面向高效乙炔加氢制乙烯的二硫化钨限域金属原子催化剂理论预测

doi:10.1016/S1872-2067(25)64734-6

催化学报 ›› 2025, Vol. 76: 221-229.DOI: 10.1016/S1872-2067(25)64734-6

面向高效乙炔加氢制乙烯的二硫化钨限域金属原子催化剂理论预测

刘欢^a, 秉琦明^a, 于良^a^,^b^,^*(), 邓德会^a^,^b^,^*()

^a中国科学院大连化学物理研究所, 能源材料化学协同创新中心, 催化基础国家重点实验室, 辽宁大连 116023
^b中国科学院大学, 北京 100049

收稿日期:2025-03-23 接受日期:2025-05-07 出版日期:2025-09-18 发布日期:2025-09-10
通讯作者: *电子信箱: lyu@dicp.ac.cn (于良),dhdeng@dicp.ac.cn (邓德会).
基金资助:
国家重点研发计划(2022YFA1504800);国家重点研发计划(2024YFA1510100);国家自然科学基金(22225204);国家自然科学基金(22472169);国家自然科学基金(22272170);中国科学院-发展中国家科学院(CAS-TWAS)

Theoretical prediction of WS₂-confined metal atoms for highly efficient acetylene hydrogenation to ethylene

Kelechi Uwakwe^a^,^b, Huan Liu^a, Qiming Bing^a, Liang Yu^a^,^b^,^*(), Dehui Deng^a^,^b^,^*()

^aState Key Laboratory of Catalysis, Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China
^bUniversity of Chinese Academy of Sciences, Beijing 100049, China

Received:2025-03-23 Accepted:2025-05-07 Online:2025-09-18 Published:2025-09-10
Contact: *E-mail: lyu@dicp.ac.cn (L. Yu),dhdeng@dicp.ac.cn (D. Deng).
Supported by:
National Key R&D Program of China(2022YFA1504800);National Key R&D Program of China(2024YFA1510100);National Natural Science Foundation of China(22225204);National Natural Science Foundation of China(22472169);National Natural Science Foundation of China(22272170);and the CAS-TWAS Presidents’ Fellowship.

摘要/Abstract

摘要：

乙炔选择加氢制乙烯(AHE)是煤化工替代石油路线生产乙烯的重要途径. 设计具有高活性和高选择性的非贵金属基催化剂是实现高效AHE的关键. 二维过渡金属硫化物(TMDs)因其三原子层结构特征、高度可调的电子结构和低成本等优势而备受关注, 其硫空位限域低配位金属位点在催化加氢反应中表现出优异的活性和选择性. 二维硫化钨(WS₂)在催化AHE反应中展现出了重要潜力. 精确调控二维WS₂的原子和电子结构, 并探究其硫空位限域金属位点的催化活性和选择性, 对于设计和开发高效、低成本WS₂基AHE催化剂具有重要指导意义.

本研究基于密度泛函理论计算, 通过构建27种过渡金属原子掺杂二维WS₂结构以替代面内硫空位处的W原子(标记为M@WS₂-Sv), 发现硫空位限域的Cu位点(Cu@WS₂-Sv)在AHE反应中展现出优于其它金属位点的催化活性、选择性和稳定性. 以乙炔吸附自由能(ΔG_C2H2*)为活性描述符, 揭示了AHE反应的两个关键速率决定基元步骤为C₂H₂与H₂的共吸附和C₂H₃*加氢生成C₂H₄*. 基于此, 建立了火山型活性趋势, 表明Cu@WS₂-Sv为非贵金属基M@WS₂-Sv催化剂中的最优选择. 通过计算Cu@WS₂-Sv硫空位限域Cu位点上乙炔加氢完整反应路径, 结果显示C₂H₃*加氢生成C₂H₄*是乙烯形成的速率控制步骤, 其总能垒为1.09 eV; 同时, C₂H₄的脱附相比其过度加氢生成乙烷的路径具有更优的反应动力学. 优先生成C₂H₄的总能垒相对较低, 表明Cu@WS₂-Sv有望在温和条件下实现高活性、高选择性AHE反应. 为了深入理解M@WS₂-Sv催化剂的本征活性, 利用独立筛选与稀疏算子(SISSO)方法构建了ΔG_C2H2*与掺杂原子的物理化学属性的机器学习关联模型, 发现掺杂金属原子的d电子数和电负性是调控AHE活性的关键因素. 其中, 掺杂金属原子的d电子数是影响催化活性的主要因素, 与催化活性存在正相关; 而d电子数相同时, 电负性的变化会进一步影响电荷转移和催化活性.

综上所述, 本研究为设计和开发乙炔选择性加氢制乙烯的高效催化剂提供了理论指导, 并为二维过渡金属硫化物催化剂的活性与选择性调控提供了新思路.

关键词: 第一性原理计算, 乙炔加氢, 二维硫化钨, 硫空位限域, 电子结构调控

Abstract:

Precise regulation of atomic and electronic structures of two-dimensional tungsten disulfide (WS₂) is significant for rational design of high-performance and low-cost catalyst for acetylene hydrogenation to ethylene (AHE), yet remains a major challenge. Herein, we report that by substituting a W atom of WS₂ with a series of transition metal atoms, sulfur vacancy-confined Cu in the WS₂ basal plane (Cu@WS₂-Sv) is theoretically screened as a superior non-noble metal-based catalyst with higher activity, selectivity, and stability for the AHE than other candidates. The co-adsorption of C₂H₂ and H₂ and hydrogenation of C₂H₃* to C₂H₄* are revealed as the key steps establishing a volcano-like activity trend among the candidates, which present Cu@WS₂-Sv as the optimum catalyst combined with molecular dynamics and reaction kinetics analyses. The kinetically more favorable desorption of C₂H₄ than the over hydrogenation path validates a higher selectivity toward C₂H₄ over C₂H₆. Furthermore, a machine-learning model reveals the significant effect of d-electron number and electronegativity of the metal heteroatoms in modulating the AHE activity.

Key words: First-principles calculation, Acetylene hydrogenation, Tungsten disulfide, Sulfur vacancy confinement, Electronic structure modulation

刘欢, 秉琦明, 于良, 邓德会. 面向高效乙炔加氢制乙烯的二硫化钨限域金属原子催化剂理论预测[J]. 催化学报, 2025, 76: 221-229.

Kelechi Uwakwe, Huan Liu, Qiming Bing, Liang Yu, Dehui Deng. Theoretical prediction of WS₂-confined metal atoms for highly efficient acetylene hydrogenation to ethylene[J]. Chinese Journal of Catalysis, 2025, 76: 221-229.

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图/表 5

Fig. 1. The calculation structures and activity descriptor determination. (a) Schematic illustration of transition metal (TM) doping and the induced formation of double-Sv in the WS2 basal plane. (b) The periodic table of elements showing the TMs considered as dopants in WS2, shaded in red. (c) Linear relationship between the doping energy of TM heteroatoms and the formation energy of double-Sv. (d) C2H2 and H2 adsorption configuration at a Sv site of the M@WS2-Sv catalysts. M represents a TM heteroatom. ST and SB represent the top and bottom sulfur atoms in M@WS2-Sv, respectively. (e) The linear relationship between the adsorption free energies of C2H2 and H2 on the M@WS2-Sv catalysts.

Fig. 2. Analyses of reaction thermodynamics for AHE. (a) Schematic diagram illustrating the reaction mechanism of the AHE process. The dark grey, white, blue, and yellow spheres represent the C, H, W, and S atoms, respectively. The linear free energy scaling relations (LFESRs) of ΔGC2H2* with ΔG2 (b) and ΔG4 (c) for the elementary steps involved in the AHE process on the M@WS2-Sv catalysts. The lines are derived from the linear fit to the data points listed in Table S3. (d) The combined LFESRs for the five elementary steps (ΔG1, ΔG2, ΔG3, ΔG4, and ΔG5) involved in the AHE process on the M@WS2-Sv catalysts. The resulting volcano plot, which shows the activity trend, is formed by the ΔG4 and ΔG2 lines and is indicated by a solid line. The green area represents the region for ideal dopants. (e) The projected density of states (PDOS) of the 3d orbitals of Cu and Ti atoms, and the C 2p orbitals for C2H2* on Cu@WS2-Sv and Ti@WS2-Sv catalysts. The Fermi level is at 0 eV. εd denote the d-band center. The Cu@WS2-Sv and Ti@WS2-Sv active sites are shown for reference. The atom encircled by the dashed line are those considered for the PDOS plot.

Fig. 3. AIMD simulations for the screened catalysts. (a) The PDOS on the d and 3p orbitals of the M-S bond for the Cu@WS2-Sv, Pd@WS2-Sv, Ag@WS2-Sv, and Au@WS2-Sv catalysts, respectively. The Fermi level is at 0 eV. The atoms denoted by red and black dotted circles in the inserted images are considered for the PDOS plots. (b) The variations of temperature vs. time for AIMD simulations of Cu@WS2-Sv, Pd@WS2-Sv, Ag@WS2-Sv, and Au@WS2-Sv catalysts at 573 K, respectively. The snapshots for the highest temperature points are shown in the right panel. The longest M-S bond distances are indicated in the snapshots, where dashed lines represent broken or partially broken bonds.

Fig. 4. Reaction free energy pathways for the AHE over the Cu@WS2-Sv and Pd@WS2-Sv. The free energy diagram and the optimized structures of the intermediates and transition states for the C2H2 hydrogenation reaction pathway on the Cu@WS2-Sv (a) and Pd@WS2-Sv (b) at 298.15 K, respectively. The values enclosed in parentheses represent the free energy barriers in eV.

Fig. 5. Machine learning-based predictive descriptor of activity. (a) Linear relation between Φ = and ΔGC2H2*. (b) Comparison between the Φ-predicted and DFT-calculated ΔGC2H2*.

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面向高效乙炔加氢制乙烯的二硫化钨限域金属原子催化剂理论预测

Theoretical prediction of WS₂-confined metal atoms for highly efficient acetylene hydrogenation to ethylene

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面向高效乙炔加氢制乙烯的二硫化钨限域金属原子催化剂理论预测

Theoretical prediction of WS2-confined metal atoms for highly efficient acetylene hydrogenation to ethylene

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Theoretical prediction of WS₂-confined metal atoms for highly efficient acetylene hydrogenation to ethylene