Plasmonic hotspots-mediated C-C coupling drives selective CO2-to-C2H6 photoreduction

doi:10.1016/S1872-2067(26)65262-X

Abstract

Abstract:

Photocatalytic CO₂ reduction to C₂₊ products remains challenging due to inefficient C-C coupling. Herein, we design a plasmonic heterostructure comprising Au nanoparticles (NPs) and Ni-doped W₁₈O₄₉ (Ni-W₁₈O₄₉) nanowires for selective CO₂-to-C₂H₆ photoreduction with H₂O. Plasmonic hotspots generated at the Au/Ni-W₁₈O₄₉ interface concentrate optical energy via localized electromagnetic field enhancement, greatly boosting hot-electron generation and enrichment at the active sites. Meanwhile, Ni dopants in W₁₈O₄₉ promote the formation of *CHO intermediates, while adjacent Au NPs favor the generation and stabilization of *CO species. Crucially, these plasmonic hotspots mediate the synergy between the dual active sites, driving efficient C-C coupling by forming the critical *COCHO intermediate and enabling selective C₂H₆ formation. Therefore, the optimized Au_1.2/Ni_0.32-W₁₈O₄₉ catalyst attains a C₂H₆ yield of 25.41 μmol g^-1 h^-1 with 72.13% selectivity, a performance unattainable with bare Ni-W₁₈O₄₉. This work establishes engineered plasmonic hotspots as a potent strategy to advance CO₂-to-C₂₊ photosynthesis.

Key words: Photocatalytic CO₂ reduction, Surface plasmon resonance, Plasmonic hotspots, C₂H₆ production, C-C coupling

Xiaolei Liu, Yinlan Liang, Jinyu Li, Huiliang Li, Zhaoke Zheng, Zeyan Wang, Jianmin Luo, Juan Li, Baojiang Jiang, Baojun Li, Zaizhu Lou. Plasmonic hotspots-mediated C-C coupling drives selective CO₂-to-C₂H₆ photoreduction[J]. Chinese Journal of Catalysis, 2027, 92: 237-247.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)65262-X

https://www.cjcatal.com/EN/Y2027/V92/I1/237

Figures/Tables 6

Fig. 1. (a) Schematic diagram of the fabrication for the Au/Ni-W18O49 heterostructures with different Au NP sizes. TEM images of Ni0.32-W18O49 (b) and Au1.2/Ni0.32-W18O49 (c). (d-g) EDS elemental mappings of Au1.2/Ni0.32-W18O49. (h) HRTEM images of Au1.2/Ni0.32-W18O49. (i) UV-Vis-NIR DRS of W18O49, Ni0.32-W18O49, and Au1.2/Ni0.32-W18O49. Normalized Ni K-edge XANES spectra (j) and FT-EXAFS spectra (k) of Ni0.32-W18O49, Ni foil, and NiO reference. WT-Ni K-edge EXAFS of Ni foil (l), NiO reference (m), and Ni0.32-W18O49 (n).

Fig. 2. (a) CH4 and CO production rates and CH4 selectivity of W18O49 and Nix-W18O49 (x = 0.15, 0.32, 0.44, and 0.59). CH4, CO, and C2H6 production rates and C2H6 selectivity of the Auy/Ni0.32-W18O49 heterostructures (y = 0.3, 0.6, 0.9, 1.2, 1.5, and 1.8) (b), and W18O49, Ni0.32-W18O49, Au1.2/Ni0.32-W18O49, and Au1.2/W18O49 (c). (d) Comparative activity of Au1.2/Ni0.32-W18O49 under different conditions. (e) Isotope-labeling MS analysis of products from photocatalytic 13CO2 reduction over Au1.2/Ni0.32-W18O49. (f) Stability test of Au1.2/Ni0.32-W18O49 over five consecutive reaction cycles.

Fig. 3. (a) CH4, CO, C2H4, and C2H6 production rates and C2H6 selectivity of Ni0.32-W18O49, Cu1.2/Ni0.32-W18O49, Ag1.2/Ni0.32-W18O49, and Au1.2/Ni0.32-W18O49. (b) Relation between the size of Au NPs and C2H6 production rate and selectivity over Auy/Ni0.32-W18O49. (c) CH4, CO, and C2H6 production rates and C2H6 selectivity of Au1.2/Ni0.32-W18O49 upon different light irradiations with the same intensity of 300 mW cm-2. (d) UV-Vis-NIR DRS and AQE of Au1.2/Ni0.32-W18O49.

Fig. 4. Spatial distributions of SPR-induced electric fields (a) and extinction spectra (b) of the single W18O49 nanowire (a length of 350 nm and a width of 10 nm), Au NP (55 nm), and 55 nm Au/W18O49 heterostructure from FDTD simulations. (c) Spatial distributions of SPR-induced electric fields of the Au/W18O49 heterostructures with different Au NP sizes of 30, 40, 50, 85, and 110 nm from FDTD simulations. Extinction spectra (d) and the ratio of absorbance to scattering (e) of the Au/W18O49 heterostructures with different Au NP sizes.

Fig. 5. W 4f (a), O 1s (b), Ni 2p (c), and Au 4f (d) XPS spectra of Au1.2/Ni0.32-W18O49 in the dark and under full-spectrum irradiation (OL: lattice oxygen, *OH: adsorbed hydroxyl species). (e) UV-Vis-NIR DRS of Ni0.32-W18O49 and Au1.2/Ni0.32-W18O49 before and after UV-irradiation for 25 s. (f) Schematic diagram of charge transfer in the Au1.2/Ni0.32-W18O49 heterostructure.

Fig. 6. In-situ FTIR spectroscopy of Ni0.32-W18O49 (a) and Au1.2/Ni0.32-W18O49 (b) under light irradiation in a CO2 and water vapor atmosphere. (c) Free energy diagrams for CO2 reduction to *CHO or CO on the W site of W18O49 and the Ni and Au sites of Au/Ni-W18O49. (d) Free energy diagrams for anchoring two C1 intermediates on different sites in Au/Ni-W18O49. (e) Free energy diagram for coupling of *CO and *CHO into *COCHO and its subsequent protonation to CH3CH3 over Au/Ni-W18O49. The structural models consist of W (gray), Ni (blue), Au (yellow), O (red), C (brown), and H (white) atoms. (f) Schematic diagram of PCR mechanism over plasmonic Au/Ni-W18O49 heterostructures.

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Plasmonic hotspots-mediated C-C coupling drives selective CO₂-to-C₂H₆ photoreduction

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