Surface Carbon Formation and its Impact on Methane Dry Reforming Kinetics on Rhodium-Based Catalysts by Operando Raman Spectroscopy.

Autor: Colombo R; Laboratory of Catalysis and Catalytic Processes, Dipartimento di Energia, Politecnico di Milano, Via La Masa 34, 20156, Milano, Italy., Moroni G; Laboratory of Catalysis and Catalytic Processes, Dipartimento di Energia, Politecnico di Milano, Via La Masa 34, 20156, Milano, Italy., Negri C; Laboratory of Catalysis and Catalytic Processes, Dipartimento di Energia, Politecnico di Milano, Via La Masa 34, 20156, Milano, Italy., Delen G; Inorganic Chemistry and Catalysis Group, Institute for Sustainable and Circular Chemistry and Debye Institute for Nanomaterials Science, Utrecht University, Universiteitsweg 99, 3584 CG, Utrecht, The Netherlands., Monai M; Inorganic Chemistry and Catalysis Group, Institute for Sustainable and Circular Chemistry and Debye Institute for Nanomaterials Science, Utrecht University, Universiteitsweg 99, 3584 CG, Utrecht, The Netherlands., Donazzi A; Laboratory of Catalysis and Catalytic Processes, Dipartimento di Energia, Politecnico di Milano, Via La Masa 34, 20156, Milano, Italy., Weckhuysen BM; Inorganic Chemistry and Catalysis Group, Institute for Sustainable and Circular Chemistry and Debye Institute for Nanomaterials Science, Utrecht University, Universiteitsweg 99, 3584 CG, Utrecht, The Netherlands., Maestri M; Laboratory of Catalysis and Catalytic Processes, Dipartimento di Energia, Politecnico di Milano, Via La Masa 34, 20156, Milano, Italy.
Jazyk: angličtina
Zdroj: Angewandte Chemie (International ed. in English) [Angew Chem Int Ed Engl] 2024 Nov 11; Vol. 63 (46), pp. e202408668. Date of Electronic Publication: 2024 Aug 23.
DOI: 10.1002/anie.202408668
Abstrakt: A mechanism for carbon deposition and its impact on the reaction kinetics of Methane Dry Reforming (MDR) using Rhodium-based catalysts is presented. By integrating Raman spectroscopy with kinetic analysis in an operando-annular chemical reactor under strict chemical conditions, we discovered that carbon deposition on a Rh/α-Al 2 O 3 catalyst follows a nucleation-growth mechanism. The dynamics of carbon aggregates at the surface is found to be ruled by the CO 2 /CH 4 ratio and the inlet CH 4 concentration. The findings elucidate the spatiotemporal development of carbon aggregates on the catalyst surface and their effects on catalytic performance. Furthermore, the proposed mechanism for carbon formation shows that the influence of CO 2 on MDR kinetics is an indirect result of carbon accumulation over time frames exceeding the turnover frequency, thus reconciling conflicting reports in the literature regarding CO 2 's kinetic role in MDR.
(© 2024 Wiley-VCH GmbH.)
Databáze: MEDLINE
Externí odkaz: