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Synergistic effect of bimetallic RuPt/TiO2 catalyst in methane combustion

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Abstract

Designing metal compounds based on their structure and chemical composition is essential in achieving desirable performance in methane oxidation, because of the synergistic effect between different metal elements. Herein, a bimetallic Ru–Pt catalyst on TiO2 support (RuPt-O/TiO2) was prepared by in situ reduction followed by calcination in air. Compared with monometallic catalysts (Ru-O/TiO2 and Pt-O/TiO2), the synergistic effect of mixed metals endowed bimetallic catalysts with excellent stability and outstanding performance in methane oxidation, with a reaction rate of 13.9 × 10–5 \({\mathrm{mol}}_{{\mathrm{CH}}_{4}}^{-1}\cdot {\mathrm{g}}_{(\mathrm{Ru}+\mathrm{Pt})}^{-1}\cdot {\mathrm{s}}^{-1}\) at 303 °C. The varied characterization results revealed that among the bimetallic catalysts, RuO2 was epitaxially grown on the TiO2 substrate owing to lattice matching between them, and part of the PtOx adhered to the RuO2 surface, in addition to a single PtOx nanoparticle with 4 nm in size. Consequently, Pt mainly existed in the form of Pt2+ and Pt4+ and a small amount of zero valence in the bimetallic catalyst, prompting the adsorption and activation of methane as the first and rate-controlling step for CH4 oxidation. More importantly, the RuO2 species provided additional oxygen species to facilitate the redox cycle of the PtOx species. This study opens a new route for structurally designing promising catalysts for CH4 oxidation.

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摘要

双金属催化剂体系因为特有的电子效应和协同效应，在氧化、加氢等众多反应中受到广泛关注。因此，设计合理结构和组成的双金属催化剂能够实现甲烷高效催化燃烧。本文通过原位还原和空气焙烧制备得到RuPt-O/TiO2双金属催化剂，相比于Ru-O/TiO2和Pt-O/TiO2催化剂，RuPt-O/TiO2催化剂由于协同效应表现出更高的甲烷燃烧活性和稳定性。在303 °C下甲烷燃烧反应速率为13.9×10-5 mol_(CH_4)^(-1)·g_((Ru+Pt))^(-1)·s^(-1)，比单金属催化剂高一个数量级。各种表征结果表明，在双金属催化剂中，由于二者之间的晶格匹配，RuO2在TiO2基底上外延生长，而部分PtOx粘附在RuO2表面，同时还单独存在4 nm的PtOx纳米颗粒，使得在双金属催化剂中Pt主要以Pt2+和Pt4+的形式存在，其高氧化态促使甲烷的吸附和活化。更重要的是，RuO2物种还可以提供额外的氧物种，以促进PtOx物种的氧化还原循环。论文为设计具有更优性能的甲烷氧化催化剂提供了一种新的思路。

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Acknowledgements

This study was financially supported by National Natural Science Foundation of China (Nos. 21922602, 22076047 and U21A20326), Shanghai Science and Technology Innovation Action Plan (No. 20dz1204200) and the Fundamental Research Funds for the Central Universities.

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Authors and Affiliations

  1. Key Laboratory for Advanced Materials and Research Institute of Industrial Catalysis, School of Chemistry and Molecular Engineering, East China University of Science and Technology, Shanghai, 200237, China

    Shi-Ying Cao, Ni-Ni Zhang, Yang-Long Guo, Yun Guo, Li Wang & Wang-Cheng Zhan

  2. Key Laboratory for Advanced Materials and Feringa Nobel Prize Scientist Joint Research Centre, Institute of Fine Chemicals, School of Chemistry and Molecular Engineering, East China University of Science and Technology, Shanghai, 200237, China

    Fan Ye & Sheng Dai

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  1. Shi-Ying Cao
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Cao, SY., Ye, F., Zhang, NN. et al. Synergistic effect of bimetallic RuPt/TiO2 catalyst in methane combustion. Rare Met. 42, 165–175 (2023). https://doi.org/10.1007/s12598-022-02118-7

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