Catalyst screening: Refinement of the origin of the volcano curve and its implication in heterogeneous catalysis

Mao, Yu; Chen, Jianfu; Wang, Haifeng; Hu, Ping

doi:10.1016/s1872-2067(15)60875-0

Cited by 69 publications

(48 citation statements)

References 46 publications

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“…6) over Cu 0.07 Ce 0.75 Zr 0.25 O 2-δ . The volcano curve also shows that the stronger (lattice oxygen) or weaker (weakly adsorbed oxygen) adsorption intensities of the different reactants slightly hinder the reactions and desorption processes in heterogeneous catalysis [43].…”

Section: Structure-activity Relationship and The Contribution Of Actimentioning

confidence: 94%

Reaction mechanism and kinetics of CO oxidation over a CuO/Ce0.75Zr0.25O2-δ catalyst

Kang

Wei

Bin

et al. 2018

Applied Catalysis A: General

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A B S T R A C T The CuO/Ce 0.75 Zr 0.25 O 2δ and Ce 0.75 Zr 0.25 O δ catalysts were prepared by the sol-gel method, and Cu 0.07 Ce 0.75 Zr 0.25 O 2-δ was obtained by treating CuO/Ce 0.75 Zr 0.25 O 2δ with nitric acid to remove the well-dispersed CuO on the surface. Various characterizations were used to reveal the different active sites, such as surface-dispersed CuO and Cu-Ce-Zr-O δ solid solutions in CuO/Ce 0.75 Zr 0.25 O 2δ , Cu-Ce-Zr-O δ solid solutions in Cu 0.07 Ce 0.75 Zr 0.25 O 2-δ and Ce-Zr-O δ solid solutions in Ce 0.75 Zr 0.25 O δ . The Raman and O 2 -TPD results showed that the concentration of oxygen vacancies in Cu-Ce-Zr-O δ solid solutions was higher than that in Ce-Zr-O δ solid solutions. CO oxidation testing suggested that the catalytic activity decreases in the order of CuO/ Ce 0.75 Zr 0.25 O 2δ > Cu 0.07 Ce 0.75 Zr 0.25 O 2-δ > Ce 0.75 Zr 0.25 O δ .Combined with the in situ diffuse-reflectance Fourier transform (in situ DRIFT) results, the reaction sensitivity followed the order of CO linear chemisorption onto dispersed CuO x species (Mars-van Krevelen mechanism) > carbonate species onto a Cu-Ce-Zr-O δ solid solution (Langmuir-Hinshelwood mechanism) > carbonate species onto a Ce-Zr-O δ solid solution (Langmuir-Hinshelwood mechanism). Kinetic studies suggested that the power-law rate expressions and apparent activation energies were r = 6.02 × 10 −7 ×P CO 0.68 P O2 0.03 (53 ± 3 kJ/mol) for CuO/Ce 0.75 Zr 0.25 O 2δ , r = 5.86 × 10 −7 ×P CO 0.8 P O2 0.07 (105 ± 5 kJ/mol) for Cu 0.07 Ce 0.75 Zr 0.25 O 2-δ and r = 5.7 × 10 −7 ×P CO 0.75 P O2 0.12 (115 ± 6 kJ/mol) for Ce 0.75 Zr 0.25 O δ . The Mars-van Krevelen mechanism should be the crucial reaction pathway over CuO/Ce 0.75 Zr 0.25 O 2δ in CO interfacial reactions, although the Langmuir-Hinshelwood mechanism cannot be ignored, and the Langmuir-Hinshelwood mechanism mainly occurred over the Cu 0.07 Ce 0.75 Zr 0.25 O 2-δ and Ce 0.75 Zr 0.25 O δ catalysts, where the contribution from the Mars-van Krevelen mechanism was negligible due to the absence of surface CuO x species.

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Section: Structure-activity Relationship and The Contribution Of Actimentioning

confidence: 94%

Reaction mechanism and kinetics of CO oxidation over a CuO/Ce0.75Zr0.25O2-δ catalyst

Kang

Wei

Bin

et al. 2018

Applied Catalysis A: General

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“…Apparently for structure insensitive reactions, when the Gibbs energy of adsorption on poorly and highly coordinated metal sites is negligible, Eq. (38) is simply reduced to a half principle in the original form for the Gibbs energy [24] or a modified form for chemical potentials [14]. For the reactions when large metal/metal oxide clusters are involved a simplified approach can be also used for a rational catalyst screening.…”

Section: Discussionmentioning

confidence: 99%

“…Later development of the theory for the optimum catalyst was associated with an assessment of the optimal adsorption energies through the use of chemical potential [13][14][15], showing for example that the chemical potential of the adsorbed species on an optimal catalyst is approximately a half sum of the chemical potential of the reactants and products in the gas phase, which is analogous to the conclusion following from [7]. The energy span model [16][17][18] was applied [16] to elucidate the adsorption energy for the optimal catalyst using a generic two-step sequence and considering that either the first or the second steps are determining the rate.…”

Section: +1mentioning

confidence: 99%

On the optimum catalyst for structure sensitive heterogeneous catalytic reactions

Murzin

2020

Reac Kinet Mech Cat

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Reaction rates in a two-step catalytic sequence, when plotted vs adsorption energy of the key or the most abundant surface intermediate, result in volcano shaped curves. In the current work, the optimal catalyst is discussed for structure sensitive reactions, which display dependence of activity on the cluster size of the active catalytic phase. An expression is derived relating the Gibbs energy for formation of the intermediate with the Gibbs energy changes in the overall reaction, difference in adsorption thermodynamics on edges and terraces and the cluster size. The kinetic expressions display dependence of activity vs the Gibbs energy of the adsorbed intermediate formation. Numerical analysis demonstrates that when the overall equilibrium constant K is high and the reaction is thermodynamically very favorable, the maxima in the rates vs the adsorption constant for the optimal catalyst are much broader being less dependent on the cluster size. When structure sensitivity is pronounced, there are smaller differences in the rates for the optimum and less optimal catalysts in comparison with reactions showing weak structure sensitivity.

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“…Similarly, the scaling relation indicates that there are linear relationships between adsorption energies of similar adsorbates, and for a complicated system, the energies of all intermediates can usually be related to one or two key intermediates . Therefore, with the BEP and scaling relations, the reaction rate can finally be expressed as a function of the adsorption energy of one or two key intermediates by solving the micro‐kinetics of the catalytic system . As shown in Figure , when the adsorption strength is weak, the whole reaction is limited by the activation of the reactant; if the binding is strong, the desorption of the product would be limited.…”

Section: General Understandings and Relationships In The Rational Desmentioning

confidence: 99%

“…Therefore, the peak of the curve would locate in a moderate bonding strength. With a full analytical derivation of the micro‐kinetics on a two‐step catalytic model, we showed that plotting this function for a heterogeneous catalytic reaction will always lead to a volcano curve, which can be deemed as an essential property, and it is the poison of the surface by intermediates rather than the desorption barrier that limited the desorption process …”

Section: General Understandings and Relationships In The Rational Desmentioning

confidence: 99%

Theory and applications of surface micro‐kinetics in the rational design of catalysts using density functional theory calculations

Mao

Wang

2017

WIREs Comput Mol Sci

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Rational design of catalysts has long been an important and challenging goal in heterogeneous catalysis. To achieve this target, density functional theory (DFT) calculations and micro‐kinetics are two of the cornerstones. The DFT calculations make it possible to obtain microscopic properties of catalytic systems by computational simulations, and the micro‐kinetic modeling of surface reactions provides a tool to link quantum‐chemical data with macroscopic behaviors of the systems. In this review, we focus on the basic concepts and latest theoretical progresses of strategies for the catalysts design, including Brønsted−Evans−Polanyi relation, the volcano curve, and the activity window. Among the progresses, the theory of chemical potential kinetics in heterogeneous catalysis and its implications on catalysts design, which was developed by our group, are described in detail with extensive derivations. Furthermore, the applications of this method on screening low‐cost counter electrodes for dye‐sensitized solar cells are presented with experimental evidences. WIREs Comput Mol Sci 2017, 7:e1321. doi: 10.1002/wcms.1321 This article is categorized under: Structure and Mechanism > Reaction Mechanisms and Catalysis Theoretical and Physical Chemistry > Reaction Dynamics and Kinetics

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Catalyst screening: Refinement of the origin of the volcano curve and its implication in heterogeneous catalysis

Cited by 69 publications

References 46 publications

Reaction mechanism and kinetics of CO oxidation over a CuO/Ce0.75Zr0.25O2-δ catalyst

Reaction mechanism and kinetics of CO oxidation over a CuO/Ce0.75Zr0.25O2-δ catalyst

On the optimum catalyst for structure sensitive heterogeneous catalytic reactions

Theory and applications of surface micro‐kinetics in the rational design of catalysts using density functional theory calculations

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