A Single Pd Atom Stabilized on Boron‐Vacancy of h‐BN Nanosheet: A Promising Catalyst for CO Oxidation

Esrafili, Mehdi D.; Asadollahi, Soheila

doi:10.1002/slct.201801848

Cited by 30 publications

(12 citation statements)

References 61 publications

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“…In the absence of CO co-adsorption the termolecular pathway, TER, yields a TOF seven orders of magnitude smaller than that of TER CO . Termolecular ER is proposed as the preferred mechanism of CO oxidation with single atoms supported on two-dimensional materials, 72 and is yet to be examined on oxide-supported catalysts. To the best of our knowledge, there is also no experimental evidence for the formation of a OCOOCO intermediate (step iv, iii in Figures 9 and 10, respectively).…”

Section: Discussionmentioning

confidence: 99%

Analysis of Preferred Mechanisms of CO Oxidation with Atomically Dispersed Pt1/TiO2 Using the Energetic Span Model

Bac

Sharada

2021

Preprint

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This work examines mechanisms of low-temperature CO oxidation over a single binding site of atomically dispersed Pt on rutile TiO2 (110) using density functional theory and the energetic span model (ESM). Of the 12 distinct pathways spanning Eley- Rideal (ER), termolecular ER (TER), Langmuir-Hinshelwood (LH), Mars-Van Krevelen (MvK) mechanisms as well as their combinations, TER with CO-assisted CO2 desorption yields the highest turnover frequency (TOF). However, this pathway is ruled out because Pt is dynamically unstable in an intermediate state in the TER cycle, determined in a prior ab initio molecular dynamics study by our group. We instead find, depending on reaction conditions, that either H1 is rendered inactive upon CO adsorption or the ER mechanism is preferred if O2 dissociatively adsorbs. ER exhibits the second highest TOF and the TOF-determining state is in qualitative agreement with experiment. TOFs for all MvK pathways are several orders of magnitude lower than ER and LH. By comparing TOFs for Pt1/TiO2 with prior mechanistic studies of various oxide-supported atomically dispersed catalysts in the literature, we identify the most active metal and support materials for low-temperature CO oxidation.

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Section: Discussionmentioning

confidence: 99%

Analysis of Preferred Mechanisms of CO Oxidation with Atomically Dispersed Pt1/TiO2 Using the Energetic Span Model

Bac

Sharada

2021

Preprint

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“…CO oxidation mechanisms on carbon‐based or boron‐nitride‐based 2‐D materials were also studied theoretically. First‐principle calculations revealed a TER mechanism for CO oxidation on Pd SACs with defect graphene, [74] a BN nanosheet, [75] or N‐doped graphene [76] as support.…”

Section: Sacs For Co Oxidationmentioning

confidence: 99%

Single‐atom Automobile Exhaust Catalysts

Zhang

Fan

et al. 2020

ChemNanoMat

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Single-atom catalysts (SACs) with isolated metal centers are attracting great research interest because of their maximized metal utilization rates and unique structures. In the last decade, significant efforts have been made to design highly efficient and cost-effective SACs with applications in automobile exhaust aftertreatment. SACs have not only demonstrated their high potential for improving the catalytic performance of current automobile exhaust catalysts but also provided an ideal platform for understanding the origins of catalyst reactivity. In this review, we summarize the general strategies for promoting the reactivity of metal SACs while maintaining their thermal stability during exhaust-abatement-related reactions. Highlights are provided on wellperformed SACs for CO oxidation, unburnt hydrocarbon (HC) oxidation, and the selective catalytic reduction of NO x. The reaction mechanism and structure-performance relationship of SAC during these reactions are also discussed. Finally, perspectives are given on the trending research fields for designing more efficient single-atom automobile exhaust catalysts in the future.

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“…The single‐atom catalyst has extremely high atom efficiency and shows excellent stability and high activity for CO oxidation The atomic form of the catalyst significantly increases the catalytic efficiency, leading to a dramatic reduction in the quantity and cost of precious metals required . Density functional theory calculations show that the high catalytic activity of a single atom is related to the partially vacant 5d orbitals of the positively‐charged, high‐valent Pt atoms, which help to reduce both the CO adsorption energy and the activation barriers for CO oxidation …”

Section: Introductionmentioning

confidence: 99%

“…[1,2,5,[12][13][14][15][16][17][18][19][20][21][22][23] The atomic form of the catalyst significantly increases the catalytic efficiency, leading to a dramatic reduction in the quantity and cost of precious metals required. [2,15,19,21,24] Density functional theory calculations show that the high catalytic activity of a single atom is related to the partially vacant 5d orbitals of the positively-charged, highvalent Pt atoms, which help to reduce both the CO adsorption energy and the activation barriers for CO oxidation. [2] CO oxidation by O 2 generally proceeds via two well-known mechanisms, i. e., Eley-Rideal (ER) and Langmuir-Hinshelwood (LH).…”

Section: Introductionmentioning

confidence: 99%

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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A Single Pd Atom Stabilized on Boron‐Vacancy of h‐BN Nanosheet: A Promising Catalyst for CO Oxidation

Cited by 30 publications

References 61 publications

Analysis of Preferred Mechanisms of CO Oxidation with Atomically Dispersed Pt1/TiO2 Using the Energetic Span Model

Analysis of Preferred Mechanisms of CO Oxidation with Atomically Dispersed Pt1/TiO2 Using the Energetic Span Model

Single‐atom Automobile Exhaust Catalysts

Enhanced Catalytic Oxidation of CO on Sulfur‐Doped Boron Nitride

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