The Brønsted−Evans−Polanyi Correlations in Oxidation Catalysis

Panov, G. I.; Parfenov, Mikhail V.; Parmon, Valentin N.

doi:10.1080/01614940.2015.1074487

Cited by 23 publications

(10 citation statements)

References 90 publications

(114 reference statements)

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“…where α is the Polanyi parameter. The BEP approach was successfully used to examine many reactions on metal surfaces including hydrogenation and dehydrogenation of ethylene, 45 ammonia synthesis, 46 and even reactions on metal oxides, as for example different oxidation reactions, 47 including oxidation of CO. 48 In a general case, the slope of eq 5 and thus the value of Polanyi parameter can be different depending on the crystallographic face, 49 as demonstrated for the activation energy of CH, CO, and trans COOH dissociation reactions on (100), (110), and (111) surfaces of several metals. In the latter case, the BEP relation was valid when the overall transition state (TS) is not varying at the conditions for which LFER is applied.…”

Section: ■ Methodsmentioning

confidence: 99%

“…Extension of this approach by Evans and Polanyi as well as Horiuti to activation energy analysis allowed utilization of the linear free energy relationship (LFER) to calculate the activation energy of many reactions, catalytic ones or proceeding without any catalyst through the following relationship where α is the Polanyi parameter. The BEP approach was successfully used to examine many reactions on metal surfaces including hydrogenation and dehydrogenation of ethylene, ammonia synthesis, and even reactions on metal oxides, as for example different oxidation reactions, including oxidation of CO …”

Section: Methodsmentioning

confidence: 99%

Section: Gibbs Energymentioning

confidence: 99%

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Coordination-Dependent Kinetics in the Catalysis of Gold Nanoclusters

2021

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A coordination-based kinetic model was used to explore the turnover frequency (TOF) in the oxidation of carbon monoxide on gold polyhedral nanoclusters. The Debye energy model was used to determine the Gibbs energy of bare nanoclusters. An empirical energy model derived from density functional theory (DFT) and thermodynamics was used to determine the size dependence of the Gibbs adsorption energy. A thermodynamic approach was used to model the kinetics of CO oxidation on gold nanoclusters. The adsorption was modeled with a Langmuir-Hinshelwood (L-H) mechanism, and also a mechanism (Eley-Rideal, E-R) where oxygen interacts with sites on the cluster support. The coordination, shape, and the Gibbs energy of adsorption were found to be important factors in replicating experimental TOF dependencies. The data from the L-H mechanism was shown to model the experimental results more closely. The mass activity of icosahedra for this reaction shows a good similarity with the experimental data. This work provides guidance for different distributions due to shape and size when determining the TOF and the mass activity.

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Section: ■ Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

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Coordination-Dependent Kinetics in the Catalysis of Gold Nanoclusters

2021

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“…Reaction (3) is the rate-determining step, whose activation energy follows the Brønsted-Evans-Polanyi (BEP) relation E 3 = E 3,0 − β•Q NH , where the universal BEP coefficient β = 0.5 [34] and E 3,0 are set the same for all sites M n . The TOF of a site M n (nominal moles of NH 3 per site per second) corresponds to the rate of Reaction (3) that is in proportion:…”

Section: Theoreticalmentioning

confidence: 99%

Design of Active Centers in Ammonia Synthesis on Mo-Based Catalysts: A Theoretical Study

Cholach

Bryliakova

2020

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The strong Mo-N bond restrains the catalytic activity of metallic Mo in ammonia synthesis. In this study, the semi-empirical calculations in conjunction with the density functional theory calculations, Brønsted-Evans-Polanyi relationship and microkinetic modeling were used to evaluate the rate of ammonia synthesis on model active sites of Mo-based alloys, nitrides, and clusters with a modified Mo-N bond. It was found that active sites of binary alloys Mo δ Me 1−δ (0 ≤ δ ≤ 1; Me = Co, Pt, Ir, Rh) show the synergetic behavior. The sites of ternary Mo 3 Me 3 N (Me = Mo, Co, Pt, Ir) and Mo 2 N-type nitrides revealed higher activities than sites on Mo planes due to an extra Mo bond with the lattice N atom. The sites of octahedral clusters Mo 3 Me 3 N (Me = Mo, Co, Ir, Pt) exhibited higher catalytic activity than the sites of nitrides because their Me-N bonds are weaker than Mo-N. It was also found that tetragonal Mo 2 Me 2 (Me = Co, Pt, Ir) and bi-tetragonal clusters Mo 3 Me 2 (Me = Co, Ir, Pt) are the best cases because their sites provide the optimal combination of local structure and thermodynamics. Catalytic activities of the most active sites, relative to the Fe-C 7 center, were found to change in the row 18.4 (threefold site Mo 2 Ir 1 in cluster Mo 3 Ir 2 ), 7.3 (Mo 2 in cluster Mo 2 Ir 2 ), 3.9 (Mo 2 Pt 1 in cluster Mo 3 Ir 3 N), 3.8 (M 3 on alloy Mo 0.78 Ir 0.22 ), 2.0 [Mo 3 Pt 1 on the plane (100) of Mo 3 Pt 3 N], 0.57 [Mo 3 on the plane (111) of Mo 2 N], and 0.03 [Mo 4 on the plane Mo(110)-(1 × 2)]. The design of tailor-made catalytic sites suggested in this paper can probably be applied to other catalytic systems.

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“…The intermediates include the polarized O 2 molecule upon adsorption, differently charged molecular or atomic species with electrophilic character in the process of O 2 dissociation, and nucleophilic O 2− ions after incorporation of oxygen into the oxide lattice. Control over occurrence and distribution of the various oxygen species on the surface of oxide catalysts under working conditions is the key issue in terms of selectivity [70][71][72][73][74][75][76]. Brønsted-Evans-Polanyi relations, which are strongly coupled to the adsorbate geometry of diatomic molecules like oxygen in the transition state, were found from density functional theory for rutile-type metal oxides and perovskites [77].…”

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confidence: 99%

Towards Experimental Handbooks in Catalysis

et al. 2020

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The “Seven Pillars” of oxidation catalysis proposed by Robert K. Grasselli represent an early example of phenomenological descriptors in the field of heterogeneous catalysis. Major advances in the theoretical description of catalytic reactions have been achieved in recent years and new catalysts are predicted today by using computational methods. To tackle the immense complexity of high-performance systems in reactions where selectivity is a major issue, analysis of scientific data by artificial intelligence and data science provides new opportunities for achieving improved understanding. Modern data analytics require data of highest quality and sufficient diversity. Existing data, however, frequently do not comply with these constraints. Therefore, new concepts of data generation and management are needed. Herein we present a basic approach in defining best practice procedures of measuring consistent data sets in heterogeneous catalysis using “handbooks”. Selective oxidation of short-chain alkanes over mixed metal oxide catalysts was selected as an example.

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The Brønsted−Evans−Polanyi Correlations in Oxidation Catalysis

Cited by 23 publications

References 90 publications

Coordination-Dependent Kinetics in the Catalysis of Gold Nanoclusters

Coordination-Dependent Kinetics in the Catalysis of Gold Nanoclusters

Design of Active Centers in Ammonia Synthesis on Mo-Based Catalysts: A Theoretical Study

Towards Experimental Handbooks in Catalysis

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