揭示TiO2相效应对Pt单原子催化剂高效CO2转化的影响

doi:10.1016/S1872-2067(25)64699-7

催化学报 ›› 2025, Vol. 73: 186-195.DOI: 10.1016/S1872-2067(25)64699-7

揭示TiO₂相效应对Pt单原子催化剂高效CO₂转化的影响

胡晓春^a, 陶龙刚^b(), 雷坤^c, 孙志强^c, 谭明务^b()

^a南京师范大学能源与机械工程学院, 江苏南京 210042, 中国
^b新加坡科技研究局(A*STAR)/可持续化工, 能源和环境研究所(ISCE2), 新加坡
^c中南大学能源科学与工程学院, 清洁低碳能源技术湖南省工程研究中心, 湖南长沙 410083, 中国

收稿日期:2025-02-14 接受日期:2025-03-28 出版日期:2025-06-18 发布日期:2025-06-12
通讯作者: *电子信箱: tao_longgang@isce2.a-star.edu.sg (陶龙刚), tan_Mingwu@isce2.a-star.edu.sg (谭明务).
基金资助:
江苏省自然科学基金(BK20240589)

Unraveling TiO₂ phase effects on Pt single-atom catalysts for efficient CO₂ conversion

Xiaochun Hu^a, Longgang Tao^b(), Kun Lei^c, Zhiqiang Sun^c, Mingwu Tan^b()

^aSchool of Energy and Mechanical Engineering, Nanjing Normal University, Nanjing 210042, Jiangsu, China
^bInstitute of Sustainability for Chemicals, Energy and Environment (ISCE²), Agency for Science, Technology and Research (A*STAR), 1 Pesek Road, Jurong Island, Singapore 627833, Singapore
^cHunan Engineering Research Center of Clean and Low-Carbon Energy Technology, School of Energy Science and Engineering, Central South University, Changsha 410083, Hunan, China

Received:2025-02-14 Accepted:2025-03-28 Online:2025-06-18 Published:2025-06-12
Contact: *E-mail: tao_longgang@isce2.a-star.edu.sg (L. Tao), tan_mingwu@isce2.a-star.edu.sg (M. Tan).
Supported by:
Natural Science Foundation of Jiangsu Province(BK20240589)

摘要/Abstract

摘要：

二氧化碳(CO₂)催化加氢制备高价值化学品和燃料是一种前景广阔的碳捕集和利用策略. 该过程不仅减少CO₂排放, 还为可持续碳基产品提供来源, 从而促进循环碳经济的发展. 单原子催化剂(SACs)通过最大化贵金属利用率, 在催化过程中展现出广阔的应用前景. 尽管SACs具有诸多优势, 但在CO₂加氢反应条件下, 其稳定性受限, 单个金属原子易迁移并聚集成较大颗粒, 导致催化效率下降. 此外, SACs的催化活性和选择性受金属-载体相互作用的显著影响. 因此, 合理选择载体不仅可稳定单金属原子, 还能提升其催化性能.

在众多CO₂转化途径中, CO₂与氢气(H₂)转化为一氧化碳(CO)和水的逆水煤气变换(RWGS)反应备受关注. RWGS反应可通过氧化还原途径或缔合途径实现. 氧化还原途径涉及催化剂的交替还原与氧化循环, 以促进RWGS反应. 缔合途径中, CO₂与H₂吸附于催化剂表面, 并通过HCO或COOH等中间体进行反应. 由于其独特的结构和电子特性, 单原子催化剂(SAC), 尤其是Pt单原子催化剂, 在RWGS反应中表现出优异的催化活性与选择性. TiO₂凭借优异的热稳定性及电子调控能力备受关注. 本研究采用强静电吸附合成法, 并结合沉积-沉淀技术, 成功合成了TiO₂负载Pt单原子催化剂(Pt₁/TiO₂), 并通过球差电镜、X射线吸收近边结构谱, 扩展X射线吸收精细结构谱以及原位CO漫反射红外傅立叶变换光谱(CO-DRIFTS)表征手段证实了Pt单原子高度分散于金红石(Pt₁/R)和锐钛矿(Pt₁/A)两种TiO₂晶相中. 在350 °C条件下, 通过RWGS反应评估了两种Pt₁/TiO₂催化剂的催化性能. 尽管两种催化剂均表现出100%的CO选择性, 但是Pt₁/A的CO₂转化率达7.5%, 显著优于Pt₁/R (3.6%). 原位DRIFTS与X射线光电子能谱(XPS)分析揭示了两者不同的反应路径: Pt₁/A主要遵循COOH路径, 而Pt₁/R则以-OH + HCO路径为主. 密度泛函理论(DFT)计算表明, TiO₂载体的晶相对Pt₁/TiO₂在RWGS反应中的催化活性起着至关重要的作用. 与金红石相(Pt₁/R)相比, 锐钛矿相(Pt₁/A)表现出更低的能垒, 并能同时促进COOH中间体的形成与直接氧化还原路径的进行, 从而在热力学与动力学上均更有利. 结合实验与DFT研究结果, Pt₁/A能够更有效地稳定金属Pt, 并促进能垒更低的优势反应路径.

综上, 本研究系统揭示了TiO₂晶相对SACs催化性能的影响, 为更高效CO₂加氢及RWGS催化剂的设计提供了新的思路.

关键词: 单原子催化剂, CO₂加氢, 电子金属-载体相互作用, 催化活性, 反应路径

Abstract:

Single-atom catalysts (SACs) offer a promising approach for maximizing noble metals utilization in catalytic processes. However, their performance in CO₂ hydrogenation is often constrained by the nature of metal-support interactions. In this study, we synthesized TiO₂ supported Pt SACs (Pt₁/TiO₂), with Pt single atoms dispersed on rutile (Pt₁/R) and anatase (Pt₁/A) phases of TiO₂for the reverse water-gas shift (RWGS) reaction. While both catalysts maintained 100% CO selectivity over time, Pt₁/A achieved a CO₂ conversion of 7.5%, significantly outperforming Pt₁/R (3.6%). In situ diffuse reflectance infrared Fourier-transform spectroscopy and X-ray photoelectron spectroscopy revealed distinct reaction pathways: the COOH pathway was dominant on Pt₁/A, whereas the -OH + HCO pathway was more competitive on Pt₁/R. Analysis of electron metal-support interactions and energy barrier calculations indicated that Pt₁/A better stabilized metallic Pt species and facilitates more favorable reaction pathways with lower energy barriers. These findings provide valuable insights for the design of more efficient SAC systems in CO₂ hydrogenation processes.

Key words: Single-atom catalyst, CO₂ hydrogenation, Electron metal-support interactions, Catalytic activity, Reaction pathways

胡晓春, 陶龙刚, 雷坤, 孙志强, 谭明务. 揭示TiO₂相效应对Pt单原子催化剂高效CO₂转化的影响[J]. 催化学报, 2025, 73: 186-195.

Xiaochun Hu, Longgang Tao, Kun Lei, Zhiqiang Sun, Mingwu Tan. Unraveling TiO₂ phase effects on Pt single-atom catalysts for efficient CO₂ conversion[J]. Chinese Journal of Catalysis, 2025, 73: 186-195.

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Fig. 1. XRD, high resolution AC-STEM images, XANES, k3-weighted Fourier transform spectra in R space, and CO-DRIFTS of fresh Pt1/A and fresh Pt1/R. (a) XRD patterns. High resolution AC-STEM images of fresh Pt1/R (b) and fresh Pt1/A(c). (d) normalized Pt L3-edge XANES. (e) Fourier-transformed k3-weighted EXAFS oscillations in R space for the Pt L3-edge in fresh Pt1/R and fresh Pt1/A catalysts. (f) Ti K-edge XANES. (g) FT-EXAFS. CO-DRIFTS of fresh Pt1/A (h) and fresh Pt1/R(i).

Fig. 2. Evaluation of catalytic performance for RWGS reaction activity. Reaction conditions: CO2:H2 = 1:4, WHSV = 100 L?g?1?h?1, temperature (t) = 350 °C. (a) CO2 conversion at 350 °C. (b) CO selectivity at 350 °C. (c) The Arrhenius plot of the RWGS reaction catalyzed by Pt1/TiO2 catalysts. (d) A summary of STY: 1.67Pt/TiO2 [16], 1.67Pt/SiO2 [16], Pt0.5Re/SiO2 [21], 1.7Pt1.5Co/TiO2 [22], 1.7Pt1.5Co/CeO2 [22], 1.7Pt1.5Co/ZrO2 [22], 0.1Pt/TiO2 [23]. Details of the entries are provided in Table S4.

Fig. 3. Identification of the RWGS reaction mechanisms of Pt single atom on TiO2 catalysts. (a) In situ DRIFTS over 30 min of TOS at 350 °C. Non situ and in situ XPS spectra over 30 min of TOS at 350 °C. C 1s XPS spectra of Pt1/R (b) and Pt1/A (c). O 1s XPS spectra of Pt1/R (d) and Pt1/A (e).

Fig. 4. Electron transfer between Pt single atoms and TiO2. Pt 4f XPS spectra of Pt1/R (a) and Pt1/A (b). (c) Charge density difference on Pt1/R and Pt1/A. The iso-surface is set at 0.01 e??1 (Light red and dark blue correspond to positive and negative modes, respectively). (d) Schematic illustration of reaction mechanisms over RWGS reaction at Pt1/R and Pt1/A, including the redox and COOH reaction pathways, respectively.

Fig. 5. DFT calculations results. (a,b) Configurations of the intermediate states and key transition states (TS) of the COOH reaction pathway for RWGS on Pt1/A and Pt1/R model structures, respectively. (c) Comparison of energy barriers associated with TS of the COOH reaction pathway between Pt1/A and Pt1/R structures. (d) Comparison of the energy barriers associated with TS of the redox reaction pathway between Pt1/A and Pt1/R structures.

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揭示TiO₂相效应对Pt单原子催化剂高效CO₂转化的影响

Unraveling TiO₂ phase effects on Pt single-atom catalysts for efficient CO₂ conversion

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