Light-Reinforced Key Intermediate for Anticoking To Boost Highly Durable Methane Dry Reforming over Single Atom Ni Active Sites on CeO₂.

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Rao, Zhiqiang, Wang, Kaiwen ORCID: 0000-0002-1046-4525, Cao, Yuehan, Feng, Yibo, Huang, Zeai ORCID: 0000-0002-7079-2504, Chen, Yaolin, Wei, Shiqian, Liu, Luyu, Gong, Zhongmiao, Cui, Yi ORCID: 0000-0002-9182-9038 et al (show 4 more authors) , Li, Lina, Tu, Xin ORCID: 0000-0002-6376-0897, Ma, Ding ORCID: 0000-0002-3341-2998 and Zhou, Ying ORCID: 0000-0001-9995-0652 (2023) Light-Reinforced Key Intermediate for Anticoking To Boost Highly Durable Methane Dry Reforming over Single Atom Ni Active Sites on CeO₂. Journal of the American Chemical Society, 145 (45). pp. 24625-24635.

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Abstract

Dry reforming of methane (DRM) has been investigated for more than a century; the paramount stumbling block in its industrial application is the inevitable sintering of catalysts and excessive carbon emissions at high temperatures. However, the low-temperature DRM process still suffered from poor reactivity and severe catalyst deactivation from coking. Herein, we proposed a concept that highly durable DRM could be achieved at low temperatures via fabricating the active site integration with light irradiation. The active sites with Ni-O coordination (Ni_SA/CeO₂) and Ni-Ni coordination (Ni_NP/CeO₂) on CeO₂, respectively, were successfully constructed to obtain two targeted reaction paths that produced the key intermediate (CH₃O*) for anticoking during DRM. In particular, the <i>operando</i> diffuse reflectance infrared Fourier transform spectroscopy coupling with steady-state isotopic transient kinetic analysis (<i>operando</i> DRIFTS-SSITKA) was utilized and successfully tracked the anticoking paths during the DRM process. It was found that the path from CH₃* to CH₃O* over Ni_SA/CeO₂ was the key path for anticoking. Furthermore, the targeted reaction path from CH₃* to CH₃O* was reinforced by light irradiation during the DRM process. Hence, the Ni_SA/CeO₂ catalyst exhibits excellent stability with negligible carbon deposition for 230 h under thermo-photo catalytic DRM at a low temperature of 472 °C, while Ni_NP/CeO₂ shows apparent coke deposition behavior after 0.5 h in solely thermal-driven DRM. The findings are vital as they provide critical insights into the simultaneous achievement of low-temperature and anticoking DRM process through distinguishing and directionally regulating the key intermediate species.

Item Type:	Article
Uncontrolled Keywords:	7 Affordable and Clean Energy
Divisions:	Faculty of Science and Engineering > School of Electrical Engineering, Electronics and Computer Science
Depositing User:	Symplectic Admin
Date Deposited:	18 Oct 2023 08:30
Last Modified:	15 Mar 2024 11:33
DOI:	10.1021/jacs.3c07077
Related URLs:	Author Publisher
URI:	https://livrepository.liverpool.ac.uk/id/eprint/3173809