Metal Dimer Sites in ZSM-5 Zeolite for Methane-to-Methanol Conversion from First-Principles Kinetic Modelling: Is the [Cu–O–Cu]2+ Motif Relevant for Ni, Co, Fe, Ag, and Au? | Sciact - CRIS-система Института катализа

Metal Dimer Sites in ZSM-5 Zeolite for Methane-to-Methanol Conversion from First-Principles Kinetic Modelling: Is the [Cu–O–Cu]2+ Motif Relevant for Ni, Co, Fe, Ag, and Au? Научная публикация

Журнал

Catalysis Science and Technology
ISSN: 2044-4753 , E-ISSN: 2044-4761

Вых. Данные

Год: 2017, Том: 7, Номер: 7, Страницы: 1470-1477 Страниц : 8 DOI: 10.1039/c6cy02521h

Ключевые слова

ACTIVE-SITE; CATALYTIC CONVERSION; POTENTIAL FUNCTION; PARTIAL OXIDATION; SYNTHESIS GAS; COPPER; CU-ZSM-5; OXYGEN; ACTIVATION; MORDENITE

Авторы

Arvidsson Adam A. ¹ , Zhdanov Vladimir P. ^1,2 , Carlsson Per-Anders ¹ , Grönbeck Henrik ¹ , Hellman Anders ¹

Организации

1	Competence Centre for Catalysis, Department of Physics, Chemistry and Chemical Engineering, Chalmers University of Technology, 412 96 Gothenburg, Sweden
2	Boreskov Institute of Catalysis, Russian Academy of Sciences, Novosibirsk 630090, Russia

Информация о финансировании (4)

1	Фонд Кнута и Элис Валленберг
2	Swedish Research Council	349-2013-567
3	Chalmers University of Technology
4	Swedish Energy Agency

Direct methane-to-methanol conversion is a desired process whereby natural gas is transformed into an energy-rich liquid. It has been realised at ambient pressure and temperature in metal ion-exchanged zeolites, where especially copper-exchanged ZSM-5 has shown promising results. The nature of the active sites in these systems is, however, still under debate. The activity has been assigned to a [Cu–O–Cu]2+ motif. One remaining question is whether this motif is general and also active in other metal-exchanged zeolites. Herein, we use first-principles micro-kinetic modelling to analyse the methane-to-methanol reaction on the [Cu–O–Cu]2+ motif, for Cu and other metals. First, we identify the cluster model size needed to accurately describe the dimer motif. Starting from the [Cu–O–Cu]2+ site, the metal ions are then systematically substituted with Ni, Co, Fe, Ag and Au. The results show that activation of Ag and Au dimer sites with oxygen is endothermic and therefore unlikely, whereas for Cu, Ni, Co and Fe, the activation is possible under realistic conditions. According to the kinetic simulations, however, the dimer motif is a plausible candidate for the active site for Cu only. For Ni, Co and Fe, close-to-infinite reaction times or unreasonably high temperatures are required for sufficient methane conversion. As Ni-, Co- and Fe-exchanged ZSM-5 are known to convert methane to methanol, these results indicate that the Cu-based dimer motif is not an appropriate model system for these metals.

Arvidsson A.A. , Zhdanov V.P. , Carlsson P-A. , Grönbeck H. , Hellman A.
Metal Dimer Sites in ZSM-5 Zeolite for Methane-to-Methanol Conversion from First-Principles Kinetic Modelling: Is the [Cu–O–Cu]2+ Motif Relevant for Ni, Co, Fe, Ag, and Au?

Catalysis Science and Technology. 2017. V.7. N7. P.1470-1477. DOI: 10.1039/c6cy02521h WOS Scopus РИНЦ CAPlusCA OpenAlex

Полный текст от издателя

Поступила в редакцию:	2 дек. 2016 г.
Принята к публикации:	15 февр. 2017 г.
Опубликована online:	16 февр. 2017 г.
Опубликована в печати:	7 апр. 2017 г.

Web of science:	WOS:000399421800003
Scopus:	2-s2.0-85019932988
РИНЦ:	31034181
Chemical Abstracts:	2017:275805
Chemical Abstracts (print):	166:353317
OpenAlex:	W2588132331

БД	Цитирований
Web of science	58
Scopus	61
РИНЦ	53
OpenAlex	60