Open Access Article
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Reply to the ‘Comment on the “Reaction intermediates recognized by in situ FTIR spectroscopy in CO2 hydrogenation over the Cu/ZnO/SPP-zeolite catalyst”’ by Comment author F. C. Meunier, RSC Appl. Interfaces, 2025, 2, https://doi.org/10.1039/D5LF00014A
Xiaobo
Yang
ab,
Xiaolong
Liu
abc,
Guangying
Fu
*ab,
Qiaolin
Lang
ab,
Ruiqin
Ding
ab,
Qiangsheng
Guo
d,
Ke
Liang
e,
Shuman
Gao
ab and
Bing
Yu
*c
aKey Laboratory of Photoelectric Conversion and Utilization of Solar Energy, Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Sciences, 266101 Qingdao, China. E-mail: fugy@qibebt.ac.cn
bShandong Energy Institute, 266101 Qingdao, China
cCollege of Chemistry and Chemical Engineering, Qingdao University, 266071 Qingdao, China. E-mail: yubing198@qdu.edu.cn
dSchool of Chemical and Environmental Engineering, Shanghai Institute of Technology, 201418 Shanghai, China
eTianjin Passion Advanced Material Technology LLC., TEDA, 300280 Tianjin, China
First published on 11th April 2025
Abstract
We agree with Professor Meunier's comment that the two IR peaks at 2075 and 2060 cm−1 belong to CO2 in the cell in the gas phase, and not to Cu–C![[double bond, length as m-dash]](https://www.rsc.org/images/entities/char_e001.gif)
O. We sincerely appreciate his insightful correction. The correction and conclusion related to the original paper are discussed.
We have re-examined the spectra in question, and agree with Professor Meunier's comment that the two IR peaks at 2075 and 2060 cm−1 belong to CO2 in the cell in the gas phase, and not to Cu–C
O.
Consequently, the text on the interpretation of these peaks should be corrected. And the discussion on the carbonyl adsorbates should focus only on the absorption bands around 1900–2000 cm−1, which represent the bridged and linear CO on Cu or ZnO surfaces.1,2
In the most efficient catalyst CuZn-SPP-E (Fig. 4), these peaks built up to a barely perceptible level within 5 minutes upon contact with the CO2 stream. And in the reactive stream of CO2 + 3H2, the ad-species were rapidly and completely consumed. In contrast, in the less active catalyst CuZn-SPP, which has larger Cu particles (Fig. 5), these bands were strong and persisted throughout the reactions. This fact that significantly larger amounts of carbonyl species form on the larger Cu particles and are slowly converted was one of the phenomena associated with the low activity.
The corrected interpretation of the IR bands therefore does not contradict the main conclusion of the work, that CuZn-SPP-E can maintain a constant carbonate coverage and low water adsorption during the catalytic reaction. Intermediates related with the hydrogenation processes, such as adsorbed carbonyl and formate species, are turned over very rapidly.
We sincerely appreciate Professor Meunier's insightful correction.
Data availability
The data supporting this article have been in the original paper and related ESI, including the preparation and characterization of the starting SPP zeolite, and additional in situ FTIR and quasi-in situ XPS spectra recorded in various reactive flows. Further details are available from the authors upon request.Conflicts of interest
There is no conflict of interest.References
- F. C. Meunier, Hydrogenation of CO and CO2: Contributions of IR operando studies, Catal. Today, 2023, 423, 113863 CrossRef CAS.
- E. Shaaban and G. Li, Probing active sites for carbon oxides hydrogenation on Cu/TiO2 using infrared spectroscopy, Commun. Chem., 2022, 5, 32 CrossRef CAS PubMed.
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