The hydrogen evolution reaction (HER) is a key process in electrochemical water splitting. To lower the cost and environmental impact of this process, it is highly motivated to develop electrocatalysts with low or no content of noble metals. Here, we report on an ingenious synthesis of hybrid PtxNi1-x electrocatalysts in the form of a nanoparticle-nanonetwork structure with very low noble metal content. The structure possesses important features such as good electrical conductivity, high surface area, strong interlinking, and substrate adhesion, which render an excellent HER activity. Specifically, the best performing Pt0.05Ni0.95 sample demonstrates a Tafel slope of 30 mV dec-1 in 0.5 M H2SO4 and an overpotential of 20 mV at a current density of 10 mA cm-2 with high stability. The impressive catalytic performance is further rationalized in a theoretical study, which provides insight into the mechanism on how such small platinum content can allow for close-to-optimal adsorption energies for hydrogen.

Photoelectrochemical (PEC) water-splitting offers a promising method to convert the intermittent solar energy into renewable and storable chemical energy. However, the most studied semiconductors generally exhibit a poor PEC performance including low photocurrent, small photovoltage, and/or large onset potential. In this work, we demonstrate a significant enhancement of photovoltage and photocurrent together with a substantial decrease of onset potential by introducing electrocatalytic and p-type NiO nanoclusters on an n-type cubic silicon carbide (3C-SiC) photoanode. Under AM1.5G 100 mW cm(-2) illumination, the NiO-coated 3C-SiC photoanode exhibits a photocurrent density of 1.01 mA cm(-2) at 0.55 V versus reversible hydrogen electrode (V-RHE), a very low onset potential of 0.20 V-RHE and a high fill factor of 57% for PEC water splitting. Moreover, the 3C-SiC/NiO photoanode shows a high photovoltage of 1.0 V, which is the highest value among reported photovoltages. The faradaic efficiency measurements demonstrate that NiO also protects the 3C-SiC surface against photo-corrosion. The impedance measurements evidence that the 3C-SiC/NiO photoanode facilitates the charge transfer for water oxidation. The valence-band position measurements confirm the formation of the 3C-SiC/NiO p-n heterojunction, which promotes the separation of the photogenerated carriers and reduces carrier recombination, thus resulting in enhanced solar water-splitting.

Gases, such as nitrogen dioxide, formaldehyde and benzene, are toxic even at very low concentrations. However, so far there are no low-cost sensors available with sufficiently low detection limits and desired response times, which are able to detect them in the ranges relevant for air quality control. In this work, we address both, detection of small gas amounts and fast response times, using epitaxially grown graphene decorated with iron oxide nanoparticles. This hybrid surface is used as a sensing layer to detect formaldehyde and benzene at concentrations of relevance (low parts per billion). The performance enhancement was additionally validated using density functional theory calculations to see the effect of decoration on binding energies between the gas molecules and the sensor surface. Moreover, the time constants can be drastically reduced using a derivative sensor signal readout, allowing the sensor to work at detection limits and sampling rates desired for air quality monitoring applications.

Anisotropic heterogenous Ni/NiO nanoparticles with controlled compositions are grown using a high-power pulsed hollow cathode process. These novel particles can be tuned to consist of single-phase Ni via two-phase Ni/NiO to fully oxidized NiO, with a size range of 5-25 nm for individual crystals. A novelty of this approach is the ability to assemble multiple particles of Ni and NiO into a single complex structure, increasing the Ni-NiO interface density. This type of particle growth is not seen before and is explained to be due to the fact that the process operates in a single-step approach, where both Ni and O can arrive at the formed nanoparticle nuclei and aid in the continuous particle growth. The finished particle will then be a consequence of the initially formed crystal, as well as the arrival rate ratio of the two species. These particles hold great potential for applications in fields, such as electro- and photocatalysis, where the ability to control the level of oxidation and/or interface density is of great importance.

Magnetic nanoparticles with average size 30 nm were utilized to build three-dimensional framework structures—nanotrusses. In dual-phase Ni/NiO nanoparticles, there is a strong correlation between the amount of magnetic Ni and the final size and shape of the nanotruss. As it decreases, the length of the individual nanowires within the trusses also decreases, caused by a higher degree of branching of the wires. The position and orientation of the non-magnetic material within the truss structure was also investigated for the different phase compositions. For lower concentrations of NiO phase, the electrically conducting Ni-wire framework is maintained through the preferential bonding between the Ni crystals. For larger concentrations of NiO phase, the Ni-wire framework is interrupted by the NiO. The ability to use nanoparticles that are only partly oxidized in the growth of nanotruss structures is of great importance. It opens the possibility for using not only magnetic metals such as pure Ni, Fe, and Co, but also to use dual-phase nanoparticles that can strongly increase the efficiency of e.g. catalytic electrodes and fuel cells.

Nanomaterials are important tools for enabling technological progress as they can provide dramatically different properties as compared to the bulk counterparts. The field of nanoparticles is one of the most investigated within nanomaterials, thanks to the existing, relatively simple, means of manufacturing. In this thesis, high-power pulsed hollow cathode sputtering is used to nucleate and grow magnetic nanoparticles in a plasma. This sputtering technique provides a high degree of ionization of the sputtered material, which has previously been shown to aid in the growth of the nanoparticles. The magnetic properties of the particles are utilized and makes it possible for the grown particles to act as building blocks for self-assembly into more sophisticated nano structures, particularly when an external magnetic field is applied. These structures created are termed “nanowires” or “nanotrusses”, depending on the level of branching and inter-linking that occurs.

Several different elements have been investigated in this thesis. In a novel approach, it is shown how nanoparticles with more advanced structures, and containing material from two hollow cathodes, can be fabricated using high-power pulses. The dual-element particles are achieved by using two distinct and individual elemental cathodes, and a pulse process that allows tuning of individual pulses separately to them. Nanoparticles grown and investigated are Fe, Ni, Pt, Fe-Ni and Ni-Pt. Alternatively, the addition of oxygen to the process allows the formation of oxide or hybrid metal oxide – metal particles. For all nanoparticles containing several elements, it is demonstrated that the stoichiometry can be easily varied, either by the amount of reactive gas let into the process or by tuning the amount of sputtered material through adjusting the electric power supplied to the different cathodes.

One aim of the presented work is to find a suitable material for the use as a catalyst in the production of H₂ gas through the process of water splitting. H₂ is a good candidate to replace fossil fuels as an energy carrier. However, rare elements (such as Ir or Pt) needs to be used as the catalyst, otherwise a high overpotential is required for the splitting to occur, leading to a low efficiency. This work demonstrates a possible route to avoid this, by using nanomaterials to increase the surface-to-volume ratio, as well as optimizing the elemental ratio between different materials to lower the amount of noble elements required. 

Tunable nanostructures that feature a high surface area are firmly attached to a conducting substrate and can be fabricated efficiently over significant areas, which are of interest for a wide variety of applications in, for instance, energy storage and catalysis. We present a novel approach to fabricate Fe nanoparticles using a pulsed-plasma process and their subsequent guidance and self-organization into well-defined nanostructures on a substrate of choice by the use of an external magnetic field. A systematic analysis and study of the growth procedure demonstrate that nondesired nanoparticle agglomeration in the plasma phase is hindered by electrostatic repulsion, that a polydisperse nanoparticle distribution is a consequence of the magnetic collection, and that the formation of highly networked nanotruss structures is a direct result of the polydisperse nanoparticle distribution. The nanoparticles in the nanotruss are strongly connected, and their outer surfaces are covered with a 2 nm layer of iron oxide. A 10 mu m thick nanotruss structure was grown on a lightweight, flexible and conducting carbon-paper substrate, which enabled the efficient production of H-2 gas from water splitting at a low overpotential of 210 mV and at a current density of 10 mA/cm(2).

In this study, we investigated means of performance enhancement in sensors based on epitaxial graphene on silicon carbide (SiC). Epitaxially grown graphene on SiC substrates were successfully decorated with metal oxide nanoparticles such as TiO2 and Fe3O4 using hollow cathode pulsed plasma sputtering. Atomic Force Microscopy and Raman data verified that no damage was added to the graphene surface. It could be shown that it was easily possible to detect benzene, which is one of the most dangerous volatile organic compounds, with the Fe3O4 decorated graphene sensor down to an ultra-low concentration of 5 ppb with a signal to noise ratio of 35 dB. Moreover, upon illumination with a UV light LED (265 nm) of the TiO2 decorated graphene sensor, the sensitivity towards a change of oxygen could be enhanced such that a clear sensor response could be seen which is a significant improvement over dark conditions, where almost no response occurred. As the last enhancement, the time derivative sensor signal was introduced for the sensor data evaluation, testing the response towards a change of oxygen. This sensor signal evaluation approach can be used to decrease the response time of the sensor by at least one order of magnitude. (C) 2018 Elsevier Ltd. All rights reserved.

Two-dimensional materials offer a unique platform for sensing where extremely high sensitivity is a priority, since even minimal chemical interaction causes noticeable changes inelectrical conductivity, which can be used for the sensor readout. However, the sensitivity has to becomplemented with selectivity, and, for many applications, improved response- and recovery times are needed. This has been addressed, for example, by combining graphene (for sensitivity) with metal/oxides (for selectivity) nanoparticles (NP). On the other hand, functionalization or modification of the graphene often results in poor reproducibility. In this study, we investigate thegas sensing performance of epitaxial graphene on SiC (EG/SiC) decorated with nanostructured metallic layers as well as metal-oxide nanoparticles deposited using scalable thin-film depositiontechniques, like hollow-cathode pulsed plasma sputtering. Under the right modification conditions the electronic properties of the surface remain those of graphene, while the surface chemistry can betuned to improve sensitivity, selectivity and speed of response to several gases relevant for airquality monitoring and control, such as nitrogen dioxide, benzene, and formaldehyde.