Plasmon resonance energy transfer and research progress in plasmon-enhanced photocatalysis

Zhou Li; Wang Qu-Quan

doi:10.7498/aps.68.20190276

Abstract

Plasmon resonance energy transfer refers to the coherent energy transfer via dipole-dipole coupling from surface plasmons to adjacent exciton nanosystems such as semiconductor quantum dots or dye molecules. The plasmon resonance energy transfer is a non-radiative plasmon decay pathway, which can also act as an available channel to extract the plasmon-harvested energy. In addition, hot electron relaxation (non-radiative channel) and scattering (radiative channel) are also the dissipation pathways of surface plasmon resonances. The plasmon-harvested energy can be effectively transferred to other nanosystems or converted into other energy forms through these correlated dissipation pathways. In this paper, the underlying mechanism and dynamics of the plasmon resonance energy transfer as well as the related energy and charge transfer processes (such as near field enhancement and coupling, far field scattering, plasmon-induced hot electron transfer) are introduced. The recent research progress of the plasmon-enhanced photocatalysis by energy and charge transfer is reviewed.

Keywords:

Authors and contacts

Zhou Li^1,2,
Wang Qu-Quan^1,3

1.
Key Laboratory of Artificial Micro- and Nano-structures of the Ministry of Education, School of Physics and Technology, Wuhan University, Wuhan 430072, China
2.
The Wallace H. Coulter Department of Biomedical Engineering, Georgia Institute of Technology and Emory University, Atlanta 30332, United States of America
3.
The Institute for Advanced Studies, Wuhan University, Wuhan 430072, China

Corresponding author: Wang Qu-Quan, qqwang@whu.edu.cn

Funds: Project supported by the National Key Research and Development Program of China (Grant No. 2017YFA0303402), the National Natural Science Foundation of China (Grant Nos. 11874293, 91750113, 11674254), the Hubei Provincial Natural Science Foundation of China (Grant No. 2018CFB572), and the Young Talent Training Program of Wuhan University, China.

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图 1 等离激元激发与弛豫, 以及由此产生的等离激元效应^[25]

Figure 1. Plasmon-mediated effects induced by light excitation and subsequent relaxation^[25]

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图 2 等离激元-激子Fano干涉引起的等离激元共振能量转移PRET^{[60, 89]}　(a) Au@IR-806的Fano干涉消光谱; (b) Au纳米棒的时间分辨差分透射谱呈现为基态漂白/饱和吸收效应(透过率变化ΔI > 0); (c) Au@IR-806核壳纳米棒的时间分辨差分透射谱呈现为吸收效应(透过率变化ΔI < 0); (d) 等离激元到叶绿素a (Chl-a)的PRET示意图; (e) Au@Chl复合体系的PRET增强光伏效应; (f) Au@Chl复合体系光伏电池和纯Au纳米颗粒膜光伏电池(AuNFs)的短路电流和开路电压随等离激元波长的变化关系

Figure 2. PRET of plasmon-exciton Fano interference^{[60, 89]}: (a) Fano resonance of Au@IR-806; dynamics of the differential transmissions (ΔI) of (b) Au nanorods and (c) Au@IR-806 at different wavelengths; (d) schematic illustration of PRET in Au@Chl-a; (e) enhanced photovoltaics by PRET of Au@Chl-a; (f) short-circuit current J_sc and open-circuit voltage V_oc of bare AuNF- and Au@Chl-sensitized solar cells as a function of λ_SPR.

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图 3 Au@SiO₂@Cu₂O体系的PRET/PIRET增强光催化^{[3, 13]}　(a) PRET/PIRET和FRET示意图, PIRET是指Au等离激元吸收能量转移至Cu₂O中, 而FRET则是Cu₂O吸收能量转移至Au中; (b) SiO₂层可以阻止等离激元热电子转移过程(DET); (c) 相对增强因子随激发波长的变化关系

Figure 3. Enhanced photocatalytic activity of Au@SiO₂@Cu₂O by PRET/PIRET^{[3, 13]}: (a) PIRET indicates the energy transfer from excited plasmon to Cu₂O, and FRET indicates the energy transfer from excited Cu₂O to plasmon; (b) SiO₂ layer is designed to prevent the plasmon-induced hot electron transfer (DET); (c) relative enhancement as a function of excitation wavelength.

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图 4 基于近场耦合的天线/反应器纳米复合体系增强光催化　(a) Al-Pd异质二聚体的光催化氢分解反应示意图^[96]; (b) 天线-反应器吸收增强的模拟计算, 红色实线为Al@Al₂O₃@Pd结构Pd中的吸收光谱, 黑色实线为单独Pd在Al₂O₃上的吸收, 蓝色实线为Al@Al₂O₃天线Al₂O₃壳层中的近场增强, 红色虚线为单独Pd的吸收乘上近场增强^[95]; (c) Al@Al₂O₃@Pd光催化HD分子脱附产量随激发波长的变化关系^[95]; (d) Al@AlO₂@Cu₂O核壳纳米颗粒的光催化CO₂还原反应示意图^[98]; (e) Au/MoS₂/Au局域场分布^[99]; (e) Au/MoS₂/Au核壳纳米颗粒的光催化制氢示意图^[99]

Figure 4. Antenna/reactor photocatalysts based on near-field coupling: (a) Al-Pd nanodisk heterodimers for hydron dissociation^[96]; (b) red solid line is absorption in Pd for Al@Al₂O₃@Pd, black solid line is absorption of isolated Pd on Al₂O₃, blue solid line is near-field enhancement in Al₂O₃ layer of Al@Al₂O₃, red dashed line is isolated Pd absorption multiplied by field enhancement^[95]; (c) wavelength dependence of HD production on Al@Al₂O₃@Pd and Al@Al₂O₃^[95]; (d) Al@Al₂O₃@Cu₂O for CO₂ conversion^[98]; (e) local field distribution of Au/MoS₂/Au^[99]; (f) Au/MoS₂/Au for hydrogen generation^[99]

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图 5 肖特基热电子注入和欧姆接触电荷转移　(a) 跨越Au/TiO₂肖特基势垒的热电子注入, Pt和Co纳米颗粒分别作为还原反应和氧化反应的共催化剂^[100]; (b) 通过Au/Ti/TiO₂欧姆接触的电荷转移, 低能的d带跃迁电子也可以转移到TiO₂中^[121]

Figure 5. Schottky barrier and Ohmic contact: (a) Plasmon-induced hot electron injection over the Schottky barrier of Au/TiO₂, Pt and Co nanoparticles act as co-catalysts for reduction and oxidation reactions, respectively^[100]; (b) low-energy electrons due to d-sp interband transition transfer to TiO₂ across the Ohmic contact of Au/Ti/TiO₂^[121]

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图 6 由等离激元金属和催化活性金属构成的双金属光催化剂　(a) 两端修饰Pt纳米颗粒的Au纳米棒用于光催化制氢的示意图(左图), 以及其消光光谱和表观量子效率与激发波长的关系(右图)^[126]; (b) 75 nm的Ag纳米立方(左图)和Ag-Pt核壳纳米立方(右图)的消光、吸收和散射光谱, 包覆约1 nm厚的超薄Pt壳层后, 等离激元消光谱由散射为主(辐射损耗)演变为吸收为主(热电子弛豫)^[128]

Figure 6. Bimetallic photocatalysts composed by plasmonic metal and catalytic metal: (a) Pt-modified Au nanorods for photocatalytic hydrogen generation (left), extinction spectra and action spectra of AQE (right)^[126]; (b) extinction, absorption and scattering spectra of Ag nanocubes (left) and Ag-Pt nanocubes with 1 nm Pt shells (right), the scattering (radiative decay) dominates the extinction of Ag nanocubes while the absorption (hot electron decay) dominants the extinction of Ag-Pt^[128]

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图 7 (a)热电子转移激发TNI态和热激发实现分子活化的示意图^[131]; (b) Cu-Ru合金纳米颗粒催化NH₃气分解过程中光催化速率与光热效应催化速率的比较^[133]

Figure 7. (a) Schematic illustration of TNI formation induced by hot electron transfer and thermal excitation for activation^[131]; (b) photocatalytic and thermocatalytic H₂ production rate by Cu-Ru, Cu, and Ru nanoparticles^[133]

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图 8 直接热电子转移过程　(a) 金属/半导体异质纳米结构中的间接热电子转移过程(左), 直接激发界面电荷转移(中)和直接热电子转移PICTT机制(右)^[134]; (b) 金属/分子界面直接热电子激发(左)和间接热电子转移(右)^[135]

Figure 8. Direct hot electron transfer: (a) Plasmon-induced hot-electron transfer (left), direct metal-to-semiconductor interfacial charge transfer transition (middle) and plasmon-induced metal-to-semiconductor interfacial charge transfer transition^[134]; (b) direct formation of energetic electron-hole pair by plasmon decay (left) and indirect process by plasmon decay induced hot electron generation and transfer (right)^[135]

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图 9 直接光激发金属-分子杂化态跃迁^[137]　(a) 间接热电子转移; (b) 弱耦合情况下光激发分子HOMO-LOMO跃迁; (c) 强耦合情况下光激发杂化态跃迁

Figure 9. Direct photoexcitation of hybridized states^[137]: (a) Indirect photoexcitation hot charge transfer; (b) direct photoexcitation of intramolecular HOMO-LUMO transition in weakly coupled nanosystem; (c) direct photoexcitation of hybridized state transition in strongly coupled nanosystem.

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Vol. 68, Issue 14 - 2019-07-20

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