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表征超薄金属氧化物催化剂薄膜在非热等离子体CO还原反应中的稳定性。

Characterizing the stability of ultra-thin metal oxide catalyst films in non-thermal plasma CO reduction reactions.

作者信息

Conlin Samuel K, Muhanga Joseph Joel, Parette David N, Coridan Robert H

机构信息

Department of Chemistry and Biochemistry, University of Arkansas Fayetteville AR 72701 USA

Materials Science and Engineering Program, University of Arkansas Fayetteville AR 72701 USA.

出版信息

Nanoscale Adv. 2024 Dec 23;7(3):876-885. doi: 10.1039/d4na00854e. eCollection 2025 Jan 28.

Abstract

The use of metal oxide catalysts to enhance plasma CO reduction has seen significant recent development towards processes to reduce greenhouse gas emissions and produce renewable chemical feedstocks. While plasma reactors are effective at producing the intended chemical transformations, the conditions can result in catalyst degradation. Atomic layer deposition (ALD) can be used to synthesize complex, hierarchically structured metal oxide plasma catalysts that, while active for plasma CO reduction, are potentially vulnerable to degradation due to their high surface area and nanoscopic thickness. In this work, we characterized the effects of extended non-thermal, glow discharge plasma exposure on ALD synthesized, ultra-thin film (<30 nm) TiO and ZnO catalysts. We used X-ray diffraction, reflectivity, and spectroscopy to compare films exposed to a CO plasma to ones exposed to an Ar plasma and to ones annealed in air. We found that the CO plasma exposure generated some surface reduction in TiO and increased surface roughening by a small amount, but did not initiate any phase changes or crystallite growth. The results suggest that ALD-deposited metal oxide films are robust to low pressure CO plasma exposure and are suitable as catalysts or catalyst supports in extended reactions.

摘要

利用金属氧化物催化剂来增强等离子体一氧化碳还原,在减少温室气体排放和生产可再生化学原料的工艺方面,近年来已取得显著进展。虽然等离子体反应器在实现预期的化学转化方面很有效,但这些条件可能导致催化剂降解。原子层沉积(ALD)可用于合成复杂的、具有分层结构的金属氧化物等离子体催化剂,这些催化剂虽然对等离子体一氧化碳还原具有活性,但由于其高表面积和纳米级厚度,可能容易降解。在这项工作中,我们表征了长时间非热辉光放电等离子体暴露对ALD合成的超薄薄膜(<30纳米)TiO和ZnO催化剂的影响。我们使用X射线衍射、反射率和光谱学,将暴露于一氧化碳等离子体的薄膜与暴露于氩等离子体的薄膜以及在空气中退火的薄膜进行比较。我们发现,一氧化碳等离子体暴露在TiO中产生了一些表面还原,并使表面粗糙度略有增加,但没有引发任何相变或微晶生长。结果表明,ALD沉积的金属氧化物薄膜对低压一氧化碳等离子体暴露具有耐受性,适合在长时间反应中作为催化剂或催化剂载体。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/af81/11774077/cbc7d5b6b1de/d4na00854e-f2.jpg

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