Molecular insight into the role of zeolite lattice constraints on methane activation over the Cu–O–Cu active site

Mahyuddin, Muhammad Haris; Saputro, Adhitya Gandaryus; Sukanli, Reza Pamungkas Putra; Fathurrahman, Fadjar; Rizkiana, Jenny; Nuruddin, Ahmad Ainuddin; Dipojono, Hermawan Kresno

doi:10.1039/d1cp05371j

Cited by 12 publications

(16 citation statements)

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“…Nonetheless, the ground state of INT remains unchanged (i.e., triplet, quartet, and doublet states, respectively, for FeN 4 G-BN, CoN 4 G-BN, and CuN 4 G-PN). Interestingly, the INT of CuN 4 G-PN is significantly more stable than that of FeN 4 G-BN and CoN 4 G-BN, which causes a lower TS2 . To understand this, we perform PDOS analysis for IS2 and INT (Figure ).…”

Section: Resultsmentioning

confidence: 99%

“…The cleaved CH Interestingly, the INT of CuN 4 G-PN is significantly more stable than that of FeN 4 G-BN and CoN 4 G-BN, which causes a lower TS2. 69 To understand this, we perform PDOS analysis for IS2 and INT (Figure 4). There are two, three, and one singly occupied orbitals in IS2 of FeN 4 G-BN, CoN 4 G-BN, and CuN 4 G-PN, respectively, which originate from the M 4+ 3d orbital.…”

Section: Active Site Formation Using O 2 On Fenmentioning

confidence: 99%

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Density Functional Theory Studies of the Direct Conversion of Methane to Methanol Using O₂ on Graphitic MN₄G-BN (M = Fe, Co, Cu) and CuN₄G-PN Single-Atom Catalysts

Sukanli

Mahyuddin

Saputro

et al. 2023

ACS Appl. Nano Mater.

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Graphene-based single-atom catalysts have attracted increasing interest due to their potential to catalyze the direct conversion of CH4 to CH3OH. In particular, the porphyrin-like FeN4 complex has recently been reported to convert CH4 to CH3OH at low temperatures with high selectivity. However, only N2O and H2O2, which are high-cost and scarce compared to O2, can be used as the oxidant of the reaction. In this paper, we perform density functional theory calculations on graphitic MN4G-BN (M = Fe, Co, Cu) and CuN4G-PN systems to evaluate the CH4 oxidation to CH3OH using O2. We found that the addition of B doping adjacent to the Fe and Co centers as well as P doing adjacent to the Cu center facilitates a facile OO bond dissociation with an activation barrier of less than 0.4 eV, resulting in active M–O and inactive B/P–O sites. This low barrier is due to the early OO bond elongation at the O2 adsorption step and the stability of the atomically adsorbed O atoms. In the subsequent CH4 oxidation, the resultant OCuN4G-OPN is found to be significantly more CH4-reactive than the OFeN4G-OBN and OCoN4G-OBN with a H–CH3 activation barrier of only 0.66 eV. Such high reactivity is due to the proximity of the electron-acceptor orbital (i.e., the Cu–O lowest unoccupied molecular orbital) toward the Fermi level. Moreover, the CH4 oxidation on CuN4G-PN is predicted to form CH3OH with high exothermicity and high resistance to overoxidation. This study suggests a high possibility for CuN4G-PN as a potential catalyst for the stepwise conversion of CH4 to CH3OH using O2 at low temperatures.

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Section: Resultsmentioning

confidence: 99%

Section: Active Site Formation Using O 2 On Fenmentioning

confidence: 99%

Density Functional Theory Studies of the Direct Conversion of Methane to Methanol Using O₂ on Graphitic MN₄G-BN (M = Fe, Co, Cu) and CuN₄G-PN Single-Atom Catalysts

Sukanli

Mahyuddin

Saputro

et al. 2023

ACS Appl. Nano Mater.

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“…Although significant attention has focused on industrially popular zeolites such as CHA, MOR, MFI, etc., recent studies have explored other frameworks such as BPH, EON, MEI, and HEU 61 . These efforts, in part, have been motivated by the possibility of finding an elusive "Goldilocks" active site or topology that can outperform known catalysts while also maintaining selectivity towards methanol [61][62][63][64][65][66][67][68] . For example, recent results from van Bokhoven and Sushkevich suggest that certain types of [CuOCu] 2+ sites (with 2.9 Å Cu--Cu separations) are more selective than others in MFI 69 .…”

Section: Introductionmentioning

confidence: 99%

Quantifying the Limits of Methane Activation in Cu-exchanged Zeolites using Reactive and Interpretable Machine Learning based Potentials

Guo

Sours

Holton

et al. 2023

Preprint

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Natural gas remains an essential energy source for the industrial and residential sectors. However, selective valorization of methane (the main component of natural gas) into more mobile liquid energy carriers such as methanol remains challenging. Inspired by pMMO enzymes, many recent studies have examined Cu-exchanged zeolites as promising catalysts, specifically through [CuOCu]2+ sites. These efforts, in part, have been motivated by the possibility of finding an elusive “Goldilocks” active site or topology that can outperform known catalysts while also maintaining selectivity towards methanol. As large-scale experiments with 1000s of material variations are impossible, theory will likely play an important role. Although computational screening studies are now routine for metals and alloys, similar studies for zeolites are not as straightforward due to the diversity of local chemical environments, and the aforementioned studies are not trivial using the traditional density functional theory (DFT)-based approach. Therefore, the overarching goal of this study is to leverage large-scale DFT calculations to develop a reactive machine learning-based potential (rMLP) capable of systematically sampling the stability and reactivity of all [CuOCu]2+ sites within a representative set of zeolites. Specifically, using methane activation as a prototypical example of an industrially relevant zeolite-catalyzed reaction, we have developed a novel multistage active learning algorithm that preferentially samples the potential energy surface of the system near the transition state of methane activation. We show that the resulting rMLP replaces the expensive DFT-based NEB calculations without any appreciable loss in accuracy (within 0.07 eV of the DFT computed energy barriers) – we evaluate C-H bond activation energies for 5,400 distinct sites across 52 zeolites and obtain 3,356 valid sites suitable for methane activation. By replacing the expensive DFT-based NEB calculations with rMLPs, we now report an exhaustive high-throughput screening study of thousands of [CuOCu]2+ sites in zeolites, comparing the maximum rates of methane activation across 52 zeolite topologies and more than 3,000 sites. To the best of our knowledge, this work represents the first example of using reactive MLPs to identify the transition state geometries and screen the catalytic performance of thousands of zeolite-based active sites at DFT accuracies.

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“…[17][18][19][20] Among them, [Cu 2 O] 2+ has been identified in different zeolite topologies. [21][22][23][24][25] The ZSM-5 zeolite was first reported to host this Cu dimer active site, 26 which is able to activate CH 4 at 175 °C with an activation energy of only 15.7 ± 0.5 kcal mol −1 . The MOR 21,27 and SSZ-13 (ref.…”

Section: Introductionmentioning

confidence: 99%

Conditions to meet for the [CuOH]⁺ site to be favorable and reactive toward the conversion of methane to methanol over Cu-MOR zeolite

Mahyuddin,

Lasiman,

Saputro

et al. 2023

Catal. Sci. Technol.

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Molecular insight into the role of zeolite lattice constraints on methane activation over the Cu–O–Cu active site

Abstract: Understanding factors influencing the activity of a catalyst toward the CH4 activation is highly important for tuning the catalyst performance or designing new better catalysts. Here, we performed a set...

Cited by 12 publications

References 59 publications

Density Functional Theory Studies of the Direct Conversion of Methane to Methanol Using O₂ on Graphitic MN₄G-BN (M = Fe, Co, Cu) and CuN₄G-PN Single-Atom Catalysts

Density Functional Theory Studies of the Direct Conversion of Methane to Methanol Using O₂ on Graphitic MN₄G-BN (M = Fe, Co, Cu) and CuN₄G-PN Single-Atom Catalysts

Quantifying the Limits of Methane Activation in Cu-exchanged Zeolites using Reactive and Interpretable Machine Learning based Potentials

Conditions to meet for the [CuOH]⁺ site to be favorable and reactive toward the conversion of methane to methanol over Cu-MOR zeolite

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Molecular insight into the role of zeolite lattice constraints on methane activation over the Cu–O–Cu active site

Abstract: Understanding factors influencing the activity of a catalyst toward the CH4 activation is highly important for tuning the catalyst performance or designing new better catalysts. Here, we performed a set...

Cited by 12 publications

References 59 publications

Density Functional Theory Studies of the Direct Conversion of Methane to Methanol Using O2 on Graphitic MN4G-BN (M = Fe, Co, Cu) and CuN4G-PN Single-Atom Catalysts

Density Functional Theory Studies of the Direct Conversion of Methane to Methanol Using O2 on Graphitic MN4G-BN (M = Fe, Co, Cu) and CuN4G-PN Single-Atom Catalysts

Quantifying the Limits of Methane Activation in Cu-exchanged Zeolites using Reactive and Interpretable Machine Learning based Potentials

Conditions to meet for the [CuOH]+ site to be favorable and reactive toward the conversion of methane to methanol over Cu-MOR zeolite

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Density Functional Theory Studies of the Direct Conversion of Methane to Methanol Using O₂ on Graphitic MN₄G-BN (M = Fe, Co, Cu) and CuN₄G-PN Single-Atom Catalysts

Density Functional Theory Studies of the Direct Conversion of Methane to Methanol Using O₂ on Graphitic MN₄G-BN (M = Fe, Co, Cu) and CuN₄G-PN Single-Atom Catalysts

Conditions to meet for the [CuOH]⁺ site to be favorable and reactive toward the conversion of methane to methanol over Cu-MOR zeolite