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

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

Abstract

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

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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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64699-7

https://www.cjcatal.com/EN/Y2025/V73/I6/186

Figures/Tables 5

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

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