Plasmonic metal nanostructures are essential for plasmon‐mediated chemical reactions (PMCRs) and surface‐enhanced Raman spectroscopy (SERS). The nanostructures are commonly made from the coinage metals gold and silver. Copper (Cu) is less used mainly due to the difficulties in fabricating stable nanostructures. However, Cu is an attractive option with its strong plasmonic properties, high catalytic activities, and relatively cheap price. Herein, we fabricated tunable, reliable, and efficient Cu nanoelectrodes (CuNEs). Using time‐resolved electrochemical SERS, we have comprehensively studied the reversible chemical transformations between aromatic amine and nitro groups modified on the CuNE surface. Their PMCRs are well‐controlled by changing the surface roughness, the oxidation states of Cu, and the applied electrode potential. We thus demonstrate that the Cu nanostructures enable better investigations in the interplays between PMCR, electrochemistry, and Cu catalysis.
- Award ID(s):
- 1829245
- NSF-PAR ID:
- 10178105
- Date Published:
- Journal Name:
- Materials Express
- Volume:
- 9
- Issue:
- 9
- ISSN:
- 2158-5849
- Page Range / eLocation ID:
- 1082 to 1086
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
Abstract -
Abstract Plasmonic metal nanostructures are essential for plasmon‐mediated chemical reactions (PMCRs) and surface‐enhanced Raman spectroscopy (SERS). The nanostructures are commonly made from the coinage metals gold and silver. Copper (Cu) is less used mainly due to the difficulties in fabricating stable nanostructures. However, Cu is an attractive option with its strong plasmonic properties, high catalytic activities, and relatively cheap price. Herein, we fabricated tunable, reliable, and efficient Cu nanoelectrodes (CuNEs). Using time‐resolved electrochemical SERS, we have comprehensively studied the reversible chemical transformations between aromatic amine and nitro groups modified on the CuNE surface. Their PMCRs are well‐controlled by changing the surface roughness, the oxidation states of Cu, and the applied electrode potential. We thus demonstrate that the Cu nanostructures enable better investigations in the interplays between PMCR, electrochemistry, and Cu catalysis.
-
Inverse Design of Plasmonic Nanohole Arrays by Combing Spectra and Structural Color in Deep Learning
Herein, deep learning (DL) is used to predict the structural parameters of Ag nanohole arrays (NAs) for spectrum‐driving and color‐driving plasmonic applications. A dataset of transmission spectra and structural parameters of NAs is generated using finite‐difference time‐domain (FDTD) calculations and is converted to vivid structural colors using the corresponding transmission spectrum. A bidirectional neural network is used to train the transmission spectrum and structural color together. The accuracy of predicting the structural parameters using a desired spectrum is tested and found to be up to 0.99, with a determination coefficient of reproducing the desired spectrum and color to be 0.97 and 0.96, respectively. These values are higher compared to those when only training for spectrum, but requiring less training time. This strategy is able to inverse design the NAs in less than 1 s to maximize surface‐enhanced Raman scattering (SERS) enhancement by matching transmission resonance and laser excitation wavelength, and accurately regenerate colored images in 7.5 s, allowing for nanoscale printing at a resolution of approximately 100 000 dots in−1. This work has important implications for the efficient design of nanostructures for various plasmonic applications, such as plasmonic sensors, optical filters, metal‐enhanced fluorescence, SERS, and super‐resolution displays.
-
Electrochemical nitrogen reduction reaction (NRR) for ammonia synthesis might offer an alternative means to the capital- and carbon-intensive thermochemical process (Haber-Bosch) in a clean, sustainable, and decentralized way if the process is coupled to renewable electricity sources. One of the challenges in electrochemical ammonia synthesis is finding catalysts with a suitable activity for breaking N2 triple bonds at or near ambient conditions. Improving the design of electrocatalysts, electrolytes, and electrochemical cells is required to overcome the selectivity and activity barrier in electrochemical NRR. In-situ and operando surface-enhanced Raman spectroscopy (SERS) is a well-suited technique to probe electrochemical reactions at the solid-liquid (electrode/electrolyte) interface. Operando SERS allows for the detection of intermediate species even in low abundance and is used to provide insights into NRR mechanisms using hybrid plasmonic nanostructures (e.g., Au-Pd) by combining spectroscopy and electrochemistry. A potentiostat is used to apply potential on a SERS active substrate that is then monitored by changes in a spectrum. The spectroelectrochemical cell is developed to operando probe the trace of NH3 and possible intermediate species produced at the electrode/electrolyte interface. This work would aid in understanding the reaction mechanism and ultimately designing more efficient catalysts for electrochemical energy conversion systems. This material is based upon work supported by the National Science Foundation under grant no. 1904351.more » « less
-
Metallic nanostructures supporting surface plasmon modes can concentrate optical fields, and enhance luminescence processes from the metal surface at plasmonic hotspots. Such nanoplasmonic metal luminescence contributes to the spectral background in surface-enhanced Raman spectroscopy (SERS) measurements and is helpful in bioimaging, nano-thermometry, and chemical reaction monitoring applications. Despite increasing interest in nanoplasmonic metal luminescence, little attention has been paid to investigating its dependence on voltage modulation. Also, the hyphenated electrochemical surface-enhanced Raman spectroscopy (EC-SERS) technique typically ignores voltage-dependent spectral background information associated with nanoplasmonic metal luminescence due to limited mechanistic understanding and poor measurement reproducibility. Here, we report a combined experiment and theory study on dynamic voltage-modulated nanoplasmonic metal luminescence from hotspots at the electrode-electrolyte interface using multiresonant nanolaminate nano-optoelectrode arrays. Our EC-SERS measurements under 785 nm laser excitation demonstrate that short-wavenumber nanoplasmonic metal luminescence associated with plasmon-enhanced electronic Raman scattering (PE-ERS) exhibits a negative voltage modulation slope (up to ≈30 % V-1) in physiological ionic solutions. Furthermore, we have developed a phenomenological model to intuitively capture plasmonic, electronic, and ionic characteristics at the metal-electrolyte interface to understand the observed dependence of the PE-ERS voltage modulation slope on voltage polarization and ionic strength. The current work represents a critical step toward the general application of nanoplasmonic metal luminescence signals in optical voltage biosensing, hybrid optical-electrical signal transduction, and interfacial electrochemical monitoring.more » « less