Self-Modification of Defective TiO2 under Controlled H2/Ar Gas Environment and Dynamics of Photoinduced Surface Oxygen Vacancies.

In recent years, defective TiO2 has caught considerable research attention because of its potential to overcome the limits of low visible light absorption and fast charge recombination present in pristine TiO2 photocatalysts. Among the different synthesis conditions for defective TiO2, ambient pressure hydrogenation with the addition of Ar as inert gas for safety purposes has been established as an easy method to realize the process. Whether the Ar gas might still influence the resulting photocatalytic properties and defective surface layer remains an open question. Here, we reveal that the gas flow ratio between H2 and Ar has a crucial impact on the defective structure as well as the photocatalyic activity of TiO2. In particular, transmission electron microscopy (TEM) in combination with electron energy loss spectroscopy (EELS) revealed a larger width of the defective surface layer when using a H2/Ar (50 %-50 %) gas mixture over pure H2. A possible reason could be the increase in dynamic viscosity of the gas mixture when Ar is added. Additionally, photoinduced enhanced Raman spectroscopy (PIERS) is implemented as a complementary approach to investigate the dynamics of the defective structures under ambient conditions which cannot be effortlessly realized by vacuum techniques like TEM.

Plasma-Engineering of Oxygen Vacancies on NiCo2O4 Nanowires with Enhanced Bifunctional Electrocatalytic Performance for Rechargeable Zinc-air Battery.

Designing an efficient, durable, and inexpensive bifunctional electrocatalyst toward oxygen evolution reactions (OER) and oxygen reduction reactions (ORR) remains a significant challenge for the development of rechargeable zinc-air batteries (ZABs). The generation of oxygen vacancies plays a vital role in modifying the surface properties of transition-metal-oxides (TMOs) and thus optimizing their electrocatalytic performances. Herein, a H2/Ar plasma is employed to generate abundant oxygen vacancies at the surfaces of NiCo2O4 nanowires. Compared with the Ar plasma, the H2/Ar plasma generated more oxygen vacancies at the catalyst surface owing to the synergic effect of the Ar-related ions and H-radicals in the plasma. As a result, the NiCo2O4 catalyst treated for 7.5 min in H2/Ar plasma exhibited the best bifunctional electrocatalytic activities and its gap potential between Ej = 10 for OER and E1/2 for ORR is even smaller than that of the noble-metal-based catalyst. In situ electrochemical experiments are also conducted to reveal the proposed mechanisms for the enhanced electrocatalytic performance. The rechargeable ZABs, when equipped with cathodes utilizing the aforementioned catalyst, achieved an outstanding charge-discharge gap, as well as superior cycling stability, outperforming batteries employing noble-metal catalyst counterparts.

Composition and Surface Optical Properties of GaSe:Eu Crystals before and after Heat Treatment.

This work studies the technological preparation conditions, morphology, structural characteristics and elemental composition, and optical and photoluminescent properties of GaSe single crystals and Eu-doped ß-Ga2O3 nanoformations on ε-GaSe:Eu single crystal substrate, obtained by heat treatment at 750-900 °C, with a duration from 30 min to 12 h, in water vapor-enriched atmosphere, of GaSe plates doped with 0.02-3.00 at. % Eu. The defects on the (0001) surface of GaSe:Eu plates serve as nucleation centers of ß-Ga2O3:Eu crystallites. For 0.02 at. % Eu doping, the fundamental absorption edge of GaSe:Eu crystals at room temperature is formed by n = 1 direct excitons, while at 3.00 at. % doping, Eu completely shields the electron-hole bonds. The band gap of nanostructured ß-Ga2O3:Eu layer, determined from diffuse reflectance spectra, depends on the dopant concentration and ranges from 4.64 eV to 4.87 eV, for 3.00 and 0.05 at. % doping, respectively. At 0.02 at. % doping level, the PL spectrum of ε-GaSe:Eu single crystals consists of the n = 1 exciton band, together with the impurity band with a maximum intensity at 800 nm. Fabry-Perrot cavities with a width of 9.3 µm are formed in these single crystals, which determine the interference structure of the impurity PL band. At 1.00-3.00 at. % Eu concentrations, the PL spectra of GaSe:Eu single crystals and ß-Ga2O3:Eu nanowire/nanolamellae layers are determined by electronic transitions of Eu2+ and Eu3+ ions.

Decontaminative Properties of Cold Atmospheric Plasma Treatment on Collagen Membranes Used for Guided Bone Regeneration.

Background cold atmospheric plasma (CAP) is known to be a surface-friendly yet antimicrobial and activating process for surfaces such as titanium. The aim of the present study was to describe the decontaminating effects of CAP on contaminated collagen membranes and their influence on the properties of this biomaterial in vitro. Material and Methods: A total of n = 18 Bio-Gide® (Geistlich Biomaterials, Baden-Baden, Germany) membranes were examined. The intervention group was divided as follows: n = 6 membranes were treated for one minute, and n = 6 membranes were treated for five minutes with CAP using kINPen® MED (neoplas tools GmbH, Greifswald, Germany) with an output of 5 W, respectively. A non-CAP-treated group (n = 6) served as the control. The topographic alterations were evaluated via X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). Afterward, the samples were contaminated with E. faecalis for 6 days, and colony-forming unit (CFU) counts and additional SEM analyses were performed. The CFUs increased with CAP treatment time in our analyses, but SEM showed that the surface of the membranes was essentially free from bacteria. However, the deeper layers showed remaining microbial conglomerates. Furthermore, we showed, via XPS analysis, that increasing the CAP time significantly enhances the carbon (carbonyl group) concentration, which also correlates negatively with the decontaminating effects of CAP. Conclusions: Reactive carbonyl groups offer a potential mechanism for inhibiting the growth of E. faecalis on collagen membranes after cold atmospheric plasma treatment.

Synthesis, Crystal Structure, and Photocatalytic Properties of Two Isoreticular Ce(IV)-MOFs with an Infinite Rod-Shaped Inorganic Building Unit.

The use of the V-shaped linker molecules 4,4'-oxydibenzoic acid (H2ODB) and 4,4'-carbonyldibenzoic acid (H2CDB) led to the discovery of two isoreticular Ce(IV)-based metal-organic frameworks (MOFs) of composition [CeO(H2O)(L)], L = ODB2-, CDB2-, denoted CAU-58 (CAU = Christian-Albrechts-University). The recently developed Ce-MOF synthesis approach in acetonitrile as the solvent proved effective in accessing Ce(IV)-MOF structures with infinite rod-shaped inorganic building units (IBUs) and circumventing the formation of the predominantly observed hexanuclear [Ce6O8] cluster. For the structure determination of the isoreticular MOFs, three-dimensional electron diffraction (3D ED) and powder X-ray diffraction (PXRD) data were used in combination with density functional theory (DFT) calculations. [CeO(H2O)(CDB)] shows reversible H2O adsorption by stirring in water and thermal treatment at 190 °C, which leads to a unit cell volume change of 11%. The MOFs feature high thermal stabilities (T > 290 °C), which exceed those of most Ce(IV)-MOFs and can be attributed to the infinite rod-shaped IBU. Surface and bulk oxidation states of the cerium ions were analyzed via X-ray photoelectron spectroscopy (XPS) and X-ray absorption near-edge spectroscopy (XANES). While Ce(III) ions are observed by the highly surface-sensitive XPS method, the bulk material contains predominantly Ce(IV) ions according to XANES. Application of the MOFs as catalysts for the catalytic degradation of methyl orange in aqueous solutions was also studied. While degradation activity for both MOFs was observed, only CAU-58-ODB revealed enhanced photocatalytic activity under ultraviolet (UV) light. The photocatalytic mechanism likely involves a ligand-to-metal charge transfer (LMCT) from the linkers to the Ce(IV) centers. Analyses by XANES and inductively coupled plasma-optical emission spectroscopy (ICP-OES) demonstrate that leaching of Cerium ions as well as partial reduction of Ce(IV) to Ce(III) takes place during catalysis. At the same time, PXRD data confirm the structural stability of the remaining MOF catalysts.

Nanoscale Synergetic Effects on Ag-TiO2 Hybrid Substrate for Photoinduced Enhanced Raman Spectroscopy (PIERS) with Ultra-Sensitivity and Reusability.

Here, a 4N-in-1 hybrid substrate concept (nanocolumnar structures, nanocrack network, nanoscale mixed oxide phases, and nanometallic structures) for ultra-sensitive and reliable photo-induced-enhanced Raman spectroscopy (PIERS), is proposed. The use of the 4N-in-1 hybrid substrate leads to an ≈50-fold enhancement over the normal surface-enhanced Raman spectroscopy, which is recorded as the highest PIERS enhancement to date. In addition to an improved Raman signal, the 4N-in-1 hybrid substrate provides a high detection sensitivity which may be attributed to the activation possibility at extremely low UV irradiation dosage and prolonged relaxation time (long measurement time). Moreover, the 4N-in-1 hybrid substrate exhibits a superior photocatalytic degradation performance of analytes, allowing its reuse at least 18 times without any loss of PIERS activity. The use of the 4N-in-1 concept can be adapted to biomedicine, forensic, and security fields easily.