Design of interface structure to enhance the operational temperature range of CuO/Cu-SSZ-13 for concurrent NOx selective catalytic reduction and CO oxidation

doi:10.1016/S1872-2067(26)64960-1

Abstract

Abstract:

The non-selective oxidation of NH₃ at CO oxidation sites is a major limitation for bifunctional catalysts used in NH₃-selective catalytic reduction and CO oxidation. This issue restricts these catalysts from achieving a wide operational temperature window, where both NO_x and CO conversions exceed 90%, thus hindering their industrial application. Herein, we propose a novel strategy to expand the temperature window of bifunctional catalysts. By exploiting the synergistic effects of interfacial electron regulation and spatial decoupling of acid sites, we demonstrate that the CuO/Cu-SSZ-13 catalyst achieves an unprecedented operational window (200-425 °C), surpassing previously reported results. Our investigation reveals a new mechanism of bifunctional synergy, driven by Cu-O bond reconstruction at the interface and the preferential anchoring of Brönsted acid sites on NH₃. This mechanism mitigates the non-selective oxidation of NH₃, thereby extending the catalyst’s temperature window. This work provides a new design paradigm for bifunctional catalysts, facilitating broader operational temperature windows and advancing the field.

Key words: NO_x selective catalytic reduction, CO oxidation, Bifunctional catalyst, Synergistic effect, Wide operational window

Zheguan Lin, Shuyi He, Tiesen Li, Qingyan Cui, Wenfu Yan, Yuanyuan Yue. Design of interface structure to enhance the operational temperature range of CuO/Cu-SSZ-13 for concurrent NO_x selective catalytic reduction and CO oxidation[J]. Chinese Journal of Catalysis, 2026, 85: 286-297.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)64960-1

https://www.cjcatal.com/EN/Y2026/V85/I6/286

Figures/Tables 5

Fig. 1. (a) Schematic diagram of the CuO/Cu-SSZ-13 preparation process. (b) XRD patterns of CuO, Cu-SSZ-13 and CuO/Cu-SSZ-13. HRTEM (c) and HAADF-STEM and corresponding elemental mapping (d) images of CuO/Cu-SSZ-13. (e) Cu 2p XPS spectra of CuO, Cu-SSZ-13 and CuO/Cu-SSZ-13. (f) Cu K-edge XANES spectra of Cu foil, self-prepared CuO, Cu-SSZ-13 and CuO/Cu-SSZ-13. (g) EXAFS spectra with Fourier transforms of self-prepared CuO and CuO/Cu-SSZ-13.

Fig. 2. Raman spectra (a) and O2 desorption capacity (b) of CuO, Cu-SSZ-13 and CuO/Cu-SSZ-13. (c) NOx conversion of CuO, Cu-SSZ-13, CuO + Cu-SSZ-13 and CuO/Cu-SSZ-13. (d) N2 selectivity of Cu-SSZ-13 and CuO/Cu-SSZ-13. (e) CO conversion of CuO, Cu-SSZ-13, CuO + Cu-SSZ-13 and CuO/Cu-SSZ-13. (f) Comparison of T90 (NOx and CO conversions ≥ 90%) and N2 selectivity ≥ 90% temperature range with reported literature. (g) NOx (rhombus) and CO (circle) conversions of CuO/Cu-SSZ-13 for 35 h at 300 °C. TOFs (h) and Arrhenius plots (i) of CuO and CuO/Cu-SSZ-13 for CO oxidation, reaction conditions: 500 × 10-6 NO, 500 × 10-6 NH3, 3000 × 10-6 CO, 5 vol% O2 and balance N2.

Fig. 3. CO-in situ DRIFTS spectra of CuO/Cu-SSZ-13 (a), Cu-SSZ-13 (b), and pure CuO (c) for 60 min at 200 °C. (d) CO and CO2 desorption capacity of Cu-SSZ-13 and CuO/Cu-SSZ-13 from CO-TPD-MS experiments. (e) CO + O2-in-situ DRIFTS spectra of CuO/Cu-SSZ-13 for 60 min at 200 °C. Dynamic evolutions in operando NAP-XPS results of Cu2+ position (f), Cu2+ content (g), lattice oxygen position (h), and lattice oxygen content (i) for CuO, Cu-SSZ-13 and CuO/Cu-SSZ-13 at 200 °C.

Fig. 4. The free energy change diagram of the CO oxidation process over CuO/Cu-SSZ-13 (a) and pure CuO (b) at 200 °C. (c) DOS and orbitals of CO adsorbed on CuO/Cu-SSZ-13, including isosurface images of the wave functions of CO. (d) Charge density difference and Bader charge of CuO/Cu-SSZ-13 and CuO for CO adsorption.

Fig. 5. NH3 (a) and NO desorption capacity (b) of Cu-SSZ-13 and CuO/Cu-SSZ-13. (c) In-situ DRIFTS spectra of CuO/Cu-SSZ-13 first exposed to a flow containing NH3 + NO + O2 for 30 min and then continuously introducing NH3 + NO + O2 + CO for 60 min at 200 °C. (d) Plausible bifunctional catalytic mechanism of CuO/Cu-SSZ-13 in the NH3-SCR and CO oxidation reaction process.

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