experimental-methods-for-efficient-solar-hydrogen-production

Experimental Methods for Efficient Solar Hydrogen Production in Microgravity Environment

Long-term space flights and cis-lunar research platforms require a sustainable and light life-support hardware which can be reliably employed outside the ...

Freie Universitat Berlin

South China Normal University

Nanoribbon plasmonic gratings and their anomalous interaction with electromagnetic waves.

Terbium fluoride nanocrystals, covered by a shell, composed of cerium fluoride were synthesized by a co-precipitation method. Their complex structure was formed spontaneously during the synthesis. The surface of these core/shell nanocrystals was additionally modified by silica. The properties of TbF@CeF and TbF@CeF@SiO nanocrystals, formed in this way, were investigated. Spectroscopic studies showed that the differences between these two groups of products resulted from the presence of the SiO shell. X-ray diffraction patterns confirmed the trigonal crystal structure of TbF@CeF nanocrystals. High resolution transmission electron microscopy in connection with energy-dispersive X-ray spectroscopy showed a complex structure of the formed nanocrystals. Crystallized as small discs, 'the products', with an average diameter around 10 nm, showed an increase in the concentration of Tb ions from surface to the core of nanocrystals. In addition to photo-physical analyses, cytotoxicity studies were performed on HSkMEC (Human Skin Microvascular Endothelial Cells) and B16F0 mouse melanoma cancer cells. The cytotoxicity of the nanomaterials was neutral for the investigated cells with no toxic or antiproliferative effect in the cell cultures, either for normal or for cancer cells. This fact makes the obtained nanocrystals good candidates for biological applications and further modifications of the SiO shell.

Structural, spectroscopic and cytotoxicity studies of TbF@CeF and TbF@CeF@SiO nanocrystals.

Anisotropic deformation of polystyrene particles in an oxygenated (O2/Ar) plasma is observed for radio frequency (rf) plasma and inductively coupled plasma (ICP). A facile model based on a ratio of completely isotropic and completely anisotropic etching is presented to describe the anisotropy of the etching process and is implemented to determine the height of the spheroid-shaped polystyrene particles. In our systems, we find the plasma etching to be 54% isotropic in the rf plasma and 79% isotropic in the ICP. With this model, the maximum material deposition thickness for nanofabrication with plasma-etched nanosphere lithography or colloid lithography can be predicted. Moreover, the etching of polystyrene particles in an oxygenated plasma is investigated versus the etching time, gas flow, gas composition, temperature, substrate material, and particle size. The results of this study allow precise shape tuning during the fabrication of nanostructured surfaces with size-dependent properties for bionic, medical, and photonic applications. 

Understanding anisotropic plasma etching of two-dimensional polystyrene opals for advanced materials fabrication.

The luminescent GdVO4:Eu(3+)5%@SiO2@NH2 core@shell nanomaterials were obtained via co-precipitation method, followed by hydrolysis and co-condensation of silane derivatives: tetraethyl orthosilicate and 3-aminopropyltriethoxysilane. Their effect on human erythrocytes sedimentation and on proliferation of human lung microvascular endothelial cells was examined and discussed. The luminescent nanoparticles were synthesized in the presence of polyacrylic acid or glycerin in order to minimalize the agglomeration and excessive growth of nanostructures. Surface coating with amine functionalized silica shell improved their biocompatibility, facilitated further organic conjugation and protected the internal core. Magnetic measurements revealed an enhanced T1-relaxivity for the synthesized GdVO4:Eu(3+)5% nanostructures. Structure, morphology and average grain size of the obtained nanomaterials were determined by X-ray diffraction, transmission electron microscopy and dynamic light scattering analysis. The qualitative elemental composition of the nanomaterials was established using energy-dispersive X-ray spectroscopy. The spectroscopic characteristic of red emitting core@shell nanophosphors was completed by measuring luminescence spectra and decays. The emission spectra revealed characteristic bands of Eu(3+) ions related to the transitions (5)D0-(7)F0,1,2,3,4 and (5)D1-(7)F1. The luminescence lifetimes consisted of two components, associated with the presence of Eu(3+) ions located at the surface of the crystallites and in the bulk. 

Spectroscopic, structural and in vitro cytotoxicity evaluation of luminescent, lanthanide doped core@shell nanomaterials GdVO4:Eu(3+)5%@SiO2@NH2.

An ideal network window electrode for photovoltaic applications should provide an optimal surface coverage, a uniform current density into and/or from a substrate, and a minimum of the overall resistance for a given shading ratio. Here we show that metallic networks with quasi-fractal structure provides a near-perfect practical realization of such an ideal electrode. We find that a leaf venation network, which possesses key characteristics of the optimal structure, indeed outperforms other networks. We further show that elements of hierarchal topology, rather than details of the branching geometry, are of primary importance in optimizing the networks, and demonstrate this experimentally on five model artificial hierarchical networks of varied levels of complexity. In addition to these structural effects, networks containing nanowires are shown to acquire transparency exceeding the geometric constraint due to the plasmonic refraction.

Optimization of hierarchical structure and nanoscale-enabled plasmonic refraction for window electrodes in photovoltaics.

Bacterial biofilms cause a considerable amount of prosthetic joint infections every year, resulting in morbidity and expensive revision surgery. To address this problem, surface modifications of implant materials such as carbon nanotube (CNT) coatings have been investigated in the past years. CNTs are biologically compatible and can be utilized as drug delivery systems. In this study, multi-walled carbon nanotube (MWCNT) coated TiAl6V4 titanium alloy discs were fabricated and impregnated with Rifampicin, and tested for their ability to prevent biofilm formation over a period of ten days. Agar plate-based assays were employed to assess the antimicrobial activity of these surfaces against Staphylococcus epidermidis. It was shown that vertically aligned MWCNTs were more stable against attrition on rough surfaces than on polished TiAl6V4 surfaces. Discs with coated surfaces caused a significant inhibition of biofilm formation for up to five days. Therefore, MWCNT-modified surfaces may be effective against pathogenic biofilm formation on endoprostheses.

Long-term release of antibiotics by carbon nanotube-coated titanium alloy surfaces diminish biofilm formation by Staphylococcus epidermidis.

Long-term space missions require extra-terrestrial production of storable, renewable energy. Hydrogen is ascribed a crucial role for transportation, electrical power and oxygen generation. We demonstrate in a series of drop tower experiments that efficient direct hydrogen production can be realized photoelectrochemically in microgravity environment, providing an alternative route to existing life support technologies for space travel. The photoelectrochemical cell consists of an integrated catalyst-functionalized semiconductor system that generates hydrogen with current densities >15 mA/cm in the absence of buoyancy. Conditions are described adverting the resulting formation of ion transport blocking froth layers on the photoelectrodes. The current limiting factors were overcome by controlling the micro- and nanotopography of the Rh electrocatalyst using shadow nanosphere lithography. The behaviour of the applied system in terrestrial and microgravity environment is simulated using a kinetic transport model. Differences observed for varied catalyst topography are elucidated, enabling future photoelectrode designs for use in reduced gravity environments.

Efficient solar hydrogen generation in microgravity environment.

Topography is a key factor that governs important properties of surfaces, such as adhesion and wettability, and materials with switchable surface topographies will have switchable surface properties. We demonstrate a principle to generate electrically switchable surface topographies on the surface of a thin nematic liquid crystal elastomer film which is sandwiched between a continuous electrode and a random metal network. Voltage-controlled displacement of the metal network toward the continuous electrode is achieved, resulting in unprecedented topographical modulations in the range of 0-2.5 μm. We show that this depth variation is significantly larger than the expected deformation because of electrostatic attraction between the network and the continuous electrode. This effect is explained by deformation due to the rotation of the liquid crystal side groups along the electric field lines.

Nanoid Canyons On-Demand: Electrically Switchable Surface Topography in Liquid Crystal Networks.

Core-virus like particles (VLPs) assembly is a kinetically complex cascade of interactions between viral proteins, nanoparticle's surface and an ionic environment. Despite many in silico simulations regarding this process, there is still a lack of experimental data. The main goal of this study was to investigate the capsid protein of hepatitis B virus (HBc) assembly into virus-like particles with superparamagnetic iron oxide nanoparticles (SPIONs) as a magnetic core in relation to their characteristics. The native form of HBc was obtained via agroinfection of  with pEAQ-HBc plasmid. SPIONs of diameter of 15 nm were synthesized and functionalized with two ligands, providing variety in ζ-potential and hydrodynamic diameter. The antigenic potential of the assembled core-VLPs was assessed with enzyme-linked immunosorbent assay (ELISA). Morphology of SPIONs and core-VLPs was evaluated via transmission electron microscopy (TEM). The most successful core-VLPs assembly was obtained for SPIONs functionalized with dihexadecyl phosphate (DHP) at SPIONs/HBc ratio of 0.2/0.05 mg/mL. ELISA results indicate significant decrease of antigenicity concomitant with core-VLPs assembly. In summary, this study provides an experimental assessment of the crucial parameters guiding SPION-HBc VLPs assembly and evaluates the antigenicity of the obtained structures.

Assembly and Characterization of HBc Derived Virus-like Particles with Magnetic Core.

The Eu and Sr ions co-doped hydroxyapatite nanopowders (Ca(PO)(OH)) were synthesized via a precipitation method and post heat-treated at 500 °C. The concentration of Eu ions was established in the range of 0.5-5 mol% to investigate the site occupancy preference. The concentration of Sr ions was set at 5 mol%. The structural and morphological properties of the obtained materials were studied by an X-ray powder diffraction, a transmission electron microscopy techniques and infrared spectroscopy. As synthesized nanoparticles were in the range of 11-17 nm and annealed particles were in the range of 20-26 nm. The luminescence properties in dependence of the dopant concentration and applied temperature were investigated. The D → F transition shown the abnormally strong intensity for annealed materials connected with the increase of covalency character of Eu-O bond, which arise as an effect of charge compensation mechanism. The Eu ions occupied three possible crystallographic sites in these materials revealed in emission spectra: one Ca(1) site with C symmetry and two Ca(2) sites with C symmetry arranged as cis and trans symmetry. The antibacterial properties of Eu and Sr ions doped and co-doped hydroxyapatite nanopowders were also determined against Gram-negative pathogens such as Pseudomonas aeruginosa, Klebsiella pneumoniae and Escherichia coli. Obtained results suggest that both europium and strontium ions may implement antibacterial properties for hydroxyapatites. In the most cases, better antibacterial effect we noticed for dopants at 5 mol% ratio. However, the effect is strongly species- and strain-dependent feature.

Article	Year
Nanoribbon plasmonic gratings and their anomalous interaction with electromagnetic waves. Advanced materials (Deerfield Beach, Fla.)\| PubMed ID: 22581718	2012
Structural, spectroscopic and cytotoxicity studies of TbF@CeF and TbF@CeF@SiO nanocrystals. Journal of nanoparticle research : an interdisciplinary forum for nanoscale science and technology\| PubMed ID: 24273438	2013
Understanding anisotropic plasma etching of two-dimensional polystyrene opals for advanced materials fabrication. Langmuir : the ACS journal of surfaces and colloids\| PubMed ID: 24580644	2014
Spectroscopic, structural and in vitro cytotoxicity evaluation of luminescent, lanthanide doped core@shell nanomaterials GdVO4:Eu(3+)5%@SiO2@NH2. Journal of colloid and interface science\| PubMed ID: 27478979	2016
Optimization of hierarchical structure and nanoscale-enabled plasmonic refraction for window electrodes in photovoltaics. Nature communications\| PubMed ID: 27667099	2016
Long-term release of antibiotics by carbon nanotube-coated titanium alloy surfaces diminish biofilm formation by Staphylococcus epidermidis. Nanomedicine : nanotechnology, biology, and medicine\| PubMed ID: 28115247	2017
Efficient solar hydrogen generation in microgravity environment. Nature communications\| PubMed ID: 29991728	2018
Nanoid Canyons On-Demand: Electrically Switchable Surface Topography in Liquid Crystal Networks. ACS applied materials & interfaces\| PubMed ID: 30280570	2018
Assembly and Characterization of HBc Derived Virus-like Particles with Magnetic Core. Nanomaterials (Basel, Switzerland)\| PubMed ID: 30691173	2019
Structural modification of nanohydroxyapatite Ca(PO)(OH) related to Eu and Sr ions doping and its spectroscopic and antimicrobial properties. Journal of inorganic biochemistry\| PubMed ID: 31683129	2019

Michael Giersig

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