多孔炭材料在纤维素催化转化中的应用

doi:10.1016/S1872-2067(15)60942-1

摘要/Abstract

摘要：

生物质作为自然界唯一可再生的有机碳资源, 其利用受到了越来越多的关注. 特别是随着能源和环境危机的日益加重, 将生物质中非可食用部分催化转化为燃料及具有高附加值的化学品被认为是高效、环保、原子经济的绿色过程. 同时, 多孔炭材料具有丰富的孔道结构、优异的水热稳定性和大比表面积, 是生物质催化转化反应中最常用的载体材料之一. 兼之炭材料表面极性、亲疏水性的可调变性, 及对酸碱溶剂的反应惰性, 也使其无论在学术研究还是在工业应用中都具有特殊的优势. 另外, 随着纳米炭材料科学的飞速发展, 合成孔径、形貌、及表面官能团可控的介孔炭和具有多级孔道结构的多孔炭材料成为可能, 将其应用到纤维素催化转化过程中, 对深入理解孔道结构、表面官能团对纤维素转化的作用, 揭示催化反应作用机制, 指导炭基催化剂的设计合成, 均具有重要意义.
在本综述中, 我们首先对纤维素转化中多孔炭的孔道结构和表面官能团性质的独特作用进行了阐述. 由于商业活性炭的孔径一般在微孔尺度, 但纤维素及可溶低聚糖的分子体积较大, 因而其在活性炭中的传质受到了极大的限制. 通过模板法获得的介孔炭材料, 可实现孔径在2-10 nm的可控合成, 大大提高了反应物的扩散速率, 使之能与催化活性位有效接触. 但孔道过于狭长, 在反应过程中堵塞的可能性增高, 进而导致催化剂失活; 因此, 在介孔孔道的基础上, 建立互通的多级孔道结构对反应物、中间物、和产物的扩散, 及催化活性的保持更为有利. 另一方面, 炭材料表面的含氧官能团不仅具有加强1,4-糖苷键吸附的作用, 还可以作为酸性活性中心催化水解反应的进行; 尤其是在传统的水相纤维素催化转化过程中, 亲水表面对多孔炭催化剂与反应物的接触非常有利.
本文以纤维素水解及纤维素水解加氢反应为例, 展开讨论了多孔炭作为固体酸及双功能催化剂载体的应用. 在水解反应中, 纤维素首先在热水中降解为可溶低聚糖, 之后再与活性炭表面官能团反应; 其中多孔炭的比表面积、酸量、及酸强度均是促进水解发生的正向因素. 在水解加氢反应中, 炭载贵金属催化剂作为最常用的加氢催化剂, 可获得以六元醇为主的纤维素转化产物. 除了加氢作用之外, 贵金属小颗粒被证实可以通过氢溢流作用提供水解所需的H⁺, 同时, 正价的贵金属也可促进反应过程中的氢转移. 另一方面, 由于钨物种可催化逆羟醛缩合反应的发生, 因此在反应体系中引入钨物种时, 水解加氢的主要产物由六元醇变为乙二醇. 需要特别指出的是, 在纤维素催化水解加氢的过程中, 多孔炭材料作为载体同样具有非常重要的作用: 一方面, 三维介孔的孔道结构不仅有利于反应物、产物的扩散, 也有利于加氢金属催化剂的分散, 进而提高金属的催化加氢能力; 另一方面, 当炭材料的表面化学性质改变时, 也会影响产物的选择性分布, 例如当炭表面显碱性时, 由于异构化作用, 丙二醇成为主要产物.
本文最后, 我们列举了一些新型多孔炭材料, 包括杂原子改性的多孔炭材料和金属氧化物-炭复合多孔材料的合成方法及其在纤维素催化转化乃至生物质转化中的潜在应用.

关键词: 生物质转化, 催化, 多孔炭, 活性炭, 介孔炭, 纤维素

Abstract:

The application of porous carbon in catalytic transformation of cellulose has received considerable interest owing to increasing energy and environmental pressures. In this mini-review, we first outline the featured properties of porous carbon in catalytic cellulose transformation in terms of porosities and surface functionalities. An interconnected hierarchical structure and enrichment of mesopores are highly desired for reactant, intermediate, and product diffusion; while hydrophilic surfaces are favored in aqueous phase transformation and certain acidic oxygen functionalities play a role of acid sites as well as enhancing the adsorption of feedstock via 1,4-glycosidic bonds. We then summarize specific reactions in cellulose transformation in the order of hydrolysis and hydrolytic hydrogenation. In the hydrolysis of cellulose, porous carbon is generally used as a solid acid by taking advantage of its enriched oxygen functionalities, while in the hydrolytic hydrogenation, carbon serves as the support of bifunctional catalysts with active acidic sites. Finally, the synthesis and potential application of specific novel porous carbon materials, such as heteroatom-modified porous carbon and mesoporous carbon composites, are highlighted.

Key words: Biomass conversion, Catalysis, Porous carbon, Activated carbon, Mesoporous carbon, Cellulose

赵晓晨, 徐金铭, 王爱琴, 张涛. 多孔炭材料在纤维素催化转化中的应用[J]. 催化学报, 2015, 36(9): 1419-1427.

Xiaochen Zhao, Jinming Xu, Aiqin Wang, Tao Zhang. Porous carbon in catalytic transformation of cellulose[J]. Chinese Journal of Catalysis, 2015, 36(9): 1419-1427.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(15)60942-1

https://www.cjcatal.com/CN/Y2015/V36/I9/1419

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