TiO2催化剂表面结构演变与单原子掺杂对CO2辅助乙烷脱氢性能调控

doi:10.1016/S1872-2067(26)65205-9

催化学报 ›› 2026, Vol. 91: 147-162.DOI: 10.1016/S1872-2067(26)65205-9

TiO₂催化剂表面结构演变与单原子掺杂对CO₂辅助乙烷脱氢性能调控

马可馨^a, 薛米风^a, 王与涵^b^,^*(), 范貌宏^c^,^d, 凌丽霞^a, 章日光^a^,^*()

^a 太原理工大学化学与化工学院, 省部共建煤基能源清洁高效利用国家重点实验室, 山西太原 030024, 中国
^b 山西大学资源与环境工程研究所, 山西太原 030031, 中国
^c 怀俄明大学工程与物理科学学院及能源资源学院, 怀俄明州拉勒米, 美国
^d 佐治亚理工学院工程学院, 佐治亚州亚特兰大, 美国

收稿日期:2026-01-08 接受日期:2026-04-14 出版日期:2026-12-18 发布日期:2026-10-13
通讯作者: ^*电子信箱: wangyuhan@sxu.edu.cn (王与涵),
zhangriguang@tyut.edu.cn (章日光).
基金资助:
国家科技重大专项(2024ZD0606500);国家自然科学基金(U23A20132);国家自然科学基金(22408119);山西省留学回国人员科技活动择优资助项目(20250008)

Unraveling the surface structural evolution and single-atom doping effect in CO₂-assisted ethane dehydrogenation over TiO₂-based catalysts

Kexin Ma^a, Mifeng Xue^a, Yuhan Wang^b^,^*(), Maohong Fan^c^,^d, Lixia Ling^a, Riguang Zhang^a^,^*()

^a State Key Laboratory of Clean and Efficient Coal Utilization, College of Chemistry and Chemical Engineering, Taiyuan University of Technology, Taiyuan 030024, Shanxi, China
^b Institute of Resources and Environmental Engineering, Shanxi University, Taiyuan 030031, Shanxi, China
^c College of Engineering and Physical Sciences, and School of Energy Resources, University of Wyoming, Laramie 82071, Wyoming, USA
^d College of Engineering, Georgia Institute of Technology, Atlanta 30332, Georgia, USA

Received:2026-01-08 Accepted:2026-04-14 Online:2026-12-18 Published:2026-10-13
Supported by:
Advanced Materials-National Science and Technology Major Project(2024ZD0606500);National Natural Science Foundation of China(U23A20132);National Natural Science Foundation of China(22408119);Fund Program for the Scientific Activities of Selected Returned Overseas Profes-sionals in Shanxi Province(20250008)

摘要/Abstract

摘要：

乙烯是生产塑料、纤维、橡胶等大宗化学品的基础化工原料. 乙烷氧化脱氢(ODHE)是生产乙烯的关键技术路线之一. 目前, 以O₂为氧化剂的ODHE虽能突破热力学平衡限制, 降低反应温度, 但O₂强氧化性易导致乙烯深度氧化生成CO_x副产物, 降低目标产物选择性. 相比之下, CO₂作为温和氧化剂, 能够有效避免乙烯的过氧化, 在提升烯烃选择性方面展现出独特优势, 但CO₂在温和条件下难以高效活化. 二氧化钛(TiO₂)基催化剂凭借其出色的表面氧化还原能力在ODHE反应中表现出良好的催化性能, 同时其表面氧空位能够吸附并活化CO₂, 有利于CO₂辅助ODHE (CO₂-ODHE)反应的进行. 然而, 反应中催化剂表面的动态演变规律及其对反应机理的影响尚不明确. 因此, 系统研究TiO₂基催化剂在CO₂-ODHE中的表面结构演化与单原子掺杂的调控作用, 对于理性设计高效稳定的催化剂具有重要的理论指导意义.
本研究采用密度泛函理论计算与动力学蒙特卡洛模拟相结合的方法, 研究了C₂H₆与CO₂共进料条件下TiO₂催化剂表面结构演变过程, 并构建15种单原子金属掺杂M-TiO₂(M=V, Cr, Mn, Fe, Co, Ni, Cu, Y, Nb, Ru, Rh, Pd, Ta, Ir和Pt)催化剂, 探究金属掺杂对反应机理与催化性能的调控规律. 在C₂H₆与CO₂共进料条件下, TiO₂催化剂表面遵循“TiO₂-O_v → CO₂-TiO₂ → TiO₂ → TiO₂-O_v”的动态演变循环, 反应遵循MvK机理, CO₂快速填补表面晶格氧, 维持氧化还原循环稳定运行, 但催化活性有限. 单原子金属掺杂抑制了CO₂在氧空位处的解离, 将反应路径从MvK机理转变为乙烷脱氢与逆水煤气变换反应相耦合机理. CO₂的作用从填补表面晶格氧转变为通过形成COOH^*中间体高效消耗表面H^*物种, 加快反应进程. 在873.15 K, C₂H₆/CO₂进料比2:1的最佳反应条件下, Pd-TiO₂-O_v催化剂的乙烯生成活性(TOF)高达4.62×10⁴ s^-1, 较未掺杂TiO₂-O_v催化剂提升约七个数量级, 同时保持高乙烯选择性. 进一步, 建立了催化活性与表面H^*物种共吸附能的线性关联, 为评估M-TiO₂催化性能提供了关键描述符. 最后, 阐明了O₂与CO₂作为氧化剂在乙烷氧化脱氢反应中的作用差异: O₂易于解离生成活性氧物种, 虽可驱动乙烷脱氢但易引发乙烯过氧化; CO₂作为软氧化剂, 在Pd-TiO₂上通过抑制自身解离、促进上述耦合路径, 实现了高选择性的乙烯生成.
综上, 本研究揭示了TiO₂催化剂表面结构演变与金属掺杂调控CO₂-ODHE反应性能的核心作用, 为高性能烷烃脱氢金属氧化物催化剂的理性设计提供了重要的结构与电子层面的见解; 所建立的描述符及反应机理为实验研究奠定了理论基础, 并为开发高性能催化剂提供了方向.

关键词: TiO₂催化剂, CO₂辅助乙烷脱氢, 反应机理, 密度泛函理论计算, 动力学蒙特卡洛模拟

Abstract:

CO₂-assisted ethane dehydrogenation (CO₂-ODHE) provides a promising route for ethylene production; however, the dynamic evolution of catalyst surface and its influence on the reaction mechanism are still not fully elucidated. In this study, we combined density functional theory calculations and kinetic Monte Carlo simulations to explore the surface evolution and catalytic behavior of CO₂-ODHE over TiO₂-based catalysts. The results show that the pristine TiO₂ follows the Mars-van Krevelen (MvK) mechanism, where CO₂ replenishes oxygen vacancies, but exhibits limited activity. Doping with single-atom metal (M-TiO₂-O_v) suppresses CO₂ dissociation at oxygen vacancy sites, shifting the reaction mechanism from MvK to a coupling mechanism that combines ethane dehydrogenation with the reverse water-gas shift reaction. In this coupled mechanism, CO₂ primarily participates in hydrogenation via the formation of a COOH^* intermediate, thereby efficiently removing surface hydrogen species. Among 15 types of M-doped TiO₂ catalysts, Pd-TiO₂ catalyst demonstrates the highest C₂H₄(g) formation activity (TOF=4.62 × 10⁴ s^-1) with 99.9% selectivity under optimal conditions (873 K, C₂H₆/CO₂=2: 1), which is seven orders of magnitude higher than that of undoped TiO₂. Furthermore, the catalytic activity exhibits a linear correlation with the adsorption energy of H^*, identifying the surface hydrogen adsorption strength as an effective descriptor for predicting C₂H₄(g) formation activity. This work provides a theoretical foundation and structural insights for designing high-performance CO₂-ODHE catalysts via second-metal doping to regulate the reaction mechanism and catalytic performance of metal oxide.

Key words: TiO₂ catalyst, CO₂-assisted ethane dehydrogenation, Reaction mechanism, Density functional theory, Kinetic Monte Carlo simulations

马可馨, 薛米风, 王与涵, 范貌宏, 凌丽霞, 章日光. TiO₂催化剂表面结构演变与单原子掺杂对CO₂辅助乙烷脱氢性能调控[J]. 催化学报, 2026, 91: 147-162.

Kexin Ma, Mifeng Xue, Yuhan Wang, Maohong Fan, Lixia Ling, Riguang Zhang. Unraveling the surface structural evolution and single-atom doping effect in CO₂-assisted ethane dehydrogenation over TiO₂-based catalysts[J]. Chinese Journal of Catalysis, 2026, 91: 147-162.

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图/表 9

Fig. 1. (a) Top and side views for the optimized configurations of TiO2-Ov, CO2-TiO2 and TiO2 catalysts (lattice O atoms: red balls, Ti atoms: grey balls, adsorbed CO2: (O atoms: green balls, C atoms: black balls)). (b) The lattice of TiO2-Ov catalyst (Ti: blue circles, Ov: purple squares, O: yellow triangles).

Fig. 2. The reaction network of CO2-ODHE over TiO2 and M-TiO2 catalysts. The left side illustrates the ethane dehydrogenation pathway, including the main reaction forming the target product C2H4(g) and the side reaction of deep dehydrogenation to CHCH(g). The right side depicts two distinct pathways for the consumption of surface H* by CO2.

Fig. 3. TiO2 structure evolution process involved in CO2-ODHE over TiO2 catalyst under the condition of C2H6(g) and CO2(g) co-feeding. The numerical values correspond to the activation free energy (Ga, eV) and reaction free energy (ΔG, eV). The blue path represents the entire cycle process on the catalyst, and the black path represents side reactions. Lattice O atoms: red balls, Ti atoms: grey balls, H atoms: white balls, C atoms: black balls, and adsorbed CO2: (O atoms: green balls, C atoms: black balls).

Fig. 4. Cycle 1 (blue) depicts the MvK redox cycle on the TiO2 catalyst, involving ethane dehydrogenation (lattice oxygen consumption) and CO2 dissociation (oxygen vacancy replenishment). Cycle 2 (green) corresponds to the coupling mechanism of ethane dehydrogenation and the RWGS reaction occurring on the metastable CO2-TiO2 surface. The numerical values correspond to the activation free energy (Ga, eV) and reaction free energy (ΔG, eV).

Fig. 5. (a) Free energy profiles of ethane dehydrogenation over TiO2-Ov, CO2-TiO2 and TiO2 catalysts at 873 K. * and (g) represent the adsorbed and gaseous states, respectively. (b) The overall energy barrier of the reaction C2H6(g) → C2H4(g), and free energy difference between C2H4(g) and CHCH2* formation, as well as that between C2H4* and CHCH3* formation at 873 K over three catalysts.

Fig. 6. (a) Energy difference ΔEb=Ebinding-Ecohesive for M-TiO2 catalysts. Ebinding is the binding energy of the single M atom over M-TiO2 catalysts, and Ecohesive is the average cohesive energy of the corresponding bulk metal. (b) The oxygen-vacancy formation energy of M-TiO2 catalysts. (c) The CO2 dissociation energy of M-TiO2 catalysts. (d) Relationship of Bader charge transfer of C atom with CO2 dissociation energy over M-TiO2 catalysts. (e) Top and side views of the initial and final states for CO2 dissociation on M-TiO2-Ov surfaces, illustrating the distinct bent (e.g., on V-doped) and linear (e.g., on Fe-doped) adsorption configurations.

Fig. 7. (a) The overall energy barrier of the reaction C2H6(g)→C2H4(g) over TiO2-Ov and M-TiO2-Ov catalysts at 873.15 K. (b) Free energy difference between C2H4(g) and CHCH2* formation, as well as that between C2H4* and CHCH3* formation over M-TiO2-Ov catalysts at 873.15 K.

Fig. 8. (a) C2H4(g) formation activity and selectivity over TiO2-Ov and M-TiO2-Ov catalysts at 873.15 K with a C2H6/CO2 feed ratio of 1:1. (b) Relationship between C2H4(g) formation activity (logTOF, s-1) and the H* + H* adsorption energy (Eads(H* + H*), eV) over M-TiO2-Ov catalysts. (c) Relationship between Eads(H* + H*) and the effective Bader charge on the C atom of adsorbed CO2 over M-TiO2-Ov catalysts. (d) Effect of temperature on C2H4(g) formation activity and selectivity over Pd-TiO2-Ov catalyst at the fixed C2H6(g)/CO2(g) feed ratio of 1:1. (e) Effect of C2H6(g)/CO2(g) feed ratio at the fixed temperature 873.15 K on catalytic performance. (f) Comparative C2H4(g) formation activity of 13 M-TiO2-Ov catalysts under O2 versus CO2 atmospheres.

Table 1 Comparisons of C2H4(g) production activity and selectivity in this work with those over different types of catalysts previously reported in C2H6(g) dehydrogenation.

Catalyst	Feed ratio (C₂:CO₂: inert gas)	T (K)	Conversion (%)	Sel. (%)	Ref.
Experimental study
NiFe/CeO₂	1: 1: 2	873	4.6	83	[53]
1 wt% Co/S-1	1: 1: 3	923	20	84	[18]
Ga₂O₃	3: 15: 82	923	13	87.4	[91]
PdFe(1: 9)/CeO₂	1: 1: 2	873	6.6	85.8	[14]
PdGa₃/CeO₂	1: 1: 2	873	0.4	95.5	[82]
PdIn₃/CeO₂	1: 1: 2	873	3.1	89	[82]
PtCe@MZ	2: 1: 17	873	34	94	[9]
Fe-10%/SiO₂	1: 2: 1	923	18.9	99.0	[15]
Fe-ZrO₂	1: 1: 3	923	9	85	[26]
Catalyst	Feed composition	T (K)	TOF (s^-1)	Sel. (%)	Ref.
Theoretical study
Pt(111)	0.2 bar C₂H₆	873	1.60 × 10³	93.4	[73]
Pt₃Sn(111)	0.2 bar C₂H₆	873	1.00 × 10²	100.0	[73]
Fe₃O₄-B2	C₂H₆:CO₂=1: 1	873	2.14 × 10³	—	[90]
Pd-TiO₂	C₂H₆:CO₂=1: 1	873	4.33 × 10⁴	99.9	This work

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TiO₂催化剂表面结构演变与单原子掺杂对CO₂辅助乙烷脱氢性能调控

Unraveling the surface structural evolution and single-atom doping effect in CO₂-assisted ethane dehydrogenation over TiO₂-based catalysts

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