Abstract: Supported MnO2-based nanomaterials were fabricated on fluorine-doped tin oxide substrates by plasma enhanced-chemical vapor deposition (PE-CVD) between 100 °C and 400 °C, starting from a fluorinated Mn(II) diamine diketonate precursor. Growth experiments yielded -MnO2 nanosystems with hierarchical morphology tuneable from dendritic structures to quasi-1D nanosystems as a function of growth temperature, whose variation enabled also a concomitant tailoring of the system fluorine content, and of the optical absorption and band gap. Preliminary photocatalytic tests were aimed at the investigation of photoinduced hydrophilic (PH) and solid phase photocatalytic (PC) performances of the present nanomaterials, as well as at the photodegradation of Plasmocorinth B azo-dye aqueous solutions. The obtained findings highlighted an attractive system photoactivity even under visible light, finely tailored by fluorine content, morphological organization and optical properties of the prepared nanostructures. The results indicate that the synthesized MnO2 nanosystems have potential applications as advanced smart materials for anti-fogging/self-cleaning end uses and water purification.

Abstract: Compared with dust-free plasmas, the existence of dust particles in plasmas may greatly influence the plasma properties. such as the plasma density, electron temperature, sheath properties, electron energy distribution function (EEDF) as well as the heating mechanism. In this work, a 1D hybrid fluid/MC model has been developed to investigate the interaction between dust and plasma in a low-pressure silane discharge sustained in a radio frequency capacitively coupled plasma, in which we assume spherical dust particles with a given radius are generated by taking the sum of the production rate of Si2H4- and Si2H5- as the nucleation rate. From our simulation, the plasma may experience definite perturbation by dust particles with a certain radius (more than 50nm) with an increase in electron temperature first, which further induces a rapid rise in the positive and negative ion densities. Then, the densities begin to decline due to the gradual lack of sufficient seed electrons. In addition, as the dust radius increases, the high energy tails of the EEDFs will be enhanced for discharge maintenance, accompanied by a decline in the population of low-energy electrons in comparison with those of pristine plasma. Furthermore, an obvious bulk heating is observed apart from the a-mode and local field reversal heating. This may contribute to the enhanced bulk electric field (also called the drift field) as a result of electron depletion via the dust. In addition, large-sized dust particles that accumulate near the sheaths tend to form two stable density peaks with their positions largely influenced by the time-averaged sheath thickness. A detailed study of the effects of the external parameters, including pressure, voltage and frequency, on the spatial distribution of dust particles is also conducted.

Abstract: Two-dimensional (2D) carbon materials play an important role in nanomaterials. We propose a new carbon monolayer, named hexagonal-4,4,4-graphyne (H-4,H-4,H-4-graphyne), which is a nanoporous structure composed of rectangular carbon rings and triple bonds of carbon. Using first-principles calculations, we systematically studied the structure, stability, and band structure of this new material. We found that its total energy is lower than that of experimentally synthesized beta-graphdiyne and it is stable at least up to 1500 K. In contrast to the single Dirac point band structure of other 2D carbon monolayers, the band structure of H-4,H-4,H-4-graphyne exhibits double Dirac points along the high-symmetry points and the corresponding Fermi velocities (1.04-1.27 x 10(6) m/s) are asymmetric and higher than that of graphene. The origin of these double Dirac points is traced back to the nodal line states, which can be well explained by a tight-binding model. The H-4,H-4,H-4-graphyne forms a moire superstructure when placed on top of a hexagonal boron nitride substrate. These properties make H-4,H-4,H-4-graphyne a promising semimetal material for applications in high-speed electronic devices. (C) 2018 Elsevier Ltd. All rights reserved.

Abstract: The emergence of micropollutants into our aquatic resources is regarded as an issue of increasing environmental concern. To protect the aquatic environment against further contamination with micropollutants, treatment with advanced oxidation processes (AOPs) is put forward as a promising technique. In this work, an innovative AOP based on electrical discharges in a continuous-flow pulsed dielectric barrier discharge (DBD) reactor with falling water film over activated carbon textile is examined for its potential application in water treatment. The effect of various operational parameters including feed gas type, gas flow rate, water flow rate and power on removal and energy efficiency has been studied. To this end, a synthetic micropollutant mixture containing five pesticides (atrazine, alachlor, diuron, dichlorvos and pentachlorophenol), two pharmaceuticals (carbamazepine and 1,7-alpha-ethinylestradiol), and 1 plasticizer (bisphenol A) is used. While working under optimal conditions, energy consumption was situated in the range 2.42-4.25 kW h/m(3), which is about two times lower than the economically viable energy cost of AOPs (5 kW h/m(3)). Hence, the application of non-thermal plasma could be regarded as a promising alternative AOP for (industrial) wastewater remediation.

Abstract: BACKGROUND Simultaneous anammox and denitrification (SAD) can remove carbon and nitrogen. However, its performance is suppressed under saline surroundings. In this work, mannitol was used to enhance a SAD process treating saline wastewater. RESULTS The optimum carbon and nitrogen removal was achieved at 0.2 mmol L-1 mannitol, during which ammonium removal efficiency (ARE), nitrite removal efficiency (NRE) and chemical oxygen demand (COD) removal efficiency were 96.95%, 93.70% and 90.05%, respectively. The maximum ammonium removal rate (ARR), nitrite removal rate (NRR) and the specific anammox activity (SAA) were increased by 25.49%, 55.84% and 33.83% with optimum addition (0.2 mmol L-1 mannitol) respectively. The diameter of sludge was enlarged with the addition of mannitol (<= 0.2 mmol L-1). The Tseng-Wayman model was more suitable to simulate the whole SAD process. The modified logistic model, the modified Boltzman model and the modified Gompertz model were all appropriate to describe nitrogen removal in a typical cycle with the addition of mannitol. CONCLUSION Mannitol was effective in enhancing a SAD process treating saline wastewater, and maximum nitrogen removal was achieved at mannitol = 0.2 mmol L-1. The Tseng-Wayman model satisfactorily predicted the whole SAD process treating saline wastewater with mannitol addition. (c) 2018 Society of Chemical Industry

Abstract: We consider an interface between two strong time-reversal invariant topological insulators having surface states with opposite spin chirality, or equivalently, opposite mirror Chern number. We show that such an interface supports gapless modes that are protected by mirror symmetry. The interface states are investigated with a continuum model for the Bi2Se3 class of topological insulators that takes into account terms up to third order in the crystal momentum, which ensures that the model has the correct symmetry. The model parameters are obtained from ab initio calculations. Finally, we consider the effect of rotational mismatch at the interface, which breaks the mirror symmetry and opens a gap in the interface spectrum.

Abstract: Encompassing a broad spectrum of methodological approaches and aims, the scholars contributing to this volume offer renewed perspectives on the multifaceted oeuvre of Diego Velázquez. The seventeenth-century artist’s exceptional religious works as well as his numerous portraits are examined within the social and historical context of Velázquez’s milieu which included both the Spanish court as well as circles comprising important intellectual figures of his time. Following a close investigation of his works, which also includes the results of recent technological examinations on his paintings, the contributors to this volume offer new, exciting findings and discussions on the inspirations, sources and possible intentions of Velázquez.

Abstract: Photocatalysis has been labeled for decades as a promising technique for air purification. The principle seems straightforward and requires a photocatalyst that is immobilized on a substrate, and one or more UV sources to activate the photocatalyst. No waste products are produced, the reactions occur in mild conditions and the supplies are relatively cheap. Yet it seems that the commercialization of photocatalytic systems does not break through on the global market. The aim of this thesis is to identify and tackle the bottlenecks that impede commercialization from an application-oriented approach. The problem of indoor air pollution is enhanced by the fact that people spend more and more time indoors and that ventilation is kept to a minimum as an energy-saving measure. This inevitably leads to an accumulation of volatile organic compounds (VOCs) that are emitted by e.g. building materials, paint and furniture. Human exposure to VOCs is directly related to the sick building syndrome leading to complaints such as headache, fatigue, dizziness and lack of concentration. In addition, exposure to VOCs is related to serious long-term health effects such as cancer or respiratory diseases. Therefore, significant research efforts are focused on advanced indoor air purification methods. Integration or retrofitting of a photocatalytic (PCO) air purifying unit into heating, ventilation and air conditioning (HVAC) equipment has been chosen as an interesting approach. As a starting point of this thesis, the operational conditions of a ventilation system were mapped. These systems are characterized by high flow rates and the necessity of minimal pressure losses. Pressure losses increase the energy demand and can lead to failure of the ventilation fan and thereby undermine the proper functioning of the ventilation system. A suitable substrate must allow the contaminated air to pass through with a minimal pressure drop, allow sufficient contact time between VOC and photocatalyst, have a large surface area available for coating with excellent adhesion, and be transparent to UV light. Therefore, the permeability and the available exposed surface were selected as main selection criteria. After a thorough quantitative analysis of potential substrates, borosilicate glass tubes were selected. Glass tubes can easily be stacked to constitute a transparent monolithic multi-tube reactor, with their length parallel to the air flow in order to minimize the pressure drop. Moreover, borosilicate glass is relatively inexpensive and has excellent UV-A light transmitting properties. Based on a literature study, a sol-gel coating procedure was selected that is extremely suitable for coating glass substrates. The next step was to optimize the amount of P25 (commercial titanium dioxide) in the photocatalytic sol-gel coating for its application. More P25 in the sol-gel coating results in a higher adsorption capacity and consequently a higher photocatalytic activity, but greatly reduces the transparency of the coating. After an in-depth study, the concentration of 10 g L-1 P25 was selected as the most feasible for multi-tube reactors. Since the operation of photocatalytic reactors is based on a complex interaction of physical and chemical processes, mathematical models were developed, supported by experimental data, that include all these phenomena as a tool for reactor design and optimization. By making use of such models, time-consuming and expensive experimental research can be minimized. However, the experimental validation of models is of utmost importance to prove its reliability and accuracy. Intrinsic kinetic parameters provide the fundamentals for these models as they describe the photocatalytic reaction rate, independent of fluid dynamics, reactor geometry and radiation field. In this work they were estimated by means of a Computational Fluid Dynamics (CFD) study, based on FTIR (Fourier-transform infrared spectroscopy) experiments with a lab scale multi-tube reactor. The kinetic parameters were validated by an alternative analytic approach, emphasizing the accuracy and reliability of the simulations. Finally, the aforementioned CFD approach, based on the simultaneously modelling of airflow, mass transfer, UV light irradiation and photocatalytic reactions, was used to obtain insights for the light source configuration in upscaled multi-tube reactors. After taking all these insights and some practical implications into account, a final upscaled multi-tube reactor design was proposed and converted into a first built prototype. Subsequently, it was evaluated according the CEN-EN-16486-1 standard for VOC removal by the external scientific research center ‘CERTECH’. The scientific results, regarding the mineralization of the VOCs and photocatalytic efficiency of the reactor, demonstrated the feasibility for indoor air purification by the upscaled multi-tube reactor and the possible implementation in ventilation systems.

Abstract: abstract not available

Abstract: The present PhD research investigated the possibility of catalytic detoxification of poplar wood based and steam exploded lignocellulosic hydrolyzate with different types of laccase enzymes, with special focus on ethanol and lactic acid products at industrially relevant parameters: high final product concentration, high initial substrate loading and integrated processes. The simultaneous saccharification and fermentation (SSF) process was taken as a base case and five types of laccases were thoroughly investigated on their utilization potential. Phenolic removal from the liquid xylose rich fraction (XRF) was higher with fungal laccases (65-90 %) compared to approximately 30 % removal with bacterial laccase. Moreover, the optimal pH of fungal laccases was close to pH 4.5, the optimum for cellulase, while the bacterial laccase worked at basic pH. Integrating laccase treatment and hydrolysis together showed that fungal laccases have negative impact on final sugar concentration, while bacterial laccase had a strong positive effect. Although bacterial laccase removed less phenol and although its optimal conditions are difficult to integrate with hydrolysis, its enhancing effect on cellulase activity makes it a better candidate for application. The presence of the solid fraction (SF) alters the phenolic concentration evolution significantly, thus screening experiments with the liquid fraction alone do not provide sufficient information for the combined process. Magnetic Cross-Linked Enzyme Aggregates (m-CLEAs) immobilization was assessed for bacterial laccase. m-CLEAs decreased phenolic concentration faster at every pH compared to free bacterial laccase; however, the removal was caused by adsorption rather than by enzyme activity. Although the size of m-CLEAs particles are in the µm range, around 90 % of the initial catalyst mass was recycled from a dense (15 % substrate loading) mixture via magnetic separation. The high recycling rate is promising; m-CLEAs immobilization method can have industrial utilization potential. Minimum sugar revenue (MSR) estimations show that currently hardwood based MSR is 70 % more expensive than corn grain based MSR. About 7-10 fold cellulase activity increase will be needed until MSR will be competitive with corn grain MSR. However, m-CLEAs cellulase can already be competitive if the corn prices are in the higher regime of last year’s prices.