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

Riccardo Colombo; Gianluca Moroni; Chiara Negri; Guusje Delen; Matteo Monai; Alessandro Donazzi; Bert M Weckhuysen; Matteo Maestri

doi:10.1002/anie.202408668

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

Riccardo Colombo
, Gianluca Moroni
, Chiara Negri
, Guusje Delen
, Matteo Monai
, Alessandro Donazzi
, Bert M Weckhuysen
, Matteo Maestri^*

^*Corresponding author for this work

CMIC-Politecnico di Milano

Research output: Contribution to journal › Article › Academic › peer-review

Abstract

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-Al2O3 catalyst follows a nucleation-growth mechanism. The dynamics of carbon aggregates at the surface is found to be ruled by the CO2/CH4 ratio and the inlet CH4 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 CO2 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 CO2's kinetic role in MDR.

Original language	English
Article number	e202408668
Number of pages	9
Journal	Angewandte Chemie-International Edition
Volume	63
Issue number	46
Early online date	3 Jul 2024
DOIs	https://doi.org/10.1002/anie.202408668
Publication status	Published - 11 Nov 2024

Bibliographical note

Publisher Copyright:
© 2024 Wiley-VCH GmbH.

Funding

Financial support from the European Research Council (Grant 677423) and the National Recovery and Resilience Plan (NRRP), Mission\u20054 Component\u20052 Investment\u20051.3\u2014Call for tender No. 1561 of 11.\u200910.\u20092022 of Ministero dell'Universit\u00E0 e della Ricerca (MUR); funded by the European Union\u2014NextGenerationEU\u2014Award Number: Project code PE0000021, Concession Decree No. 1561 of 11.\u200910.\u20092022 adopted by Ministero dell'Universit\u00E0 e della Ricerca (MUR), CUP D43C22003090001, according to attachment E of Decree No. 1561/2022, Project title \u201CNetwork 4 Energy Sustainable Transition\u2014NEST\u201D. B.M.W. acknowledges financial support from the Netherlands Organization for Scientific Research (NWO) for a Gravitation Program (Multiscale Catalytic Energy Conversion, MCEC). M.M. and B.M.W. acknowledge the Advanced Research Center Chemical Building Blocks Consortium (ARC CBBC) for funding.

Funders	Funder number
Advanced Research Center Chemical Building Blocks Consortium
Nederlandse Organisatie voor Wetenschappelijk Onderzoek
Amaldi Research Center
European Commission
Ministero dell’Istruzione, dell’Università e della Ricerca
MCEC
European Research Council	677423
National Recovery and Resilience Plan	PE0000021, 1561

Keywords

carbon formation
catalyst deactivation
methane dry reforming
operando spectroscopy
structure-composition-performance relationship

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10.1002/anie.202408668

Angew Chem Int Ed - 2024 - Colombo - Surface Carbon Formation and its Impact on Methane Dry Reforming Kinetics onFinal published version, 6.23 MBLicence: Taverne

Cite this

@article{e1478e9b5c1d4c5a80b182c2be5b3881,

title = "Surface Carbon Formation and its Impact on Methane Dry Reforming Kinetics on Rhodium-based Catalysts by Operando Raman Spectroscopy",

abstract = "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-Al2O3 catalyst follows a nucleation-growth mechanism. The dynamics of carbon aggregates at the surface is found to be ruled by the CO2/CH4 ratio and the inlet CH4 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 CO2 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 CO2's kinetic role in MDR.",

keywords = "carbon formation, catalyst deactivation, methane dry reforming, operando spectroscopy, structure-composition-performance relationship",

author = "Riccardo Colombo and Gianluca Moroni and Chiara Negri and Guusje Delen and Matteo Monai and Alessandro Donazzi and Weckhuysen, \{Bert M\} and Matteo Maestri",

note = "Publisher Copyright: {\textcopyright} 2024 Wiley-VCH GmbH.",

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doi = "10.1002/anie.202408668",

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T1 - Surface Carbon Formation and its Impact on Methane Dry Reforming Kinetics on Rhodium-based Catalysts by Operando Raman Spectroscopy

AU - Colombo, Riccardo

AU - Moroni, Gianluca

AU - Negri, Chiara

AU - Delen, Guusje

AU - Monai, Matteo

AU - Donazzi, Alessandro

AU - Weckhuysen, Bert M

AU - Maestri, Matteo

PY - 2024/11/11

Y1 - 2024/11/11

N2 - 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-Al2O3 catalyst follows a nucleation-growth mechanism. The dynamics of carbon aggregates at the surface is found to be ruled by the CO2/CH4 ratio and the inlet CH4 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 CO2 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 CO2's kinetic role in MDR.

AB - 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-Al2O3 catalyst follows a nucleation-growth mechanism. The dynamics of carbon aggregates at the surface is found to be ruled by the CO2/CH4 ratio and the inlet CH4 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 CO2 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 CO2's kinetic role in MDR.

KW - carbon formation

KW - catalyst deactivation

KW - methane dry reforming

KW - operando spectroscopy

KW - structure-composition-performance relationship

UR - https://www.scopus.com/pages/publications/85201790631

U2 - 10.1002/anie.202408668

DO - 10.1002/anie.202408668

M3 - Article

C2 - 38958601

SN - 1433-7851

VL - 63

JO - Angewandte Chemie-International Edition

JF - Angewandte Chemie-International Edition

IS - 46

M1 - e202408668

ER -

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

Abstract

Bibliographical note

Funding

Keywords

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