Boosting graphene reactivity with co-doping of boron and nitrogen atoms: CO oxidation by O2 molecule

Esrafili, Mehdi D.; Mousavian, Parisasadat

doi:10.1016/j.apsusc.2018.06.053

Cited by 40 publications

(15 citation statements)

References 66 publications

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“…For example, an earlier experimental study by Yoo and coworkers has proposed that small Pt nanoparticles supported on graphene can act as a high active electrocatalyst for methanol oxidation reaction . Although the interaction between perfect graphene and deposited metal atoms is weak due to its π‐conjugated structure, however, a number of theoretical studies have shown that chemical doping of graphene with foreign atoms can remarkably improve the dispersion of metal atoms and hence enhance their catalytic activity . For instance, it has been theoretically reported that chemically‐doped graphene with a single metal (Fe, Cu, Ni, and Ti) or nonmetal (Si, Al, and P) atom exhibits an exceptional catalytic activity for low‐temperature oxidation of CO molecule.…”

Section: Introductionmentioning

confidence: 99%

A DFT study on the possibility of using a single Cu atom incorporated nitrogen‐doped graphene as a promising and highly active catalyst for oxidation of CO

Esrafili

Mousavian

2018

Int J of Quantum Chemistry

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Using dispersion-corrected density functional theory (DFT) calculations, a single Cu adatom incorporated nitrogen-doped graphene (CuN 3 -Gr) is proposed as a new and highly active noble-metalfree catalyst for carbon monoxide (CO) oxidation reaction. According to our results, the Cu adatom can be stably anchored onto the monovavancy site of the nitrogen-doped graphene, and the resulting large diffusion barrier suggests that the metal clustering is avoided in CuN 3 -Gr. Three possible reaction mechanisms for CO oxidation (ie, Eley-Rideal, Langmuir-Hinshelwood, and termolecular Eley-Rideal) are systematically studied. It is found that the activation energy for the ratedetermining step of the termolecular Eley-Rideal mechanism is only 0.13 eV, which is much smaller than those of others. The results of this study may provide a useful guideline for the design of highly active and promising single-metal catalysts for the CO oxidation reaction based on graphene.

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Section: Introductionmentioning

confidence: 99%

A DFT study on the possibility of using a single Cu atom incorporated nitrogen‐doped graphene as a promising and highly active catalyst for oxidation of CO

Esrafili

Mousavian

2018

Int J of Quantum Chemistry

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“…The first oxygen transfers from O 2 to CO, generating CO 2 ; this occurs exothermically by −61.0/−63.8 kcal/mol with an activation energy barrier (TS1) of 15.5/12.1 kcal/mol for V B −S…O 2 …CO/ V N −S…O 2 …CO (Figure ). This barrier is lower compared to those of metal‐doped catalysts (such as M−BN (M=Co, Si), M‐PMA (M=Pt, Fe, Ir, Rh, and Ru)), and that of boron‐ and nitrogen‐doped graphene (19.4 kcal/mol) . Although the barrier of this step for Ru‐embedded h‐BN (9.7 kcal/mol) and Pt 1 /FeO x (11.3 kcal/mol) is lower, the barrier of the second oxygen transfer (16.4 and 18.2 kcal/mol) is higher compared to that of sulfur‐doped h‐BN (1.8 kcal/mol).…”

Section: Resultsmentioning

confidence: 92%

“…Therefore, the coupling mode between the generated CO 2 and the sulfur dopant should be physisorption. Energetically, the second oxygen transfer is an exothermic process with an enthalpy change of −64.0/−29.9 kcal/mol and a barrier (TS2) of 3.6/1.8 kcal/mol, which is lower than that of the first oxygen transfer and that (9.2 kcal/mol) of boron‐ and nitrogen‐doped graphene …”

Section: Resultsmentioning

confidence: 94%

“…In the ER, the O 2 molecule is first adsorbed over the catalytic site and activated by charge exchange with the support, then CO attacks the activated O 2 molecule (O 2 *) to form a CO 2 molecule and an activated O atom (CO+O 2 *→CO 2 +O*). On the other hand, the LH mechanism involves the co‐adsorption of CO and O 2 molecules to form a peroxo‐type intermediate (OCOO) and then dissociates into CO 2 and O* (CO+O 2 →OCOO→CO 2 +O*) . Activation of the adsorbed O 2 is a crucial step in the CO oxidation reaction.…”

Section: Introductionmentioning

confidence: 99%

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Enhanced Catalytic Oxidation of CO on Sulfur‐Doped Boron Nitride

2019

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Bridging the gap between homogeneous and heterogeneous catalysis, the single-atom catalyst supported on a substrate shows extremely high atom efficiency, low cost, excellent stability, and high activity for CO oxidation. Here, we report the catalytic mechanism of CO oxidation on sulfur-doped h-BN. The chemisorption activates O 2 via electron transfer from sulfur-doped h-BN, inducing a reduction in the bond order of O 2 and lengthening the OÀ O distance. This variation is helpful for the subsequent oxidation of CO. The oxidation process includes O 2 adsorption, electron reorganization, and two instances each of CO adsorption, oxygen transfer, and CO 2 desorption. The first oxygen transfer from O 2 to CO occurs exothermically byÀ 63.8 kcal/mol with a barrier of~12.1 kcal/mol, which is thus the rate-determining step. The significantly enhanced catalytic performance implies that sulfur doping on h-BN should have potential applications in the areas of metal-free catalysts with low cost and high activity.[a] Dr. . The CO oxidation mechanism catalyzed by V B À S and V N À S (Path 1). The primary geometrical parameters and energy variations along the pathway are presented. OA: oxygen adsorption; RO: electron reorganization; CA: CO adsorption; OT: oxygen transfer. Figure 3. The CO oxidation mechanism catalyzed by V B À S and V N À S (Path 2). The primary geometrical parameters and energy variations along the pathway are presented. OA: oxygen adsorption; RO: electron reorganization; CA: CO adsorption; OT: oxygen transfer.

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“…This barrier is lower as compared to metal‐doped catalysts (such as M‐BN (M =Co)) . M‐PMA (M=Pt, Fe, Ir, Rh, Ru,Cu(111) and Ni(111))), and lower than that of boron and nitrogen doped grapheme (0.84 eV) . Although the barrier of this step for Ru‐embedded h‐BN (0.41 eV) and Pt 1 /FeO x (0.48 eV) is lower, the barriers of the second oxygen transfer (0.71 and 0.77 eV) in these two systems are higher as compared to that of three silicon‐doped h‐BN (0.72/0.43 eV).…”

Section: Resultsmentioning

confidence: 95%

Catalytic Mechanism of CO Oxidation on Three‐Silicon‐Doped Hexagonal Boron Nitride

Liu

Hai

et al. 2019

ChemNanoMat

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Doped nanomaterials show extremely high atom efficiency, low cost, high stability and activity for CO oxidation, bridging the gap between homogeneous and heterogeneous catalysis. The catalytic mechanism of CO oxidation on three‐silicon‐doped h‐BN is reported. The adsorption of O2 is more advantageous than CO. The electron transfer from the dopant activates the adsorbed O2 and initiates the following CO oxidation. The oxidation process includes O2 adsorption, electron transfer, CO adsorption, oxygen transfer, and CO2 desorption. The energy barriers for the generation of two CO2 molecules in N vacancy dopant are 0.50 and 0.33 eV, respectively. The enhanced catalytic performance indicates that three‐silicon‐doped h‐BN has potential applications to fabricate low cost and high activity BN‐based metal‐free catalysts.

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Boosting graphene reactivity with co-doping of boron and nitrogen atoms: CO oxidation by O2 molecule

Cited by 40 publications

References 66 publications

A DFT study on the possibility of using a single Cu atom incorporated nitrogen‐doped graphene as a promising and highly active catalyst for oxidation of CO

A DFT study on the possibility of using a single Cu atom incorporated nitrogen‐doped graphene as a promising and highly active catalyst for oxidation of CO

Enhanced Catalytic Oxidation of CO on Sulfur‐Doped Boron Nitride

Catalytic Mechanism of CO Oxidation on Three‐Silicon‐Doped Hexagonal Boron Nitride

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