Hot Electron-Driven Photocatalysis Using Sub-5 nm Gap Plasmonic Nanofinger Arrays

Wang, Yunxiang; Chen, Buyun; Meng, Deming; Song, Boxiang; Liu, Zerui; Hu, Pan; Yang, Hao; Ou, Tse-Hsien; Liu, Fanxin; Pi, Halton; Pi, Irene; Pi, Isleen; Wu, Wei

doi:10.3390/nano12213730

Hot Electron-Driven Photocatalysis Using Sub-5 nm Gap Plasmonic Nanofinger Arrays

Journal Article · Mon Oct 24 04:00:00 EDT 2022 · Nanomaterials

DOI:https://doi.org/10.3390/nano12213730· OSTI ID:1894522

; Chen, Buyun; ; Song, Boxiang; Liu, Zerui; Hu, Pan; Yang, Hao; Ou, Tse-Hsien; Liu, Fanxin; Pi, Halton; Pi, Irene; Pi, Isleen;

Semiconductor photocatalysis has received increasing attention because of its potential to address problems related to the energy crisis and environmental issues. However, conventional semiconductor photocatalysts, such as TiO2 and ZnO, can only be activated by ultraviolet light due to their wide band gap. To extend the light absorption into the visible range, the localized surface plasmon resonance (LSPR) effect of noble metal nanoparticles (NPs) has been widely used. Noble metal NPs can couple incident visible light energy to strong LSPR, and the nonradiative decay of LSPR generates nonthermal hot carriers that can be injected into adjacent semiconductor material to enhance its photocatalytic activity. Here we demonstrate that nanoimprint-defined gap plasmonic nanofinger arrays can function as visible light-driven plasmonic photocatalysts. The sub-5 nm gaps between pairs of collapsed nanofingers can support ultra-strong plasmon resonance and thus boost the population of hot carriers. The semiconductor material is exactly placed at the hot spots, providing an efficient pathway for hot carrier injection from plasmonic metal to catalytic materials. This nanostructure thus exhibits high plasmon-enhanced photocatalytic activity under visible light. The hot carrier injection mechanism of this platform was systematically investigated. The plasmonic enhancement factor was calculated using the finite-difference time-domain (FDTD) method and was consistent with the measured improvement of the photocatalytic activity. This platform, benefiting from the precise controllable geometry, provides a deeper understanding of the mechanism of plasmonic photocatalysis.

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Sponsoring Organization:: USDOE

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1894522

Alternate ID(s):: OSTI ID: 2422844

Journal Information:: Nanomaterials, Journal Name: Nanomaterials Journal Issue: 21 Vol. 12; ISSN 2079-4991; ISSN NANOKO

Publisher:: MDPI AGCopyright Statement

Country of Publication:: Switzerland

Language:: English

References (54)

A Review of Surface Plasmon Resonance-Enhanced Photocatalysis Hou, Wenbo; Cronin, Stephen B. Advanced Functional Materials, Vol. 23, Issue 13, p. 1612-1619 https://doi.org/10.1002/adfm.201202148	journal	October 2012
Mechanistic Understanding of the Plasmonic Enhancement for Solar Water Splitting Zhang, Peng; Wang, Tuo; Gong, Jinlong Advanced Materials, Vol. 27, Issue 36 https://doi.org/10.1002/adma.201500888	journal	August 2015
Recent Advances in Plasmonic Nanostructures for Enhanced Photocatalysis and Electrocatalysis Li, Siwei; Miao, Peng; Zhang, Yuanyuan Advanced Materials, Vol. 33, Issue 6 https://doi.org/10.1002/adma.202000086	journal	March 2020
Plasmonic Active “Hot Spots”‐Confined Photocatalytic CO ₂ Reduction with High Selectivity for CH ₄ Production Jiang, Xiaoyi; Huang, Jindou; Bi, Zhenhua Advanced Materials, Vol. 34, Issue 14 https://doi.org/10.1002/adma.202109330	journal	February 2022
4‐Aminothiophenol Photodimerization Without Plasmons** Alessandri, Ivano Angewandte Chemie, Vol. 134, Issue 28 https://doi.org/10.1002/ange.202205013	journal	May 2022
Prolonged Hot Electron Dynamics in Plasmonic-Metal/Semiconductor Heterostructures with Implications for Solar Photocatalysis DuChene, Joseph S.; Sweeny, Brendan C.; Johnston-Peck, Aaron C. Angewandte Chemie International Edition, Vol. 53, Issue 30 https://doi.org/10.1002/anie.201404259	journal	June 2014
Probing Long-Lived Plasmonic-Generated Charges in TiO ₂ /Au by High-Resolution X-ray Absorption Spectroscopy Amidani, Lucia; Naldoni, Alberto; Malvestuto, Marco Angewandte Chemie International Edition, Vol. 54, Issue 18 https://doi.org/10.1002/anie.201412030	journal	March 2015
Enhanced Photocatalytic Degradation of Methyl Orange by Au/TiO₂Nanoparticles under Neutral and Acidic Solutions Tsuji, Masaharu; Matsuda, Kanako; Tanaka, Mayu ChemistrySelect, Vol. 3, Issue 5 https://doi.org/10.1002/slct.201702664	journal	February 2018
Triggering and Monitoring Plasmon-Enhanced Reactions by Optical Nanoantennas Coupled to Photocatalytic Beads Salmistraro, Marco; Schwartzberg, Adam; Bao, Wei Small https://doi.org/10.1002/smll.201300211	journal	April 2013
Sculpting Extreme Electromagnetic Field Enhancement in Free Space for Molecule Sensing Liu, Fanxin; Song, Boxiang; Su, Guangxu Small, Vol. 14, Issue 33 https://doi.org/10.1002/smll.201801146	journal	July 2018
Fabrication of gold nanoantennas on SiO2/TiO2 core/shell beads to study photon-driven surface reactions Salmistraro, Marco; Sassolini, Simone; Weber-Bargioni, Alexander Microelectronic Engineering, Vol. 143 https://doi.org/10.1016/j.mee.2015.03.056	journal	August 2015
Dynamic Tuning of Gap Plasmon Resonances Using a Solid-State Electrochromic Device Li, Yiyang; van de Groep, Jorik; Talin, A. Alec Nano Letters, Vol. 19, Issue 11 https://doi.org/10.1021/acs.nanolett.9b03143	journal	September 2019
Au–TiO₂-Loaded Cubic g-C₃N₄ Nanohybrids for Photocatalytic and Volatile Organic Amine Sensing Applications Malik, Ritu; Tomer, Vijay K.; Joshi, Nirav ACS Applied Materials & Interfaces, Vol. 10, Issue 40 https://doi.org/10.1021/acsami.8b08091	journal	September 2018
Probing the Mechanisms of Strong Fluorescence Enhancement in Plasmonic Nanogaps with Sub-nanometer Precision Song, Boxiang; Jiang, Zhihao; Liu, Zerui ACS Nano, Vol. 14, Issue 11 https://doi.org/10.1021/acsnano.0c01973	journal	October 2020
Polarization State of Light Scattered from Quantum Plasmonic Dimer Antennas Yang, Longkun; Wang, Hancong; Fang, Yan ACS Nano, Vol. 10, Issue 1 https://doi.org/10.1021/acsnano.5b07223	journal	December 2015
Toward Cavity Quantum Electrodynamics with Hybrid Photon Gap-Plasmon States Todisco, Francesco; Esposito, Marco; Panaro, Simone ACS Nano, Vol. 10, Issue 12 https://doi.org/10.1021/acsnano.6b06611	journal	November 2016
Metal-Substrate-Mediated Plasmon Hybridization in a Nanoparticle Dimer for Photoluminescence Line-Width Shrinking and Intensity Enhancement Li, Guang-Can; Zhang, Yong-Liang; Jiang, Jing ACS Nano, Vol. 11, Issue 3 https://doi.org/10.1021/acsnano.7b00048	journal	February 2017
Probing Gap Plasmons Down to Subnanometer Scales Using Collapsible Nanofingers Song, Boxiang; Yao, Yuhan; Groenewald, Roelof E. ACS Nano, Vol. 11, Issue 6 https://doi.org/10.1021/acsnano.7b01468	journal	May 2017
Environmental Applications of Semiconductor Photocatalysis Hoffmann, Michael R.; Martin, Scot T.; Choi, Wonyong. Chemical Reviews, Vol. 95, Issue 1 https://doi.org/10.1021/cr00033a004	journal	January 1995
Plasmons in Strongly Coupled Metallic Nanostructures Halas, Naomi J.; Lal, Surbhi; Chang, Wei-Shun Chemical Reviews, Vol. 111, Issue 6 https://doi.org/10.1021/cr200061k	journal	June 2011
Atomic Layer Deposition: An Overview George, Steven M. Chemical Reviews, Vol. 110, Issue 1, p. 111-131 https://doi.org/10.1021/cr900056b	journal	January 2010
Study of Molecular Trapping Inside Gold Nanofinger Arrays on Surface-Enhanced Raman Substrates Kim, Ansoon; Ou, Fung Suong; Ohlberg, Douglas A. A. Journal of the American Chemical Society, Vol. 133, Issue 21 https://doi.org/10.1021/ja200247x	journal	June 2011
Au/TiO ₂ Superstructure-Based Plasmonic Photocatalysts Exhibiting Efficient Charge Separation and Unprecedented Activity Bian, Zhenfeng; Tachikawa, Takashi; Zhang, Peng Journal of the American Chemical Society, Vol. 136, Issue 1 https://doi.org/10.1021/ja410994f	journal	December 2013
Spatial Nonlocality in the Optical Response of Metal Nanoparticles David, Christin; García de Abajo, F. Javier The Journal of Physical Chemistry C, Vol. 115, Issue 40 https://doi.org/10.1021/jp204261u	journal	September 2011
Theory of Photoinjection of Hot Plasmonic Carriers from Metal Nanostructures into Semiconductors and Surface Molecules Govorov, Alexander O.; Zhang, Hui; Gun’ko, Yurii K. The Journal of Physical Chemistry C, Vol. 117, Issue 32 https://doi.org/10.1021/jp405430m	journal	July 2013
Nonlocal Effects in the Plasmons of Strongly Interacting Nanoparticles, Dimers, and Waveguides García de Abajo, F. Javier The Journal of Physical Chemistry C, Vol. 112, Issue 46 https://doi.org/10.1021/jp807345h	journal	October 2008
Plasmon Hybridization in Nanoparticle Dimers Nordlander, P.; Oubre, C.; Prodan, E. Nano Letters, Vol. 4, Issue 5 https://doi.org/10.1021/nl049681c	journal	May 2004
On the Universal Scaling Behavior of the Distance Decay of Plasmon Coupling in Metal Nanoparticle Pairs: A Plasmon Ruler Equation Jain, Prashant K.; Huang, Wenyu; El-Sayed, Mostafa A. Nano Letters, Vol. 7, Issue 7 https://doi.org/10.1021/nl071008a	journal	July 2007
Optical Properties of Nanowire Dimers with a Spatially Nonlocal Dielectric Function McMahon, Jeffrey M.; Gray, Stephen K.; Schatz, George C. Nano Letters, Vol. 10, Issue 9 https://doi.org/10.1021/nl101606j	journal	September 2010
Plasmon Resonant Enhancement of Photocatalytic Water Splitting Under Visible Illumination Liu, Zuwei; Hou, Wenbo; Pavaskar, Prathamesh Nano Letters, Vol. 11, Issue 3 https://doi.org/10.1021/nl104005n	journal	March 2011
Quantum Plasmonics: Nonlinear Effects in the Field Enhancement of a Plasmonic Nanoparticle Dimer Marinica, D. C.; Kazansky, A. K.; Nordlander, P. Nano Letters, Vol. 12, Issue 3 https://doi.org/10.1021/nl300269c	journal	February 2012
Electron Mobility and Injection Dynamics in Mesoporous ZnO, SnO ₂ , and TiO ₂ Films Used in Dye-Sensitized Solar Cells Tiwana, Priti; Docampo, Pablo; Johnston, Michael B. ACS Nano, Vol. 5, Issue 6 https://doi.org/10.1021/nn201243y	journal	May 2011
Direct and Reliable Patterning of Plasmonic Nanostructures with Sub-10-nm Gaps Duan, Huigao; Hu, Hailong; Kumar, Karthik ACS Nano, Vol. 5, Issue 9 https://doi.org/10.1021/nn2025868	journal	August 2011
Seeing Is Believing: Hot Electron Based Gold Nanoplasmonic Optical Hydrogen Sensor Sil, Devika; Gilroy, Kyle D.; Niaux, Aurelia ACS Nano, Vol. 8, Issue 8 https://doi.org/10.1021/nn500765t	journal	July 2014
Plasmon-Induced Hot Carriers in Metallic Nanoparticles Manjavacas, Alejandro; Liu, Jun G.; Kulkarni, Vikram ACS Nano, Vol. 8, Issue 8 https://doi.org/10.1021/nn502445f	journal	July 2014
Gap-Plasmon Enhanced Gold Nanoparticle Photoluminescence Lumdee, Chatdanai; Yun, Binfeng; Kik, Pieter G. ACS Photonics, Vol. 1, Issue 11 https://doi.org/10.1021/ph500304v	journal	October 2014
A visible light-driven plasmonic photocatalyst Pincella, Francesca; Isozaki, Katsuhiro; Miki, Kazushi Light: Science & Applications, Vol. 3, Issue 1 https://doi.org/10.1038/lsa.2014.14	journal	January 2014
Plasmonic hot electron transport drives nano-localized chemistry Cortés, Emiliano; Xie, Wei; Cambiasso, Javier Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/ncomms14880	journal	March 2017
Bridging quantum and classical plasmonics with a quantum-corrected model Esteban, Ruben; Borisov, Andrei G.; Nordlander, Peter Nature Communications, Vol. 3, Issue 1 https://doi.org/10.1038/ncomms1806	journal	January 2012
Theoretical predictions for hot-carrier generation from surface plasmon decay Sundararaman, Ravishankar; Narang, Prineha; Jermyn, Adam S. Nature Communications, Vol. 5, Issue 1 https://doi.org/10.1038/ncomms6788	journal	December 2014
Plasmonic-metal nanostructures for efficient conversion of solar to chemical energy Linic, Suljo; Christopher, Phillip; Ingram, David B. Nature Materials, Vol. 10, Issue 12 https://doi.org/10.1038/nmat3151	journal	November 2011
Photochemical transformations on plasmonic metal nanoparticles Linic, Suljo; Aslam, Umar; Boerigter, Calvin Nature Materials, Vol. 14, Issue 6 https://doi.org/10.1038/nmat4281	journal	May 2015
An autonomous photosynthetic device in which all charge carriers derive from surface plasmons Mubeen, Syed; Lee, Joun; Singh, Nirala Nature Nanotechnology, Vol. 8, Issue 4 https://doi.org/10.1038/nnano.2013.18	journal	February 2013
Plasmon-induced hot-electron generation at nanoparticle/metal-oxide interfaces for photovoltaic and photocatalytic devices Clavero, César Nature Photonics, Vol. 8, Issue 2 https://doi.org/10.1038/nphoton.2013.238	journal	January 2014
Quantum plasmonics Tame, M. S.; McEnery, K. R.; Özdemir, Ş. K. Nature Physics, Vol. 9, Issue 6 https://doi.org/10.1038/nphys2615	journal	June 2013
Flow and extraction of energy and charge carriers in hybrid plasmonic nanostructures Linic, Suljo; Chavez, Steven; Elias, Rachel Nature Materials, Vol. 20, Issue 7 https://doi.org/10.1038/s41563-020-00858-4	journal	January 2021
Nano-p–n junctions on surface-coarsened TiO2 nanobelts with enhanced photocatalytic activity Lin, Jianjian; Shen, Jianxing; Wang, Ruijun Journal of Materials Chemistry, Vol. 21, Issue 13 https://doi.org/10.1039/c0jm04131a	journal	January 2011
Optical response in subnanometer gaps due to nonlocal response and quantum tunneling Dong, Tianyu; Ma, Xikui; Mittra, Raj Applied Physics Letters, Vol. 101, Issue 23 https://doi.org/10.1063/1.4769348	journal	December 2012
Robust Subnanometric Plasmon Ruler by Rescaling of the Nonlocal Optical Response Teperik, T. V.; Nordlander, P.; Aizpurua, J. Physical Review Letters, Vol. 110, Issue 26 https://doi.org/10.1103/PhysRevLett.110.263901	journal	June 2013
Plasmons in nearly touching metallic nanoparticles: singular response in the limit of touching dimers Romero, Isabel; Aizpurua, Javier; Bryant, Garnett W. Optics Express, Vol. 14, Issue 21 https://doi.org/10.1364/OE.14.009988	journal	January 2006
Quantum effects and nonlocality in strongly coupled plasmonic nanowire dimers Teperik, Tatiana V.; Nordlander, Peter; Aizpurua, Javier Optics Express, Vol. 21, Issue 22 https://doi.org/10.1364/OE.21.027306	journal	January 2013
Surface-enhanced Raman spectroscopy: nonlocal limitations Toscano, G.; Raza, S.; Xiao, S. Optics Letters, Vol. 37, Issue 13 https://doi.org/10.1364/OL.37.002538	journal	January 2012
Advances in Photocatalytic CO2 Reduction with Water: A Review Nahar, Samsun; Zain, M.; Kadhum, Abdul Materials, Vol. 10, Issue 6 https://doi.org/10.3390/ma10060629	journal	June 2017
Recent Advances in the Design of Plasmonic Au/TiO2 Nanostructures for Enhanced Photocatalytic Water Splitting Abed, Jehad; Rajput, Nitul S.; Moutaouakil, Amine El Nanomaterials, Vol. 10, Issue 11 https://doi.org/10.3390/nano10112260	journal	November 2020

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