银纳米颗粒等离激元促进光电催化二氧化碳制乙醇

doi:10.6023/A25070257

摘要/Abstract

利用太阳辐射驱动光电催化还原CO₂制备碳基化学品可减少碳排放, 同时将不稳定的太阳能转化为可长期存储的化学能, 极具吸引力. 但半导体光电极的太阳光谱吸收范围窄且载流子复合严重制约了效率的提升, 并且将CO₂还原为具有高附加值的C₂及以上碳基化学品需要多电子转移, 十分具有挑战性. 本工作构建了Ag纳米颗粒(AgNPs)与Cu₂O的复合光电阴极, 通过负载AgNPs形成局域表面等离激元共振效应将太阳光谱吸收范围拓宽至近红外区, 光电流提升至2.02 mA•cm^–2, 并通过热电子注入与能带弯曲共同抑制析氢、促进C—C偶联, 在0 V vs. RHE下将CO₂还原为乙醇, 法拉第效率可达81.3%. 证实了等离激元效应促进光电催化还原CO₂制备C₂以上碳基化学品的可行性, 并为高效光电极设计提供了新思路.

关键词: 局域表面等离激元共振, 银纳米颗粒, 氧化亚铜, 光电催化, CO₂还原

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

引用此文

张梓菡, 詹小鹏, 梅晋豪, 刘一, 马娅诺, 魏弋茗, 许辰宇. 银纳米颗粒等离激元促进光电催化二氧化碳制乙醇[J]. 化学学报, 2026, 84(1): 43-52.

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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图/表 11

图1. (a)银纳米颗粒的TEM全貌图像; (b) AgNPs的TEM局部放大图像, 右上角插图是所选区域快速傅里叶变换图, 右下角显示AgNPs晶格间距; (c) Cu2O负载AgNPs (红色虚线区域)的TEM图像; (d) Cu2O/ AgNPs复合结构的局部放大TEM图像, 左、右插图分别对应Ag、Cu2O结构所选区域快速傅里叶变换图与晶格间距; (e~h)氧化亚铜负载银纳米颗粒EDS元素分布

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

图2. (a, b) FTO/CuSCN/Cu2O和(c) FTO/CuSCN/Cu2O/AgNPs光电阴极SEM图

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

图3. (a) FTO/CuSCN/Cu2O/AgNPs光电阴极的XPS全谱图; 不同AgNPs负载量的FTO/CuSCN/Cu2O/AgNPs光电阴极XPS谱图对比: (b) Cu 2p轨道精细谱图; (c) Ag 3d轨道精细谱图

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

图4. (a) AgNPs溶液的光吸收特性; (b)不同AgNPs负载的复合光电阴极光吸收特性; (c) CuSCN改进与AgNPs负载修饰前后光电阴极的光致发光光谱

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.

图5. 不同负载量的FTO/CuSCN/Cu2O/AgNPs的(a) LSV曲线和(b) Tafel图; (c)不同负载量的FTO/CuSCN/Cu2O/AgNPs的入射光子-电流转换效率图谱IPCE

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

图6. (a)不同负载量的FTO/CuSCN/Cu2O/AgNPs的Nyquist图谱; (b)不同负载量的FTO/CuSCN/Cu2O/AgNPs的莫特肖特基曲线

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

图7. 不同负载量的FTO/CuSCN/Cu2O/AgNPs的: (a)开路电压衰减曲线; (b)光照和黑暗条件下开路电压变化; (c)电位依赖载流子寿命

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

图8. (a)乙醇; (b)甲醇; (c)氢气的产率及法拉第效率随电位变化图; (d)总产物法拉第效率随电位变化图

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

图9. 银纳米颗粒不同波长下FDTD模拟

Figure 9. FDTD simulation of silver nanoparticles at different wavelengths

图10. 等离激元促进光电催化CO2还原反应机理示意图

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

图11. 在Cu2O和Cu2O-Ag表面CO2还原为CH3CH2OH的吉布斯自由能计算图及相应稳定构型

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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