Screening Cu-Zeolites for Methane Activation Using Curriculum-Based Training DOI Creative Commons
Jiawei Guo, Tyler Sours,

Sam Holton

и другие.

ACS Catalysis, Год журнала: 2024, Номер 14(3), С. 1232 - 1242

Опубликована: Янв. 10, 2024

Machine learning (ML), when used synergistically with atomistic simulations, has recently emerged as a powerful tool for accelerated catalyst discovery. However, the application of these techniques been limited by lack interpretable and transferable ML models. In this work, we propose curriculum-based training (CBT) philosophy to systematically develop reactive machine potentials (rMLPs) high-throughput screening zeolite catalysts. Our CBT approach combines several different types calculations gradually teach model about relevant regions potential energy surface. The resulting rMLPs are accurate, transferable, interpretable. We further demonstrate effectiveness exhaustively thousands [CuOCu]2+ sites across hundreds Cu-zeolites industrially methane activation reaction. Specifically, large-scale analysis entire International Zeolite Association (IZA) database identifies set previously unexplored zeolites (i.e., MEI, ATN, EWO, CAS) that show highest ensemble-averaged rates [CuOCu]2+-catalyzed activation. believe can be generally applied other zeolite-catalyzed reactions and, subsequently, heterogeneous Thus, represents an important step toward overcoming long-standing barriers within computational catalysis community.

Язык: Английский

Methane Oxidation to Methanol DOI Creative Commons
Nicholas F. Dummer, David J. Willock, Qian He

и другие.

Chemical Reviews, Год журнала: 2022, Номер 123(9), С. 6359 - 6411

Опубликована: Дек. 2, 2022

The direct transformation of methane to methanol remains a significant challenge for operation at larger scale. Central this is the low reactivity conditions that can facilitate product recovery. This review discusses issue through examination several promising routes and an evaluation performance targets are required develop process We explore methods currently used, emergence active heterogeneous catalysts their design reaction mechanisms provide critical perspective on future operation. Initial experiments discussed where identification gas phase radical chemistry limited further development by approach. Subsequently, new class catalytic materials based natural systems such as iron or copper containing zeolites were explored milder conditions. key issues these technologies conversion often overoxidation products. Despite this, interest high in wider appeal effective route products from C–H activation, particularly with need transition net carbon zero renewable sources exciting.

Язык: Английский

Процитировано

180
Atomic Insights into the Cu Species Supported on Zeolite for Direct Oxidation of Methane to Methanol via Low‐Damage HAADF‐STEM DOI
Xuan Tang, Jiajie Ye, Lisheng Guo

и другие.

Advanced Materials, Год журнала: 2023, Номер 35(25)

Опубликована: Апрель 4, 2023

Precise determination of the structure-property relationship zeolite-based metal catalysts is critical for development toward practical applications. However, scarcity real-space imaging low-atomic-number (LAN) materials due to electron-beam sensitivity zeolites has led continuous debates regarding exact LAN configurations. Here, a low-damage high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) technique employed direct visualization and (Cu) species in ZSM-5 zeolite frameworks. The structures Cu are revealed based on evidence also proved by complementary spectroscopy results. correlation between characteristic size Cu/ZSM-5 their oxidation methane methanol reaction properties unveiled. As result, mono-Cu stably anchored Al pairs inside channels identified as key structure higher C1 oxygenates yield selectivity methane. Meanwhile, local topological flexibility rigid frameworks induced agglomeration revealed. This work exemplifies combination characterization serves complete arsenal revealing relationships supported metal-zeolite catalysts.

Язык: Английский

Процитировано

61
Maximizing Active Fe Species in ZSM-5 Zeolite Using Organic-Template-Free Synthesis for Efficient Selective Methane Oxidation DOI Creative Commons
Qingpeng Cheng, Guanna Li,

Xueli Yao

и другие.

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(10), С. 5888 - 5898

Опубликована: Фев. 14, 2023

The selective oxidation of CH4 in the aqueous phase to produce valuable chemicals has attracted considerable attention due its mild reaction conditions and simple process. As most widely studied catalyst for this reaction, Fe-ZSM-5 demonstrates high intrinsic activity selectivity; however, prepared using conventional methods a limited number active Fe sites, resulting low conversion per unit mass catalyst. This study reports facile organic-template-free synthesis strategy that enables incorporation more into zeolite framework with higher dispersion degree compared methods. Because incorporated way is readily transformed isolated extra-framework species under thermal treatment, overall effect method (Fe-HZ5-TF) 3 times as many catalytically sites Fe-ZSM-5. When used 0.5 M H2O2 at 75 °C, Fe-HZ5-TF produced C1 oxygenate yield 109.4 mmol gcat-1 h-1 (a HCOOH selectivity 91.1%), surpassing other catalysts reported date. Spectroscopic characterization density functional theory calculations revealed are mononuclear form [(H2O)3Fe(IV)═O]2+ bound Al pairs framework. differs from Fe-ZSM-5, where binuclear acts site. Analysis product evolution during suggests radical-driven pathway explain activation site subsequent oxygenates.

Язык: Английский

Процитировано

48
In Situ UV–Vis–NIR Absorption Spectroscopy and Catalysis DOI
Max L. Bols,

Jing Ma,

Fatima Rammal

и другие.

Chemical Reviews, Год журнала: 2024, Номер 124(5), С. 2352 - 2418

Опубликована: Фев. 26, 2024

This review highlights

Язык: Английский

Процитировано

26
Competition between Mononuclear and Binuclear Copper Sites across Different Zeolite Topologies DOI Creative Commons
Asanka Wijerathne,

Allison M. Sawyer,

Rohil Daya

и другие.

JACS Au, Год журнала: 2024, Номер 4(1), С. 197 - 215

Опубликована: Янв. 4, 2024

A key challenge for metal-exchanged zeolites is the determination of metal cation speciation and nuclearity under synthesis reaction conditions. Copper-exchanged zeolites, which are widely used in automotive emissions control potential catalysts partial methane oxidation, have particular evidenced a wide variety Cu structures that observed to change with exposure conditions, zeolite composition, topology. Here, we develop predictive models CHA, MOR, BEA, AFX, FER topologies using interatomic potentials, quantum chemical calculations, Monte Carlo simulations interrogate this vast configurational compositional space. Model predictions rationalize experimentally differences between Cu-zeolites wide-body literature, including populations, structural variations, methanol per yields. Our results show both topological features commonly Al-siting biases MOR increase population binuclear sites, explaining small mononuclear sites these materials relative other such as CHA BEA. Finally, machine learning classification model determine preference form or at different Al configurations 200 international database. reveal several extreme ends vs spectrum, highlighting synthetic options realization strong preferences.

Язык: Английский

Процитировано

20
Selective Catalytic Oxidation of Methane to Methanol in Aqueous Medium over Copper Cations Promoted by Atomically Dispersed Rhodium on TiO2 DOI
Fubo Gu, Xuetao Qin, Mengwei Li

и другие.

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(18)

Опубликована: Фев. 24, 2022

Direct conversion of methane into value-added chemicals, such as methanol under mild conditions, is a promising route for industrial applications. In this work, atomically dispersed Rh on TiO2 suspended in an aqueous solution was used the oxidation to methanol. Promoted by copper cations (as co-catalyst) solution, catalysts exhibited high activity and selectivity production using molecular oxygen with presence carbon monoxide at 150 °C reaction pressure 31 bar. Millimole level yields were reached higher than 99 % Rh/TiO2 promotion cation. CO reductive agent generate H2 from O, which led formation O2 through . Atomically activated C-H bond CH4 catalyzed Copper maintained low-valence state Rh. Moreover, acted scavenger suppressing overoxidation, thus leading

Язык: Английский

Процитировано

50
Exploring the Impact of Active Site Structure on the Conversion of Methane to Methanol in Cu‐Exchanged Zeolites DOI Creative Commons
Florian Göltl, Saurabh Bhandari, Edgard A. Lebrón‐Rodríguez

и другие.

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(23)

Опубликована: Апрель 4, 2024

Abstract In the past, Cu‐oxo or ‐hydroxy clusters hosted in zeolites have been suggested to enable selective conversion of methane methanol, but impact active site's stoichiometry and structure on methanol production is still poorly understood. Herein, we apply theoretical modeling conjunction with experiments study these two factors partial oxidation Cu‐exchanged zeolite SSZ‐13. Phase diagrams developed from first‐principles suggest that Cu‐hydroxy dimers are stabilized when O 2 N used activate catalyst, respectively. We confirm predictions experimentally determine a stepwise process, can convert twice as much compared Cu‐hydroxyl dimers. Our models rationalize how Cu‐di‐oxo up molecules while Cu‐di‐hydroxyl only one molecule per catalytic cycle. These findings imply Cu clusters, at least oxo group hydroxyl groups needed This simple structure–activity relationship allows intuitively understand potential small oxygenated hydroxylated transition metal methanol.

Язык: Английский

Процитировано

11
Direct Methane to Methanol Conversion: An Overview of Non‐Syn Gas Catalytic Strategies DOI Creative Commons

Anjana Rajeev,

Thasnim P Mohammed,

Akhila George

и другие.

The Chemical Record, Год журнала: 2025, Номер unknown

Опубликована: Янв. 16, 2025

Abstract Direct methane to methanol conversion is a dream reaction in industrial chemistry, which takes inspiration from the biological production catalysed by monooxygenase enzymes (MMOs). Over years, extensive studies have been conducted on this topic bioengineering MMOs, and tailoring methods isolate MMOs active form. Similarly, remarkable achievements noted other activation strategies such as use of heterogeneous catalysts or molecular catalysts. In review, we outline metabolism performed methanotrophs detail latest advancements site structures catalytic mechanisms both types MMOs. Also, recent progress bioinspired approaches using various catalysts, especially first‐row transition metal zeolites mechanistic insights are discussed. addition, complexes “Periana catalyst” for through methyl ester formation presence strong acids also detailed. Compared zeolites‐mediated field, utilisation application still its nascent phase further research required overcome limitations these effectively.

Язык: Английский

Процитировано

2
Formation of HCHO, CO and H2 by methane oxidation with O2 over Cu catalysts stabilized in silicoaluminophosphates DOI Creative Commons
Mana Shimakawa,

Rieko Nagase,

Ryoya Kugo

и другие.

Catalysis Science & Technology, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

The catalytic performance of Cu catalysts supported on SAPO34 (denoted as Cu/SAPO) for methane oxidation with O 2 has been investigated in detail.

Язык: Английский

Процитировано

2
Methane Activation by a Mononuclear Copper Active Site in the Zeolite Mordenite: Effect of Metal Nuclearity on Reactivity DOI
Alexander J. Heyer, Dieter Plessers, Augustin Braun

и другие.

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(42), С. 19305 - 19316

Опубликована: Окт. 11, 2022

The direct conversion of methane to methanol would have a wide reaching environmental and industrial impact. Copper-containing zeolites can perform this reaction at low temperatures pressures previously defined O

Язык: Английский

Процитировано

39