Dankar Joudy, Rouchon Virgile, Rivallan Mickael, Pagis Céline, El-Roz Mohamad
IFP Energies nouvelles, Rond-point de l'échangeur de Solaize, BP 3, Solaize 69360, France.
Laboratoire Catalyse et Spectrochimie, Normandie Université, Caen 14050, France.
ACS Appl Mater Interfaces. 2024 Aug 14;16(32):42210-42220. doi: 10.1021/acsami.4c07256. Epub 2024 Jul 31.
Photocatalytic conversion of CO with HO is an attractive application that has the potential to mitigate environmental and energy challenges through the conversion of CO to hydrocarbon products such as methane. However, the underlying reaction mechanisms remain poorly understood, limiting real progress in this field. In this work, a mechanistic investigation of the CO photocatalytic reduction on Pt/TiO is carried out using an operando FTIR approach, combined with chemometric data processing and isotope exchange of (CO + HO) toward (CO + HO). Multivariate curve resolution analysis applied to operando spectra across numerous cycles of photoactivation and the CO reaction facilitates the identification of principal chemical species involved in the reaction pathways. Moreover, specific probe-molecule-assisted reactions, including CO and CHCOOH, elucidate the capacity of selected molecules to undergo methane production under irradiation conditions. Finally, isotopic exchange reveals conclusive evidence regarding the nature of the identified species during CO conversion and points to the significant role of acetates resulting from the C-C coupling reaction as key intermediates in methane production from the CO photocatalytic reduction reaction.
利用HO将CO进行光催化转化是一个具有吸引力的应用，它有潜力通过将CO转化为甲烷等烃类产物来缓解环境和能源挑战。然而，其潜在的反应机制仍知之甚少，这限制了该领域的实际进展。在这项工作中，采用操作傅里叶变换红外光谱（operando FTIR）方法，并结合化学计量学数据处理以及(CO + HO)向(CO + HO)的同位素交换，对Pt/TiO上的CO光催化还原进行了机理研究。将多元曲线分辨分析应用于光活化和CO反应的多个循环中的操作光谱，有助于识别反应途径中涉及的主要化学物种。此外，特定的探针分子辅助反应，包括CO和CHCOOH，阐明了所选分子在辐照条件下产生甲烷的能力。最后，同位素交换揭示了关于CO转化过程中所识别物种性质的确凿证据，并指出由C-C偶联反应产生的乙酸盐作为CO光催化还原反应中甲烷生成的关键中间体所起的重要作用。
