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化学进展 2023, Vol. 35 Issue (6): 918-927 DOI: 10.7536/PC221235 前一篇   后一篇

• 综述 •

二氧化碳氢化制多碳化合物金属纳米簇催化

王远1,2,*(), 于聿律1,2, 谭心1,2   

  1. 1 北京大学化学与分子工程学院 北京 100871
    2 北京分子科学国家研究中心 北京 100871
  • 收稿日期:2023-01-02 修回日期:2023-05-22 出版日期:2023-06-24 发布日期:2023-06-10
  • 基金资助:
    国家自然科学基金项目(91961103); 国家自然科学基金项目(21821004); 北京分子科学国家研究中心(BNLMS-CXXM-202001); 国家重点研发计划(2021YFA1501000)
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Metal Nanocluter Catalysts for Hydrogenation of Carbon Dioxide to Multicarbon Compounds

Yuan Wang1,2(), Yulv Yu1,2, Xin Tan1,2   

  1. 1 College of Chemistry and Molecular Engineering, Peking University,Beijing 100871, China
    2 Beijing National Laboratory for Molecular Sciences,Beijing 100871, China
  • Received:2023-01-02 Revised:2023-05-22 Online:2023-06-24 Published:2023-06-10
  • Contact: *e-mail:wangy@pku.edu.cn
  • Supported by:
    The National Natural Science Foundation of China(91961103); The National Natural Science Foundation of China(21821004); The Beijing National Laboratory for Molecular Sciences(BNLMS-CXXM-202001); The National Key Research and Development Program(2021YFA1501000)

二氧化碳催化氢化合成多碳化合物的研究对于减少碳排放和实现碳资源的可再生利用具有重要意义。本文总结概述了近年来二氧化碳氢化合成多碳化合物催化体系研究进展,着重介绍了低温下催化CO2氢化合成多碳烃或多碳醇的金属纳米簇基催化剂的研究进展,讨论了CO2氢化反应中C1和C2+产物选择性调控的化学基础,介绍了具有低温催化CO2氢化合成多碳化合物功能和高C2+化合物选择性的PtRu双金属纳米簇催化剂的合成和构-效关系研究进展。在此基础上,进一步阐述了所提出的金属纳米簇催化剂局域电荷分布效应理论。

关键词： 二氧化碳, 氢化, 多碳烃, 多碳醇, Pt-Ru双金属纳米簇催化剂, 局域电荷分布

Selectively catalytic hydrogenation of CO2 to multi-carbon compounds is of great significance for reducing carbon dioxide emissions and regenerating carbon-containing resources. In this review, we summarize the development of catalytic systems for CO2 hydrogenation to multi-carbon compounds in recent years. The development of metal nanocluster catalysts for CO2 hydrogenation to multi-carbon hydrocarbons or alcohols at low temperatures are introduced, and the chemical basis for regulating C1 and C2+ product selectivity in CO2 hydrogenation is discussed. The progresses in preparing and understanding the structure-function relationship of Pt-Ru bimetallic nanocluster catalysts with the high selectivity for C2+ compounds in the CO2 hydrogenation at low temperatures are discussed. Finally, we elaborate the theory of local charge distribution effect of metal nanocluster catalysts.

Contents

1 Introduction

2 Performance and conversion pathways of CO2 hydrogenation over metal nanocluster catalysts at low temperatures

3 Chemical basis for controlling the product selectivity

4 Preparation and properties of a highly selective PtRu bimetallic nanoclusters catalyst

5 Structural characteristics of active sites of metal nanoclusters

6 Conclusion and perspective

Key words: carbon dioxide, hydrogenation, multi-carbon hydrocarbons, multi-carbon alcohols, Pt-Ru bimetallic nanocluster catalysts, local charge distribution
()
图1 (A~C) Ru-Pt/FeCO3的透射电镜照片、高分辨透射电镜照片和高角度环形暗场扫描透射电镜照片,(D) C图中选区高分辨照片,(E~G) 选区内Pt、Fe和Ru的元素分布图,(H) 图E和图G的合并图片[28]
Fig.1 (A~C) TEM image, high-resolution TEM image, and HAADF-STEM image of Ru-Pt/FeCO3, (D) High-resolution TEM image of the selected area in (C), (E~G) EDX elemental mapping of Pt, Fe, and Ru in the same area, (H) Merged image of (E) and (G)[28]. Reproduced from Ref. 28 with permission from the Royal Society of Chemistry
图2 (A)在不同温度下Ru-Pt/FeCO3催化CO2氢化产物分布图, (B)该催化体系中CO2氢化生成甲烷和多碳化合物的表观活化能[28]
Fig.2 (A) Product distributions for CO2 hydrogenation over Ru-Pt/FeCO3 at different temperatures. (B) Apparent activation energy measurements for the formation of methane and higher hydrocarbons (C2+) in CO2 hydrogenation over Ru-Pt/FeCO3, respectively[28]. Reproduced from Ref. 28 with permission from the Royal Society of Chemistry
图3 碳酸亚铁中的碳酸根加氢和表面亚铁物种的碳酸化反应耦合生成多碳化合物机理示意图[28]
Fig.3 A scheme of the mechanism for the generation of multi-carbon compounds by the hydrogenation of carbonate in FeCO3 coupled with carbonation of surface ferrous species[28]. Modified from Ref. 28 with permission from the Royal Society of Chemistry
图4 (A, B)在18O标记水中Ru-Pt/Fe3O4催化CO2氢化反应生成的丙醇和丁醇的质谱图,(C)低温下金属烷基水解生成多碳醇的反应途径示意图[30]
Fig.4 (A, B) The mass spectra of propanol and butanol formed in CO2 hydrogenation over Ru-Pt/Fe3O4 in18O labeled water, (C) reaction mechanism for multi-carbon alcohols formation based on metal-alkyl hydrolysis over Ru-Pt/Fe3O4[30]
图5 低温CO2氢化产物选择性调控机制示意图
Fig.5 A scheme for regulating product selectivity in CO2 hydrogenation at low temperatures
图6 (A) Ru-co-Pt/C的高角度环形暗场扫描透射电镜照片,(B~D) 选区中Pt、Ru以及Pt和Ru叠加的元素分布图像,(E) 选区中金属纳米粒子的原子级分辨图像,(F) Ru-co-Pt模型,其中红色球代表一列原子柱中主要含有Pt原子,绿色球代表一列原子柱中主要含有Ru原子,(G) E图中选区中粒子的放大图像,(H) 双金属纳米粒子中原子(或柱)Z-衬度线扫分析结果[31]
Fig.6 (A) The HAADF-STEM image of Ru-co-Pt/C. (B~D) Energy dispersive X-ray spectroscopy (EDX) elemental mapping image of Pt (B), Ru (C), and Pt + Ru (D) in the selected area. (E) The atomic-resolution HADDF-STEM image of a typical particle in the selected area. (F) A model for the structure of Ru-co-Pt, in which the atom columns mainly composed of Pt and Ru are marked with red and green balls, respectively. (G) The enlarged HAADF-STEM image of the selected typical bimetallic particle in (E). (H) Line scan Z-contrast analysis of atom columns in the bimetallic nanoparticle in (E) along the arrow in (F)[31]. Reproduced from Ref. 31 with permission from the Royal Society of Chemistry
图7 (A,B) Ru-co-Pt/C中Ru和Pt的X射线光电子能谱图, (C, D) Ru-co-Pt/C样品的Ru K边和Pt L3边的扩展X射线吸收精细结构谱图[31]
Fig.7 (A, B) XPS spectra of Ru 3d (A) and Pt 4f levels (B) in Ru-co-Pt/C, respectively. (C, D) Fourier transform (FT) EXAFS spectra of Ru K edge (C) and Pt L3 edge (D) for Ru-co-Pt/C, respectively[31]. Reproduced from Ref. 31 with permission from the Royal Society of Chemistry
图8 (A)Ru-co-Ru/C、Pt-co-Pt/C和Ru-co-Pt/C三种催化剂催化CO2加氢反应性能,(B)Ru-co-Pt/C在不同温度下催化CO2加氢反应性能,(C)Ru-co-Pt/C在130℃下催化CO2加氢稳定性测试,(D~F)Ru-co-Ru/C、Pt-co-Pt/C和Ru-co-Pt/C催化CO2加氢生成的产物分布图,Wn代表Cn物质的质量分数[31]
Fig.8 (A) Catalytic performance of Ru-co-Ru/C, Pt-co-Pt/C, and Ru-co-Pt/C in CO2 hydrogenation, respectively. (B) Catalytic performance of Ru-co-Pt/C in CO2 hydrogenation at different temperatures. (C) The stability of Ru-co-Pt/C in CO2 hydrogenation at 130℃. (D~F) Product distributions in CO2 hydrogenation over Ru-co-Ru/C (D), Pt-co-Pt/C (E), and Ru-co-Pt/C (F) at 130℃, respectively. Wn represents the mass percentage of Cn compounds in the products [31]. Reproduced from Ref. 31 with permission from the Royal Society of Chemistry
图9 Pt42-Ru8纳米簇的俯视图(A)和侧视图(B)
Fig.9 The (A) top view and (B) side view of Pt42-Ru8 nanocluster. Reproduced from Ref. 31 with permission from the Royal Society of Chemistry
表1 由DFT理论计算获得的CO2氢化反应中若干基元反应能垒[31]
Table 1 The energy barriers of several primitive reactions in CO2 hydrogenation calculated via DFT. [31] Reproduced from Ref. 31 with permission from the Royal Society of Chemistry.
Catalyst Reaction energy barriers (eV)
CH2+CH2 coupling CH2 + H CH3 +H
Pt42-Ru8 0.31 0.55 0.53
Ru50 1.44 0.85 0.77
Pt50 0.78 0.92 0.81
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