Reversible encapsulation tailored interfacial dynamics for boosting the water-gas shift performance

doi:10.1016/S1872-2067(24)60193-2

Abstract

Abstract:

Revealing the structure evolution of interfacial active species during a dynamic catalytic process is a challenging but pivotal issue for the rational design of high-performance catalysts. Here, we successfully prepare sub-nanometric Pt clusters (~0.8 nm) encapsulated within the defects of CeO₂ nanorods via an in-situ defect engineering methodology. The as-prepared Pt@d-CeO₂ catalyst significantly boosts the activity and stability in the water-gas shift (WGS) reaction compared to other analogs. Based on controlled experiments and complementary (in-situ) spectroscopic studies, a reversible encapsulation induced by active site transformation between the Pt²⁺-terminal hydroxyl and Pt^δ⁺-O vacancy species at the interface is revealed, which enables to evoke the enhanced performance. Our findings not only offer practical guidance for the design of high-efficiency catalysts but also bring a new understanding of the exceptional performance of WGS in a holistic view, which shows a great application potential in materials and catalysis.

Key words: Interfacial dynamics, Hydroxyls, Water-gas shift reaction, In-situ spectroscopy

Nanfang Tang, Qinghao Shang, Shuai Chen, Yuxia Ma, Qingqing Gu, Lu Lin, Qike Jiang, Guoliang Xu, Chuntian Wu, Bing Yang, Zhijie Wu, Hui Shi, Jian Liu, Wenhao Luo, Yu Cong. Reversible encapsulation tailored interfacial dynamics for boosting the water-gas shift performance[J]. Chinese Journal of Catalysis, 2025, 68: 394-403.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60193-2

https://www.cjcatal.com/EN/Y2025/V68/I1/394

Figures/Tables 5

Fig. 1. Catalyst preparation and AC-STEM analysis of Pt@d-CeO2. (A) Schematic illustration of the in-situ defect engineering synthesis approach for Pt@d-CeO2. (B,C,D) Bright field AC-STEM images of Pt@d-CeO2.

Fig. 2. Catalytic performance of Pt@d-CeO2 and Pt/CeO2 catalysts in the WGS reaction. (A) CO conversion during the WGS reaction as a function of temperature over the Pt@d-CeO2 and Pt/CeO2 catalysts. (B) TOF values (mole specific activities) obtained at CO conversion levels below 15% at different reaction temperatures. (C) CO conversion as a function of time on stream during WGS reaction over Pt@d-CeO2 at 350 °C and Pt/CeO2 at 400 °C. Reaction conditions: 8% CO/20% H2O/20% N2/52% Ar, GHSV=150000 h?1.

Fig. 3. Characterization of the Pt-based catalysts. AC-HAADF-STEM image (A) and linear-scan EDS spectra (B) of Pt@d-CeO2. Linear-scan follows orange arrow on the AC-HAADF-STEM image. AC-HAADF-STEM image of Pt@d-CeO2 (C) and its corresponding EELS spectra (D) of three selected regions. The yellow circle in the figures represents the Pt clusters. (E,F) Low temperature TM-FT-IR spectra of CO upon a stepwise adsorption and evacuation on the Pt@d-CeO2 and Pt/CeO2. All the TM-FT-IR spectra were collected at ?150 °C. (G) XPS spectra of Pt@d-CeO2 and Pt/CeO2 in the Pt 4f region. (H) Low temperature TM-FT-IR spectra of CO adsorption for Pt@d-CeO2 and Pt/CeO2 with and without CO prereduction at 300 °C.

Fig. 4. Characterization of Pt-based catalysts via various temperature-programmed techniques. (A) TPSR profiles of Pt@d-CeO2. Signals of CO (m/z = 28), H2O (m/z = 18), H2 (m/z = 2) and CO2 (m/z = 44) were detected. The sample was flushed with pure He at 300 °C for 30 min before test. The signal evolution was collected under 0.5% CO/2% H2O at a ramping rated of 5 °C min?1. (B) CO-TPR profiles of Pt@d-CeO2, d-CeO2, Pt/CeO2 and CeO2. The samples were firstly pretreated with a flow of pure He at 350 °C for 30 min, and the TPR were performed from ?50 to 700 °C at a ramping rate of 10 °C min?1 under 5% CO/He. (C) TPSR profiles of H2O dissociation over Pt@d-CeO2 with or without CO introduction at 300 °C. (D) Dynamic TM-FT-IR spectra of ?OH region for CO activation over Pt@d-CeO2. The sample is first exposed to 2 mbar CO and subsequently outgassed at temperatures ranging from ?150 to 50 °C.

Fig. 5. In-situ characterization of Pt@d-CeO2 in the WGS reaction. (A) In-situ TM-FT-IR spectra of -OH region over Pt@d-CeO2 at 300 °C when altering introduction of a flow of CO or H2O. (B) In-situ TM-FT-IR spectra of -OH region with CO re-introduction at 300 °C with stepwise increase of CO pressure from 1 to 75 mbar over Pt@d-CeO2 after H2O exposure. (C) Pt 4f NAP-XPS of the Pt@d-CeO2 at 300 °C. NAP-XPS spectra conducted at 300 °C with peak fittings. The spectra of Pt@d-CeO2 were acquired after the first 10 mbar Ar exposure for 30 min, the second CO exposure for 30 min, and the final H2O exposure for 30 min. (D) Schematic illustration of the dynamic evolution of interfacial species of Pt@d-CeO2 in the WGS reaction.

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