Nano-Sized Copper (Oxide) on Alumina Granules for Water Filtration: Effect of Copper Oxidation State on Virus Removal Performance.

Virus removal can be successfully achieved based on an electrostatic adsorption mechanism. The key requirement for this process is to develop filter materials that can be produced by low-cost technologies and are suitable in large-scale production for real applications. In this study, we report development of spray-dried alumina granules modified with copper (oxide) nanoparticles and critically assess the effect of copper oxidation state on virus removal capacity. Using plate-shaped alumina as a support material resulted in porous structure, which in turn ensured prolonged contact time of contaminated water with the material. Subsequently, copper (oxide) nanoparticles provided a large number of adsorption sites. Flow experiments revealed that copper(I) oxide and metallic copper were the active phases in virus removal and 99.9% of MS2 bacteriophages could be removed. However, almost no virus removal was observed in the presence of copper(II) oxide. Contrasting virus removal characteristics are associated with the different surface charge of copper species, as determined by zeta potential measurements.

Functional Role of Fe-Doping in Co-Based Perovskite Oxide Catalysts for Oxygen Evolution Reaction.

Perovskite oxides have been at the forefront among catalysts for the oxygen evolution reaction (OER) in alkaline media offering a higher degree of freedom in cation arrangement. Several highly OER active Co-based perovskites have been known to show extraordinary activities and stabilities when the B-site is partially occupied by Fe. At the current stage, the role of Fe in enhancing the OER activity and stability is still unclear. In order to elucidate the roles of Co and Fe in the OER mechanism of cubic perovskites, two prospective perovskite oxides, La0.2Sr0.8Co1- xFe xO3-δ and Ba0.5Sr0.5Co1- xFe xO3-δ with x = 0 and 0.2, were prepared by flame spray synthesis as nanoparticles. This study highlights the importance of Fe in order to achieve high OER activity and stability by drawing relations between their physicochemical and electrochemical properties. Ex situ and operando X-ray absorption spectroscopy (XAS) was used to study the local electronic and geometric structure under oxygen evolving conditions. In parallel, density function theory computational studies were conducted to provide theoretical insights into our findings. Our findings show that the incorporation of Fe into Co-based perovskite oxides alters intrinsic properties rendering efficient OER activity and prolonged stability.

Draw-spun, photonically annealed Ag fibers as alternative electrodes for flexible CIGS solar cells.

We explore the feasibility of Ag fiber meshes as electron transport layer for high-efficiency flexible Cu(In,Ga)Se2 (CIGS) solar cells. Woven meshes of Ag fibers after UV illumination and millisecond flash-lamp treatment results in a sheet resistance of 17 Ω/sq and a visible transmittance above 85%. Conductive Ag meshes are integrated into flexible CIGS cells as transparent conductive electrode (TCE) alone or together with layers of Al-doped ZnO (AZO) with various thickness of 0…900 nm. The Ag mesh alone is not able to function as a current collector. If used together with a thin AZO layer (50 nm), the Ag mesh markedly improves the fill factor and cell efficiency, in spite of the adverse mesh shadowing. When Ag mesh is combined with thicker (200 nm or 900 nm) AZO layers, no improvements in photovoltaic parameters are obtained. When comparing a hybrid TCE consisting of 50 nm AZO and Ag fiber mesh with a thick 900 nm reference AZO device, an improved charge carrier collection in the near-infrared range is observed. Regardless of the AZO thickness, the presence of Ag mesh slows down cell degradation upon mechanical tensile stress, which could be interesting for implementation into flexible thin film CIGS modules.

Dynamic surface self-reconstruction is the key of highly active perovskite nano-electrocatalysts for water splitting.

The growing need to store increasing amounts of renewable energy has recently triggered substantial R&D efforts towards efficient and stable water electrolysis technologies. The oxygen evolution reaction (OER) occurring at the electrolyser anode is central to the development of a clean, reliable and emission-free hydrogen economy. The development of robust and highly active anode materials for OER is therefore a great challenge and has been the main focus of research. Among potential candidates, perovskites have emerged as promising OER electrocatalysts. In this study, by combining a scalable cutting-edge synthesis method with time-resolved X-ray absorption spectroscopy measurements, we were able to capture the dynamic local electronic and geometric structure during realistic operando conditions for highly active OER perovskite nanocatalysts. Ba0.5Sr0.5Co0.8Fe0.2O3-δ as nano-powder displays unique features that allow a dynamic self-reconstruction of the material's surface during OER, that is, the growth of a self-assembled metal oxy(hydroxide) active layer. Therefore, besides showing outstanding performance at both the laboratory and industrial scale, we provide a fundamental understanding of the operando OER mechanism for highly active perovskite catalysts. This understanding significantly differs from design principles based on ex situ characterization techniques.

Effect of structure of cationic comb copolymers on their adsorption and stabilization of titania nanoparticles.

Cationic linear polymer poly([2-(methacryloyloxy)ethyl] trimethylammonium chloride) p(METAC), neutral brush polymer poly(poly(ethylene glycol) methyl ether methacrylate) p(PEO22MEMA), and cationic comb copolymers p(METAC-PEO(x)MEMA) were used for the stabilization of titania dispersions under neutral and alkaline conditions. Random comb copolymers p(METAC-PEO(x)MEMA) differing in charge density and length of PEO side chains were synthesized by RAFT. The adsorption of cationic polymers on titania nanoparticles was evaluated by thermogravimetric analysis; changes in surface potential, by measuring the zeta potential; and the stability of the treated TiO2 dispersions, by laser diffraction and DLS. Cationic linear and comb copolymers containing relatively short PEO side chains promoted the inversion of nanoparticle surface potential from strongly negative (-60 mV) to moderately positive (10-35 mV). Cationic comb copolymers containing longer PEO side chains increased the zeta potential of the treated nanoparticles but did not invert it to positive. Aqueous dispersions of titania nanoparticles stabilized by cationic comb copolymers under alkaline conditions (pH 10) were dispersed by high-energy planetary ball milling up to a primary particle size of 20 nm and were stable for at least 2 days.

WO3/CeO2/TiO2 Catalysts for Selective Catalytic Reduction of NO(x) by NH3: Effect of the Synthesis Method.

WO3/CeO2/TiO2, CeO2/TiO2 and WO3/TiO2 catalysts were prepared by wet impregnation. CeO2/TiO2 and WO3/TiO2 showed activity towards the selective catalytic reduction (SCR) of NO(x) by NH3, which was significantly improved by subsequent impregnation of CeO/TiO2 with WO3. Catalytic performance, NH3 oxidation and NH3 temperature programmed desorption of wet-impregnated WO3/CeO2/TiO2 were compared to those of a flame-made counterpart. The flame-made catalyst exhibits a peculiar arrangement of W-Ce-Ti-oxides that makes it very active for NH3-SCR. Catalysts prepared by wet impregnation with the aim to mimic the structure of the flame-made catalyst were not able to fully reproduce its activity. The differences in the catalytic performance between the investigated catalysts were related to their structural properties and the different interaction of the catalyst components.

Cobalt-free layered perovskites RBaCuFeO5+δ (R = 4f lanthanide) as electrocatalysts for the oxygen evolution reaction.

Co-based perovskite oxides are intensively studied as promising catalysts for electrochemical water splitting in an alkaline environment. However, the increasing Co demand by the battery industry is pushing the search for Co-free alternatives. Here we report a systematic study of the Co-free layered perovskite family RBaCuFeO5+δ (R = 4f lanthanide), where we uncover the existence of clear correlations between electrochemical properties and several physicochemical descriptors. Using a combination of advanced neutron and X-ray synchrotron techniques with ab initio DFT calculations we demonstrate and rationalize the positive impact of a large R ionic radius in their oxygen evolution reaction (OER) activity. We also reveal that, in these materials, Fe3+ is the transition metal cation the most prone to donate electrons. We also show that similar R3+/Ba2+ ionic radii favor the incorporation and mobility of oxygen in the layered perovskite structure and increase the number of available O diffusion paths, which have an additional, positive impact on both, the electric conductivity and the OER process. An unexpected result is the observation of a clear surface reconstruction exclusively in oxygen-rich samples (δ > 0), a fact that could be related to their superior OER activity. The encouraging intrinsic OER values obtained for the most active electrocatalyst (LaBaCuFeO5.49), together with the possibility of industrially producing this material in nanocrystalline form should inspire the design of other Co-free oxide catalysts with optimal properties for electrochemical water splitting.

Improved virus removal in ceramic depth filters modified with MgO.

Ceramic filters, working on the depth filtration principle, are known to improve drinking water quality by removing human pathogenic microorganisms from contaminated water. However, these microfilters show no sufficient barrier for viruses having diameters down to 20 nm. Recently, it was shown that the addition of positively charged materials, for example, iron oxyhydroxide, can improve virus removal by adsorption mechanisms. In this work, we modified a common ceramic filter based on diatomaceous earth by introducing a novel virus adsorbent material, magnesium oxyhydroxide, into the filter matrix. Such filters showed an improved removal of about 4-log in regard to bacteriophages MS2 and PhiX174. This is explained with the electrostatic enhanced adsorption approach that is the favorable adsorption of negatively charged viruses onto positively charged patches in an otherwise negatively charged filter matrix. Furthermore, we provide theoretical evidence applying calculations according to Derjaguin-Landau-Verwey-Overbeek theory to strengthen our experimental results. However, modified filters showed a significant variance in virus removal efficiency over the course of long-term filtration experiments with virus removal increasing with filter operation time (or filter aging). This is explained by transformational changes of MgO in the filter upon contact with water. It also demonstrates that filter history is of great concern when filters working on the adsorption principles are evaluated in regard to their retention performance as their surface characteristics may alter with use.

Spectroscopic assessment of the role of hydrogen in surface defects, in the electronic structure and transport properties of TiO2, ZnO and SnO2 nanoparticles.

The interaction of metal oxides with gases is very important for the operation of energy devices such as fuel cells and gas sensors, and also relevant for materials synthesis and processing. The electronic transport properties of metal oxides for the aforementioned devices strongly depend on the chemistry of these gases and on the presence or absence of defects on the surface and in the bulk. The Debye screening length is in this respect a material specific property which becomes particularly significant when the material is comprised of nanoparticles. In the present study, poly-crystalline TiO(2), ZnO and SnO(2) nanoparticles were synthesized by a high temperature flame spray combustion process and investigated for their interaction with hydrogen. The chemistry of the reduced and oxidized surfaces of these metal oxides, where the interaction with gases takes place, was investigated in detail with X-ray photoelectron spectroscopy (XPS). The transitions found near E(F) with XPS are consistent with those found by diffuse reflectance spectroscopy (DRS) and were assigned to surface states originating from non-equilibrium oxygen vacancies. We show how the non-stoichiometric character of the metal oxide surface constitutes electronic surface defects, in particular oxygen vacancies which allow for additional transitions near the Fermi energy (E(F)). The concentration of these surface defects can be strongly reduced by thermal after-treatment under air or increased by Ar(+)-sputtering, after which significant spectral features appear near E(F). Such prominent changes are particularly observed for TiO(2) and SnO(2), whereas the stoichiometry of the ZnO surface seems to be less responsive to such reducing and oxidizing conditions. Pronounced changes of the electrical conductivity upon changing from reducing to oxidizing conditions at elevated temperatures were monitored by electrochemical impedance spectroscopy (EIS). The lowering of the potential barrier for the charge transport particularly at lower temperatures already at reducing conditions is confirmed. The impedance response indicates that charge transfer is governed predominantly by one single process, i.e. by interaction of surface-like states localized within depletion layer with gas molecules. This implies that the free charge carriers in the material are determined by the intrinsic property like non-stoichiometry. Gas sensors made from such FSS nanoparticulate metal oxides showed well developed sensing characteristics of the hydrogen sensing at moderate temperatures.

Iron resonant photoemission spectroscopy on anodized hematite points to electron hole doping during anodization.

Anodization of α-Fe(2)O(3) (hematite) electrodes in alkaline electrolyte under constant potential conditions the electrode surface in a way that an additional current wave occurs in the cyclic voltammogram. The energy position of this current wave is closely below the potential of the anodization treatment. Continued cycling or exchanging of the electrolyte causes depletion of this new feature. The O 1s and Fe 2p core-level X-ray photoelectron spectra (XPS) and near-edge X-ray absorption fine structure (NEXAFS) spectra of such conditioned hematite exhibit a chemical shift towards higher binding energies, in line with the general perception that anodization generates oxide species with dielectric properties. The valence band XPS and particularly the iron resonant valence band photoemission spectra, however, are shifted towards the opposite direction, that is, towards the Fermi energy, suggesting that hole doping on hematite has taken place during anodization. Quantitative analysis of the Fe 2p resonant valence band photoemission spectra shows that the spectra obtained at the Fe 2p absorption threshold are shifted by virtually the same energy as the anodization potential towards the Fermi energy. The tentative interpretation of this observation is that anodization forms a surface film on the hematite that is specific to the anodization potential.

Electrodeposition of gold thin films with controlled morphologies and their applications in electrocatalysis and SERS.

Here, an easy and effective electrochemical route towards the synthesis of gold thin films with well-controlled roughness, morphology and crystallographic orientation is reported. To control these different factors, the applied potential during deposition played a major role. A tentative nucleation and growth mechanism is demonstrated by means of electrochemical characterizations and a formation mechanism is proposed. Interestingly, the differences in geometry and orientation of the different gold deposits have shown a clear correlation with the electrocatalytical activity in the case of oxygen sensing. In addition, not only the electrocatalytical activity but also the surface-enhanced Raman scattering of the gold deposits have been found to depend both on the roughness and on the size of the surface nanostructures, allowing a fine tuning by controlling these two parameters during deposition.

Virus removal in ceramic depth filters based on diatomaceous earth.

Ceramic filter candles, based on the natural material diatomaceous earth, are widely used to purify water at the point-of-use. Although such depth filters are known to improve drinking water quality by removing human pathogenic protozoa and bacteria, their removal regarding viruses has rarely been investigated. These filters have relatively large pore diameters compared to the physical dimension of viruses. However, viruses may be retained by adsorption mechanisms due to intermolecular and surface forces. Here, we use three types of bacteriophages to investigate their removal during filtration and batch experiments conducted at different pH values and ionic strengths. Theoretical models based on DLVO-theory are applied in order to verify experimental results and assess surface forces involved in the adsorptive process. This was done by calculation of interaction energies between the filter surface and the viruses. For two small spherically shaped viruses (MS2 and PhiX174), these filters showed no significant removal. In the case of phage PhiX174, where attractive interactions were expected, due to electrostatic attraction of oppositely charged surfaces, only little adsorption was reported in the presence of divalent ions. Thus, we postulate the existence of an additional repulsive force between PhiX174 and the filter surface. It is hypothesized that such an additional energy barrier originates from either the phage's specific knobs that protrude from the viral capsid, enabling steric interactions, or hydration forces between the two hydrophilic interfaces of virus and filter. However, a larger-sized, tailed bacteriophage of the family Siphoviridae was removed by log 2 to 3, which is explained by postulating hydrophobic interactions.

Differences in electrophysical and gas sensing properties of flame spray synthesized Fe2O3(gamma-Fe2O3 and alpha-Fe2O3).

Nanoscaled Fe2O3 powders as candidates for gas sensing material for hydrogen detection were synthesized by the high temperature flame spray assisted combustion of ferrocene dissolved in benzene. X-ray diffraction (XRD) and selected area electron diffraction (SAED) show that the as prepared nanopowder consists of maghemite (gamma-Fe2O3) with low crystallinity. Thermal post-treatment causes a phase transformation towards hematite (alpha-Fe2O3) accompanied by an increase in the crystallinity. Upon exposure to air and hydrogen at elevated temperatures, both phases show a significant variation of conductivity and activation energy-as evidenced by impedance spectra-and thus a favorable sensor response, surpassing even that of flame-synthesized nanocrystalline tin dioxide. The conductivity has been identified as of electronic origin, affected by trap states located in the region adjacent to grain boundaries. Quantitative analysis of the impedance spectra with equivalent circuits shows that the conductivity is thermally activated and affected by the interaction of hydrogen with the sensor material. The calculated Debye screening length of gamma-Fe2O3 and alpha-Fe2O3 is about 27 nm and 16 nm, respectively, what contributes significantly to the sensitivity of the material. Gamma-Fe2O3 and alpha-Fe2O3 exhibit high sensor response towards hydrogen in a wide concentration range. Gamma-Fe2O3 shows n-type semiconducting behavior up to 573 K. Alpha-Fe2O3 shows p-type semiconducting behavior, as reflected in the dynamic changes of the resistivity. For both sensor materials, 523 K was the optimal operating temperature.

Low Temperature Transient Liquid Phase Bonding of Alumina Ceramics with the Bi2O3-ZnO Interlayer.

Alumina ceramics were joined by a transient liquid phase (TLP) bonding method at relatively lower temperatures, using mixed powders of Bi2O3 and ZnO with different weight ratios as interlayers between the ceramic components. Bonding was achieved at 750 °C for several of the prepared interlayer mixtures, which makes the applied approach attractive due to the relatively lower joining temperature and potentially low fabrication costs. Measurements by SEM and EDX were used to study the microstructure and chemical analysis of the obtained joints. It also allowed us to investigate the diffusion mechanism occurring in the systems, which resulted in the hypothesis that Zn2+/ZnO diffuses through the ceramics. XRD and Raman spectra were acquired to examine the reaction products that formed during the thermal treatment. The results showed that both ZnO and Bi2O3 react with each other as well as with alumina to form spinel and other products.

Aerosol-Assisted Deposition for TiO2 Immobilization on Photocatalytic Fibrous Filters for VOC Degradation.

Atomization and spraying are well-established methods for the production of submicrometer- and micrometer- sized powders. In addition, they could be of interest to the immobilization of photocatalytic nanoparticles onto supports because they enable the formation of microporous films with photocatalytic activity. Here, we provide a comparison of aerosol-assisted immobilization methods, such as spray-drying (SD), spray atomization (SA), and spray gun (SG), which were used for the deposition of TiO2 dispersions onto fibrous filter media. The morphology, microstructure, and electronic properties of the structures with deposited TiO2 were characterized by SEM and TEM, BET and USAXS, and UV-Vis spectrometry, respectively. The photocatalytic performances of the functionalized filters were evaluated and compared to the benchmark dip-coating method. Our results showed that the SG and SA immobilization methods led to the best photocatalytic and operational performance for the degradation of toluene, whereas the SD method showed the lowest degradation efficiency and poor stability of coating. We demonstrated that TiO2 sprays using the SG and SA methods with direct deposition onto filter media involving dispersed colloidal droplets revealed to be promising alternatives to the dip-coating method owing to the ability to uniformly cover the filter fibers. In addition, the SA method allowed for fast and simple control of the coating thickness as the dispersed particles were continuously directed onto the filter media without the need for repetitive coatings, which is common for the SG and dip-coating methods. Our study highlighted the importance of the proper immobilization method for the efficient photocatalytic degradation of VOCs.

Removal of MS2 and fr Bacteriophages Using MgAl2O4-Modified, Al2O3-Stabilized Porous Ceramic Granules for Drinking Water Treatment.

Point-of-use ceramic filters are one of the strategies to address problems associated with waterborne diseases to remove harmful microorganisms in water sources prior to its consumption. In this study, development of adsorption-based ceramic depth filters composed of alumina platelets was achieved using spray granulation (calcined at 800 °C). Their virus retention performance was assessed using cartridges containing granular material (4 g) with two virus surrogates: MS2 and fr bacteriophages. Both materials showed complete removal, with a 7 log10 reduction value (LRV) of MS2 up to 1 L. MgAl2O4-modified Al2O3 granules possessed a higher MS2 retention capacity, contrary to the shortcomings of retention limits in pure Al2O3 granules. No significant decline in the retention of fr occurred during filtration tests up to 2 L. The phase composition and morphology of the materials were preserved during filtration, with no magnesium or aluminum leakage during filtration, as confirmed by X-ray diffractograms, electron micrographs, and inductively coupled plasma-optical emission spectrometry. The proposed MgAl2O4-modified Al2O3 granular ceramic filter materials offer high virus retention, achieving the criterion for virus filtration as required by the World Health Organization (LRV ≥ 4). Owing to their high thermal and chemical stability, the developed materials are thus suitable for thermal and chemical-free regeneration treatments.

Hydrothermal synthesis of multi-cationic high-entropy layered double hydroxides.

High-entropy materials are compositionally complex materials which often contain five or more elements. The most commonly studied materials in this field are alloys and oxides, where their composition allows for tunable materials properties. High-entropy layered double hydroxides have been recently touted as the next focus for the field of high-entropy materials to expand into. However, most previous work on multi-cationic layered double hydroxides has focused on syntheses with 5 or less cations in the structure. To bridge this gap into high-entropy materials, this work explores the range and extent of different compositional combinations for high-entropy double layered hydroxides. Specifically, pure layered double hydroxides were synthesized with different combinations of 7 cations (Mg, Co, Cu, Zn, Ni, Al, Fe, Cr) as well as one combination of 8 cations by utilizing a hydrothermal synthesis method. Furthermore, magnetic properties of the 8-cation LDH were investigated.

Virus removal from drinking water using modified activated carbon fibers.

Activated carbon (AC) exhibits superior sorption properties compared to other porous materials, due to well-developed porous structures and high surface areas. Therefore, it is widely applied in its various forms in water purification to remove a diverse range of contaminating species. The presence of viruses in fresh water bodies poses a serious issue for human health. However, AC has not yet been commonly applied to waterborne virus removal. In this study, we present oxidation and copper impregnation treatment procedures of activated carbon fibers (ACFs) that resulted in porous structure and surface chemistry modifications. The effect of these modifications on virus removal was investigated by experimental flow studies and revealed up to 2.8 log10 reduction value (LRV) and 3.6 LRV of MS2 bacterio-phages for non-modified and oxidized ACFs, respectively, emphasizing the advantages of ACF surface functionalization. Copper modified fibers demonstrated a high sensitivity to media composition, resulting in a release of metal and therefore limited virucidal capacity.

Effect of Loading and Heating History on Deformation of LaCoO3.

The aim of this work was to study cyclic stress-strain deformation behavior of LaCoO3 as a function of loading and heating history. The ferroelastic hysteretic deformation of LaCoO3 at different stresses and temperatures was characterized using effective Young's modulus, hysteresis loop area and creep strain shift parameters. The deformation behavior of LaCoO3 was not significantly affected by the previous loading and heating history when tested at constant temperature. The high temperature strength and Young's modulus of LaCoO3 were higher compared to at room temperature. A creep strain shift parameter was introduced to characterize creep strain in LaCoO3 for the first time.

Strength Analysis and Stress-Strain Deformation Behavior of 3 mol% Y-TZP and 21 wt.% Al2O3-3 mol% Y-TZP.

The mechanical behavior of 3 mol% Y2O3-ZrO2 ceramic and 21 wt.% Al2O3-3 mol% Y2O3-ZrO2 ceramic composite with submicron grain size was studied. Mechanical properties, such as hardness, Young's modulus, four-point bending strength, and fracture toughness of both materials were measured. Linear stress-strain deformation behavior of both 3 mol% Y2O3-ZrO2 and 21 wt.% Al2O3-3 mol% Y2O3-ZrO2 was observed in flexure, both at room temperature and at 400 °C. A small deviation from linear elastic deformation was detected in 21 wt.% Al2O3-3 mol% Y2O3-ZrO2 ceramic composite when loaded above a stress of 1500 MPa. Therefore, it was concluded that only elastic deformation occurred at low stresses upon loading, which exclude the presence of domain switching in zirconia upon bending under the loading conditions of this study.