Synergistic Effects of Co3O4-gC3N4-Coated ZnO Nanoparticles: A Novel Approach for Enhanced Photocatalytic Degradation of Ciprofloxacin and Hydrogen Evolution via Water Splitting.

This research evaluates the efficacy of catalysts based on Co3O4-gC3N4@ZnONPs in the degradation of ciprofloxacin (CFX) and the photocatalytic production of H2 through water splitting. The results show that CFX experiences prompt photodegradation, with rates reaching up to 99% within 60 min. Notably, the 5% (Co3O4-gC3N4)@ZnONPs emerged as the most potent catalyst. The recyclability studies of the catalyst revealed a minimal activity loss, approximately 6%, after 15 usage cycles. Using gas chromatography-mass spectrometry (GC-MS) techniques, the by-products of CFX photodegradation were identified, which enabled the determination of the potential degradation pathway and its resultant products. Comprehensive assessments involving photoluminescence, bandgap evaluations, and the study of scavenger reactions revealed a degradation mechanism driven primarily by superoxide radicals. Moreover, the catalysts demonstrated robust performance in H2 photocatalytic production, with some achieving outputs as high as 1407 µmol/hg in the visible spectrum (around 500 nm). Such findings underline the potential of these materials in environmental endeavors, targeting both water purification from organic pollutants and energy applications.

Fine-Tuning Intrinsic and Doped Hydrogenated Amorphous Silicon Thin-Film Anodes Deposited by PECVD to Enhance Capacity and Stability in Lithium-Ion Batteries.

Silicon is a promising alternative to graphite as an anode material in lithium-ion batteries, thanks to its high theoretical lithium storage capacity. Despite these high expectations, silicon anodes still face significant challenges, such as premature battery failure caused by huge volume changes during charge-discharge processes. To solve this drawback, using amorphous silicon as a thin film offers several advantages: its amorphous nature allows for better stress mitigation and it can be directly grown on current collectors for material savings and improved Li-ion diffusion. Furthermore, its conductivity is easily increased through doping during its growth. In this work, we focused on a comprehensive study of the influence of both electrical and structural properties of intrinsic and doped hydrogenated amorphous silicon (aSi:H) thin-film anodes on the specific capacity and stability of lithium-ion batteries. This study allows us to establish that hydrogen distribution in the aSi:H material plays a pivotal role in enhancing battery capacity and longevity, possibly masking the significance of the conductivity in the case of doped electrodes. Our findings show that we were able to achieve high initial specific capacities (3070 mAhg-1 at the 10th cycle), which can be retained at values higher than those of graphite for a significant number of cycles (>120 cycles), depending on the structural properties of the aSi:H films. To our knowledge, this is the first comprehensive study of the influence of these properties of thin films with different doping levels and hydrogen distributions on their optimization and use as anodes in lithium-ion batteries.

Hydrogenated Amorphous Silicon-Based Nanomaterials as Alternative Electrodes to Graphite for Lithium-Ion Batteries.

Graphite is the material most used as an electrode in commercial lithium-ion batteries. On the other hand, it is a material with low energy capacity, and it is considered a raw critical material given its large volume of use. In the current energy context, we must promote the search for alternative materials based on elements that are abundant, sustainable and that have better performance for energy storage. We propose thin materials based on silicon, which has a storage capacity eleven times higher than graphite. Nevertheless, due to the high-volume expansion during lithiation, it tends to crack, limiting the life of the batteries. To solve this problem, hydrogenated amorphous silicon has been researched, in the form of thin film and nanostructures, since, due to its amorphous structure, porosity and high specific surface, it could better absorb changes in volume. These thin films were grown by plasma-enhanced chemical vapor deposition, and then the nanowires were obtained by chemical etching. The compositional variations of films deposited at different temperatures and the incorporation of dopants markedly influence the stability and longevity of batteries. With these optimized electrodes, we achieved batteries with an initial capacity of 3800 mAhg-1 and 82% capacity retention after 50 cycles.

Biomimetic Catalysts Based on Au@TiO2-MoS2-CeO2 Composites for the Production of Hydrogen by Water Splitting.

The photocatalytic hydrogen evolution reaction (HER) by water splitting has been studied, using catalysts based on crystalline TiO2 nanowires (TiO2NWs), which were synthesized by a hydrothermal procedure. This nanomaterial was subsequently modified by incorporating different loadings (1%, 3% and 5%) of gold nanoparticles (AuNPs) on the surface, previously exfoliated MoS2 nanosheets, and CeO2 nanoparticles (CeO2NPs). These nanomaterials, as well as the different synthesized catalysts, were characterized by electron microscopy (HR-SEM and HR-TEM), XPS, XRD, Raman, Reflectance and BET surface area. HER studies were performed in aqueous solution, under irradiation at different wavelengths (UV-visible), which were selected through the appropriate use of optical filters. The results obtained show that there is a synergistic effect between the different nanomaterials of the catalysts. The specific area of the catalyst, and especially the increased loading of MoS2 and CeO2NPs in the catalyst substantially improved the H2 production, with values of ca. 1114 µm/hg for the catalyst that had the best efficiency. Recyclability studies showed only a decrease in activity of approx. 7% after 15 cycles of use, possibly due to partial leaching of gold nanoparticles during catalyst use cycles. The results obtained in this research are certainly relevant and open many possibilities regarding the potential use and scaling of these heterostructures in the photocatalytic production of H2 from water.

One-Dimensional (1D) Nanostructured Materials for Energy Applications.

At present, the world is at the peak of production of traditional fossil fuels. Much of the resources that humanity has been consuming (oil, coal, and natural gas) are coming to an end. The human being faces a future that must necessarily go through a paradigm shift, which includes a progressive movement towards increasingly less polluting and energetically viable resources. In this sense, nanotechnology has a transcendental role in this change. For decades, new materials capable of being used in energy processes have been synthesized, which undoubtedly will be the cornerstone of the future development of the planet. In this review, we report on the current progress in the synthesis and use of one-dimensional (1D) nanostructured materials (specifically nanowires, nanofibers, nanotubes, and nanorods), with compositions based on oxides, nitrides, or metals, for applications related to energy. Due to its extraordinary surface-volume relationship, tunable thermal and transport properties, and its high surface area, these 1D nanostructures have become fundamental elements for the development of energy processes. The most relevant 1D nanomaterials, their different synthesis procedures, and useful methods for assembling 1D nanostructures in functional devices will be presented. Applications in relevant topics such as optoelectronic and photochemical devices, hydrogen production, or energy storage, among others, will be discussed. The present review concludes with a forecast on the directions towards which future research could be directed on this class of nanostructured materials.

Photocatalytic Activity of Silver-Based Biomimetics Composites.

Different Ag@TiO2 and Ag@ZnO catalysts, with nanowire (NW) structure, were synthesized containing different amounts of silver loading (1, 3, 5, and 10 wt.%) and characterized by FE-SEM, HRTEM, BET, XRD, Raman, XPS, and UV-vis. The photocatalytic activity of the composites was studied by the production of hydrogen via water splitting under UV-vis light and the degradation of the antibiotic ciprofloxacin. The maximum hydrogen production of all the silver-based catalysts was obtained with a silver loading of 10 wt.% under irradiation at 500 nm. Moreover, 10%Ag@TiO2 NWs was the catalyst with the highest activity in the hydrogen production reaction (1119 µmol/hg), being 18 times greater than the amount obtained with the pristine TiO2 NW catalyst. The most dramatic difference in hydrogen production was obtained with 10%Ag@TiO2-P25, 635 µmol/hg, being 36 times greater than the amount reported for the unmodified TiO2-P25 (18 µmol/hg). The enhancement of the catalytic activity is attributed to a synergism between the silver nanoparticles incorporated and the high surface area of the composites. In the case of the degradation of ciprofloxacin, all the silver-based catalysts degraded more than 70% of the antibiotic in 60 min. The catalyst that exhibited the best result was 3%Ag@ZnO commercial, with 99.72% of degradation. The control experiments and stability tests showed that photocatalysis was the route of degradation and the selected silver-based catalysts were stable after seven cycles, with less than 1% loss of efficiency per cycle. These results suggest that the catalysts could be employed in additional cycles without the need to be resynthesized, thus reducing remediation costs.

Biomimetic Catalysts Based on Au@ZnO-Graphene Composites for the Generation of Hydrogen by Water Splitting.

For some decades, the scientific community has been looking for alternatives to the use of fossil fuels that allow for the planet's sustainable and environmentally-friendly development. To do this, attempts have been made to mimic some processes that occur in nature, among which the photosystem-II stands out, which allows water splitting operating with different steps to generate oxygen and hydrogen. This research presents promising results using synthetic catalysts, which try to simulate some natural processes, and which are based on Au@ZnO-graphene compounds. These catalysts were prepared by incorporating different amounts of gold nanoparticles (1 wt.%, 3 wt.%, 5 wt.%, 10 wt.%) and graphene (1 wt.%) on the surface of synthesized zinc oxide nanowires (ZnO NWs), and zinc oxide nanoparticles (ZnO NPs), along with a commercial form (commercial ZnO) for comparison purposes. The highest amount of hydrogen (1127 µmol/hg) was reported by ZnO NWs with a gold and graphene loadings of 10 wt.% and 1 wt.%, respectively, under irradiation at 400 nm. Quantities of 759 µmol/hg and 709 µmol/hg were obtained with catalysts based on ZnO NPs and commercial ZnO, respectively. The photocatalytic activity of all composites increased with respect to the bare semiconductors, being 2.5 times higher in ZnO NWs, 8.8 times higher for ZnO NPs, and 7.5 times higher for commercial ZnO. The high photocatalytic activity of the catalysts is attributed, mainly, to the synergism between the different amount of gold and graphene incorporated, and the surface area of the composites.

0D-1D Hybrid Silicon Nanocomposite as Lithium-Ion Batteries Anodes.

Lithium ion batteries (LIBs) are the enabling technology for many of the societal changes that are expected to happen in the following years. Among all the challenges for which LIBs are the key, vehicle electrification is one of the most crucial. Current battery materials cannot provide the required power densities for such applications and therefore, it makes necessary to develop new materials. Silicon is one of the proposed as next generation battery materials, but still there are challenges to overcome. Poor capacity retention is one of those drawbacks, and because it is tightly related with its high capacity, it is a problem rather difficult to address with common and scalable fabrication processes. Here we show that combining 0D and 1D silicon nanostructures, high capacity and stability can be achieved even using standard electrode fabrication processes. Capacities as high as 1200 mAh/g for more than 500 cycles at high current densities (2 A/g) were achieved with the produced hybrid 0D/1D electrodes. In this research, it was shown that while 0D nanostructures provide good strain relaxation capabilities, 1D nanomaterials contribute with enhanced cohesion and conductive matrix integrity.

Catalytic use of TiO2 nanowires in the photodegradation of Benzophenone-4 as an active ingredient in sunscreens.

Water contamination has compromised the quality of this resource during the last years with the presence of persistent organic pollutants. Because of the resistance of these compounds to degradation, several advance oxidation techniques have been proposed. In this study, we report the employment of an advance oxidation technique in the degradation of benzophenone-4 (BP-4), using TiO2 as catalyst, which was obtained following a fast-hydrothermal method. TiO2 nanowires (TiO2NWs) were fully characterized considering the morphology, elemental composition, oxidation states, vibrational modes and crystalline structure with SEM and TEM, EDS, XPS, FTIR and XRD, respectively. The photocatalytic degradation was carried out using a home-made photoreactor under slightly acidic conditions achieving an average of 90% removal. It was determined that the photocatalysis is the most probable route of degradation since the photolysis or catalysis procedures produce negligible contributions. An apparent kinetic constant of 1.29 × 10-2 min-1 was determined, according to a pseudo-first order reaction.

Synthesis Procedure of Highly Densely Packed Carbon Nanotube Forests on TiN.

The goal of this research was to obtain high-density single-walled carbon nanotube forests (SWNTs) on conductive substrates for different applications, including field emission. For this, dip-coating was chosen as the catalyst deposition method, to subsequently grow SWNTs by Alcohol Catalytic Chemical Vapor Deposition (AC-CVD). Si (100) was chosen as the substrate, which was then coated with a TiN thin film. By sputtering with Ar, it was possible to generate alternating TiN and Si lanes, with a different wettability and, therefore, a different affinity for the catalysts. As a result, the Mo‒Co catalyst was mainly deposited on TiN and not on sputtered-Si, which allowed the selective growth of SWNT forests on the TiN conductive surfaces. These as-synthesized SWNTs were used for field emission measurements in a high vacuum chamber.

TiO2-Based Nanomaterials for the Production of Hydrogen and the Development of Lithium-Ion Batteries.

The photocatalytic activity of different titanium oxide nanowires containing gold (Au@TiO2NWs), and gold-graphene (Au@TiO2NWs-graphene), was evaluated by studying the reaction of hydrogen production by water splitting under UV-vis light. The composites showed high surface areas, with values above 300 m2 per gram, even after the incorporation of gold and graphene on the surface of titanium oxide nanowires. The highest hydrogen production of Au@TiO2NWs was 1436 µmol h-1 g-1, under irradiation at 400 nm, and with a gold loading of 10 wt %. This photocatalytic activity was 11.5 times greater than that shown by the unmodified TiO2NWs. For the Au@TiO2NWs-graphene composites, the highest hydrogen amount obtained was 1689 µmol h-1 g-1, at loadings of 10 and 1 wt % of gold and graphene, respectively. The photocatalytic activity of the gold-graphene compounds was 1.2 times greater than that shown by the titanium oxide catalysts and 13.5 times higher than the bare TiO2NWs. Even at wavelengths greater than 500 nm, the compounds exhibited yields of hydrogen above 1000 µmol h-1 g-1, demonstrating the high catalytic activity of the compounds. In addition, TiO2-based materials are of great interest for energy storage and conversion devices, in particular for rechargeable lithium ion batteries. TiO2 has a significant advantage due to its low volume change (<4%) during the Li ion insertion/desertion process, short paths for fast lithium ion diffusion, and large exposed surface, offering more lithium insertion channels. However, the relatively low theoretical capacity and electrical conductivity of TiO2 greatly hamper its practical application. In this work, free-standing electrodes composed by TiO2NWs and carbon nanotubes, CNT@TiO2NWs, were used as anode materials for Li-ion batteries. As a result, the electronic conductivity and mechanical properties of the composite were greatly improved and a good cycling performance was obtained in these batteries. This research shows the potential of TiO2-based materials for the development of new catalysts for hydrogen production and energy storage systems.

Synthesis and photocatalytic activity of TiO2 nanowires in the degradation of p-aminobenzoic acid: A comparative study with a commercial catalyst.

The photocatalytic degradation of p-aminobenzoic acid was studied using TiO2 nanowires as the catalyst synthesized through a hydrothermal procedure. The as-synthesized TiO2 nanowires were fully characterized by SEM, TEM, XRD and Raman with a very high surface area of 512 m(2) g(-1). The photocatalytic degradation of p-aminobenzoic acid was carried out under 180 min of constant radiation and the results were compared with P25 as commercial catalyst. Optimal experimental conditions were determined for TiO2 nanowires with a catalyst dosage of 1.0 g L(-1) under acidic conditions with a 20 µM p-aminobenzoic acid solution obtaining 95% of degradation. Under similar experimental conditions comparative studies were performed obtaining 98% of degradation when P25 is employed. In both systems, a pseudo first order reaction was found to provide the best correlations, with constant rates of 2.0 × 10(-2) min(-1) and 2.4 × 10(-2) min(-1) for TiO2 nanowires and P25, respectively.

Preparation of hollow magnetite microspheres and their applications as drugs carriers.

Hollow magnetite microspheres have been synthesized by a simple process through a template-free hydrothermal approach. Hollow microspheres were surface modified by coating with a silica nanolayer. Pristine and modified hollow microparticles were characterized by field-emission electron microscopy, transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, FT-IR and Raman spectroscopy, and VSM magnetometry. The potential application of the modified hollow magnetite microspheres as a drug carrier was evaluated by using Rhodamine B and methotrexate as model drugs. The loading and release kinetics of both molecules showed a clear pH and temperature dependent profile. GRAPHICAL Hollow magnetite microspheres have been synthesized. Load-release experiments with Rhodamine-B as a model drug and with Methotrexate (chemotherapy drug used in treating certain types of cancer) demonstrated the potential applications of these nanostructures in biomedical applications.

An alternative route for the synthesis of silicon nanowires via porous anodic alumina masks.

Amorphous Si nanowires have been directly synthesized by a thermal processing of Si substrates. This method involves the deposition of an anodic aluminum oxide mask on a crystalline Si (100) substrate. Fe, Au, and Pt thin films with thicknesses of ca. 30 nm deposited on the anodic aluminum oxide-Si substrates have been used as catalysts. During the thermal treatment of the samples, thin films of the metal catalysts are transformed in small nanoparticles incorporated within the pore structure of the anodic aluminum oxide mask, directly in contact with the Si substrate. These homogeneously distributed metal nanoparticles are responsible for the growth of Si nanowires with regular diameter by a simple heating process at 800°C in an Ar-H2 atmosphere and without an additional Si source. The synthesized Si nanowires have been characterized by field emission scanning electron microscopy, high-resolution transmission electron microscopy, X-ray photoelectron spectroscopy, and Raman.

Anodic aluminium oxide membranes used for the growth of carbon nanotubes.

The suitability of anodic aluminum oxide (AAO) membranes as template supported on Si substrates for obtaining organized iron catalyst for carbon nanotube (CNT) growth has been investigated. The iron catalyst was confined in the holes of the AAO membrane. CVD synthesis with ethylene as carbon source led to a variety of carbon structures (nanotubes, helices, bamboo-like, etc). In absence of AAO membrane the catalyst was homogeneously distributed on the Si surface producing a high density of micron-length CNTs.