Ab initio molecular dynamics simulation reveals the influence of entropy effect on Co@BEA zeolite-catalyzed dehydrogenation of ethane

doi:10.1016/S1872-2067(24)60116-6

Abstract

Abstract:

The C-H bond activation in alkane dehydrogenation reactions is a key step in determining the reaction rate. To understand the impact of entropy, we performed ab initio static and molecular dynamics free energy simulations of ethane dehydrogenation over Co@BEA zeolite at different temperatures. AIMD simulations showed that a sharp decrease in free energy barrier as temperature increased. Our analysis of the temperature dependence of activation free energies uncovered an unusual entropic effect accompanying the reaction. The unique spatial structures around the Co active site at different temperatures influenced both the extent of charge transfer in the transition state and the arrangement of 3d orbital energy levels. We provided explanations consistent with the principles of thermodynamics and statistical physics. The insights gained at the atomic level have offered a fresh interpretation of the intricate long-range interplay between local chemical reactions and extensive chemical environments.

Key words: Ethane dehydrogenation, C-H bond activation, Ab initio molecular dynamics simulation, Entropy, Heterogeneous catalysis

Yumeng Fo, Shaojia Song, Kun Yang, Xiangyang Ji, Luyuan Yang, Liusai Huang, Xinyu Chen, Xueqiu Wu, Jian Liu, Zhen Zhao, Weiyu Song. Ab initio molecular dynamics simulation reveals the influence of entropy effect on Co@BEA zeolite-catalyzed dehydrogenation of ethane[J]. Chinese Journal of Catalysis, 2024, 65: 195-205.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60116-6

https://www.cjcatal.com/EN/Y2024/V65/I10/195

Figures/Tables 5

Fig. 1. The catalyst model applied in the simulations. (A) Structure of the periodic Co@BEA model (Color code: red for O, white for H, yellow for Si, and purple for Co). (B) CVs applied in the MTD simulations.

Fig. 2. MTD simulation of EDH on Co@BEA at 750K. (A) Two-dimensional free energy profile of the first proton dissociation. The profile is depicted as a function of the CNs between C-H and C-Co, reconstructed from MTD run at 750 K. (B) Movie snapshots showing the IS, TS, and FS. (Color code: brown for C, blue for O, pink for H, yellow for Si, and navy for Co). (C) Evolution of CVs as a function of time (CV1 grey dots, CV2 navy dots).

Fig. 3. (A) The free energies profile of the H+ dissociation from ethane to the Co site under different temperature calculated using AIMD. (B) Temperature dependence of activation free energies (ΔG?). Free energies are referenced to those of the reactant states. The solid and dashed lines represent the free energies calculated using AIMD (ΔG?d) and static geometry optimization methods (ΔG?s), followed by fitting. (C) Relationship between the pulse-shaped entropy change and the specific heat. (a) Temperature dependence of activation entropy (ΔS?). (b) and (c) The specific heat curves Cv(T) of the TS and IS. (D) Structural analysis for the calculation trajectory of reaction completion at 750 and 825 K. (d) Probability distributions of the angle θ (∠O-Co-O). (e) Probability distributions of selected dC-H in the EDH reaction at 750 K (dashed lines) and 825 K (solid lines).

Fig. 4. Calculation of electronic properties using AIMD simulation structures at 750 K. (A) Projected DOS of Co@BEA, C2H6-Co@BEA (IS), (H5C2···Co···H)?-Co@BEA (TS), (C2H5)H-Co@BEA (FS) and ethane. (B) Interaction between C2H6 molecule and Co active site. (C) Localization of Co 3d Orbitals of (H5C2···Co···H)?-Co@BEA and ethane. (D) Projected COHP of the Co-H pair and its Co(3d)-H(s), Co(dyz)-H(s), Co(dxz)-H(s) components. From left to right are C2H6-Co@BEA, (H5C2···Co···H)?-Co@BEA, (C2H5)H-Co@BEA in sequence.

Fig. 5. Calculation of electronic properties using AIMD simulation structures. (A) Projected DOS of Co@BEA, C2H6-Co@BEA (IS), (H5C2···Co···H)?-Co@BEA (TS), (C2H5)H-Co@BEA (FS) and ethane. The structures are extracted from AIMD simulation at 825 K. (B) Interaction between C2H6 molecule and Co active site, relative to A. (C) Mayer bond order analysis of Co 3d orbitals occupation number perturbation in different states. (D) Projected COHP of the Co-H pair and its Co(3d)-H(s), Co(dx2-y2)-H(s), Co(dyz)-H(s) components. From left to right are C2H6-Co@BEA, (H5C2···Co···H)?-Co@BEA, (C2H5)H-Co@BEA in sequence. (E) Bader charge changes involving C, H, and O atoms. The navy solid line and the burgundy dashed line correspond to the structures at 825 and 750 K, respectively. The estimated statistical uncertainties of Bader charges are shown by error bars. (F) The spin charge density for (H5C2···Co···H)?-Co@BEA (left: 750 K, right: 825 K) and calculated charge density difference with 2D plots. (Color code: brown for C, pink for H, yellow for O, and blue for Si).

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