Examining Silver Deposition Pathways onto Gold Nanorods with Liquid-Phase Transmission Electron Microscopy

Liquid-phase transmission electron microscopy (LP-TEM) enables one to directly visualize the formation of plasmonic nanoparticles and their postsynthetic modification, but the relative contributions of plasmonic hot electrons and radiolysis to metal precursor reduction remain unclear. Here we show silver deposition onto plasmonic gold nanorods (AuNRs) during LP-TEM is dominated by water radiolysis-induced chemical reduction. Silver was observed with LP-TEM to form bipyramidal shells at higher surfactant coverage and tip-preferential lobes at lower surfactant coverage. Ex situ silver photodeposition formed nanometer-thick shells on AuNRs with preferential deposition in inter-rod gaps, while chemical reduction deposited silver at AuNR tips at low surfactant coverage and formed pyramidal shells at higher surfactant coverage, consistent with LP-TEM. Silver deposition locations during LP-TEM were inconsistent with simulated near-field enhancement and hot electron generation hot spots. Collectively, the results indicate chemical reduction dominated during LP-TEM, indicating observation of plasmonic hot electron-induced photoreduction will necessitate suppression of radiolysis

Examining Silver Deposition Pathways onto Gold Nanorods with Liquid-Phase Transmission Electron Microscopy

Liquid-phase transmission electron microscopy (LP-TEM) enables one to directly visualize the formation of plasmonic nanoparticles and their postsynthetic modification, but the relative contributions of plasmonic hot electrons and radiolysis to metal precursor reduction remain unclear. Here we show silver deposition onto plasmonic gold nanorods (AuNRs) during LP-TEM is dominated by water radiolysis-induced chemical reduction. Silver was observed with LP-TEM to form bipyramidal shells at higher surfactant coverage and tip-preferential lobes at lower surfactant coverage. Ex situ silver photodeposition formed nanometer-thick shells on AuNRs with preferential deposition in inter-rod gaps, while chemical reduction deposited silver at AuNR tips at low surfactant coverage and formed pyramidal shells at higher surfactant coverage, consistent with LP-TEM. Silver deposition locations during LP-TEM were inconsistent with simulated near-field enhancement and hot electron generation hot spots. Collectively, the results indicate chemical reduction dominated during LP-TEM, indicating observation of plasmonic hot electron-induced photoreduction will necessitate suppression of radiolysis

Examining Silver Deposition Pathways onto Gold Nanorods with Liquid-Phase Transmission Electron Microscopy

Liquid-phase transmission electron microscopy (LP-TEM) enables one to directly visualize the formation of plasmonic nanoparticles and their postsynthetic modification, but the relative contributions of plasmonic hot electrons and radiolysis to metal precursor reduction remain unclear. Here we show silver deposition onto plasmonic gold nanorods (AuNRs) during LP-TEM is dominated by water radiolysis-induced chemical reduction. Silver was observed with LP-TEM to form bipyramidal shells at higher surfactant coverage and tip-preferential lobes at lower surfactant coverage. Ex situ silver photodeposition formed nanometer-thick shells on AuNRs with preferential deposition in inter-rod gaps, while chemical reduction deposited silver at AuNR tips at low surfactant coverage and formed pyramidal shells at higher surfactant coverage, consistent with LP-TEM. Silver deposition locations during LP-TEM were inconsistent with simulated near-field enhancement and hot electron generation hot spots. Collectively, the results indicate chemical reduction dominated during LP-TEM, indicating observation of plasmonic hot electron-induced photoreduction will necessitate suppression of radiolysis

Examining Silver Deposition Pathways onto Gold Nanorods with Liquid-Phase Transmission Electron Microscopy

Liquid-phase transmission electron microscopy (LP-TEM) enables one to directly visualize the formation of plasmonic nanoparticles and their postsynthetic modification, but the relative contributions of plasmonic hot electrons and radiolysis to metal precursor reduction remain unclear. Here we show silver deposition onto plasmonic gold nanorods (AuNRs) during LP-TEM is dominated by water radiolysis-induced chemical reduction. Silver was observed with LP-TEM to form bipyramidal shells at higher surfactant coverage and tip-preferential lobes at lower surfactant coverage. Ex situ silver photodeposition formed nanometer-thick shells on AuNRs with preferential deposition in inter-rod gaps, while chemical reduction deposited silver at AuNR tips at low surfactant coverage and formed pyramidal shells at higher surfactant coverage, consistent with LP-TEM. Silver deposition locations during LP-TEM were inconsistent with simulated near-field enhancement and hot electron generation hot spots. Collectively, the results indicate chemical reduction dominated during LP-TEM, indicating observation of plasmonic hot electron-induced photoreduction will necessitate suppression of radiolysis

Examining Silver Deposition Pathways onto Gold Nanorods with Liquid-Phase Transmission Electron Microscopy

Liquid-phase transmission electron microscopy (LP-TEM) enables one to directly visualize the formation of plasmonic nanoparticles and their postsynthetic modification, but the relative contributions of plasmonic hot electrons and radiolysis to metal precursor reduction remain unclear. Here we show silver deposition onto plasmonic gold nanorods (AuNRs) during LP-TEM is dominated by water radiolysis-induced chemical reduction. Silver was observed with LP-TEM to form bipyramidal shells at higher surfactant coverage and tip-preferential lobes at lower surfactant coverage. Ex situ silver photodeposition formed nanometer-thick shells on AuNRs with preferential deposition in inter-rod gaps, while chemical reduction deposited silver at AuNR tips at low surfactant coverage and formed pyramidal shells at higher surfactant coverage, consistent with LP-TEM. Silver deposition locations during LP-TEM were inconsistent with simulated near-field enhancement and hot electron generation hot spots. Collectively, the results indicate chemical reduction dominated during LP-TEM, indicating observation of plasmonic hot electron-induced photoreduction will necessitate suppression of radiolysis

Examining Silver Deposition Pathways onto Gold Nanorods with Liquid-Phase Transmission Electron Microscopy

Liquid-phase transmission electron microscopy (LP-TEM) enables one to directly visualize the formation of plasmonic nanoparticles and their postsynthetic modification, but the relative contributions of plasmonic hot electrons and radiolysis to metal precursor reduction remain unclear. Here we show silver deposition onto plasmonic gold nanorods (AuNRs) during LP-TEM is dominated by water radiolysis-induced chemical reduction. Silver was observed with LP-TEM to form bipyramidal shells at higher surfactant coverage and tip-preferential lobes at lower surfactant coverage. Ex situ silver photodeposition formed nanometer-thick shells on AuNRs with preferential deposition in inter-rod gaps, while chemical reduction deposited silver at AuNR tips at low surfactant coverage and formed pyramidal shells at higher surfactant coverage, consistent with LP-TEM. Silver deposition locations during LP-TEM were inconsistent with simulated near-field enhancement and hot electron generation hot spots. Collectively, the results indicate chemical reduction dominated during LP-TEM, indicating observation of plasmonic hot electron-induced photoreduction will necessitate suppression of radiolysis

Examining Silver Deposition Pathways onto Gold Nanorods with Liquid-Phase Transmission Electron Microscopy

Liquid-phase transmission electron microscopy (LP-TEM) enables one to directly visualize the formation of plasmonic nanoparticles and their postsynthetic modification, but the relative contributions of plasmonic hot electrons and radiolysis to metal precursor reduction remain unclear. Here we show silver deposition onto plasmonic gold nanorods (AuNRs) during LP-TEM is dominated by water radiolysis-induced chemical reduction. Silver was observed with LP-TEM to form bipyramidal shells at higher surfactant coverage and tip-preferential lobes at lower surfactant coverage. Ex situ silver photodeposition formed nanometer-thick shells on AuNRs with preferential deposition in inter-rod gaps, while chemical reduction deposited silver at AuNR tips at low surfactant coverage and formed pyramidal shells at higher surfactant coverage, consistent with LP-TEM. Silver deposition locations during LP-TEM were inconsistent with simulated near-field enhancement and hot electron generation hot spots. Collectively, the results indicate chemical reduction dominated during LP-TEM, indicating observation of plasmonic hot electron-induced photoreduction will necessitate suppression of radiolysis

Surface- and Structural-Dependent Reactivity of Titanium Oxide Nanostructures with 2‑Chloroethyl Ethyl Sulfide under Ambient Conditions

Robust materials capable of heterogeneous reactivity are valuable for addressing toxic chemical clean up. Synthetic manipulations for generating titanium oxide nanomaterials have been utilized to alter both photochemical (1000 nm > λ > 400 nm) and chemical heterogeneous reactivity with 2-chloroethyl ethyl sulfide (2-CEES). Synthesizing TiO2 nanomaterials in the presence of long-chain alkylphosphonic acids enhanced the visible light-driven oxidation of the thioether sulfur of 2-CEES. Photooxidation reaction rates of 99 and 168 μmol/g/h (quantum yields of 5.07 × 10–4 and 8.58 × 10–4 molecules/photon, respectively) were observed for samples made with two different alkylphosphonic acids (C14H29PO3H2 and C9H19PO3H2, respectively). These observations are correlated with (i) generation of new surface defects/states (i.e., oxygen vacancies) as a result of TiO2 grafting by alkylphosphonic acid that may serve as reaction active sites, (ii) better light absorption by assemblies of nanorods and nanowires in comparison to individual nanorods, (iii) surface area differences, and (iv) the exclusion of OH groups due to the surface functionalization with alkylphosphonic acids via Ti–O–P bonds on the TiO2. Alternatively, nanowire-form H2Ti2O5·H2O was produced and found to be capable of highly efficient hydrolysis of the carbon–chlorine (C–Cl) bond of 2-CEES in the dark with a reaction rate of 279.2 μmol/g/h due to the high surface area and chemical nature of the titanate structure