Laser-based analytical techniques in cultural heritage science - Tutorial review.

This tutorial review combines the fundamentals of the design and operation of lasers with their usage in applications related to conservation and cultural heritage (CH) science - as components of analytical devices for the study of the chemical composition of materials. The development of laser instruments and their fundamental physical background, including a short explanation of their properties and parameters, are briefly summarised, and an overview of different laser-based analytical techniques is given. The analytical techniques covered in this tutorial are divided into three groups based on their technical aspects and properties: (1) vibrational spectroscopy, (2) elemental analysis, and (3) different molecular mass spectrometric techniques.

Iron, Cobalt, and Nickel Phthalocyanine Tri-Doped Electrospun Carbon Nanofibre-Based Catalyst for Rechargeable Zinc-Air Battery Air Electrode.

The goal of achieving the large-scale production of zero-emission vehicles by 2035 will create high expectations for electric vehicle (EV) development and availability. Currently, a major problem is the lack of suitable batteries and battery materials in large quantities. The rechargeable zinc-air battery (RZAB) is a promising energy-storage technology for EVs due to the environmental friendliness and low production cost. Herein, iron, cobalt, and nickel phthalocyanine tri-doped electrospun carbon nanofibre-based (FeCoNi-CNF) catalyst material is presented as an affordable and promising alternative to Pt-group metal (PGM)-based catalyst. The FeCoNi-CNF-coated glassy carbon electrode showed an oxygen reduction reaction/oxygen evolution reaction reversibility of 0.89 V in 0.1 M KOH solution. In RZAB, the maximum discharge power density (Pmax) of 120 mW cm-2 was obtained with FeCoNi-CNF, which is 86% of the Pmax measured with the PGM-based catalyst. Furthermore, during the RZAB charge-discharge cycling, the FeCoNi-CNF air electrode was found to be superior to the commercial PGM electrocatalyst in terms of operational durability and at least two times higher total life-time.

Bifunctional Oxygen Electrocatalysis on Mixed Metal Phthalocyanine-Modified Carbon Nanotubes Prepared via Pyrolysis.

Non-precious-metal catalysts are promising alternatives for Pt-based cathode materials in low-temperature fuel cells, which is of great environmental importance. Here, we have investigated the bifunctional electrocatalytic activity toward the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER) of mixed metal (FeNi; FeMn; FeCo) phthalocyanine-modified multiwalled carbon nanotubes (MWCNTs) prepared by a simple pyrolysis method. Among the bimetallic catalysts containing nitrogen derived from corresponding metal phthalocyanines, we report the excellent ORR activity of FeCoN-MWCNT and FeMnN-MWCNT catalysts with the ORR onset potential of 0.93 V and FeNiN-MWCNT catalyst for the OER having EOER = 1.58 V at 10 mA cm-2. The surface morphology, structure, and elemental composition of the prepared catalysts were examined with scanning electron microscopy, X-ray diffraction, and X-ray photoelectron spectroscopy. The FeCoN-MWCNT and FeMnN-MWCNT catalysts were prepared as cathodes and tested in anion-exchange membrane fuel cells (AEMFCs). Both catalysts displayed remarkable AEMFC performance with a peak power density as high as 692 mW cm-2 for FeCoN-MWCNT.

Enhanced oxygen reduction reaction activity and durability of Pt nanoparticles deposited on graphene-coated alumina nanofibres.

The oxygen reduction reaction (ORR) activity and stability of Pt catalysts deposited on graphene-coated alumina nanofibres (GCNFs) were investigated. The GCNFs were fabricated by catalyst-free chemical vapour deposition. Pt nanoparticles (NPs) were deposited on the nanofibres by sonoelectrochemical and plasma-assisted synthesis methods. Scanning and transmission electron microscopy analyses revealed different surface morphologies of the prepared Pt catalysts, depending on the synthesis procedure. Sonoelectrochemical deposition resulted in a uniform distribution of smaller Pt NPs on the support surface, while plasma-assisted synthesis, along with well-dispersed smaller Pt NPs, led to particle agglomeration at certain nucleation sites. Further details about the surface features were obtained from cyclic voltammetry and CO stripping experiments in 0.1 M HClO4 solution. Rotating disk electrode investigations revealed that the Pt/GCNF catalyst is more active towards the ORR in acid media than the commercial Pt/C (20 wt%). The prepared catalyst also showed significantly higher durability than commercial Pt/C, with no change in the half-wave potential after 10 000 potential cycles.

Oxygen reduction reaction on Pd nanocatalysts prepared by plasma-assisted synthesis on different carbon nanomaterials.

In this work He/H2 plasma jet treatment was used to reduce Pd ions in the aqueous solution with simultaneous deposition of created Pd nanoparticles to support materials. Graphene oxide (GO) and nitrogen-doped graphene oxide (NrGO) were both co-reduced with the Pd ions to formulate catalyst materials. Pd catalyst was also deposited on the surface of carbon black. The prepared catalyst materials were physically characterized using transmission electron microscopy, scanning electron microscopy and x-ray photoelectron spectroscopy. The plasma jet method yielded good dispersion of small Pd particles with average sizes of particles being: Pd/rGO 2.9 ± 0.6 nm, Pd/NrGO 2.3 ± 0.5 nm and Pd/Vulcan 2.8 ± 0.6 nm. The electrochemical oxygen reduction reaction (ORR) kinetics was explored using the rotating disk electrode method. Pd catalyst deposited on nitrogen-doped graphene material showed slightly improved ORR activity as compared to that on the nondoped substrate, however Vulcan carbon-supported Pd catalyst exhibited a higher specific activity for oxygen electroreduction.

Transition metal-containing nitrogen-doped nanocarbon catalysts derived from 5-methylresorcinol for anion exchange membrane fuel cell application.

Highly active electrocatalysts for electrochemical oxygen reduction reaction (ORR) were prepared by high-temperature pyrolysis from 5-methylresorcinol, Co and/or Fe salts and dicyandiamide, which acts simultaneously as a precursor for reactive carbonitride template and a nitrogen source. The electrocatalytic activity of the catalysts for ORR in alkaline solution was studied using the rotating disc electrode (RDE) method. The bimetallic catalyst containing iron and cobalt (FeCoNC-at) showed excellent stability and remarkable ORR performance, comparable to that of commercial Pt/C (20 wt%). The superior activity was attributed to high surface metal and nitrogen contents. The FeCoNC-at catalyst was further tested in anion exchange membrane fuel cell (AEMFC) with poly-(hexamethyl-p-terphenylbenzimidazolium) (HMT-PMBI) membrane, where a high value of peak power density (Pmax = 415 mW cm-2) was achieved.

Stabilizer-free silver nanoparticles as efficient catalysts for electrochemical reduction of oxygen.

In this work we demonstrated the potential of the He+5% H2+1% N2 plasma jet treatment for the synthesis of surfactant-free silver nanoparticles (Ag NPs) with narrow size distribution. The obtained colloidal solutions of electrostatically stabilized Ag NPs do not show any agglomeration for several months. Apart from an atomic thin oxide layer and the relatively weakly bound OH- ions, the surface of Ag NPs can be considered as stabilizer-free. The surface charge (characterized by the zeta potential) of Ag NPs in solution was measured by electrophoretic light scattering technique. Plasmonic band position and width in the UV/VIS extinction spectra was utilized for the assessment of Ag NPs size distribution. Highly concentrated Ag NPs were uniformly deposited on the surface of the glassy carbon (GC) electrodes by vacuum-drying technique. The deposition process was monitored with a digital camera attached to a microscope. The assemblies of Ag NPs on the electrode surface were characterized by scanning electron microscopy. The Ag NP/GC catalysts were electrochemically tested in alkaline solution using the rotating disk electrode method. The Ag NP/GC electrodes exhibited high electrocatalytic activity toward the oxygen reduction reaction (ORR) in 0.1M KOH solution, indicating their potential applicability as cathode materials for alkaline fuel cells.