Combining Atomic Layer Deposition with Surface Organometallic Chemistry to Enhance Atomic-Scale Interactions and Improve the Activity and Selectivity of Cu–Zn/SiO2 Catalysts for the Hydrogenation of CO2 to Methanol | Sciact - CRIS-система Института катализа

Combining Atomic Layer Deposition with Surface Organometallic Chemistry to Enhance Atomic-Scale Interactions and Improve the Activity and Selectivity of Cu–Zn/SiO2 Catalysts for the Hydrogenation of CO2 to Methanol Научная публикация

Журнал

JACS Au
ISSN: 2691-3704

Вых. Данные

Год: 2023, Том: 3, Номер: 9, Страницы: 2536–2549 Страниц : 14 DOI: 10.1021/jacsau.3c00319

Ключевые слова

ALD; CO2 hydrogenation; CuZn alloy; dealloying; operando DRIFTS; SOMC

Авторы

Zhou Hui ^1,2 , Docherty Scott R. ³ , Phongprueksathat Nat ⁴ , Chen Zixuan ¹ , Bukhtiyarov Andrey V. ⁵ , Prosvirin Igor P. ⁶ , Safonova Olga V. ⁷ , Urakawa Atsushi ⁴ , Copéret Christophe ³ , Müller Christoph R. ¹ , Fedorov Alexey ¹

Организации

1	Department of Mechanical and Process Engineering, ETH Zürich, CH-8092 Zürich, Switzerland
2	Department of Energy and Power Engineering, Tsinghua University, 100084 Beijing, China
3	Department of Chemistry and Applied Biosciences, ETH Zürich, CH-8093 Zürich, Switzerland
4	Department of Chemical Engineering, Delft University of Technology, 2629 HZ Delft, The Netherlands
5	Synchrotron Radiation Facility SKIF, Boreskov Institute of Catalysis SB RAS, 630559 Kol’tsovo, Russia
6	Boreskov Institute of Catalysis, SB RAS, 630090 Novosibirsk, Russia
7	Paul Scherrer Institute, CH-5232 Villingen, Switzerland

Информация о финансировании (6)

1	European Commission	800419 H2020-MSCA-IF-2017
2	Swiss Federal Institute of Technology in Zurich	ETH-4017-2
3	Министерство науки и высшего образования Российской Федерации (с 15 мая 2018)	ГЗ-2021-2023
4	Swiss National Science Foundation	200021_169134
5	Swiss National Science Foundation	200020B_192050
6	Swiss National Science Foundation	CRSII5-183495

The direct synthesis of methanol via the hydrogenation of CO2, if performed efficiently and selectively, is potentially a powerful technology for CO2 mitigation. Here, we develop an active and selective Cu–Zn/SiO2 catalyst for the hydrogenation of CO2 by introducing copper and zinc onto dehydroxylated silica via surface organometallic chemistry and atomic layer deposition, respectively. At 230 °C and 25 bar, the optimized catalyst shows an intrinsic methanol formation rate of 4.3 g h–1 gCu–1 and selectivity to methanol of 83%, with a space-time yield of 0.073 g h–1 gcat–1 at a contact time of 0.06 s g mL–1. X-ray absorption spectroscopy at the Cu and Zn K-edges and X-ray photoelectron spectroscopy studies reveal that the CuZn alloy displays reactive metal support interactions; that is, it is stable under H2 atmosphere and unstable under conditions of CO2 hydrogenation, indicating that the dealloyed structure contains the sites promoting methanol synthesis. While solid-state nuclear magnetic resonance studies identify methoxy species as the main stable surface adsorbate, transient operando diffuse reflectance infrared Fourier transform spectroscopy indicates that μ-HCOO*(ZnOx) species that form on the Cu–Zn/SiO2 catalyst are hydrogenated to methanol faster than the μ-HCOO*(Cu) species that are found in the Zn-free Cu/SiO2 catalyst, supporting the role of Zn in providing a higher activity in the Cu–Zn system.

Zhou H. , Docherty S.R. , Phongprueksathat N. , Chen Z. , Bukhtiyarov A.V. , Prosvirin I.P. , Safonova O.V. , Urakawa A. , Copéret C. , Müller C.R. , Fedorov A.
Combining Atomic Layer Deposition with Surface Organometallic Chemistry to Enhance Atomic-Scale Interactions and Improve the Activity and Selectivity of Cu–Zn/SiO2 Catalysts for the Hydrogenation of CO2 to Methanol
JACS Au. 2023. V.3. N9. P.2536–2549. DOI: 10.1021/jacsau.3c00319 WOS Scopus РИНЦ CAPlusCA PMID OpenAlex

Поступила в редакцию:	18 июн. 2023 г.
Принята к публикации:	9 авг. 2023 г.
Опубликована online:	23 авг. 2023 г.
Опубликована в печати:	25 сент. 2023 г.

Web of science:	WOS:001079748400001
Scopus:	2-s2.0-85170418523
РИНЦ:	54975424
Chemical Abstracts:	2023:1739632
Chemical Abstracts (print):	184:74340
PMID (PubMed):	37772188
OpenAlex:	W4386090888

БД	Цитирований
Scopus	7
OpenAlex	5
Web of science	7
РИНЦ	6