Plasmonics of Ag Nanoparticles for Enhancing Photoelectrocatalytic CO2 to Ethanol

doi:10.6023/A25070257

Abstract

This study achieves highly selective photoelectrocatalytic CO₂ reduction to ethanol through plasmon-enhanced Cu₂O/Ag photocathodes, overcoming inherent limitations of Cu₂O including narrow light absorption and rapid charge recombination. The fabrication involved sequential electrodeposition on fluorine-doped tin oxide transparent conducting glass (FTO): CuSCN at –0.3 V vs. Ag/AgCl (0.1 mol/L CuSO₄•5H₂O, 0.1 mol/L ethylenediaminetetraacetic acid (EDTA), 0.1 mol/L KSCN) followed by Cu₂O at –0.1 mA•cm^–2 (0.4 mol/L CuSO₄, 3 mol/L lactic acid, pH 12.5). Triangular Ag nanoparticles (AgNPs) synthesized via light-assisted reduction were deposited via drop-casting at 70 ℃, with 100 μL•cm^–2 identified as optimal loading. Comprehensive characterization validated the structure and mechanism: field emission transmission electron microscope (FE-TEM) confirmed epitaxial Ag(111)/Cu₂O(110) growth; XPS revealed interfacial electron transfer via Cu⁺2p_3/2(931.04→931.66 eV) and Ag 3d_5/2(369.08→368.52 eV) shifts; UV-Vis DRS demonstrated localized surface plasmon resonance (LSPR)-mediated absorption extension to 700 nm; and 40% PL quenching indicated suppressed recombination. Under AM 1.5G illumination in 0.1 mol/L KHCO₃, the optimized photocathode achieved a photocurrent density of –2.02 mA•cm^–2 at 0 V vs. RHE, a 30% enhancement versus bare Cu₂O (–1.56 mA•cm^–2). Electrochemical analyses revealed increased carrier concentration (5.56×10¹⁶ cm^–3) and reduced Tafel slope, signifying accelerated kinetics. Crucially, CO₂ reduction at –0.2 V vs. RHE yielded ethanol with 81.3% Faradaic efficiency (0.358 μmol•h^–1•cm^–2) while suppressing hydrogen evolution (<1% FE). Total carbon product FE exceeding 100% suggests participation of non-Faradaic catalytic cycles. Performance degradation at excessive loading (300 μL•cm^–2; 32% photocurrent reduction) confirmed aggregation effects. Finite-Difference Time-Domain (FDTD) simulations corroborated the mechanism, showing 15-fold electromagnetic field enhancement at AgNPs tips under 600 nm illumination, aligning with peak Incident Photon-to-Current Efficiency (IPCE). The record ethanol selectivity stems from synergistic LSPR effects: near-field enhancement facilitates *CO intermediate formation and adsorption, hot electron injection promotes multi-electron transfers crucial for C—C coupling, and the Ag/Cu₂O Schottky barrier effectively suppresses parasitic hydrogen evolution reaction (HER). This work establishes a material design paradigm for efficient solar-to-fuel conversion targeting value-added multi-carbon products.

Key words: localized surface plasmon resonance, silver nanoparticles, cuprous oxide, photoelectrocatalysis, carbon dioxide reduction

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Zihan Zhang, Xiaopeng Zhan, Jinhao Mei, Yi Liu, Yanuo Ma, Yiming Wei, Chenyu Xu. Plasmonics of Ag Nanoparticles for Enhancing Photoelectrocatalytic CO₂ to Ethanol[J]. Acta Chimica Sinica, 2026, 84(1): 43-52.

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Fig. & Tab. 11

Figure 1. (a) TEM image of AgNPs; (b) magnified TEM image of AgNPs, with the inset in the upper right corner showing the fast Fourier transform (FFT) pattern of the selected area, and the lower right corner displaying the lattice spacing of the AgNPs; (c) TEM image of Cu2O loaded with AgNPs (red dashed area); (d) magnified TEM image of the Cu2O/AgNPs composite structure, with the left and right insets showing the FFT pattern and lattice spacing of the selected Ag and Cu2O regions, respectively; (e~h) EDS elemental distribution of silver nanoparticles supported on cuprous oxide

Figure 2. SEM images of (a, b) FTO/CuSCN/Cu2O and (c) FTO/ CuSCN/Cu2O/AgNPs photocathode

Figure 3. (a) XPS survey spectrum of FTO/CuSCN/Cu2O/AgNPs photocathode; Comparison of XPS spectra of FTO/CuSCN/Cu2O/AgNPs photocathodes with different AgNPs loadings: (b) fine spectrum of Cu 2p orbital; (c) fine spectrum of Ag 3d orbital

Figure 4. (a) Optical absorption characteristics of AgNPs solution; (b) optical absorption characteristics of composite photocathodes with different AgNPs loadings; (c) PL of the photocathode before and after modification with CuSCN improvement and AgNPs loading.

Figure 5. (a) LSV cur (a) LSV curves and (b) Tafel plots of FTO/CuSCN/ Cu2O/AgNPs with different loading; (c) IPCE spectra of FTO/CuSCN/ CuO/AgNPs with different loading amounts

Figure 6. (a) Nyquist plots of FTO/CuSCN/Cu2O/AgNPs with different loading amounts; (b) Mott-Schottky plots of FTO/CuSCN/Cu2O/AgNPs with varying loading amounts

Figure 7. FTO/CuSCN/Cu2O/AgNPs with varied loading amounts: (a) OPCD kinetics; (b) Light/dark-switching OCP dynamics; (c) Potential-resolved carrier lifetime characteristics

Figure 8. (a) Ethanol; (b) methanol; (c) hydrogen—plots of yield and Faraday efficiency versus potential; (d) total product Faraday efficiency versus potential

Figure 9. FDTD simulation of silver nanoparticles at different wavelengths

Figure 10. Schematic diagram of the mechanism of LSPR-enhanced photoelectrocatalytic CO2 reduction reaction

Figure 11. The calculated Gibbs free energy diagrams for CO2 reduction to CH3CH2OH on the surface of Cu2O and Cu2O-Ag and corresponding energetically favorable structures

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银纳米颗粒等离激元促进光电催化二氧化碳制乙醇

Plasmonics of Ag Nanoparticles for Enhancing Photoelectrocatalytic CO₂ to Ethanol

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