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.

The effect of copper on the redox behaviour of iron oxide for chemical-looping hydrogen production probed by in situ X-ray absorption spectroscopy.

The production of high purity hydrogen with the simultaneous capture of CO2, can be achieved through a chemical looping (CL) cycle relying on an iron oxide-based oxygen carrier. Indeed, the availability of active and cyclically stable oxygen carriers is a key criterion for the practical implementation of this technology. In this regard, improving our understanding of the reduction pathway(s) of iron-based oxygen carriers and the development of concepts to increase the reduction kinetics are important aspects. The aim of this work is to evaluate the effect of the addition of copper on the redox behaviour of iron oxide based oxygen carriers stabilized on ZrO2. In situ pulsed-H2 XANES (Fe K-edge) experiments allowed for the determination of the reduction pathways in these materials, viz. the reduction of both Fe2O3 and CuFe2O4 proceeded via a Fe2+ intermediate: Fe2O3 (CuFe2O4) → Fe3O4 (Cu0) → FeO (Cu0) → Fe0 (Cu0). In the first step CuFe2O4 is reduced to Cu0 and Fe3O4, whereby Cu0 promotes the further reduction of iron oxide, increasing their rate of formation. In particular, the rate of reduction of FeO → Fe0 is accelerated most dramatically by Cu0. This is an encouraging result as the FeO → Fe0 transition is the slowest reduction reaction.

Surface oxidation/spin state determines oxygen evolution reaction activity of cobalt-based catalysts in acidic environment.

Co-based catalysts are promising candidates to replace Ir/Ru-based oxides for oxygen evolution reaction (OER) catalysis in an acidic environment. However, both the reaction mechanism and the active species under acidic conditions remain unclear. In this study, by combining surface-sensitive soft X-ray absorption spectroscopy characterization with electrochemical analysis, we discover that the acidic OER activity of Co-based catalysts are determined by their surface oxidation/spin state. Surfaces composed of only high-spin CoII are found to be not active due to their unfavorable water dissociation to form CoIII-OH species. By contrast, the presence of low-spin CoIII is essential, as it promotes surface reconstruction of Co oxides and, hence, OER catalysis. The correlation between OER activity and Co oxidation/spin state signifies a breakthrough in defining the structure-activity relationship of Co-based catalysts for acidic OER, though, interestingly, such a relationship does not hold in alkaline and neutral environments. These findings not only help to design efficient acidic OER catalysts, but also deepen the understanding of the reaction mechanism.

Formation of Highly Conductive Interfaces in Crystalline Ionic Liquid-Gated Unipolar MoTe2/h-BN Field-Effect Transistor.

2H MoTe2 (molybdenum ditelluride) has generated significant interest because of its superconducting, nonvolatile memory, and semiconducting of new materials, and it has a large range of electrical properties. The combination of transition metal dichalcogenides (TMDCs) and two dimensional (2D) materials like hexagonal boron nitride (h-BN) in lateral heterostructures offers a unique platform for designing and engineering novel electronic devices. We report the fabrication of highly conductive interfaces in crystalline ionic liquid-gated (ILG) field-effect transistors (FETs) consisting of a few layers of MoTe2/h-BN heterojunctions. In our initial exploration of tellurium-based semiconducting TMDs, we directed our attention to MoTe2 crystals with thicknesses exceeding 12 nm. Our primary focus centered on investigating the transport characteristics and quantitatively assessing the surface interface heterostructure. Our transconductance (gm) measurements indicate that the very efficient carrier modulation with an ILG FET is two times larger than standard back gating, and it demonstrates unipolarity of the device. The ILG FET exhibited highly unipolar p-type behavior with a high on/off ratio, and it significantly increased the mobility in MoTe2/h-BN heterochannels, achieving improvement as one of the highest recorded mobility increments. Specifically, we observed hole and electron mobility values ranging from 345 cm2 V-1 s-1 to 285 cm2 V-1 s-1 at 80 K. We predict that our ability to observe the intrinsic, heterointerface conduction in the channels was due to a drastic reduction of the Schottky barriers, and electrostatic gating is suggested as a method for controlling the phase transitions in the few layers of TMDC FETs. Moreover, the simultaneous structural phase transitions throughout the sample, achieved through electrostatic doping control, presents new opportunities for developing phase change devices using atomically thin membranes.

Na-ß-Al2O3 stabilized Fe2O3 oxygen carriers for chemical looping water splitting: correlating structure with redox stability.

Chemical looping is an emerging technology to produce high purity hydrogen from fossil fuels or biomass with the simultaneous capture of the CO2 produced at the distributed scale. This process requires the availability of stable Fe2O3-based oxygen carriers. Fe2O3-Al2O3 based oxygen carriers exhibit a decay in the H2 yield with cycle number, due to the formation of FeAl2O4 that possesses a very low capacity for water splitting at typical operating conditions of conventional chemical looping schemes (700-1000 °C). In this study, the addition of sodium (via a sodium salt) in the synthesis of Fe2O3-Al2O3 oxygen carriers was assessed as a means to counteract the cyclic deactivation of the oxygen carrier. Detailed insight into the oxygen carrier's structure was gained by combined X-ray powder diffraction (XRD), X-ray absorption spectroscopy (XAS) at the Al, Na and Fe K-edges and scanning transmission electron microscopy/energy-dispersive X-ray spectroscopy (STEM/EDX) analyses. The addition of sodium prevented the formation of FeAl2O4 and stabilized the oxygen carrier via the formation of a layered structure, Na-ß-Al2O3 phase. The material, i.e. Na-ß-Al2O3 stabilized Fe2O3, showed a stable H2 yield of ca. 13.3 mmol g-1 over 15 cycles.

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.

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.

Atomic Layer Deposition of a Film of Al2O3 on Electrodeposited Copper Foams To Yield Highly Effective Oxygen Carriers for Chemical Looping Combustion-Based CO2 Capture.

A rapid electrochemical deposition protocol is reported to synthesize highly porous Cu foams serving as model oxygen carriers for chemical looping, a promising technology to reduce anthropogenic CO2 emission. To overcome the sintering-induced decay in the oxygen carrying capacity of unsupported Cu foams, Al2O3 films of different thicknesses (0.1-25 nm) are deposited onto the Cu foams via atomic layer deposition (ALD). An ALD-grown Al2O3 overcoat of 20 nm thickness (∼4 wt % Al2O3) is shown to be sufficient to ensure excellent redox cyclic stability. Al2O3-coated Cu foams exhibit a capacity retention of 96% over 10 redox cycles, outperforming their coprecipitated counterpart (equal Al2O3 content). The structural evolution of the stabilized foams is probed in detail and compared to benchmark materials to elucidate the stabilizing role of the Al2O3 overcoat. Upon heat treatment, the initially conformal Al2O3 overcoat induces a fragmentation of large Cu(O) branches into small particles. After multiple redox cycles, the Al2O3 overcoat transforms into sub-micrometer-sized grains of aluminum-containing phases (δ-Al2O3, CuAl2O4, and CuAlO2) that are dispersed homogeneously within the CuO matrix. Finally, the diffusion of Cu through an Al2O3 layer upon heat treatment in an oxidizing atmosphere is probed in model thin films.