Tailoring CuNi heteronuclear diatomic catalysts: Precision in structural design for exceptionally selective CO2 photoreduction to ethanol

doi:10.1016/S1872-2067(23)64630-3

Abstract

Abstract:

The photocatalytic reduction of CO₂to ethanol has attracted extensive attention, particularly for intricate C-C coupling. In this study, we propose a synthetic pathway for asymmetric CuNi heteronuclear diatoms (CuNi HDAs) by anchoring single Cu atoms on the Ni sites of (Ni, Zr)-UiO-66-NH₂ to enhance C-C coupling. Cu-(Ni,Zr)-UiO-66-NH₂ efficiently performs photocatalytic CO₂ conversion with a mass-specific activity (selectivity) of 3218 μmol·g_Cu^-1·h^-1 (97.3%). Spectroscopic analyses and density functional theory calculations revealed that CuNi HDAs with an asymmetric electronic distribution facilitated the activation of CO₂ molecules and lowered the C-C coupling barrier energy, thus promoting the formation of *OCCHO intermediates. This, in turn, led to a significant enhancement of ethanol selectivity. Furthermore, with interfacial Cu-Ni-O bonds as a rapid electron transport channel, CuNi HDAs enrich enough electrons for 12-electron CO₂ reduction, thereby enhancing ethanol productivity. This study provides a novel strategy for designing highly selective photocatalysts for CO₂ conversion at the atomic scale.

Key words: CuNi heteronuclear diatoms, Photocatalysis, CO₂-to-ethanol conversion, Asymmetric electronic distribution, Electron enrichment

Entian Cui, Yulian Lu, Jizhou Jiang, Arramel , Dingsheng Wang, Tianyou Zhai. Tailoring CuNi heteronuclear diatomic catalysts: Precision in structural design for exceptionally selective CO₂photoreduction to ethanol[J]. Chinese Journal of Catalysis, 2024, 59: 126-136.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(23)64630-3

https://www.cjcatal.com/EN/Y2024/V59/I4/126

Figures/Tables 5

Fig. 1. (a) Structure of Cu-(Ni,Zr)-UiO-66-NH2. (b) Gibbs free energy difference between C-C coupling and *CO protonation on UiO-66-NH2, (Ni,Zr)-UiO-66-NH2, and Cu-(Ni,Zr)-UiO-66-NH2. (c) Geometries of *CO, *CHO, and *OCCHO intermediates on Cu-(Ni,Zr)-UiO-66-NH2. (d,e) Charge density difference distribution and ELF of UiO-66-NH2, (Ni, Zr)-UiO-66-NH2, and Cu-(Ni,Zr)-UiO-66-NH2.

Fig. 2. (a) Schematic diagram of the synthesis. TEM image (b), EDS mapping (c), STEM image (d), Cu K-edge XANES spectra (e), Ni K-edge XANES spectra (f), Cu K-edge EXAFS spectra (g), Ni K-EXAFS spectra (h), Ni 2p (i), and Cu 3d (j) XPS spectra of Cu-(Ni, Zr)-UiO-66-NH2.

Fig. 3. (a,b) Comparative production and selectivity of CH3OH and CH3CH2OH on different photocatalysts. (c) MS spectra of 13C and 12C liquid products from the 13CO2 and 12CO2 photoreduction products, respectively, of Cu-(Ni,Zr)-UiO-66-NH2. Cyclic activity tests (d), diffuse reflectance spectra (e), photocurrent plots (f), Nyquist plots of EIS (g), PL (h), and time-resolved fluorescence spectra (i) of Cu-(Ni,Zr)-UiO-66-NH2.

Fig. 4. 2D mapping of TA spectra, TA spectra signals, and normalized decay kinetic curves of UiO-66-NH2 (a-c), (Ni,Zr)-UiO-66-NH2 (d-f), and Cu-(Ni, Zr)-UiO-66-NH2 (g-i).

Fig. 5. Cu 2p in-situ XPS spectra (a) and Ni 2p in-situ XPS spectra (b). In-situ FT-IR spectra (c) and corresponding mapping result (d), TDOS plots (e), PDOS plots (f). Calculated adsorption energy of CO on Cu-(Ni,Zr)-UiO-66-NH2 (g) and free energy diagram (h) of the mechanism of CO2 reduction.

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Tailoring CuNi heteronuclear diatomic catalysts: Precision in structural design for exceptionally selective CO₂photoreduction to ethanol

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