硅酸盐学报

聚合物先驱体转化法制备复相陶瓷：从组成结构设计到催化性能

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周聪 ¹^,² , 冯珧 ²^,³ , 余兆菊 ²^,⁴

硅酸盐学报 | 聚合物先驱体陶瓷专题—综合评述 2024,52(9): 2847-2861

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硅酸盐学报 |聚合物先驱体陶瓷专题—综合评述 2024 , 52 (9) : 2847 -2861

聚合物先驱体转化法制备复相陶瓷：从组成结构设计到催化性能

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周聪¹^,², 冯珧²^,³, 余兆菊²^,⁴

作者信息

^1．安徽工程大学材料科学与工程学院，先进陶瓷研究中心，安徽芜湖 241000

^2．厦门大学材料学院，高性能陶瓷纤维教育部重点实验室，福建厦门 361000

^3．深圳鲲鹏股权投资管理有限公司，广东深圳 518042

^4．厦门大学材料学院，厦门市电子陶瓷材料与元器件重点实验室，福建厦门 361005

作者简介:

周聪（1987—），男，博士，副教授。

Polymer-Derived Ceramic Nanocomposites: From Composition and Structure Design to Catalytic Properties

Cong ZHOU¹^,², Yao FENG²^,³, Zhaoju YU²^,⁴

Affiliations

^1.Center for Advanced Ceramics, School of Materials Science and Engineering, Anhui Polytechnic University, Wuhu 241000, China

^2.College of Materials, Key Laboratory of High Performance Ceramic Fibers, Ministry of Education, Xiamen University, Xiamen 361000, Fujian, China

^3.Shenzhen Kunpeng Equity Investment Management Co. Ltd., Shenzhen 518042, Guangdong, China

^4.College of Materials, Xiamen Key Laboratory of Electronic Ceramic Materials and Devices, Xiamen University, Xiamen 361005, Fujian, China

ZHOU Cong (1987-), male, Ph.D., Associate Professor. E-mail: congzhou2006@163.com

出版时间: 2024-09-20 doi: 10.14062/j.issn.0454-5648.20240151

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摘要

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聚合物先驱体陶瓷具备优异的物理化学性能、成分结构可设计性和易加工性，并能在介观尺度上控制孔洞的形貌尺寸，使其成为锚定和分散活性金属的良好支撑材料。以聚合物先驱体转化法为基础，通过掺杂不同的金属元素，可制备一系列具有独特结构和优异性能的催化剂。本文综述了近20年来聚合物先驱体转化法制备复相陶瓷并用于催化方面所做的研究工作。主要聚焦先驱体的化学成分设计、介孔结构的构建以及催化性能的研究，并对聚合物先驱体陶瓷在催化领域面临的挑战和发展前景进行了分析和展望。

关键词

聚合物先驱体陶瓷 / 复相陶瓷 / 多孔陶瓷 / 催化性能

Abstract

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Polymer-derived ceramics (PDCs) are a kind of advanced materials prepared by high-temperature pyrolysis of silicon-based precursors, and they exhibit a series of excellent properties, such as outstanding physical and chemical stabilities, flexible designability and easy processability. Furthermore, suitable modification of the precursors leads to multiphase ceramics known as polymer-derived ceramic nanocomposites (PDC-NCs), which in some cases exhibit enhanced properties compared to those of the original materials. Nowadays, the application of PDC-NCs is no longer limited to the high-temperature and high-strength structural materials, by doping different metals, a series of heterogeneous catalysts with unique microstructures and excellent catalytic properties can be synthesized via PDC approach. This article proposed an overview of the research progress on the preparation of PDC-NCs and their catalytic properties in the last 20 a. The main topics is related to the chemical composition design of polymeric precursors, the construction of porous structure, and the characterization of catalytic properties. Finally, the current challenges and perspectives on the field of porous PDC-NCs preparation and their application in catalysis are discussed.

The properties of PDC-NCs were directly affected by the composition and the architecture of the precursors, which provided enormous potential in tuning the microstructure and properties of the PDC-NCs via the various dopants. Metal containing PDC-NCs can be conveniently synthesized via the chemical modification of the precursors and physical blending, the obtained ceramics were endowed with different catalytic properties. In chemical modification, metal elements were linked to silicon-based precursor molecules via chemical reactions between precursors and metallic compounds. Three typical of metallic compounds have been summarized here: metal chlorides, acetylacetonate metal compounds and metal complex. Active groups like Si—H, N—H and C=C of precursors were convenience to the chemical modification. The metallic elements were homogeneously introduced into single-source precursors at the molecular level, which of great significance to prepare heterogeneous catalysts with high activity and stability. In physical blending, metallic compounds have been simply mixed with precursors through ultrasound, ball milling, or impregnation, and then PDC-NCs can be obtained via a simply pyrolysis process of these mixtures. Although there were still some drawbacks such as nonuniform element dispersion and relatively low catalytic performance, the physical blending approach is still a promising route to produce catalysts owing to the simple technologic process, cheap and wide source of raw materials, etc.

Additionally, the porous structure in heterogeneous catalysts exhibited a crucial influence on its properties, as high porosity could increase the specific surface area (SSA) of ceramics, and more catalytic active sites can be exposed, which is beneficial for improving catalytic efficiency. While appropriate pore size and porous structure are conducive to the diffusion and transport of reactants and products. Mesopores can be constructed in PDC-NCs via the introduction of hard/soft templates and even template-free method. The porous morphology and pore size can be regulated at the meso-scale by changing the templates and pyrolysis program, thereby further promoting the catalytic performance.

Many studies indicated that PDC-NCs with precise composition and structure design could be used as heterogeneous catalysts and showed excellent catalytic performance in the fields of catalytic synthesis, pollution treatment and new energy development. The polymeric precursors can be modified easily by various metallic compounds due to its superior molecular designability, after high-temperature pyrolysis, the ceramic skeleton can be applied as robust support materials to disperse and anchor active metallic nanoparticles. Moreover, the distinct characteristics such as adjustable SSA, pore volume, surface hydrophilicity or lipophilicity, as well as chemical resistance towards reaction medium, making porous PDC-NCs showed significant advantages for catalysis in harsh environments.

Summary and Prospects

Although significant progress has been achieved in the design and preparation of PDC-NCs for the heterogeneous catalysts, the prevenient research of this field is still superficial and unsystematic, and the "structure-property relationship" of porous PDC-NCs is also unclear. Based on the above-mentioned deficiencies, the challenges faced to PDC-NCs in the field of catalysis preparation have been analyzed in this review and a series of prospects have been proposed as follow: 1) Precursors played an important role in the preparation of PDC-NCs, in order to design and synthesize single-source precursors accurately, the reaction mechanism of chemical modification of polymeric precursors with metallic compounds needed to be studied intensively; 2) Preparing multi-doped PDC-NCs and exploring the synergistic effect of multiple elements in catalytic reactions; 3) In order to prepare catalysts with controllably and optimized catalytic performance, the catalytic mechanism of PDC-NCs need to be investigated thoroughly via the combination of experimental research with theoretical models to establish a scientific connection between "chemical composition, microstructure, catalytic properties" of PDC-NCs; 4) Further explore should focused on the catalytic properties and application of PDC-NCs, especially in the clean energy fields such as water-splitting and fuel cells; 5) Based on the excellent physical and chemical stabilities, high-temperature resistance of PDC-NCs, the catalytic application can be further explored in extreme environments where oxide-based or carbon-based supports did not use because of the lower structural and chemical instabilities; 6) Due to the complex molecular structure of precursors and pyrolysis process, the research on simulation of the microstructure of PDC-NCs is difficult, new technologies such as machine learning should be used to accelerate the development of new PDCs-based catalysts.

In addition, silicon carbide crystal with nanostructure exhibits great potential in photocatalytic water-splitting and photocatalytic CO₂ reduction due to its unique characteristic of semi-conductivity. However, because of the intrinsic defects such as low quantum efficiency, severe carrier recombination, and complex nanostructures, the development and application of SiC in photocatalysis fields have been seriously restricted. SiC nanomaterials with various low dimensional structures, like nanospheres, nanowires, and nanosheets can be prepared easily via PDC approach, the surface decoration and heterojunction construction can also be conveniently achieved. The semi-conductivity of PDCs and their applications in photocatalysis deserved further study, which can expand the application scope of PDCs and explore synthesis strategies of new materials.

Key words

polymer-derived ceramics / ceramic nanocomposites / porous ceramics / catalytic properties

引用本文

周聪, 冯珧, 余兆菊. 聚合物先驱体转化法制备复相陶瓷：从组成结构设计到催化性能. 硅酸盐学报, 2024 , 52 (9) : 2847 -2861 . DOI: 10.14062/j.issn.0454-5648.20240151

Cong ZHOU, Yao FENG, Zhaoju YU. Polymer-Derived Ceramic Nanocomposites: From Composition and Structure Design to Catalytic Properties[J]. Journal of the Chinese Ceramic Society, 2024 , 52 (9) : 2847 -2861 . DOI: 10.14062/j.issn.0454-5648.20240151

基金

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国家自然科学基金(52002002)
安徽省高校优秀青年骨干教师国外研修项目(gxgwfx2022017)
安徽工程大学中青年拔尖人才培养计划(S022021040)

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2024年第52卷第9期

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文章信息

doi: 10.14062/j.issn.0454-5648.20240151

接收时间：2024-02-27
首发时间：2026-10-22
出版时间：2024-09-20

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收稿日期：2024-02-27
修回日期：2024-04-03

基金

国家自然科学基金(52002002)

安徽省高校优秀青年骨干教师国外研修项目(gxgwfx2022017)

安徽工程大学中青年拔尖人才培养计划(S022021040)

作者信息

^1．安徽工程大学材料科学与工程学院，先进陶瓷研究中心，安徽芜湖 241000

^2．厦门大学材料学院，高性能陶瓷纤维教育部重点实验室，福建厦门 361000

^3．深圳鲲鹏股权投资管理有限公司，广东深圳 518042

^4．厦门大学材料学院，厦门市电子陶瓷材料与元器件重点实验室，福建厦门 361005

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https://castjournals.cast.org.cn/joweb/gsyxb/CN/10.14062/j.issn.0454-5648.20240151

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2种不同金属材料的力学参数

科 Family	属数 Number of genus	种数 Number of species	占总种数比例 Percentage of total species (%)	属 Genus	种数 Number of species	占总种数比例 Percentage of total species (%)
鹅膏菌科Amanitaceae	2	11	5.26	鹅膏菌属 Amanita	10	4.78
小菇科 Mycenaceae	2	12	5.74	丝盖伞属 Inocybe	5	2.39
多孔菌科 Polyporaceae	8	14	6.70	蜡蘑属 Laccaria	5	2.39
红菇科 Russulaceae	3	23	11.00	小皮伞属 Marasmius	6	2.87
				小菇属 Mycena	11	5.26
				光柄菇属 Pluteus	5	2.39
				红菇属 Russula	17	8.13
				栓菌属 Trametes	5	2.39

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