Modulation of Pt-Cu interaction in Pt/Cu-SSZ-13 for selective catalytic oxidation of ammonia

doi:10.1016/S1872-2067(26)64958-3

Abstract

Abstract:

Modulating the potent oxidative nature of Pt sites is the central strategy for optimizing the selective catalytic oxidation of NH₃ (NH₃-SCO). The primary challenge is to suppress byproduct formation (N₂O, NO_x) while preserving the intrinsic activity for N₂ production, a balance governed by the metal-support interaction. Herein, a facile physical-mixing strategy is demonstrated to engineer a Pt/Cu-SSZ-13 catalyst that simultaneously establishes a moderate Pt-Cu interaction while preserving the integrity of isolated Z₂Cu sites. This catalyst demonstrates superior performance, achieving 98% NH₃ conversion at 180 °C and over 90% N₂ selectivity (280‒300 °C), outperforming its counterpart prepared by intensive grinding. It also exhibits exceptional hydrothermal stability (750 °C, 10 h). Electronic structure and in-situ spectroscopy results reveal that the Pt-Cu electronic interaction tunes the reactivity of Pt sites to selectively catalyze the formation of *NO_x intermediates. Concurrently, the preserved Z₂Cu sites act as distinct active centers for NH₃ adsorption, which then readily reduce these intermediates to N₂.

Key words: Cu-SSZ-13, Internal-selective catalytic reduction mechanism, NH₃-selective catalytic oxidation, N₂ selectivity enhancement, Hydrothermal aging resistance

Jiaxing Li, Yue Peng, Yifan Li, Yunpeng Long, William Orbell, Chuan Gao, Xiao Zhu, Xing Yuan, Lin Chen, Junhua Li. Modulation of Pt-Cu interaction in Pt/Cu-SSZ-13 for selective catalytic oxidation of ammonia[J]. Chinese Journal of Catalysis, 2026, 83: 376-387.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)64958-3

https://www.cjcatal.com/EN/Y2026/V83/I4/376

Figures/Tables 6

Fig. 1. (a) XRD patterns of Cu-SSZ-13, Pt/Cu-CHA-PM and Pt/Cu-CHA-GR catalyst. HR-TEM images of Pt/Cu-CHA-PM (b) and Pt/Cu-CHA-GR (c) catalysts obtained after different treatments. (d) Metal particle size distributions of the Pt/Cu-CHA-PM and Pt/Cu-CHA-GR. The histograms were obtained from the statistical analysis of over 150 particles for each catalyst. (e) EDX-mapping and line scan of selected area of Pt/Cu-CHA-PM.

Fig. 2. (a) XANES spectra at Pt L3-edge of Pt foil, PtO2, Pt/Cu-CHA-PM and Pt/Cu-CHA-GR. (b) In-situ DRIFTS of CO adsorption at 25 °C on Pt/Cu- CHA-PM and Pt/Cu-CHA-GR. (c) H2-TPR profiles for Cu-SSZ-13, Pt/Cu-CHA-GR and Pt/Cu-CHA-PM. (d) Fourier-transformed EXAFS k2-weighted χ(k) function spectra of Pt foil, PtO2, Pt/Cu-CHA-PM and Pt/Cu-CHA-GR. (e) WT k2-weighted EXAFS contour plots for Cu foil, CuO, Pt/Cu-CHA-PM and Pt/Cu-CHA-GR.

Fig. 3. (a) TOF of Pt/Cu-CHA-PM and Pt/Cu-CHA-GR at 160 °C. (b) N2 selectivity on Pt/Cu-CHA-PM, Pt/Cu-CHA-GR, Cu-SSZ-13 and Pt/Al2O3 in the NH3 SCO reaction. Reaction conditions: 500 ppm NH3, 2 vol% O2, balance with N2, WHSV = 60000 mL·gcat?1·h?1. (c) Reaction orders for NH3 and O2 of Pt/Cu-CHA-PM, Pt/Cu-CHA-GR and Cu-SSZ-13. (d) NH3 SCO performance as a function of NH3 conversion at 180 °C on different catalysts. (e) Concentrations of N2O, NOx and N2 selectivity at 300 °C of different catalysts.

Fig. 4. In-situ DRIFTS contour image during the reaction between the pulsed O2 with NH3 ad at 180 °C of Pt/Cu-CHA-PM (a) and Pt/Cu-CHA-GR (b). Evolution of the UV-vis spectra of Pt/Cu-CHA-PM (c) and Pt/Cu-CHA-GR (d) during successive feed of NH3+O2 at 180 °C. Comparison of time-dependent peak intensities between the LMCT band at 265 nm in DRUVS of Pt/Cu-CHA-PM (e) and Pt/Cu-CHA-GR (f) during the reduction (in NH3) and reoxidation (in NH3 + O2) half-cycles. NH3 atmosphere: 500 ppm NH3; NH3 + O2 atmosphere: 500 ppm NH3, 2 vol% O2. All feedings had a total flow rate of 100 mL·min?1 and were balanced with Ar. In-situ DRUVS spectra of Pt/Cu-CHA-PM (g) and Pt/Cu-CHA-GR (h) in different gas mixtures at 300 °C.

Fig. 5. Mass signals of O species during in-situ pulses of 16O16O/18O18O over the Pt/Cu-CHA-PM (a) and Pt/Cu-CHA-GR (b) catalyst. In-situ DRIFTS spectra during the reaction between the pulsed O2 with NH3 ad as a function of temperature over the Pt/Cu-CHA-PM (c) and Pt/Cu-CHA-GR (d) catalyst. (e) A schematic illustration of selective NH3-to-N2 oxidation over Pt/Cu-CHA-PM via the fast i-SCR mechanism.

Fig. 6. (a) NH3 conversion on Pt/Cu-CHA-PM, Pt/Cu-CHA-PM(aged), Pt/Cu-CHA-GR and Pt/Cu-CHA-GR(aged) in the NH3 SCO reaction. (b) Correlation between PtCu nanoparticle size and NH3 conversion rate at 180 °C. (c) N2 selectivity on Pt/Cu-CHA-PM, Pt/Cu-CHA-PM(aged), Pt/Cu-CHA-GR and Pt/Cu-CHA-GR(aged) in the NH3 SCO reaction. Reaction conditions: 500 ppm NH3, 2 vol% O2, balance with N2, WHSV = 60000 mL·gcat?1·h?1. (d) Product distribution of Pt/Cu-CHA-PM, Pt/Cu-CHA-PM(aged), Pt/Cu-CHA-GR and Pt/Cu-CHA-GR(aged). (e) The Cu sites proportion on Pt/Cu-CHA-PM, Pt/Cu-CHA-PM(aged), Pt/Cu-CHA-GR and Pt/Cu-CHA-GR(aged), obtained from normalized peak area results in in-situ DRIFTS. (f) In-situ DRIFTS contour image during the reaction between the pulsed O2 with NH3 ad at 180 °C of Pt/Cu-CHA-GR(aged).

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