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

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 operando diffuse reflectance infrared Fourier transform spectroscopy coupling with steady-state isotopic transient kinetic analysis (operando 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.