铜的化学状态对甲醇分解和氧化的影响

IF 3.2 3区 化学 Q2 CHEMISTRY, PHYSICAL
Jianyu Wang, Chaoran Li, Yaguang Zhu, Shyam Patel, Jorge Anibal Boscoboinik and Guangwen Zhou*, 
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引用次数: 0

摘要

通过结合使用原位常压 X 射线光电子能谱、欧杰尔电子能谱和密度泛函理论计算,研究了 CH3OH 在金属 Cu(100) 和 Cu2O 覆盖的 Cu(100) 表面上的分解和氧化反应。我们确定了在操作条件下从键的裂解到中间产物和最终产物的形成的顺序化学转化途径。CH3O 物种在金属铜(100)上的累积表面吸附阻碍了 CH3OH 的分解。在 1 × 10-4 托 CH3OH + 1 × 10-4 托 O2 的低压下,金属铜(100)上的共剂量会导致 CH3OH 的部分氧化,其中化学吸附的 Oads 会减少可用于吸附 CH3O 的表面位点,从而降低 CH3OH 分解的表面活性。与此相反,在 0.33 托 CH3OH + 0.66 托 O2 的高压下形成的 Cu2O 覆盖层会促进 CH3OH 全部氧化成最终产物 CO2 和 H2O,这是由于 Cu2O 内晶格 O 与中间产物 CH3O、CH2O、HCOO 和 CO 之间的活性反应所致。尽管 O-H 键断裂更为有利,但 C-O 键断裂也会导致 CHx 在金属铜(100)表面聚集,从而阻断 CH3OH 和 CH3O 分解反应的活性位点。相比之下,Cu2O 覆盖的 Cu(100)上的 CHx 物种会与 Cu2O 覆盖层中的晶格 O 一起氧化成 CO2 和 H2O,从而释放出活性位点用于 CH3OH 的全氧化反应。这些结果突显了金属铜和 Cu2O 在 CH3OH 分解和氧化反应途径中的不同作用,为设计具有定制反应性和选择性的铜基催化剂提供了实用的见解。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

Effect of the Chemical States of Copper on Methanol Decomposition and Oxidation

Effect of the Chemical States of Copper on Methanol Decomposition and Oxidation

Effect of the Chemical States of Copper on Methanol Decomposition and Oxidation

The decomposition and oxidation reactions of CH3OH over metallic Cu(100) and Cu2O-covered Cu(100) surfaces are studied by using a combination of in situ ambient-pressure X-ray photoelectron spectroscopy, Auger electron spectroscopy, and density functional theory calculations. We identify the sequential chemical transformation pathways from bond cleavage to the formation of intermediates and final products under operational conditions. Accumulative surface adsorption of CH3O species on metallic Cu(100) impedes the decomposition of CH3OH. Co-dosing on metallic Cu(100) with low pressures of 1 × 10–4 Torr CH3OH + 1 × 10–4 Torr O2 results in partial oxidation of CH3OH, where the chemisorbed Oads reduces surface sites available for CH3O adsorption, decreasing the surface activity for CH3OH decomposition. In contrast, the Cu2O overlayer formed under the elevated pressures of 0.33 Torr CH3OH + 0.66 Torr O2 promotes the total oxidation of CH3OH into the final products of CO2 and H2O, arising from the active reaction between lattice O within Cu2O and intermediates of CH3O, CH2O, HCOO, and CO. Despite the more favorable O–H bond scission, C–O bond scission also occurs to result in surface accumulation of CHx on metallic Cu(100), blocking active sites for decomposition reactions of CH3OH and CH3O. By comparison, the CHx species on the Cu2O-covered Cu(100) undergo oxidation into CO2 and H2O with lattice O in the Cu2O overlayer, thereby freeing active sites for the total oxidation of CH3OH. These results highlight the distinct roles of metallic Cu and Cu2O in the pathways of CH3OH decomposition and oxidation reactions, offering practical insights for the design of Cu-based catalysts with tailored reactivity and selectivity.

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来源期刊
The Journal of Physical Chemistry C
The Journal of Physical Chemistry C 化学-材料科学:综合
CiteScore
6.50
自引率
8.10%
发文量
2047
审稿时长
1.8 months
期刊介绍: The Journal of Physical Chemistry A/B/C is devoted to reporting new and original experimental and theoretical basic research of interest to physical chemists, biophysical chemists, and chemical physicists.
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