Density Functional Theory Study of Cu-ZSM-5-Catalyzed C–H Bond Activation: The Importance of Active Centers

Liu, Xin; Zhang, Jie; Huang, Chongpin; Sun, Xueliang

doi:10.1021/acs.jpcc.8b08137

Cited by 8 publications

(7 citation statements)

References 44 publications

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“…Figure 5b shows the optimized model of the binuclear Cu-ZSM-5 cluster [Si 8 Al l2 O 12 H 16 Cu 2 ]. After intercepting the binuclear Cu-ZSM-5 cluster model, the broken chemical bonds are supplemented by H atoms [18,62,63]. The structural parameters of the binuclear Cu-ZSM-5 model are highly consistent with those reported by Goodman et al [33], and the distance between two Cu atoms is 2.46 Å, which is consistent with the reported results (2.48 Å).…”

Section: Computational Methods and Modelsupporting

confidence: 88%

DFT Study on the Combined Catalytic Removal of N2O, NO, and NO2 over Binuclear Cu-ZSM-5

Gao

Zhang

et al. 2022

Catalysts

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The large amount of nitrogen oxides (N2O, NO, NO2, etc.) contained in the flue gas of industrial adipic acid production will seriously damage the environment. A designed binuclear Cu-ZSM-5 catalyst can be applied to decompose N2O and reduce NO and NO2, purifying the air environment. Using the density functional theory method, the catalytic decomposition mechanisms of N2O, NOX-NH3-SCR, and NOX-assisted N2O decomposition is simulated over the Cu-ZSM-5 model. The results indicate that N2O can be catalytically decomposed over the binuclear Cu active site in the sinusoidal channel. The speed-limiting step is the second N2O molecule activation process. After the decomposition of the first N2O molecule, a stable extra-frame [Cu-O-Cu]2+ structure will generate. The subsequent discussion proved that the NOX-NH3-SCR reaction can be realized over the [Cu-O-Cu]2+ active site. In addition, it proved that the decomposition reaction of NO and NO2 can be carried out over the [Cu-O-Cu]2+ active site, and NO can greatly reduce the energy barrier for the conversion of the active site from [Cu-O-Cu]2+ to the binuclear Cu form, while NO2 can be slightly reduced. Through discussion, it is found that the binuclear Cu-ZSM-5 can realize the combined removal of N2O and NOX from adipic acid flue gas, hoping to provide a theoretical basis for the development of a dual-functional catalyst.

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Section: Computational Methods and Modelsupporting

confidence: 88%

DFT Study on the Combined Catalytic Removal of N2O, NO, and NO2 over Binuclear Cu-ZSM-5

Gao

Zhang

et al. 2022

Catalysts

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“…Various factors such as structure and composition of the zeolite used, the structure of copper active species, and reaction conditions should be considered to produce methanol selectively by direct partial oxidation of methane. Depending on the structure of the zeolite, different environment in which oxygen or methane is stabilized at the active copper species can be formed (Kulkarni et al, 2016; Zhao et al, 2016; Pappas et al, 2017; Liu et al, 2018). The C-H bond activation barrier energy of methane depending on the type of metal active species present in the zeolite pores was estimated (Kulkarni et al, 2018).…”

Section: Methane Reactivity and Methanol Yield In Cu-zeolite Systemmentioning

confidence: 99%

Recent Progress in Direct Conversion of Methane to Methanol Over Copper-Exchanged Zeolites

Park

Ahn

2019

Front. Chem.

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The conversion of methane into an easily transportable liquid fuel or chemicals has become a highly sought-after goal spurred by the increasing availability of cheap and abundant natural gas. While utilization of methane for the production of syngas and its subsequent conversion via an indirect route is typical, it is cost-intensive, and alternative direct conversion routes have been investigated actively. One of the most promising directions among these is the low-temperature partial oxidation of methane to methanol over a metal-loaded zeolite, which mimics facile enzymatic chemistry of methane oxidation. Thus mono-, bi-, and trinuclear oxide compounds of iron and copper stabilized on ZSM-5 or mordenite, which are structurally analogous to those found in methane monooxygenases, have demonstrated promising catalytic performances. The two major problems of theses metal-loaded zeolites are low yield to methanol and batch-like non-catalytic reaction systems challenging to extend to an industrial scale. In this mini-review, attention was given to the direct methane oxidation to methanol over copper-loaded zeolite systems. A brief introduction on the catalytic methane direct oxidation routes and current status of the applied metal-containing zeolites including the ones with copper ions are given. Next, by analyzing the extensive experimental and theoretical data available, the consensus among the researchers to achieve the target of high methanol yield is discussed in terms of zeolite topology, active species, and reaction parameters. Finally, the recent efforts on continuous methanol production from the direct methane oxidation aiming for an industrial process are summarized.

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“…In the simulation study of geometry optimization and transition state search, the LANL2DZ basis set was used to describe the atomic Cu, and the 6-31G(d) basis set was used for the other atoms (Al, Si, N, O and H). However, the 6-311++G (d, p) set was applied for energy change calculations on top of the structural optimization results to calculate the energy barrier values [45][46][47]. In the frequency calculation, zero-point energy (ZPE) was used for energy correction [48][49][50][51][52][53].…”

Section: Discussionmentioning

confidence: 99%

DFT Study on Mechanisms of the N2O Direct Catalytic Decomposition over Cu-ZSM-5: The Detailed Investigation on NO Formation Mechanism

Gao

Zhang

et al. 2020

Catalysts

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Nitrous oxide (N2O) is an industrial emission that causes the greenhouse effect and damages the ozone layer. Density functional theory study on the N2O direct catalytic decomposition over Cu–ZSM-5 has been performed in this paper. Two possible reaction mechanisms for N2O direct catalytic decomposition over Cu-ZSM-5 were proposed (O2 formation mechanism and Nitric oxide (NO) formation mechanism). The geometrical parameters, vibration frequency and thermodynamic data of the intermediate states in each step have been examined. The results indicate that N2O can be adsorbed on active site Cu in two ways (O-terminal or N-terminal), and N2O decomposition reactions can occur in both cases. The NO formation mechanism exhibits higher N2O dissociation reaction due to lower energy barrier.

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Density Functional Theory Study of Cu-ZSM-5-Catalyzed C–H Bond Activation: The Importance of Active Centers

Cited by 8 publications

References 44 publications

DFT Study on the Combined Catalytic Removal of N2O, NO, and NO2 over Binuclear Cu-ZSM-5

DFT Study on the Combined Catalytic Removal of N2O, NO, and NO2 over Binuclear Cu-ZSM-5

Recent Progress in Direct Conversion of Methane to Methanol Over Copper-Exchanged Zeolites

DFT Study on Mechanisms of the N2O Direct Catalytic Decomposition over Cu-ZSM-5: The Detailed Investigation on NO Formation Mechanism

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