Cu-Mo synergistic doping of metal-organic framework double-shelled hollow nanospheres: Surface reconstruction activates adsorbate evolution and lattice oxygen mechanisms

doi:10.1016/S1872-2067(25)64862-5

Abstract

Abstract:

In order to attain high catalytic activity and long-term stability in the oxygen evolution reaction (OER), it is essential to design catalysts with hollow structures that integrate both the adsorbate evolution mechanism (AEM) and the lattice oxygen mechanism (LOM). Based on the above issues, we developed a novel templating method and, for the first time, synthesized double-shelled hollow nanospheres of ZIF-67. Utilizing the inherent hollow structure and chemical activity of ZIF-67, and through Cu-Mo co-doping, we prepared a CuCo₂S₄/MoS₂ OER catalyst with dual mechanisms. The Jahn-Teller effect of copper activates lattice oxygen, facilitating LOM in OER. The cooperative interaction between copper and molybdenum atoms induces surface reconstruction in the catalyst, accelerates the deprotonation step in LOM, and aids in the formation of *OOH in AEM, thus reducing energy barriers and optimizing the adsorption of reaction intermediates. The addition of molybdenum further boosts catalytic performance by enhancing both mechanisms, owing to the spatial disparity between Cu and Mo atoms. Due to the compatibility of the dual mechanisms, the catalyst demonstrates outstanding electrochemical performance in alkaline media (320 mV at 100 mA cm⁻²) and maintains a stable catalytic current in a commercial water-splitting device (500 mA cm⁻² for 300 h). This study presents an innovative strategy for designing oxygen evolution reaction catalysts that integrate both AEM and LOM mechanisms. Considering the widespread applications of ZIF-67 in electrocatalysis and electrochemical energy storage, CuCo-G@ZIF-67 not only serves as a versatile precursor for the synthesis of various catalysts but also paves the way for the development of novel transition metal catalysts and multi-shell energy storage materials.

Key words: Adsorbate evolution mechanism, Lattice oxygen mechanism, Oxygen evolution reaction, CuCo₂S₄/MoS₂, Double-shelled hollow nanospheres

Yu Tang, Yang Chen, Kerun Chen, Edmund Qi, Xiaoyang Liu, Haiyan Lu, Yu Gao. Cu-Mo synergistic doping of metal-organic framework double-shelled hollow nanospheres: Surface reconstruction activates adsorbate evolution and lattice oxygen mechanisms[J]. Chinese Journal of Catalysis, 2026, 81: 159-171.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64862-5

https://www.cjcatal.com/EN/Y2026/V81/I2/159

Figures/Tables 6

Fig. 1. Schematic representation of the formation process for CuCo2S4/MoS2 (CCZMS) and CuCo-G@ZIF-67 (CCZ-0,12 and 36).

Fig. 2. Synthesis and structural characterizations of CCZMS. SEM images of CCG (a), CCZ-36 (b) and CCZMS-4 (c). TEM images of CCZ-36 (d), CCZM (e) and CCZMS-4 (f). (g) Elemental mapping images of CCZ-36. (h)Elemental mapping images of CCZMS-4.

Fig. 3. The Cu K-edge XANES spectra (a) and Fourier transform (FT) of the Cu K-edge EXAFS spectra (d) of Cu foil, and CuCo2S4/MoS2. The Co K-edge XANES spectra (b) and FT of the Co K-edge EXAFS spectra (e) of Co foil, and CuCo2S4/MoS2. The Mo K-edge XANES spectra (c) and FT of the Mo K-edge EXAFS spectra (f) of Mo foil, and CuCo2S4/MoS2. (g) The Cu K-edge EXAFS fitting results in k-space for CuCo2S4/MoS2. (h) The Co K-edge EXAFS fitting results in k-space for CuCo2S4/MoS2. (i) The Mo K-edge EXAFS fitting results in k-space for CuCo2S4/MoS2. (j) Wavelet transform-EXAFS at Cu K-edge of CuCo2S4. (k) WT-EXAFS at Co K-edge of CuCo2S4. (l) WT-EXAFS at Mo K-edge of CuCo2S4.

Fig. 4. Electrochemical performances of the as-prepared electrocatalysts in 1.0 mol L−1 KOH. Linear sweep voltammetry (LSV) curves (a) and Tafel plots (b) of CCZS, CCZMS and RuO2. (c) Cdl values of CCZS, CCZMS and RuO2 towards OER from current density versus the scan rate. (d) Experimental and theoretical value of gas production. Electrolyte: 1 mol L−1 KOH. (e) The overpotentials to achieve the current densities of 50 and 100 mA cm−2. (f) Optical image of the AEM water splitting device. (g) Performance comparison of CCZMS-4 with reported OER catalysts in the alkaline electrolyte. (h) Durability test of the AEM water splitting device with Pt/C||CCZMS-4 at 0.5 A cm−2.

Fig. 5. (a) CuCo2S4/MoS2 in electrolytes with different pH conditions. (b) OER polarization curves of catalysts in 1 mol L−1 KOH and 1 mol L−1 TMAOH, respectively, without iR compensation. (c) The relationship between the logarithm of current density of catalysts at the potential of 1.7 V versus RHE and pH. (d) In-situ Raman spectra of CuCo2S4/MoS2. (e) In-situ ATR-FTIR spectra of CuCo2S4/MoS2. (f) Mass signals of O2 products for 18O-labeled CCZMS.

Fig. 6. (a−c) Free energies of OER steps via AEM and LOM pathways on CuMo-CoO2 at 1.23 V. (d−f) pDOS of CuMo-CoO2 slabs. (g) Schematic energy bands of CoOOH and Mn-CoO2 slabs. (g) Schematic illustration of the proposed overall OER pathway for CuMo-CoOOH catalyst. (h) Schematic illustration of the proposed overall OER pathway for CuMo-CoO2 catalyst. (i) The COHP plots. (j,k) Configuration diagram of COHP.

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