Pr(OH)3 nanorods on Cu generates asymmetric active sites through interplay and geometric deformation for CO2 electroreduction

doi:10.1016/S1872-2067(26)65193-5

Abstract

Abstract:

Leveraging the asymmetric active motifs with high precision holds potential and presents substantial challenge due to design constraints and complex interphase. Herein, Pr(OH)₃ nanorods are introduced onto Cu nanosheets to spontaneously regulate the interplay aiming to prevent Cu over-reduction during the CO₂ electroreduction. Specifically, the 12.7% Pr(OH)₃/Cu catalyst achieves a 50.2% Faradaic efficiency of C₂H₄ at industrially relevant current density of 250 mA cm^-2. Complementary structural characterizations combined with in-situ/operando spectroscopy studies prove that Pr(OH)₃ incorporation facilitates the generation of asymmetric Pr³⁺/Pr⁴⁺ and Cu⁺/Cu motifs, synergizing the formation of C₂ products-related intermediates through increasing the number of active sites on the Pr(OH)₃/Cu⁺/Cu heterogeneous interphase. This work demonstrates that the introduction of rare earth hydroxide can activate the asymmetric active sites on Cu, providing a sustainable pathway for efficient CO₂-to-C₂ conversion.

Key words: Pr(OH)₃, Cu nanosheets, Asymmetric active sites, Catalytic mechanism, CO₂ electroreduction

Heng Zhang, Zeyu Zhang, Kunming Hou, Lin Jia, Yingxin Guo, Haorun Li, Mengbo Zou, Xianhu Sun, Shanghong Zeng. Pr(OH)₃ nanorods on Cu generates asymmetric active sites through interplay and geometric deformation for CO₂ electroreduction[J]. Chinese Journal of Catalysis, 2026, 90: 158-168.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)65193-5

https://www.cjcatal.com/EN/Y2026/V90/I11/158

Figures/Tables 5

Fig. 1. Structural and microscopic characterizations of CuO, Pr(OH)3/CuO and Pr(OH)3/Cu. (a) Schematic diagram for the preparation of Pr(OH)3/CuO and Pr(OH)3/Cu. Representative TEM (b) and AFM (c) images of the CuO. Representative TEM (d,e), HRTEM (f,g), HAADF-STEM images and corresponding EDS mappings (h) of the 12.7% Pr(OH)3/CuO pre-catalyst. Representative TEM (i) and HRTEM (j,k) images of the12.7% Pr(OH)3/Cu catalyst.

Fig. 2. Normalized Cu k-edge XANES spectra (a) and the corresponding FT-EXAFS spectra (b) of 12.7% Pr(OH)3/Cu, Cu nanosheet and references in R space. (c) WT plots for the k3-weighted EXAFS signal of 12.7% Pr(OH)3/Cu, Cu nanosheet and Cu foil. (d) Pr L3-edge XANES spectra of the 12.7% Pr(OH)3/Cu, 12.7% Pr(OH)3/CuO, Pr(OH)3 and Pr2O3. (e) FT EXAFS spectra of 12.7% Pr(OH)3/Cu, 12.7% Pr(OH)3/CuO, Pr(OH)3 and Pr2O3 at R space. (f) WT plots for the k3-weighted EXAFS signal of 12.7% Pr(OH)3/CuO, 12.7% Pr(OH)3/Cu and Pr2O3.

Fig. 3. (a) LSV curves of Cu and Pr(OH)3/Cu catalysts in 1 mol L-1 KOH in a flow cell. FE of Cu (b) and 12.7% Pr(OH)3/Cu (c) catalyst at applied current density in the range from 100 to 300 mA cm-2. (d) Relationship between Pr(OH)3 content and FE. (e) Stability test results for the 12.7% Pr(OH)3/Cu catalyst at 250 mA cm-2.

Fig. 4. In-situ potential-dependent surface-enhanced Raman spectra of 12.7% Pr(OH)3/CuO catalyst (a) and CuO nanosheet (b) in the regions of 200-1200 and 1600-2200 cm-1.

Fig. 5. Operando ATR-SEIRAS spectra of 12.7% Pr(OH)3/Cu (a,c) and Cu nanosheet (b,d) with 0.1 V interval from -0.6 to -1.4 V in a CO2-saturated 0.1 mol L-1 KHCO3 electrolyte.

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Pr(OH)₃ nanorods on Cu generates asymmetric active sites through interplay and geometric deformation for CO₂ electroreduction

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