Name: photodeposition of pd onto colloidal au nanorods by surface plasmon excitation
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This work was sponsored by the Army Research Laboratory and was accomplished under USARL Cooperative Agreement Number W911NF&#8208;17&#8208;2&#8208;0057 awarded to G.T.F. The views and conclusions contained in this document are those of the authors and should not be interpreted as representing official policies, either expressed or implied, of the Army Research Laboratory or the U.S. Government. The U.S. Government is authorized to reproduce and distribute reprints for Government purposes notwithstanding any copyright notation herein.

1. Allocation of Au nanorods
NOTE: Cetyltrimethylammonium bromide (CTAB)-covered AuNR may be synthesized by wet-chemistry (step 1.1) or purchased commercially (step 1.2) according to the reader&#8217;s preference, with each yielding similar results. Results in this work were based on commercially-sourced, AuNR with penta-twinned crystal structure. Impact of AuNR seed crystal structure (i.e., monocrystalline vs. penta-twinned) on ultimate morphology of the secondary metal shell remains unclear wi...

<ol>
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Monitoring changes in optical absorbance using transmission UV-vis spectroscopy is useful to assess status of the photocatalytic reaction, with particular attention to the LMCT features of H2PdCl4. Wavelength maxima of LMCT features after injection of H2PdCl4 at step 2.3.1 (going from solid black to solid blue in Figure 1) provide insights into the local &#8220;environment&#8221; of the [PdCl4]2- molecules1</...

Guiding metal deposition onto plasmonic substrates via plasmonic hot carriers generated from a resonant external field could support 2-step formation of heterometallic, anisotropic nanostructures at ambient conditions with new degrees-of-freedom1,2,3. Conventional redox chemistry, vapor deposition, and/or electrodeposition approaches are ill-suited for high-volume processing. This is primarily due to excess/sacrificial reagent waste, low throughput 5+ step lithography processes, and energy intensive environments (0.01-10 Torr and/or 400-1000 &#176;C temperatures) with little or no direct control over resultant material characteristics. Immersion of a plasmonic substrate (e.g., Au nanoparticle/seed) into a precursor environment (e.g., aqueous Pd salt solution) under illumination at the localized surface plasmon resonance (SPR) initiates externally-tunable (i.e., field polarization and intensity) photochemical deposition of the precursor via plasmonic hot electrons and/or photothermal gradients3,4. For example, protocol parameters/requirements for plasmonically-driven photothermal decomposition of Au, Cu, Pb, and Ti organometallics and Ge hydrides onto nanostructured Ag and Au substrates have been detailed5,6,7,8,9. However, utilization of femtosecond plasmonic hot electrons to directly photoreduce metal salts at a metal-solution interface remains largely undeveloped, absent processes employing citrate or poly(vinylpyrrolidone) ligands acting as intermediary charge relays to direct nucleation/growth of the secondary metal2,10,11,12. Anisotropic Pt-decoration of Au nanorods (AuNR) under longitudinal SPR (LSPR) excitation was recently reported1,13 where the Pt distribution coincided with the dipole polarity (i.e., the assumed spatial distribution of hot carriers).
The protocol herein expands upon recent Pt-AuNR work to include Pd and highlights key synthesis metrics that can be observed in real-time, showing the reductive plasmonic photodeposition technique is applicable toward other metal halide salts (Ag, Ni, Ir, etc.).

<table>
	<tbody>
		<tr>
			<td>Aspheric Condenser Lens w/ Diffuser</td>
			<td>Thorlabs</td>
			<td>ACL5040U-DG15</td>
			<td>f=40 mm, NA=0.60, 1500 grit, uncoated</td>
		</tr>
		<tr>
			<td>Deuterium + Tungsten-Halogen Lightsource</td>
			<td>StellarNet</td>
			<td>SL5</td>
			<td></td>
		</tr>
		<tr>
			<td>Gold Nanorods, AuNR</td>
			<td>NanoPartz</td>
			<td>A12-40-808-CTAB</td>
			<td>CTAB surfactant, 808 nm LSPR, 40 nm diameter</td>
		</tr>
		<tr>
			<td>Ground Glass Diffuser</td>
			<td>Thorlabs</td>
			<td>DG20-1500</td>
			<td>1500 grit, N-BK7</td>
		</tr>
		<tr>
			<td>Hydrochloric acid, HCl</td>
			<td>J.T. Baker</td>
			<td>9539-03</td>
			<td>concentrated, 37%</td>
		</tr>
		<tr>
			<td>Low Profile Magnetic Stirrer</td>
			<td>VWR</td>
			<td>10153-690</td>
			<td></td>
		</tr>
		<tr>
			<td>Macro Disposable Cuvettes, UV Plastic</td>
			<td>FireFlySci</td>
			<td>1PUV</td>
			<td>10 mm path length</td>
		</tr>
		<tr>
			<td>Methanol, MeOH</td>
			<td>J.T. Baker</td>
			<td>9073-05</td>
			<td>&#8805;99.9%</td>
		</tr>
		<tr>
			<td>Palladium (II) chloride, PdCl2</td>
			<td>Sigma Aldrich</td>
			<td>520659</td>
			<td>&#8805;99.9%</td>
		</tr>
		<tr>
			<td>Plano-Convex Lens</td>
			<td>Thorlabs</td>
			<td>LA1145</td>
			<td>f=75 mm, N-BK7, uncoated</td>
		</tr>
		<tr>
			<td>Quartz Tungsten-Halogen Lamp</td>
			<td>Thorlabs</td>
			<td>QTH10</td>
			<td></td>
		</tr>
		<tr>
			<td>UV-vis Spectrometer</td>
			<td>Avantes</td>
			<td>ULS2048L-USB2-UA-RS</td>
			<td>AvaSpec-ULS2048L</td>
		</tr>
	</tbody>
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photodeposition of pd onto colloidal au nanorods by surface plasmon excitation

A protocol is described to photocatalytically guide Pd deposition onto Au nanorods (AuNR) using surface plasmon resonance (SPR). Excited plasmonic hot electrons upon SPR irradiation drive reductive deposition of Pd on colloidal AuNR in the presence of [PdCl4]2-. Plasmon-driven reduction of secondary metals potentiates covalent, sub-wavelength deposition at targeted locations coinciding with electric field &#8220;hot-spots&#8221; of the plasmonic substrate using an external field (e.g., laser). The process described herein details a solution-phase deposition of a catalytically-active noble metal (Pd) from a transition metal halide salt (H2PdCl4) onto aqueously-suspended, anisotropic plasmonic structures (AuNR). The solution-phase process is amenable to making other bimetallic architectures. Transmission UV-vis monitoring of the photochemical reaction, coupled with ex situ XPS and statistical TEM analysis, provide immediate experimental feedback to evaluate properties of the bimetallic structures as they evolve during the photocatalytic reaction. Resonant plasmon irradiation of AuNR in the presence of [PdCl4]2- creates a thin, covalently-bound Pd0 shell without any significant dampening effect on its plasmonic behavior in this representative experiment/batch. Overall, plasmonic photodeposition offers an alternative route for high-volume, economical synthesis of optoelectronic materials with sub-5 nm features (e.g., heterometallic photocatalysts or optoelectronic interconnects).

Transmission UV-vis spectra, X-ray photoelectron spectroscopy (XPS) data, and transmission electron microscopy (TEM) images were acquired for the CTAB-covered AuNR in the presence/absence of H2PdCl4 in dark and under resonant irradiation at their longitudinal SPR (LSPR) to catalyze nucleation/growth of Pd. Transmission UV-vis spectra in Figure 1 and Figure 2 provide insights into the reaction dynamics according to changes in: (a) precursor ...

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Photodeposition of Pd onto Colloidal Au Nanorods by Surface Plasmon Excitation

A protocol for anisotropic photodeposition of Pd onto aqueously-suspended Au nanorods via localized surface plasmon excitation is presented.

A protocol is described to photocatalytically guide Pd deposition onto Au nanorods (AuNR) using surface plasmon resonance (SPR). Excited plasmonic hot ...

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Chemistry

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