Nanostructured Systems for Electrocatalysis of Reduction Reactions for Energy Conversion Applications

Oxygen Reduction Reaction (ORR) requires a platinum-based catalyst to reduce the activation barrier. One of the most promising materials as alternative catalysts are carbon-based, graphene and carbon nanotubes (CNT) derivatives. ORR on a carbon-based substrate involves the less efficient two electrons process and the optimal four electrons process. New synthetic strategies to produce tunable graphene-based materials utilizing graphene oxide (GO) as a base inspired the first part of this work. Hydrogen Evolution Reaction (HER) is a slow process requiring also platinum or palladium as catalyst. In the second part of this work, we develop and use a technique for Ni nanoparticles electrodeposition using NiCl2 as precursor in the presence of ascorbate ligands. Electrodeposition of nano-nickel onto flat glassy carbon (GC) and onto nitrogen-doped reduced graphene oxide (rGO-N) substrates are studied. State of the art catalysts for CO2RR requires rare metals rhenium or rhodium. In recent years significant research has been done on non-noble metals and molecular systems to use as electro and photo-catalysts (artificial photosynthesis). As Cu-Zn alloys show good CO2RR performance, here we applied the same nanoparticle electrosynthesis technique using as precursors CuCl2 and Cl2Zn and observed successful formation of the nanoparticles and a notable activity in presence of CO2. Using rhenium complexes as catalysts is another popular approach and di-nuclear complexes have a positive cooperative effect. More recently a growing family of pre-catalysts based on the earth-abundant metal manganese, has emerged as a promising, cheaper alternative. Here we study the cooperative effects of di-nuclear manganese complexes derivatives when used as homogeneous electrocatalysts, as well as a rhenium functionalized polymer used as heterogeneous electrocatalyst.

Electrochemical surface modification of Single walled carbon nanotubes and graphene-based electrodes for (bio)sensing applications

Sensors are devices that have shown widespread use, from the detection of gas molecules to the tracking of chemical signals in biological cells. Single walled carbon nanotube (SWCNT) and graphene based electrodes have demonstrated to be an excellent material for the development of electrochemical biosensors as they display remarkable electronic properties and the ability to act as individual nanoelectrodes, display an excellent low-dimensional charge carrier transport, and promote surface electrocatalysis. The present work aims at the preparation and investigation of electrochemically modified SWCNT and graphene-based electrodes for applications in the field of biosensors. We initially studied SWCNT films and focused on their topography and surface composition, electrical and optical properties. Parallel to SWCNTs, graphene films were investigated. Higher resistance values were obtained in comparison with nanotubes films. The electrochemical surface modification of both electrodes was investigated following two routes (i) the electrografting of aryl diazonium salts, and (ii) the electrophylic addition of 1, 3-benzodithiolylium tetrafluoroborate (BDYT). Both the qualitative and quantitative characteristics of the modified electrode surfaces were studied such as the degree of functionalization and their surface composition. The combination of Raman, X-ray photoelectron spectroscopy, atomic force microscopy, electrochemistry and other techniques, has demonstrated that selected precursors could be covalently anchored to the nanotubes and graphene-based electrode surfaces through novel carbon-carbon formation.

Nanocarbon-Supported Electrocatalysts for the Alkaline Water Splitting and Fuel Cells

Electrocatalysts play a significant role in the processes of electrochemical energy conversion. This thesis focuses on the preparation of carbon-supported nanomaterials and their application as electrocatalysts for alkaline water electrocatalysis and fuel cell. A general synthetic route was developed, i.e., species intercalate into carbon layers of graphite forming graphite intercalation compound, followed by dispersion producing graphenide solution, which then as reduction agent reacts with different metal sources generating the final materials. The first metal precursor used was non-noble metal iron salt, which generated iron (oxide) nanoparticles finely dispersed on carbon layers in the final composite materials. Meanwhile, graphite starting materials differing in carbon layer size were utilized, which would diversify corresponding graphenide solutions, and further produce various nanomaterials. The characterization results showed that iron (oxide) nanoparticles varying in size were obtained, and the size was determined by the starting graphite material. It was found that they were electrocatalytically active for oxygen reactions. In particular, the one with small iron (oxide) nanoparticles showed excellent electrocatalytic activity for both oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). Afterwards, the metal precursor was tuned from non-noble metal salt to noble metal salt. It was confirmed that carbon-supported Rh, Pt, and RhPt (oxide) nanoparticle composite materials were also successfully obtained from the reaction between graphenide solution and corresponding noble metal precursor. The electrochemical measurements showed that the prepared noble metal-based nanomaterials were quite effective for hydrogen evolution reaction (HER) electrocatalysis, and the Rh sample could also display excellent electrocatalytic property towards OER. Moreover, by this synthetic approach carbon-supported noble metal Pt and non-noble metal nickel (Ni) composite material was also prepared. Therefore, the utilization efficiency of noble metal could be improved. The prepared NiPt sample displayed a property close to benchmark HER electrocatalyst.

Crystal engineering of co-crystals and host-guest systems for environmentally friendly applications: sunscreens stabilization, pollutant sequestering and herbicide reformulation.

Solid state engineered materials have proven to be useful and suitable tools in the quest of new materials. In this thesis different crystalline compounds were synthesized to provide more sustainable products for different applications, as in cosmetics or in agrochemistry, to propose pollutants removal strategy or to obtain materials for electrocatalysis. Therefore, the research projects presented here can be divided into three main topics: (i) sustainable preparation of solid materials of widely used active ingredients aimed at the reduction of their occurrence in the natural environment. The systems studied in this section are cyclodextrins host-guest compounds, obtained via mechanochemical and slurry synthesis. The first chemicals studied are sunscreens inclusion complexes, that proved to have enhanced photostability and desired photoprotection. The same synthetic methods were applied to obtain inclusion complexes of bentazon, a herbicide often found to leach in groundwaters. The resulting products showed to have desired water solubility properties. The same herbicide was also adsorbed on amorphous calcium phosphate nanoparticles, to obtain a biocompatible formulation of this agrochemical. This herbicide could benefit by the adsorption on nanoparticles for what concerns its kinetic release in different media as well as its photostability. (ii) Sustainable synthesis of co-crystals based on polycyclic aromatic hydrocarbons, for the proposal of a sequestering method with a resulting material with enhanced properties. The co-crystallization via mechanochemical means proved that these pollutants can be sequestered via simple solvent-free synthesis and the obtained materials present better photochemical properties when compared to the starting co-formers. (iii) Crystallization from mild solvents of nanosized materials useful for the application in electrocatalysis. The study of compounds based on nickel and cobalt metal ions resulted in the obtainment of 2D and 1D coordination polymers. Moreover, solid solutions were obtained. These crystals showed layered structures and, according to preliminary results, they can be exfoliated.