Atomic-level Mn incorporation into Co3O4 for selective CO2 photoreduction in pure water under dilute CO2 atmosphere

doi:10.1016/S1872-2067(25)64861-3

Abstract

Abstract:

The photocatalytic carbon dioxide reduction represents a promising route for solar-to-chemical energy conversion, enabling the sustainable production of carbon-neutral fuels. Achieving high selectivity toward specific products remains a major challenge due to the complex multi-electron transfer pathways and competing reaction intermediates. Herein, the Mn-doped Co₃O₄ (MMC) photocatalysts are synthesized based on an “impregnation-pyrolysis” strategy using in situ synthesized Mn-doped ZIF-67 as a precursor. The MOF-templated approach enables uniform Mn incorporation into the Co₃O₄ lattice while preserving a hierarchical porous architecture, thereby enhancing active-site accessibility and modulating the electronic environment of catalyst. The introduction of guest Mn effectively suppresses the competing hydrogen evolution reaction. As a result, the optimized 2MMC catalyst shows a 12.8-fold increase in CO production over undoped Co₃O₄ and enables selective CO₂ conversion in pure water with diluted CO₂. Photoelectrochemical characterizations reveal that guest Mn doping accelerates charge separation dynamics. In-situ irradiated X-ray photoelectron spectroscopy, in-situ Fourier transformed infrared spectra, and theoretical calculations unveil a Mn-mediated pathway that selectively promotes the formation of *CO₂ and *CO intermediates. This work provides new atomic-level insights into the selective photocatalytic conversion of CO₂ under green and sustainable conditions.

Key words: Photocatalysis, CO₂ conversion, Selective reduction, Metal oxides, Carbon monoxide

Ganghua Zhou, Jie Liu, Longyun Zhang, Chuanzhou Bi, Hangmin Xu, Weiyi Jiang, Xingwang Zhu, Xin Ning, Hui Xu, Xiaozhi Wang. Atomic-level Mn incorporation into Co₃O₄ for selective CO₂ photoreduction in pure water under dilute CO₂ atmosphere[J]. Chinese Journal of Catalysis, 2026, 81: 216-226.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64861-3

https://www.cjcatal.com/EN/Y2026/V81/I2/216

Figures/Tables 6

Fig. 1. Synthesis, morphology, and structural characterization of prepared catalysts. (a) Illustration of synthesized MMC catalyst. SEM (b), HR-TEM (c) images, and SAED (d) of 2MMC. (e) HRTEM image of 2MMC. (f) Intensity profiles along the blue and red lines in (e). HAADF (g) and EDX elements mapping (h?j) of 2MMC. Calculated work function of MC (k) and 2MMC (l). (m) Differential charge density and Bader charge analyses based on DFT calculations.

Fig. 2. Surface composition and chemical states. (a) XRD patterns of the as-prepared catalysts. (b) Enlarged view of the dominant (311) crystal plane diffraction peak. (c) Raman spectra of the as-prepared catalysts. High-resolution XPS spectra of prepared catalysts: Co 2p (d), O 1s (e), and Mn 2p (f).

Fig. 3. PCRR performance evaluation. (a) The PCRR activity of MC and 2MMC catalysts in TEOA-containing systems using high-concentration and low-concentration CO2 as the feed gas. (b) The PCRR durability of the 2MMC catalyst in a TEOA-containing system using high- and low-concentration CO2 as the feed gas. (c) The PCRR activity of MC and 2MMC catalysts in a pure-water system using high-concentration and low-concentration CO2 as the feed gas. (d) The PCRR durability of the 2MMC catalyst in a pure-water system using high- and low-concentration CO2 as the feed gas.

Fig. 4. Evaluation of charge separation dynamics. EIS (a), transient photocurrent response (b), PL spectra (c), and TRPL spectra (d) of the as-prepared catalysts. Tafel curves of MC (e) and 2MMC (f) catalysts.

Fig. 5. Investigation of the surface properties of the catalyst. (a) N2 adsorption-desorption isotherms of MC and 2MMC. Pore size distribution plots of MC (b) and 2MMC (c). CO2 adsorption isotherms (d), Zeta potential (e), and CO2-TPD (f) of MC and 2MMC. (g) CA of as-prepared samples.

Fig. 6. Mechanism exploration. DOS for MC (a) and 2MMC (b). In-situ XPS Mn 2p spectrum (c) and in-situ FT-IR spectrum (d) of 2MMC. (e) Calculated Gibbs free energy of MC and 2MMC. (f) Proposed PCRR pathway.

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Atomic-level Mn incorporation into Co₃O₄ for selective CO₂ photoreduction in pure water under dilute CO₂ atmosphere

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