Triple Play of Band Gap, Interband, and Plasmonic Excitations for Enhanced Catalytic Activity in Pd/HxMoO3 Nanoparticles in the Visible Region.

Plasmonic photocatalysis has been limited by the high cost and scalability of plasmonic materials, such as Ag and Au. By focusing on earth-abundant photocatalyst/plasmonic materials (HxMoO3) and Pd as a catalyst, we addressed these challenges by developing a solventless mechanochemical synthesis of Pd/HxMoO3 and optimizing photocatalytic activities in the visible range. We investigated the effect of HxMoO3 band gap excitation (at 427 nm), Pd interband transitions (at 427 nm), and HxMoO3 localized surface plasmon resonance (LSPR) excitation (at 640 nm) over photocatalytic activities toward the hydrogen evolution and phenylacetylene hydrogenation as model reactions. Although both excitation wavelengths led to comparable photoenhancements, a 110% increase was achieved under dual excitation conditions (427 + 640 nm). This was assigned to a synergistic effect of optical excitations that optimized the generation of energetic electrons at the catalytic sites. These results are important for the development of visible-light photocatalysts based on earth-abundant components.

Preparation of polymer gold nanoparticle composites with tunable plasmon coupling and their application as SERS substrates.

The controlled surface functionalisation of polystyrene beads (200 nm) with a lipoic acid derivative is used to assemble composites with between 4 to 20% loadings of citrate stabilised gold nanoparticles (13 nm-30 nm), which exhibit variable optical properties arising from interactions of the nanoparticle surface plasmon resonance (SPR). The decrease in average interparticle distance at higher loadings results in a red-shift in the SPR wavelength, which is well described by a universal ruler equation. The composite particles are shown to act as good SERS substrates for the standard analyte 4-mercaptophenol. The direct assessment of the SERS activity for individual composite particles solution is achieved by Raman optical tweezer measurements on 5.3 µm composite particles. These measurements show an increase in performance with increasing AuNP size. Importantly, the SERS activity of the individual particles compares well with the bulk measurements of samples deposited on a surface, indicating that the SERS activity arises primarily from the composite and not due to composite-composite interactions. In both studies the optimum SERS response is obtained with 30 nm AuNPs.

The UCD nanosafety workshop (03 December 2018): towards developing a consensus on safe handling of nanomaterials within the Irish university labs and beyond - a report.

Careful handling of the nanomaterials (NMs) in research labs is crucial to ensure a safe working environment. As the largest university in Ireland, University College Dublin (UCD) has invested significant resources to update researchers working with NMs. Due to sizes often <100 nm, the NMs including nanoparticles, harbor unprecedented materialistic properties, for example, enhanced reactivity, conductivity, fluorescence, etc. which albeit conferring the NMs an edge over bulk materials regarding the applied aspects; depending on the dose, also render them to be toxic. Thus, a set of regulatory guidelines have emerged regarding safe handling of the NMs within occupational set-ups. Unfortunately, the current regulations based on the toxic chemicals and carcinogens are often confusing, lack clarity, and difficult to apply for the NMs. As a research-intensive university, a diverse range of research activities occur within the UCD labs, and it is difficult, at times impossible, for the UCD Safety, Insurance, Operational Risk & Compliance (SIRC) office to develop a set of common guidelines and cater throughout all its labs conducting research with the NMs. Hence, a necessity for dialog and exchange of ideas was felt across the UCD which encouraged the researchers including early stage researchers (e.g. PhDs, Postdocs) from multiple schools to participate in a workshop held on the 03 December 2018. The workshop tried to follow a pragmatic approach, where apart from discussing both the in vitro and in vivo scenarios, practical cases simulating situations faced frequently in the labs were discussed. This report summarizes the findings made during the workshop by this emerging critical mass in UCD.

Template-Assisted Synthesis of Luminescent Carbon Nanofibers from Beverage-Related Precursors by Microwave Heating.

Luminescent carbon nanomaterials are important materials for sensing, imaging, and display technologies. This work describes the use of microwave heating for the template-assisted preparation of luminescent carbon nanofibers (CNFs) from the reaction of a range of beverage-related precursors with the nitrogen-rich polyethyleneimine. Highly luminescent robust carbon fibers that were 10 to 30 m in length and had a diameter of 200 nm were obtained under moderate conditions of temperature (250-260 °C) and a short reaction time (6 min). The high aspect ratio fibers showed wavelength-dependent emission that can be readily imaged using epifluorescence. The development of these multi-emissive one-dimensional (1D) carbon nanomaterials offers potential for a range of applications.

Templated microwave synthesis of luminescent carbon nanofibers.

Carbon based nanomaterials offer the potential to provide solutions to key technological challenges. This work describes the preparation of luminescent carbon nanofibers by template-assisted microwave pyrolysis of environmentally friendly precursors, citric acid and polyethyleneimine, in aqueous solution. SEM reveals a dense forest of vertically aligned cylindrical carbon nanofibers with an average diameter of ca. 200 nm, which are shown by TEM to be amorphous. Compositional analysis indicated the incorporation of amino and pyrrolic nitrogen, and carbon-oxygen moieties. These species contribute to UV light absorption with an absorption shoulder and tail towards visible wavelengths. UV excitation gave visible (blue) emission at ca. 450 nm with a quantum yield of ca. 5%; emission decay under pulsed excitation was predominantly mono-exponential with a lifetime of ca. 1 ns. The emission maximum is largely excitation wavelength independent suggesting the involvement of citrazinic acid-type functionalities in the fiber photophysics. Reversible pH-dependent excitation and emission behaviour was observed, with maximum emission at ca. pH 7. Nanofiber emission was also quenched in aqueous solutions of metal cations, in a concentration-dependent manner. Single nanofiber emission intensity was quite stable under continuous excitation permitting single fiber quenching-based metal ion detection whereby a significant (>90%) and prompt (sub-10 s) quenching was observed upon exposure to sub-millimolar Fe(iii) solutions. The introduction of these new 1D luminescent carbon nanofibers offers the potential for exciting developments across a range of applications.

Multifunctional and robust composite materials comprising gold nanoparticles at a spherical polystyrene particle surface.

The preparation of a family of composite particles comprising gold nanoparticles (AuNP) assembled at a polystyrene (PS) surface is reported. Tunable loading is demonstrated for AuNP sizes (4.5-26 nm). The robust composites are stable to multiple centrifugation and dispersion cycles and to conditions of high ionic strength, physiological buffer and cell culture media. These properties provide potential for a variety of applications from cellular studies to catalysis.