基于天然生物模板构建纳米材料及集成催化剂研究进展

doi:10.11949/0438-1157.20230456

摘要/Abstract

摘要：

新型纳米催化材料的设计、制备与应用是近年来催化领域的研究热点之一。具有复杂精细分级结构的生物模板在自然界中普遍存在，可作为软模板、硬模板或载体制备高连通性多级孔纳米材料，且通过制备条件参数的调控，其既能保留生物模板的宏观形貌和微纳结构，又能将生物模板原先的化学组成置换或负载所需催化组分（金属、金属氧化物、分子筛等），为纳米材料和集成催化剂的设计提供了新思路。而该类集成催化材料的“多层次空间结构”是现有制备技术很难获得的或者所需制备流程相对烦琐。本文从几种不同来源的典型生物模板出发，介绍了基于生物模板构建纳米材料及集成催化剂的方法，总结了该类集成纳米材料在催化领域的研究现状与应用实例，并对未来采用生物模板制备多化学组成的集成催化剂进行了展望。

关键词: 生物模板, 纳米材料, 集成催化剂, 组装, 多级孔

Abstract:

The design, preparation and application of new nano-catalytic materials are one of the research hotspots in the field of catalysis in recent years. Biological templates with complex and fine hierarchically porous structures are ubiquitous and can be used as soft templates, hard templates, or support to prepare nanomaterials with highly connective and hierarchical pores. Based on the regulation of preparation process parameters, the macro-morphology and micro-nano structure of the biological templates could be retained, as well as replacing the original biological components with the required catalytic components (e.g., metals, metal oxides, zeolites, etc.). This strategy provides new ideas for the design of nanomaterial and integrated nanocatalysts. In particularly, the “multi-level space” of such integrated catalytic materials is very difficult to be prepared by the existing traditional methods or the preparation process would be cumbersome in most cases. Starting from several typical biological templates from different sources, this review introduces the common preparation methods of nanomaterials and integrated nanocatalysts using natural biological templates, summarizes the research status of such integrated materials in catalysis, and looks forward to future research works on the utilization of biological templates to fabricate integrated nanocatalysts with multi-components.

Key words: biological template, nanomaterial, integrated catalyst, assembly, hierarchical pore

中图分类号:

TQ 018

余娅洁, 李静茹, 周树锋, 李清彪, 詹国武. 基于天然生物模板构建纳米材料及集成催化剂研究进展[J]. 化工学报, 2023, 74(7): 2735-2752.

Yajie YU, Jingru LI, Shufeng ZHOU, Qingbiao LI, Guowu ZHAN. Construction of nanomaterial and integrated catalyst based on biological template: a review[J]. CIESC Journal, 2023, 74(7): 2735-2752.

图/表 13

图1 集成催化剂（集成纳米催化剂）的结构示意图

Fig.1 Schematic diagram of the structure of integrated catalysts (integrated nanocatalysts)

图2 基于生物模板制备纳米材料和集成催化剂及其主要催化应用示意图

Fig.2 Schematic diagram of the fabrication of nanomaterial and integrated catalyst based on biological templates and the dominant catalytic applications

图3 基于不同尺寸的生物模板制备纳米材料概览

Fig.3 An overview of the synthesis of nanomaterials based on biological templates with different sizes

表1 生物模板的分类及其制备集成催化剂的特点

Table 1 Classification of biological templates and characteristics of the derived integrated catalysts

分类	模板优势及集成催化剂特点
植物模板^[13-14]	①表面官能团丰富，可诱导纳米材料沉积; ②尺寸均匀、空间结构精细，可调控集成催化剂的形貌; ③具有贯通孔结构和高孔隙率，利于反应物和产物分子扩散; ④可实现元素自掺杂（N、P等）
动物模板^[15-16]	①具有多层次空间结构，可提供更多活性位点; ②部分夹层结构具有空间限域作用; ③具有较大比表面积和丰富表面官能团; ④集成催化材料的内部结构和孔隙率可调控
微生物模板^[17-18]	①生物模板的生长繁殖快，人工培养较容易; ②具有丰富的氨基酸基团，利于制备多组分集成催化剂; ③可通过基因工程改造技术进行表面修饰; ④还原型生物酶可还原金属离子实现原位负载金属纳米颗粒
生物大分子模板^[19-20]	①衍生的集成催化剂生物兼容性好; ②可通过后修饰或降解调控生物大分子分子量或活性; ③分子识别特性强，可调控集成催化剂化学组成; ④自组装能力强，可二次组装

表2 基于生物模板制备催化剂材料的部分报道

Table 2 A summary of the preparation of catalyst materials based on biological templates

生物模板	纳米催化剂	制备方法	应用
蝴蝶翅膀^[21]	CuO/CBW	湿化学法	热分解高氯酸铵
荷花花粉^[22]	ZnO/Co₃O₄	浸渍法（湿化学法）	光降解亚甲基蓝和四环素
稻谷壳^[23]	Bi₂WO₆/TiO₂	溶剂热法（湿化学法）	光降解微囊藻素
天然竹子^[24]	BCP/TiO₂	直接煅烧法	光降解亚甲基蓝
菠菜叶^[25]	CS@Au/ZnO	湿化学法	光降解罗丹明B和环丙沙星
废蛋壳^[26]	CuO/ZnO/ES	湿化学法	光催化还原4-硝基苯酚
蝴蝶翅膀^[27]	ZnO	原子层沉积法	光催化降解罗丹明B
蝴蝶翅膀^[28]	Au/TiO₂_PW	湿化学法	光热催化降解亚甲基蓝和十二烷基苯磺酸钠
松花粉^[29]	Ce/TiO₂	溶胶-凝胶法+浸渍法（湿化学法）	光催化抗菌
牛皮胶原纤维^[30]	$S O 4 2 -$ /ZrO₂-NiO	湿化学法	酯化反应
玫瑰花瓣^[31]	CeO₂/Co₃O₄	湿化学法	光降解亚甲基蓝和四环素
玫瑰花瓣^[32]	ZnWO₄	浸渍法（湿化学法）	光降解亚甲基蓝
花粉^[33]	$S O 4 2 -$ /M1 _x O _y -M2 _x O _y	湿化学法	氯苯的硝化反应
松树花粉^[34]	ZnAl-LDH/ZnCo₂O₄	湿化学法	光降解刚果红
芭蕉叶^[35]	TiO₂	湿化学法	光降解亚甲基蓝
A.vitifolia Buch.树叶^[36]	Pt/N-TiO₂	溶胶-凝胶法（湿化学法）	光催化产氢

表2 基于生物模板制备催化剂材料的部分报道

Table 2 A summary of the preparation of catalyst materials based on biological templates

生物模板	纳米催化剂	制备方法	应用
蝴蝶翅膀^[21]	CuO/CBW	湿化学法	热分解高氯酸铵
荷花花粉^[22]	ZnO/Co₃O₄	浸渍法（湿化学法）	光降解亚甲基蓝和四环素
稻谷壳^[23]	Bi₂WO₆/TiO₂	溶剂热法（湿化学法）	光降解微囊藻素
天然竹子^[24]	BCP/TiO₂	直接煅烧法	光降解亚甲基蓝
菠菜叶^[25]	CS@Au/ZnO	湿化学法	光降解罗丹明B和环丙沙星
废蛋壳^[26]	CuO/ZnO/ES	湿化学法	光催化还原4-硝基苯酚
蝴蝶翅膀^[27]	ZnO	原子层沉积法	光催化降解罗丹明B
蝴蝶翅膀^[28]	Au/TiO₂_PW	湿化学法	光热催化降解亚甲基蓝和十二烷基苯磺酸钠
松花粉^[29]	Ce/TiO₂	溶胶-凝胶法+浸渍法（湿化学法）	光催化抗菌
牛皮胶原纤维^[30]	$S O 4 2 -$ /ZrO₂-NiO	湿化学法	酯化反应
玫瑰花瓣^[31]	CeO₂/Co₃O₄	湿化学法	光降解亚甲基蓝和四环素
玫瑰花瓣^[32]	ZnWO₄	浸渍法（湿化学法）	光降解亚甲基蓝
花粉^[33]	$S O 4 2 -$ /M1 _x O _y -M2 _x O _y	湿化学法	氯苯的硝化反应
松树花粉^[34]	ZnAl-LDH/ZnCo₂O₄	湿化学法	光降解刚果红
芭蕉叶^[35]	TiO₂	湿化学法	光降解亚甲基蓝
A.vitifolia Buch.树叶^[36]	Pt/N-TiO₂	溶胶-凝胶法（湿化学法）	光催化产氢

图4 （a）鳞状壁二氧化锆空心球和多孔二氧化锆空心微球的制备流程及其吸附过程；（b）油菜花粉的SEM图；（c）具有鳞状壁空心微球的SEM图；（d）以盐酸蚀刻花粉为模板制备的多孔空心微球的SEM图[13]

Fig.4 (a) The fabrication routes of scale-walled zirconia hollow sphere, porous zirconia hollow microsphere and their adsorption process; (b) SEM image of rape pollen; (c) SEM image of hollow microspheres with scaly surfaces; (d) SEM image of porous hollow microspheres prepared by using HCl-etched pollen as a template[13]

图5 （a）ZnZrO x & bio-SAPO-34双功能催化剂的制备流程；（b）原始稻壳的SEM图；（c）双功能催化剂的SEM图；（d）双功能催化剂在CO2热催化串联加氢反应中的性能评价结果[62]

Fig.5 (a) The fabrication route of ZnZrO x & bio-SAPO-34 bifunctional catalysts; (b) SEM image of the raw rice husk; (c) SEM image of the bifunctional catalysts; (d) The catalytic performance of CO2 thermal catalytic hydrogenation[62]

图6 （a）基于两种不同Si含量的生物模板制备bio-ZSM-5示意图；（b）原始丝瓜瓤的照片；（c）、（d）丝瓜瓤的SEM图；（e）基于丝瓜瓤模板制备的bio-ZSM-5的照片；（f）、（g）bio-ZSM-5的SEM图[14]

Fig.6 (a) Schematic diagram of the synthesis of bio-ZSM-5 based on two biological templates with different Si content; (b) A photo of luffa sponge; (c), (d) SEM images of luffa sponge; (e) A photo of bio-ZSM-5 prepared by using luffa sponge as template; (f), (g) SEM images of bio-ZSM-5[14]

图7 （a）BW@SS催化剂的制备流程；（b）蝴蝶翅膀（BW）的SEM图；（c）BW@SS催化剂的SEM图[71]

Fig.7 (a) The synthetic route of BW@SS catalysts; (b) SEM image of the butterfly wings; (c) SEM image of the obtained BW@SS catalysts[71]

图8 （a）TiO2-PEI-ESM复合光催化剂的制备流程；（b）~（d）原始蛋壳膜生物模板的 SEM图；（e）~（g）TiO2-PEI-ESM复合光催化剂的SEM图[79]

Fig.8 (a) Preparation route of TiO2-PEI-ESM composite photocatalyst; (b)—(d) SEM images of the original eggshell membrane; (e)—(g) SEM images of TiO2-PEI-ESM composite photocatalyst[79]

图9 （a）锂锰氧化物微管（LMO-MT）及其酸洗获得的尖晶石锰氧化物（HMO-MT）的制备流程；（b）真菌衍生的水钠锰矿微管（BB-MTs）的SEM图；（c）LMO-MT的SEM图；（d）HMO-MT的SEM图[84]

Fig.9 (a) Synthesis route of LMO-MTs and HMO-MTs; (b) SEM image of BB-MTs (biogenic birnessite-microtubes); (c) SEM image of LMO-MT; (d) SEM image of HMO-MT[84]

图10 （a）利用DNA模板合成SiO2纳米颗粒的制备流程；（b）“i”型DNA模板的结构示意图；（c）“i”型SiO2纳米材料的AFM图；（d）“i”型SiO2纳米材料的SEM图；（e）,（f）“i”型SiO2纳米材料的STEM图及EDX元素线扫图[90]

Fig.10 (a) Schematic illustration of silica nanostructures based on DNA template; (b) Schematic illustration of the “i” pattern DNA template; (c) AFM image of the “i” pattern silica nanomaterial; (d) SEM image of the “i” pattern silica nanomaterial; (e), (f) STEM image and the corresponding EDX elemental line-scanning of the “i”pattern silica nanomaterial[90]

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