Exploring the Chemical Enhancement of Surface-Enhanced Raman Scattering with a Designed Silver/Silica Cavity Substrate

Silver nanoparticles were assembled onto the bottom of closed-packed silica cavity using polystyrene (PS) spheres as template. Charge transfer between the adsorbed 4-aminothiophenol (PATP) and the silver nanoparticles was studied using surface-enhanced Raman spectroscopy with 514, 633, 785, and 1064 nm excitation, and compared to that of the immobilized silver nanoparticles without the modification of silica cavity. Using the concept of degree of charge transfer, we directly observed the additional chemical enhancement without a deliberate distinction between electromagnetic (EM) enhancement and chemical enhancement. It was demonstrated that the negative charges of the silica could induce the formation of the dipole in the nanoparticles, thus enlarging the electron density at the sites where probe molecules adsorbed, and leading to higher charge transfer from the metal to the adsorbed PATP molecules. We also proposed another model to further elucidate the relationship between the electron density and the charge transfer. The result showed that the reduction of the electron density of silver nanoparticles will cause the redistribution of the dipole, thereby reducing the charge transfer degree

Nanoparticle-Mediated, Light-Induced Phase Separations

Nanoparticles that both absorb and scatter light, when dispersed in a liquid, absorb optical energy and heat a reduced fluid volume due to the combination of multiple scattering and optical absorption. This can induce a localized liquid–vapor phase change within the reduced volume without the requirement of heating the entire fluid. For binary liquid mixtures, this process results in vaporization of the more volatile component of the mixture. When subsequently condensed, these two steps of vaporization and condensation constitute a distillation process mediated by nanoparticles and driven by optical illumination. Because it does not require the heating of a large volume of fluid, this process requires substantially less energy than traditional distillation using thermal sources. We investigated nanoparticle-mediated, light-induced distillation of ethanol-H₂O and 1-propanol-H₂O mixtures, using Au–SiO₂ nanoshells as the absorber-scatterer nanoparticle and nanoparticle-resonant laser irradiation to drive the process. For ethanol-H₂O mixtures, the mole fraction of ethanol obtained in the light-induced process is substantially higher than that obtained by conventional thermal distillation, essentially removing the ethanol-H₂O azeotrope that limits conventional distillation. In contrast, for 1-propanol-H₂O mixtures the distillate properties resulting from light-induced distillation were very similar to those obtained by thermal distillation. In the 1-propanol-H₂O system, a nanoparticle-mediated, light-induced liquid–liquid phase separation was also observed

Surfactant-Assisted Synthesis of Fe₂O₃ Nanoparticles and F‑Doped Carbon Modification toward an Improved Fe₃O₄@CF_<i>x</i>/LiNi_0.5Mn_1.5O₄ Battery

A simple surfactant-assisted reflux method was used in this study for the synthesis of cocklebur-shaped Fe₂O₃ nanoparticles (NPs). With this strategy, a series of nanostructured Fe₂O₃ NPs with a size distribution ranging from 20 to 120 nm and a tunable surface area were readily controlled by varying reflux temperature and the type of surfactant. Surfactants such as cetyltrimethylammonium bromide (CTAB), polyvinylpyrrolidone (PVP), poly­(ethylene glycol)-<i>block</i>-poly­(propylene glycol)-<i>block</i>-poly­(ethylene glycol) (F127) and sodium dodecyl benzenesulfonate (SDBS) were used to achieve large-scale synthesis of uniform Fe₂O₃ NPs with a relatively low cost. A new composite of Fe₃O₄@CF_<i>x</i> was prepared by coating the primary Fe₂O₃ NPs with a layer of F-doped carbon (CF_<i>x</i>) with a one-step carbonization process. The Fe₃O₄@CF_<i>x</i> composite was utilized as the anode in a lithium ion battery and exhibited a high reversible capacity of 900 mAh g^–1 at a current density of 100 mA g^–1 over 100 cycles with 95% capacity retention. In addition, a new Fe₃O₄@CF_<i>x</i>/LiNi_0.5Mn_1.5O₄ battery with a high energy density of 371 Wh kg^–1 (vs cathode) was successfully assembled, and more than 300 cycles were easily completed with 66.8% capacity retention at 100 mA g^–1. Even cycled at the high temperature of 45 °C, this full cell also exhibited a relatively high capacity of 91.6 mAh g^–1 (vs cathode) at 100 mA g^–1 and retained 54.6% of its reversible capacity over 50 cycles. Introducing CF_<i>x</i> chemicals to modify metal oxide anodes and/or any other cathode is of great interest for advanced energy storage and conversion devices

Aluminum Nanocrystals: A Sustainable Substrate for Quantitative SERS-Based DNA Detection

Since its discovery in the 1970s, surface-enhanced Raman scattering (SERS) has been primarily associated with substrates composed of nanostructured noble metals. Here we investigate chemically synthesized nanocrystal aggregates of aluminum, an inexpensive, highly abundant, and sustainable metal, as SERS substrates. Al nanocrystal aggregates are capable of substantial near-infrared SERS enhancements, similar to Au nanoparticles. The intrinsic nanoscale surface oxide of Al nanocrystals supports molecule–substrate interactions that differ dramatically from noble metal substrates. The preferential affinity of the single-stranded DNA (ssDNA) phosphate backbone for the Al oxide surface preserves both the spectral features and nucleic acid cross sections relative to conventional Raman spectroscopy, enabling quantitative ssDNA detection and analysis

Combining Solar Steam Processing and Solar Distillation for Fully Off-Grid Production of Cellulosic Bioethanol

Conventional bioethanol for transportation fuel typically consumes agricultural feedstocks also suitable for human consumption and requires large amounts of energy for conversion of feedstock to fuel. Alternative feedstocks, optimally those not also in demand for human consumption, and off-grid energy sources for processing would both contribute to making bioethanol far more sustainable than current practices. Cellulosic bioethanol production involves three steps: the extraction of sugars from cellulosic feedstock, the fermentation of sugars to produce ethanol, and the purification of ethanol through distillation. Traditional production methods for extraction and distillation are energy intensive and therefore costly, limiting the advancement of this approach. Here we report an initial demonstration of the conversion of cellulosic feedstock into ethanol by completely off-grid solar processing steps. Our approach is based on nanoparticle-enabled solar steam generation, in which high-efficiency steam can be produced by illuminating light-absorbing nanoparticles dispersed in H₂O with sunlight. We used solar-generated steam to successfully hydrolyze feedstock into sugars; we then used solar steam-distillation to purify ethanol in the final processing step. Coastal hay, a grass grown for livestock feed across the southern United States, and sugar cane as a control are successfully converted to ethanol in this proof-of-concept study. This entirely off-grid solar production method has the potential to realize the long-dreamed-of goal of sustainable cellulosic bioethanol production

Aluminum Nanocrystals as a Plasmonic Photocatalyst for Hydrogen Dissociation

Hydrogen dissociation is a critical step in many hydrogenation reactions central to industrial chemical production and pollutant removal. This step typically utilizes the favorable band structure of precious metal catalysts like platinum and palladium to achieve high efficiency under mild conditions. Here we demonstrate that aluminum nanocrystals (Al NCs), when illuminated, can be used as a photocatalyst for hydrogen dissociation at room temperature and atmospheric pressure, despite the high activation barrier toward hydrogen adsorption and dissociation. We show that hot electron transfer from Al NCs to the antibonding orbitals of hydrogen molecules facilitates their dissociation. Hot electrons generated from surface plasmon decay and from direct photoexcitation of the interband transitions of Al both contribute to this process. Our results pave the way for the use of aluminum, an earth-abundant, nonprecious metal, for photocatalysis