Song-Bo Li

Synthesis, Characterization, and 3D-FDTD Simulation of Ag@SiO2 Nanoparticles for Shell-Isolated Nanoparticle-Enhanced Raman Spectroscopy

Au-seed Ag-growth nanoparticles of controllable diameter (50-100 nm), and having an ultrathin SiO(2) shell of controllable thickness (2-3 nm), were prepared for shell-isolated nanoparticle-enhanced Raman spectroscopy (SHINERS). Their morphological, optical, and material properties were characterized; and their potential for use as a versatile Raman signal amplifier was investigated experimentally using pyridine as a probe molecule and theoretically by the three-dimensional finite-difference time-domain (3D-FDTD) method. We show that a SiO(2) shell as thin as 2 nm can be synthesized pinhole-free on the Ag surface of a nanoparticle, which then becomes the core. The dielectric SiO(2) shell serves to isolate the Raman-signal enhancing core and prevent it from interfering with the system under study. The SiO(2) shell also hinders oxidation of the Ag surface and nanoparticle aggregation. It significantly improves the stability and reproducibility of surface-enhanced Raman scattering (SERS) signal intensity, which is essential for SERS applications. Our 3D-FDTD simulations show that Ag-core SHINERS nanoparticles yield at least 2 orders of magnitude greater enhancement than Au-core ones when excited with green light on a smooth Ag surface, and thus add to the versatility of our SHINERS method.

Synthesis and Characterization of Gold Nanoparticles Coated with Ultrathin and Chemically Inert Dielectric Shells for SHINERS Applications

We very recently reported a new spectroscopic application for expanding the versatility of surface Raman called “shell-isolated nanoparticle-enhanced Raman spectroscopy” or “SHINERS”. The most important and most difficult part of the SHINERS experiment is the effective transfer of the strong electromagnetic field from a gold core through the isolating silica or alumina shell to the probed surface. For this it is essential that the chemically inert dielectric shell be ultrathin (2–5 nm) yet pinhole-free. Herein we describe experimental and theoretical aspects of our SHINERS method in more detail. We provide a protocol for the synthesis and characterization of optimized shell-isolated nanoparticles (SHINs), and we examine the advantages of SHINERS nanoparticles over bare gold nanoparticles. We also present high-quality Raman spectra obtained from gold and platinum single-crystal surfaces in an electrochemical environment by our SHINERS technique. SHINERS is a simple and cost-effective approach that expands the flexibility of surface-enhanced Raman scattering (SERS) for an unprecedented diversity of applications in materials and surface sciences.

Electrochemical shell-isolated nanoparticle-enhanced Raman spectroscopy: correlating structural information and adsorption processes of pyridine at the Au(hkl) single crystal/solution interface.

Electrochemical methods are combined with shell-isolated nanoparticle-enhanced Raman spectroscopy (EC-SHINERS) for a comprehensive study of pyridine adsorption on Au(111), Au(100) and Au(110) single crystal electrode surfaces. The effects of crystallographic orientation, pyridine concentration, and applied potential are elucidated, and the formation of a second pyridine adlayer on Au(111) is observed spectroscopically for the first time. Electrochemical and SHINERS results correlate extremely well throughout this study, and we demonstrate the potential of EC-SHINERS for thorough characterization of processes occurring on single crystal surfaces. Our method is expected to open up many new possibilities in surface science, electrochemistry and catalysis. Analytical figures of merit are discussed.

Quantitative SHINERS analysis of temporal changes in the passive layer at a gold electrode surface in a thiosulfate solution.

Shell-isolated gold nanoparticles (SHINs) were employed to record shell-isolated nanoparticle-enhanced Raman spectra (SHINERS) of a passive layer formed at a gold surface during gold leaching from thiosulfate solutions. The (3-aminopropyl)triethoxysilane (APTES) and a sodium silicate solution were used to coat gold nanoparticles with a protective silica layer. This protective silica layer prevented interactions between the thiosulfate electrolyte and the gold core of the SHINs when the SHINs-modified gold electrode was immersed into the thiosulfate lixiviant. The SHINERS spectra of the passive layer, formed from thiosulfate decomposition, contained bands indicative of hydrolyzed APTES. We have demonstrated how to exploit the presence of these APTES bands as an internal standard to compensate for fluctuations of the surface enhancement of the electric field of the photon. We have also developed a procedure that allows for removal of the interfering APTES bands from the SHINERS spectra. These methodological advancements have enabled us to identify the species forming the passive layer and to determine that the formation of elemental sulfur, cyclo-S8, and polymeric sulfur chains is responsible for inhibition of gold dissolution in oxygen rich thiosulfate solutions.

Direct Spectroscopic Detection and EPR Investigation of a Ground State Triplet Phenyl Oxenium Ion.

Oxenium ions are important reactive intermediates in synthetic chemistry and enzymology, but little is known of the reactivity, lifetimes, spectroscopic signatures, and electronic configurations of these unstable species. Recent advances have allowed these short-lived ions to be directly detected in solution from laser flash photolysis of suitable photochemical precursors, but all of the studies to date have focused on aryloxenium ions having closed-shell singlet ground state configurations. To study alternative spin configurations, we synthesized a photoprecursor to the m-dimethylamino phenyloxenium ion, which is predicted by both density functional theory and MRMP2 computations to have a triplet ground state electronic configuration. A combination of femtosecond and nanosecond transient absorption spectroscopy, nanosecond time-resolved Resonance Raman spectroscopy (ns-TR(3)), cryogenic matrix EPR spectroscopy, computational analysis, and photoproduct studies allowed us to trace essentially the complete arc of the photophysics and photochemistry of this photoprecursor and permitted a first look at a triplet oxenium ion. Ultraviolet photoexcitation of this precursor populates higher singlet excited states, which after internal conversion to S1 over 800 fs are followed by bond heterolysis in ∼1 ps, generating a hot closed-shell singlet oxenium ion that undergoes vibrational cooling in ∼50 ps followed by intersystem crossing in ∼300 ps to generate the triplet ground state oxenium ion. In contrast to the rapid trapping of singlet phenyloxenium ions by nucleophiles seen in prior studies, the triplet oxenium ion reacts via sequential H atom abstractions on the microsecond time domain to ultimately yield the reduced m-dimethylaminophenol as the only detectable stable photoproduct. Band assignments were made by comparisons to computed spectra of candidate intermediates and comparisons to related known species. The triplet oxenium ion was also detected in the ns-TR(3) experiments, permitting a more clear assignment and identifying the triplet state as the π,π* triplet configuration. The triplet ground state of this ion was further supported by photolysis of the photoprecursor in an ethanol glass at ∼4 K and observing a triplet species by cryogenic EPR spectroscopy.

Investigation of the Role of Protonation of Benzophenone and Its Derivatives in Acidic Aqueous Solutions Using Time-Resolved Resonance Raman Spectroscopy: How Are Ketyl Radicals Formed in Aqueous Solutions?

The formation mechanism of ketyl radicals and several other selective photoreactions of benzophenone and its derivatives are initiated by the protonation of their triplet state and have been investigated using nanosecond time-resolved resonance Raman spectroscopy (ns-TR(3)) in solutions of varying conditions. Evidence is found that the ketyl radical is generated by the combined action of a ketone protonation and a subsequent electron transfer based on the results from previous studies on the photochemistry and photophysics of benzophenone and the ns-TR(3) results reported here for benzophenone, 1,4-dibenzoylbenzene, 3-(hydroxymethyl)benzophenone, and ketoprofen in neutral and acidic solution. In order to better understand the role of the protonated ketone, results are summarized for some selective photochemical reactions of benzophenone and its derivatives induced by protonation in acidic solutions. For the parent benzophenone, the protonation of the ketone leads to the photohydration reactions at the ortho- and meta-positions of the benzene ring in acidic aqueous solutions. For 3-(hydroxymethyl)benzophenone, the protonation promotes an interesting photoredox reaction to become very efficient and the predominant reaction in a pH = 2 aqueous solution. While for ketoprofen, the protonation can initiate a solvent-mediated excited-state intramolecular proton transfer (ESIPT) from the carboxyl group to the carbonyl group that then leads to a decarboxylation reaction in a pH = 0 acidic aqueous solution. We briefly discuss the key role of the protonation of the ketone in the photochemistry of these aromatic ketones.