In Situ Transmission Electron Microscopy to Study the Location and Distribution Effect of Pt on the Reduction of Co3O4–SiO2

Min Tang; Petra E. de Jongh; Krijn P. de Jong

doi:10.1002/smll.202304683

In Situ Transmission Electron Microscopy to Study the Location and Distribution Effect of Pt on the Reduction of Co₃O₄–SiO₂

Min Tang, Petra E. de Jongh, Krijn P. de Jong^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › Academic › peer-review

Abstract

The addition of Pt generally promotes the reduction of Co₃O₄ in supported catalysts, which further improves their activity and selectivity. However, due to the limited spatial resolution, how Pt and its location and distribution affect the reduction of Co₃O₄ remains unclear. Using ex situ and in situ ambient pressure scanning transmission electron microscopy, combined with temperature-programmed reduction, the reduction of silica-supported Co₃O₄ without Pt and with different location and distribution of Pt is studied. Shrinkage of Co₃O₄ nanoparticles is directly observed during their reduction, and Pt greatly lowers the reduction temperature. For the first time, the initial reduction of Co₃O₄ with and without Pt is studied at the nanoscale. The initial reduction of Co₃O₄ changes from surface to interface between Co₃O₄ and SiO₂. Small Pt nanoparticles located at the interface between Co₃O₄ and SiO₂ promote the reduction of Co₃O₄ by the detachment of Co₃O₄/CoO from SiO₂. After reduction, the Pt and part of the Co form an alloy with Pt well dispersed. This study for the first time unravels the effects of Pt location and distribution on the reduction of Co₃O₄ nanoparticles, and helps to design cobalt-based catalysts with efficient use of Pt as a reduction promoter.

Original language	English
Article number	2304683
Journal	Small
Volume	20
Issue number	1
Early online date	30 Aug 2023
DOIs	https://doi.org/10.1002/smll.202304683
Publication status	Published - 4 Jan 2024

Bibliographical note

Funding Information:
Utrecht University was acknowledged for funding this project. The authors thank Nikolay Kosinov from Technical University of Eindhoven for measuring and analyzing the XPS data. Savannah Turner was thanked for her help with precursor synthesis and in situ TEM setup. Hans Meeldijk, Laura Barberis, and Dennie Wezendonk were acknowledged for the help with TEM, TPR, and XRD measurements, respectively.

Publisher Copyright:
© 2023 The Authors. Small published by Wiley-VCH GmbH.

Funding

Utrecht University was acknowledged for funding this project. The authors thank Nikolay Kosinov from Technical University of Eindhoven for measuring and analyzing the XPS data. Savannah Turner was thanked for her help with precursor synthesis and in situ TEM setup. Hans Meeldijk, Laura Barberis, and Dennie Wezendonk were acknowledged for the help with TEM, TPR, and XRD measurements, respectively.

Funders	Funder number
Technical University of Eindhoven
Utrecht University

Keywords

cobalt oxide reduction
cobalt-based catalyst
in situ ambient pressure transmission electron microscopy (TEM)
Pt location and distribution
Pt promoting effect
temperature-programmed reduction

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Cite this

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title = "In Situ Transmission Electron Microscopy to Study the Location and Distribution Effect of Pt on the Reduction of Co3O4–SiO2",

abstract = "The addition of Pt generally promotes the reduction of Co3O4 in supported catalysts, which further improves their activity and selectivity. However, due to the limited spatial resolution, how Pt and its location and distribution affect the reduction of Co3O4 remains unclear. Using ex situ and in situ ambient pressure scanning transmission electron microscopy, combined with temperature-programmed reduction, the reduction of silica-supported Co3O4 without Pt and with different location and distribution of Pt is studied. Shrinkage of Co3O4 nanoparticles is directly observed during their reduction, and Pt greatly lowers the reduction temperature. For the first time, the initial reduction of Co3O4 with and without Pt is studied at the nanoscale. The initial reduction of Co3O4 changes from surface to interface between Co3O4 and SiO2. Small Pt nanoparticles located at the interface between Co3O4 and SiO2 promote the reduction of Co3O4 by the detachment of Co3O4/CoO from SiO2. After reduction, the Pt and part of the Co form an alloy with Pt well dispersed. This study for the first time unravels the effects of Pt location and distribution on the reduction of Co3O4 nanoparticles, and helps to design cobalt-based catalysts with efficient use of Pt as a reduction promoter.",

keywords = "cobalt oxide reduction, cobalt-based catalyst, in situ ambient pressure transmission electron microscopy (TEM), Pt location and distribution, Pt promoting effect, temperature-programmed reduction",

author = "Min Tang and {de Jongh}, {Petra E.} and {de Jong}, {Krijn P.}",

note = "Funding Information: Utrecht University was acknowledged for funding this project. The authors thank Nikolay Kosinov from Technical University of Eindhoven for measuring and analyzing the XPS data. Savannah Turner was thanked for her help with precursor synthesis and in situ TEM setup. Hans Meeldijk, Laura Barberis, and Dennie Wezendonk were acknowledged for the help with TEM, TPR, and XRD measurements, respectively. Publisher Copyright: {\textcopyright} 2023 The Authors. Small published by Wiley-VCH GmbH.",

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N2 - The addition of Pt generally promotes the reduction of Co3O4 in supported catalysts, which further improves their activity and selectivity. However, due to the limited spatial resolution, how Pt and its location and distribution affect the reduction of Co3O4 remains unclear. Using ex situ and in situ ambient pressure scanning transmission electron microscopy, combined with temperature-programmed reduction, the reduction of silica-supported Co3O4 without Pt and with different location and distribution of Pt is studied. Shrinkage of Co3O4 nanoparticles is directly observed during their reduction, and Pt greatly lowers the reduction temperature. For the first time, the initial reduction of Co3O4 with and without Pt is studied at the nanoscale. The initial reduction of Co3O4 changes from surface to interface between Co3O4 and SiO2. Small Pt nanoparticles located at the interface between Co3O4 and SiO2 promote the reduction of Co3O4 by the detachment of Co3O4/CoO from SiO2. After reduction, the Pt and part of the Co form an alloy with Pt well dispersed. This study for the first time unravels the effects of Pt location and distribution on the reduction of Co3O4 nanoparticles, and helps to design cobalt-based catalysts with efficient use of Pt as a reduction promoter.

AB - The addition of Pt generally promotes the reduction of Co3O4 in supported catalysts, which further improves their activity and selectivity. However, due to the limited spatial resolution, how Pt and its location and distribution affect the reduction of Co3O4 remains unclear. Using ex situ and in situ ambient pressure scanning transmission electron microscopy, combined with temperature-programmed reduction, the reduction of silica-supported Co3O4 without Pt and with different location and distribution of Pt is studied. Shrinkage of Co3O4 nanoparticles is directly observed during their reduction, and Pt greatly lowers the reduction temperature. For the first time, the initial reduction of Co3O4 with and without Pt is studied at the nanoscale. The initial reduction of Co3O4 changes from surface to interface between Co3O4 and SiO2. Small Pt nanoparticles located at the interface between Co3O4 and SiO2 promote the reduction of Co3O4 by the detachment of Co3O4/CoO from SiO2. After reduction, the Pt and part of the Co form an alloy with Pt well dispersed. This study for the first time unravels the effects of Pt location and distribution on the reduction of Co3O4 nanoparticles, and helps to design cobalt-based catalysts with efficient use of Pt as a reduction promoter.

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