从头算分子动力学模拟揭示熵效应对Co@BEA分子筛催化乙烷脱氢反应的影响

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

催化学报 ›› 2024, Vol. 65: 195-205.DOI: 10.1016/S1872-2067(24)60116-6

从头算分子动力学模拟揭示熵效应对Co@BEA分子筛催化乙烷脱氢反应的影响

佛雨萌, 宋少佳, 杨坤, 纪向阳, 杨璐源, 黄刘赛, 陈欣宇, 吴学秋, 刘坚(), 赵震, 宋卫余()

中国石油大学(北京)重质油国家重点实验室, 北京102249

收稿日期:2024-06-25 接受日期:2024-08-07 出版日期:2024-10-18 发布日期:2024-10-15
通讯作者: *电子信箱: songwy@cup.edu.cn (宋卫余), liujian@cup.edu.cn (刘坚).
基金资助:
国家自然科学基金(22035009);国家自然科学基金(22178381);国家重点研发计划(2021YFA1501301);国家重点研发计划(2021YFC2901100)

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

Yumeng Fo, Shaojia Song, Kun Yang, Xiangyang Ji, Luyuan Yang, Liusai Huang, Xinyu Chen, Xueqiu Wu, Jian Liu(), Zhen Zhao, Weiyu Song()

State Key Laboratory of Heavy Oil Processing, China University of Petroleum (Beijing), Beijing 102249, China

Received:2024-06-25 Accepted:2024-08-07 Online:2024-10-18 Published:2024-10-15
Contact: *E-mail: songwy@cup.edu.cn (W. Song), liujian@cup.edu.cn (J. Liu).
Supported by:
National Natural Science Foundation of China(22035009);National Natural Science Foundation of China(22178381);National Key R&D Program of China(2021YFA1501301);National Key R&D Program of China(2021YFC2901100)

摘要/Abstract

摘要：

在化学反应动力学中, 温度对反应速率的影响至关重要. Eyring方程揭示了温度如何通过调控活化焓和活化熵, 进而影响反应速率. 特别是在高温条件下, 熵效应对反应路径和速率的影响更加显著. 分子筛的限域效应能够调控反应分子的吸附、扩散和转化过程, 这种效应可能导致结构的演变, 从而影响反应体系的熵变化. 此外, 非简谐效应在高温催化反应中不仅影响活化熵, 还可能改变反应路径的自由能势垒, 对催化效率产生深远影响. 因此, 量化和研究高温下非简谐效应对活化熵的影响, 不仅有助于深入理解分子筛限域催化反应的动力学行为, 还能为优化催化剂设计和提高反应效率提供重要的理论支持.

虽然理论上预测的熵效应已经在一些实验中得到验证, 但关于温度如何导致活化熵发生异常波动的具体物理机制, 目前的研究尚不充分. 通过系统分析Co@BEA分子筛催化乙烷脱氢反应过程中C-H键在不同温度下活化自由能的具体变化, 可以深入理解在分子筛限域条件下乙烷脱氢反应的机制, 以及不同温度下熵效应对反应活化过程的影响. 由于脱氢过程发生在皮秒级, 与实际催化过程在同一个时间尺度上进行, 因此需要用计算模拟的方法来描述. 采用从头算分子动力学(AIMD)模拟结合Metadynamics(MTD)增强自由能采样方法进行深入研究. 相比于传统的静态DFT计算, 熵的作用或者被忽略, 或者用过渡态理论的谐波近似来估计. 而本研究考虑非简谐效应后, 更能捕捉真实反应条件下的自由能变化. 首先, 选取温度范围从550到1050 K(每50 K间隔)内C-H键的活化自由能变化进行计算模拟分析. 结果表明, C-H键通过氧化加成方式断裂, 形成三中心过渡态(H₅C₂···Co···H)^ǂ. 随着温度升高, 自由能变化曲线在700-900 K间出现异常波动, 在825 K时自由能达到最小值. 对温度取自由能的一阶偏导数, 得出熵变随温度的变化. 活化熵(ΔS^‡)曲线随温度变化显示出有趣的脉冲形状. 根据熵差与热容的关系, 该现象可能是由于该温度范围内(H₅C₂···Co···H)^ǂ过渡态的比热容发生剧烈变化引起的, 特别是在800-850 K范围内, 过渡态的比热出现显著跃升, 导致活化熵剧烈波动. 其物理原因是温度范围内的过渡态与活性Co位点间局部空间构型(如∠O-Co-O角度和C-H键长度)差异引起熵的变化, 进而导致电子结构的不同. 通过晶体轨道哈密顿量计算和自旋分辨投影态密度计算, 进一步确认了不同温度下参与反应的Co 3d轨道发生了不同的分裂和排列, 导致电子转移行为不同. 在825 K下, Co活性位点的电子密度更加丰富, 显示出更强的质子稳定能力, C-H键的活化程度更高.

综上, 本研究通过结合先进的计算模拟和统计方法, 系统分析了Co@BEA分子筛催化乙烷脱氢反应中的熵效应, 在原子水平上获得的见解为局部化学反应和广泛化学环境之间复杂的长程相互作用提供了新的诠释, 为理解高温催化反应的动力学行为提供新的理论依据.

关键词: 乙烷脱氢, C-H键活化, 从头计算分子动力学模拟, 熵, 多相催化

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

佛雨萌, 宋少佳, 杨坤, 纪向阳, 杨璐源, 黄刘赛, 陈欣宇, 吴学秋, 刘坚, 赵震, 宋卫余. 从头算分子动力学模拟揭示熵效应对Co@BEA分子筛催化乙烷脱氢反应的影响[J]. 催化学报, 2024, 65: 195-205.

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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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(24)60116-6

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

图/表 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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从头算分子动力学模拟揭示熵效应对Co@BEA分子筛催化乙烷脱氢反应的影响

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

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