Single PdO loaded on boron nanosheet for methane oxidation: A DFT study

Dong, Ani; Xu, Guoliang; Dai, Zhongxu; Yu, Aimin; Qiu, Siyao; Sun, Chenghua

doi:10.1016/j.pnsc.2019.05.005

Cited by 13 publications

(6 citation statements)

References 35 publications

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“…Psofogiannakis and coworkers (32) showed that CH 4 oxidation to CO is preferable through the dissociative chemisorption of CH 4 on Pt with the sequence p CH 3 → p CH 2 → p CH → p CHOH → p CHO → p CO. A similar study showed, depending on the surface structure, the oxygen-assisted dehydrogenation drives the selectivity of the reaction to either CH x O y or CO x products (33). The presence of oxygen on transition metals in the form of metal oxides has been determined to play a key role in C-H bond activation and the oxidation of CH 4 (34)(35)(36) (37)(38)(39)(40). The participation of *O species in both MOR and OER is the primary cause for the competitive kinetics determining the selectivity of CH 4 oxidation on TMOs.…”

Section: Significancementioning

confidence: 92%

Fundamental insight into electrochemical oxidation of methane towards methanol on transition metal oxides

Prajapati

Collins

Goodpaster

et al. 2021

Proc. Natl. Acad. Sci. U.S.A.

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Electrochemical oxidation of CH4 is known to be inefficient in aqueous electrolytes. The lower activity of methane oxidation reaction (MOR) is primarily attributed to the dominant oxygen evolution reaction (OER) and the higher barrier for CH4 activation on transition metal oxides (TMOs). However, a satisfactory explanation for the origins of such lower activity of MOR on TMOs, along with the enabling strategies to partially oxidize CH4 to CH3OH, have not been developed yet. We report here the activation of CH4 is governed by a previously unrecognized consequence of electrostatic (or Madelung) potential of metal atom in TMOs. The measured binding energies of CH4 on 12 different TMOs scale linearly with the Madelung potentials of the metal in the TMOs. The MOR active TMOs are the ones with higher CH4 binding energy and lower Madelung potential. Out of 12 TMOs studied here, only TiO2, IrO2, PbO2, and PtO2 are active for MOR, where the stable active site is the O on top of the metal in TMOs. The reaction pathway for MOR proceeds primarily through *CHx intermediates at lower potentials and through *CH3OH intermediates at higher potentials. The key MOR intermediate *CH3OH is identified on TiO2 under operando conditions at higher potential using transient open-circuit potential measurement. To minimize the overoxidation of *CH3OH, a bimetallic Cu2O3 on TiO2 catalysts is developed, in which Cu reduces the barrier for the reaction of *CH3 and *OH and facilitates the desorption of *CH3OH. The highest faradaic efficiency of 6% is obtained using Cu-Ti bimetallic TMO.

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Section: Significancementioning

confidence: 92%

Fundamental insight into electrochemical oxidation of methane towards methanol on transition metal oxides

Prajapati

Collins

Goodpaster

et al. 2021

Proc. Natl. Acad. Sci. U.S.A.

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“…Conversely, such high reactivity results in poor stability due to metal atom aggregation during both the synthesis and catalytic processes. , Therefore, the support material plays a critical role in stabilizing single atoms. In the past few decades, various catalytic materials such as zeolites, , metal–organic frameworks (MOFs), , and 2D materials (graphene, , Mxenes, boron sheet) have been derived for methanol formation from methane. In particular, zeolites have been extensively studied, but extreme hydrophilicity is a major drawback of such materials, which makes methanol desorption difficult .…”

Section: Introductionmentioning

confidence: 99%

Mechanistic Insights into Direct Methane Oxidation to Methanol on Single-Atom Transition-Metal-Modified Graphyne

Arachchige

Dong

Wang

et al. 2021

ACS Appl. Nano Mater.

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Methane is the major component in natural gas and flares wastefully at remote sites since the collection and use are not economical. The direct conversion of methane into liquid fuels such as methanol has been identified as a fruitful solution to this issue. Herein, density functional theory calculations and microkinetic studies were employed on 3d late-transition-metal atom (Fe, Co, Ni, Cu)-loaded graphyne as catalysts for methane-tomethanol conversion. Single metal atoms showed decent stability at pores of graphyne. The oxidant used for this work was abundant O 2 instead of high-cost H 2 O 2 or N 2 O. This systematic study revealed that both iron and cobalt single atoms dispersed at adjoining pores of graphyne are capable of forming catalytically active metal−oxygen (M−O) moieties upon dissociative adsorption of O 2 . Further, the Co−O moiety loaded on graphyne demonstrated reasonable catalytic activity for methane-to-methanol conversion with sufficient selectivity. Interestingly, dispersed single metal atoms on graphyne support were able to mimic the enzymatic formation of catalytically active M−O moieties. Moreover, it is further noticed that methane activation and methanol production kinetics are strongly correlated with the strength of the metal−oxygen bond.

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“…According to the previous reports, the first CÀ H bond activation of CH 4 is toughest, which requires a high energy barrier. [39][40][41][42][43] As shown in Figure 4 and Figure S2-S4, the energy barrier of the first CÀ H bond activation for FeÀ O@BP, CoÀ O@BP, NiÀ O@BP and CuÀ O@BP is 1.60 eV, 1.01 eV, 0.80 eV, and 0.29 eV respectively, indicating that the CuÀ O@BP is most likely to catalyze the methane oxidation, followed by NiÀ O@BP, CoÀ O@BP, and FeÀ O@BP. In addition, the Bader charge on oxygen in TMÀ O@BP was calculated.…”

Section: Oxidation Of Methane To Methanolmentioning

confidence: 95%

“…Recently, single-atom catalysts (SACs) are extensively studied and reported as promising catalysts in various reactions due to their maximum atomic utilization and high selectivity. [40][41][42][43] Nowadays, SACs have been successfully applied in N 2 reduction reaction, CO 2 reduction reaction, hydrogen evolution reaction and oxygen reduction reaction. [44,45] In addition, Yuan et al designed a single vacant graphene supported Co catalyst to promote methane activation, and the reaction mechanisms for different products were studied based on the density functional theory (DFT) calculations.…”

Section: Introductionmentioning

confidence: 99%

Computational Study of Single Metal Atom Anchored on Black Phosphorus for Methane Oxidation to Methanol by Nitrous Oxide

Wang

2023

Chemistry A European J

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Direct conversion of methane to high-value-added transportable methanol is a great challenge, which requires high energy input to break the strong CÀ H bond. Developing efficient catalysts for methane oxidation to methanol under mild conditions is of vital importance. In this work, single transition metal atoms (TM=Fe, Co, Ni, Cu) anchored on black phosphorus (TM@BP) were studied as catalysts to assist the methane oxidation to methanol by means of first-principles calculations. The results indicate that Cu@BP exhibits an outstanding catalytic activity through the radical reaction pathways and the formation of the CuÀ O active site is ratedetermining with an energy barrier of 0.48 eV. Meanwhile, electronic structure calculations and dynamic simulations show that Cu@BP offers excellent thermal stability. Our calculations provide a new approach for the rational design of single atom catalysts for methane oxidation to methanol.

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Single PdO loaded on boron nanosheet for methane oxidation: A DFT study

Cited by 13 publications

References 35 publications

Fundamental insight into electrochemical oxidation of methane towards methanol on transition metal oxides

Fundamental insight into electrochemical oxidation of methane towards methanol on transition metal oxides

Mechanistic Insights into Direct Methane Oxidation to Methanol on Single-Atom Transition-Metal-Modified Graphyne

Computational Study of Single Metal Atom Anchored on Black Phosphorus for Methane Oxidation to Methanol by Nitrous Oxide

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