χ-Fe5C2：结构，合成与催化性质调控

引用本文: 赵华博, 马丁. χ-Fe₅C₂：结构，合成与催化性质调控[J]. 物理化学学报, 2020, 36(1): 190608. doi: 10.3866/PKU.WHXB201906087 shu

Citation: Zhao Huabo, Ma Ding. χ-Fe₅C₂: Structure, Synthesis, and Tuning of Catalytic Properties[J]. Acta Physico-Chimica Sinica, 2020, 36(1): 190608. doi: 10.3866/PKU.WHXB201906087 shu

χ-Fe₅C₂：结构，合成与催化性质调控

赵华博 ^1, ,
马丁 ^{2,
,}

1.
北京低碳清洁能源研究院，北京 102211
2.
北京大学化学与分子工程学院，北京 100871

作者简介:
马丁教授，2001年在中国科学院大连化学物理研究所取得博士学位，2009年加入北京大学化学与分子工程学院物理学研究所，从事多相催化研究，着力于发展新的催化体系，结合原位表征手段来解决催化过程中的重要科学问题;

通讯作者: 马丁, dma@pku.edu.cn

基金项目:
国家重大专项项目(2017YFB0602500)资助

摘要: 铁碳化物, 特别是χ-Fe₅C₂，因在多个不同领域的应用长期以来受到研究者的密切关注。事实上，χ-Fe₅C₂已经被认定为铁基费托合成催化剂的活性相。除了作为催化剂外，χ-Fe₅C₂在电化学、磁成像和治疗等方面也有应用价值。自发现以来，人们对χ-Fe₅C₂的结构、稳定性、催化性能等物理化学性质开展了研究。χ-Fe₅C₂的C2/c结构在上世纪60年代初次得到解析，但是受限于样品中常常混合其他氧化铁和碳化铁，在结构方面还存在争议。研究者仍致力于结合先进表征技术和理论方法，利用高纯度的样品来建立更加准确的模型。作为一种亚稳态结构，传统合成方法很难制备高纯度的χ-Fe₅C₂。经过对合成方法的不断探索，物相单一和尺寸形貌可控的合成已经实现。多种铁和碳的前驱体可以用来合成χ-Fe₅C₂，而固-固、固-气和固-液相的碳化过程均能够用来制备不同粒度和形貌的χ-Fe₅C₂。合成方法方面的成果来了对χ-Fe₅C₂物相形成机理的新认识。利用原位表征方法，研究者已经揭示了气固相和液固相制备过程中物相形成的一些细节。无定形的Fe-C复合物的形成与晶化有可能是关键步骤。在新的制备方法基础上，出现了多种调控χ-Fe₅C₂催化活性的新手段。低钴含量的有钴纳米粒子和χ-Fe₅C₂组成的复合体具有非常高的低温费托合成活性。通过第二组分的修饰后可以使χ-Fe₅C₂突破传统的费托合成反应的局限，成为制备低碳烯烃、长链α烯烃、芳烃和含氧化物的新型催化剂。在这篇综述中，我们将回顾自上世纪中期以来对χ-Fe₅C₂物相的研究成果，聚焦于对结构解析，制备方法，生成机制以及在催化性能调控等方面的进展。我们总结了一系列用于制备χ-Fe₅C₂的方法以及控制催化性质的路径。合成方法的突破是更好认识χ-Fe₅C₂物理化学的关键。

关键词:

English

χ-Fe₅C₂: Structure, Synthesis, and Tuning of Catalytic Properties

Zhao Huabo ^1, ,
Ma Ding ^{2,
,}

1.
National institute of Low Carbon and Clean Energy, Beijing 102211, P. R. China
2.
College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, P. R. China

Corresponding author: Email: dma@pku.edu.cn; Tel.: +86-10-62758603

Received Date: 27 June 2019
Accepted Date: 19 August 2019
Revised Date: 03 August 2019
Available Online: 15 January 2020
Fund Project:
The project was supported by the National Key Research and Development Program of China (2017YFB0602500)

Abstract: Iron carbides, especially Hägg carbide (χ-Fe₅C₂), have become a topic of significant research interest due to their potential application in various fields over the past decades. For Fischer-Tr psch (F-T) synthesis, χ-Fe₅C₂ has been confirmed as an active phase. In addition, this well-known catalytic material is a candidate for potential application in electrochemistry, magnetic imaging, and various therapies. The physical chemistry, including structure, stability, and catalytic properties of χ-Fe₅C₂ has been studied since its discovery. The C2/c crystal structure of Hägg carbide was initially resolved in the 1960s. Because various iron oxides and carbides always co-exist in the synthesized χ-Fe₅C₂ samples, the structure model still faces challenges. The crystal structure is being revised with high-purity samples using modern characterization techniques and theoretical methods. However, it is very difficult to obtain the pure phase of χ-Fe₅C₂ via traditional preparation methods owing to the metastable phase of χ-Fe₅C₂. Hence, tremendous efforts have been devoted to the synthesis of χ-Fe₅C₂. Recently, some processes to prepare single-phase and structure-controlled χ-Fe₅C₂ nanostructures have been reported. Many iron and carbon precursors can be used to prepare Hägg carbide. Carburization in solid-solid, solid-gas, and solid-liquid phases can be adopted to synthesize χ-Fe₅C₂ of various sizes and morphologies. The success of synthetic chemistry has provided novel insights into the mechanism of phase transformation in χ-Fe₅C₂. More details regarding the formation of the χ-Fe₅C₂ structure in the solid-gas and solid-liquid phases have been revealed via in situ characterization methods. The formation and crystallization of an Fe-C amorphous composite is likely the key step. The application of χ-Fe₅C₂ in catalysis has also benefited from novel synthesis strategies. With the development of these preparation methods, tuning the activity and selectivity of χ-Fe₅C₂ has become possible. A heterostructure of small Co/χ-Fe₅C₂ with low cobalt loading showed an unexpectedly high CO conversion rate at low temperature. Beyond classical F-T synthesis, χ-Fe₅C₂ is a promising catalyst for the production of light olefins, long chain α-olefins, aromatics, and alcohol synthesis by modification with other elements. Combining density functional theory (DFT) calculations and kinetic analysis, the roles of promoters and interaction with χ-Fe₅C₂ have been evaluated to some extent. Herein, the recent progress in the synthesis, structural analysis, formation mechanisms, and catalytic performance of χ-Fe₅C₂ is summarized. A collection of synthesis methods is presented, and novel methods for regulating catalytic properties are reviewed. We believe that advanced synthesis methods are key to a deeper understanding and better utilization of this material.

Key words:

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沈阳化工大学材料科学与工程学院沈阳 110142

χ-Fe₅C₂：结构，合成与催化性质调控

通讯作者: 马丁, dma@pku.edu.cn

English

χ-Fe₅C₂: Structure, Synthesis, and Tuning of Catalytic Properties

Corresponding author: Email: dma@pku.edu.cn; Tel.: +86-10-62758603

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