单原子催化剂制备方法的研究进展

doi:10.15541/jim20240302

摘要/Abstract

摘要：

为了应对能源供应紧张和环境保护的挑战, 探索和开发高效催化剂成为解决能源和环境问题的关键策略。单原子催化剂(Single-atom catalysts, SACs)作为近年来新兴的催化剂类型, 其独特的性质吸引了科研界的广泛关注。金属以单原子的形式负载在载体表面, 实现了电子、几何结构的特殊性以及原子利用率的最大化。在能源催化、环境催化、有机催化等多个领域, SACs都表现出优异的活性、选择性和稳定性, 为相关催化反应提供了强有力的支撑。更重要的是, SACs在贵金属利用方面展现出巨大的潜力。通过精确调控可以最大限度地提高贵金属的催化效率, 进而降低催化剂制造成本。因此, SACs的制备方法和作用机理成为国际催化领域的研究热点。本文综述了SACs的合成策略, 包括自下而上、自上而下和量子点交联/自组装, 具体介绍了共沉淀法、浸渍法、原子层沉积(Atomic layer deposition, ALD)法、高温原子热迁移法和高温热解法等制备SACs的研究进展, 并对SACs制备面临的挑战和未来前景进行了总结和展望。

关键词: 单原子催化剂, 自上而下策略, 自下而上策略, 合成, 综述

Abstract:

Nowadays, we are facing increasingly serious energy and environmental problems, which urgently need more efficient chemical industry technologies to meet the requirements of low cost, high yield and sustainability. Developing efficient catalysts is of great significance for improving production efficiency, expanding economic benefits, optimizing energy structure, and ameliorating industrial structure. Single-atom catalysts (SACs), featuring unique properties arising from their single-atom dispersion on support surface, have demonstrated exceptional activity, selectivity and stability in energy catalysis, environmental catalysis and organic catalysis. Therefore, preparation methods and catalytic mechanisms of SACs have become a hot research topic on the international catalytic community. This review describes three strategies for preparing SACs: bottom-up synthesis, top-down synthesis and quantum dots cross-linking/self-assembly. Specifically, methods such as co-precipitation, immersion, atomic layer deposition, high-temperature atom thermal transfer, and high-temperature pyrolysis are presented in detail. These approaches precisely control the location and distribution of metal atoms, maximizing their utilization and catalytic efficiency. In addition, the challenges and development prospects faced by SACs related to stability, integrated control and industrial scalability are also summarized.

Key words: single-atom catalyst, top-down strategy, bottom-up strategy, synthesis, review

中图分类号:

TQ174

孙树娟, 郑南南, 潘昊坤, 马猛, 陈俊, 黄秀兵. 单原子催化剂制备方法的研究进展[J]. 无机材料学报, 2025, 40(2): 113-127.

SUN Shujuan, ZHENG Nannan, PAN Haokun, MA Meng, CHEN Jun, HUANG Xiubing. Research Progress on Preparation Methods of Single-atom Catalysts[J]. Journal of Inorganic Materials, 2025, 40(2): 113-127.

图/表 11

图1 SACs合成策略及应用

Fig. 1 Synthesis strategies and applications for SACs

图2 rWGS过程示意图[33]

Fig. 2 Diagram of reverse water gas shift (rWGS) process[33]

图3 Ir1/Ni LDH-T和Ir1/Ni LDH-V的OER机理研究[37]

Fig. 3 Research on OER mechanism for Ir1/Ni LDH-T and Ir1/Ni LDH-V[37] (a, b) Schematic structure models of Ir1/Ni LDH-T (a) and Ir1/Ni LDH-V (b) from top views; (c, d) Charge density differences of Ir atoms on Ir1/Ni LDH-T (c) and Ir1/Ni LDH-V (d) with yellow and cyan areas indicating electron accumulation and depletion, respectively; (e, f) Projected density of states (PDOS) in Ir1/Ni LDH-T (e) and Ir1/Ni LDH-V (f); (g) Free energy diagram of Ir1/Ni LDH-T and Ir1/Ni LDH-V with Ir as the active site; (h, i) Schematic OER pathways for Ir1/Ni LDH-T (h) and Ir1/Ni LDH-V (i) with pink, red, gray, and purple spheres representing H, O, Ni, and Ir atoms, respectively, and blue circles indicating reaction intermediates. Colorful figures are available on website

图4 (a~c)Pt SACs-ZIF-8-NC(30 s)、(d~f)Pt subclusters-ZIF-8-NC(1 min)和(g~i)Pt NPs-ZIF-8-NC(5 min)的高角度环形暗场扫描透射电子显微镜(HAADF-STEM)照片[57]

Fig. 4 High angle annular dark field-scanning transmission electron microscopy (HAADF-STEM) images of (a-c) Pt SACs-ZIF-8-NC (30 s), (d-f) Pt subclusters-ZIF-8-NC (1 min), and (g-i) Pt NPs-ZIF-8-NC (5 min)[57] Colorful figures are available on website

图5 Pd原子分散催化剂(PdSA+C/g-C3N4)的构建策略示意图[68]

Fig. 5 Construction strategy of Pd atomically dispersed catalysts (PdSA+C/g-C3N4)[68] Colorful figure is available on website

图6 使用冷冻前驱体溶液(实验组)和使用液体前驱体溶液(对照组)制备SACs的对比示意图[63]

Fig. 6 Schematic preparation of SACs samples using frozen precursor solutions (experimental groups) and using liquid precursor solutions (control groups)[63]

图7 Pt纳米颗粒烧结示意图[89]

Fig. 7 Diagram of Pt nanoparticle sintering[89]

图8 (a)Cu SACs/S−N[91]和(b)Bi-SACs-NS/C[92]的制备示意图

Fig. 8 Schematic preparation of (a) Cu SACs/S−N[91] and (b) Bi-SACs-NS/C[92] Colorful figures are available on website

图9 Pt-LrEGO的合成示意图[96]

Fig. 9 Schematic illustration of Pt-LrEGO formation[96] Colorful figure is available on website

图10 高温热解法制备示意图[115⇓-117]

Fig. 10 Schematic diagrams of high-temperature pyrolysis preparative method[115⇓-117] (a) Preparation of Fe SACs/GO[115]; (b) N-doped carbon atomization of Pd NPs/TiO2[116]; (c) Single atomic catalyst using atomic Co site and polarization carrier[117]. Colorful figures are available on website

图11 SACs合成过程示意图[120]

Fig. 11 Schematic illustration for synthesis processes of SACs[120] (a) Top-down synthesis strategy; (b) Bottom-up synthesis strategy; (c) Crosslinking and self-assembly based on graphene quantum dots (GQDs). Colorful figures are available on website

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