的金属甚至贵金属催化剂.此外,本文还计算了两个反应的各类动力学和热力学参数,并分析了可能的催化反应机理.本文不仅为生物质的高附加值利用提供了新的思路,而且为廉价和丰富的生物质基碳催化剂在有机反应中的进一步应用开辟了更多的可能性.

关键词: 氮掺杂, 碳, 生物质, 对硝基苯酚, 苯乙烯

Abstract: The scarcity and weak durability of metal, especially precious metal catalysts are big obstacles for their large-scale application in many reactions. The state-of-the-art of the catalytic science prefers such type of catalysts, which can replace metal-based catalysts to alleviate energy and environmental crises and exhibit catalytic performance comparable to or even exceeding these metal catalysts. Herein, we report that N-doped porous carbon (NKC) derived from cheap and abundant radish can be employed as versatile and efficient bifunctional catalysts in both the catalytic reduction of 4-nitrophenol (NRR) and oxidation of styrene (SOR). The series of NKC catalysts were prepared with a simple and facile one-pot strategy by coupling the N-doping, carbonization and KOH activation processes. These catalysts show hierarchical porosity, with the specific surface area, total pore volume and N-doping content ranging from 918.9-3062.7 m2 g-1, 1.01-2.04 cm3 g-1 and 1.29-15.3 at%, respectively. Interestingly, our finding suggests that the catalytic performance is not directly related to these parameters but correlates positively with the content of graphitic N dopants, which is the dominant contributor for impelling both the NRR and SOR. Another intriguing finding is that for both reactions, the optimal catalyst was found to be the NKC-3-800 which possesses the highest graphitic N content of 3.13 at%. In addition, to gain insight into the catalytic behavior, analyses of kinetics and thermodynamics were performed, and the catalytic mechanisms were postulated. This work paves the way for the construction of biomass-derived N-doped carbon catalysts for bi-or even multi-functional applications in various organic reactions.

Key words: Nitrogen-doping, Carbon, Biomass, 4-Nitrophenol, Styrene