An Amiable Design of Cobalt Single Atoms as the Active Sites for Oxygen Evolution Reaction in Desalinated Seawater.

Green fuel from water splitting is hardcore for future generations, and the limited source of fresh water (<1%) is a bottleneck. Seawater cannot be used directly as a feedstock in current electrolyzer techniques. Until now single atom catalysts were reported by many synthetic strategies using notorious chemicals and harsh conditions. A cobalt single-atom (CoSA) intruding cobalt oxide ultrasmall nanoparticle (Co3 O4 USNP)-intercalated porous carbon (PC) (CoSA-Co3 O4 @PC) electrocatalyst was synthesized from the waste orange peel as a single feedstock (solvent/template). The extended X-ray absorption fine structure spectroscopy (EXAFS) and theoretical fitting reveal a clear picture of the coordination environment of the CoSA sites (CoSA-Co3 O4 and CoSA-N4 in PC). To impede the direct seawater corrosion and chlorine evolution the seawater has been desalinated (Dseawater) with minimal cost and the obtained PC is used as an adsorbent in this process. CoSA-Co3 O4 @PC shows high oxygen evolution reaction (OER) activity in transitional metal impurity-free (TMIF) 1 M KOH and alkaline Dseawater. CoSA-Co3 O4 @PC exhibits mass activity that is 15 times higher than the commercial RuO2 . Theoretical interpretations suggest that the optimized CoSA sites in Co3 O4 USNPs reduce the energy barrier for alkaline water dissociation and simultaneously trigger an excellent OER followed by an adsorbate evolution mechanism (AEM).

An environmentally benign synthesis of Fe3O4 nanoparticles to Fe3O4 nanoclusters: Rapid separation and removal of Hg(II) from an aqueous medium.

In the field of nanotechnology, nanoadsorbents have emerged as a powerful tool for the purification of contaminated aqueous environments. Among the variety of nanoadsorbents developed so far, magnetite (Fe3O4) nanoparticles have drawn particular interest because of their quick separation, low cost, flexibility, reproducibility, and environmentally benign nature. Herein, we describe a new strategy for the synthesis of Fe3O4 nanoclusters, which is based on the use of naturally available edible mushrooms (Pleurotus eryngii) and environmentally benign propylene glycol as a solvent medium. By tuning the temperature, we successfully convert Fe3O4 nanoparticles into Fe3O4 nanoclusters via hydrothermal treatment, as evidenced by transmission electron microscopy. The Fe3O4 nanoclusters are functionalized with an organic molecule linker (dihydrolipoic acid, DHLA) to remove hazardous Hg(II) ions selectively. Batch adsorption experiments demonstrate that Hg(II) ions are strongly adsorbed on the material surface, and X-ray photoelectron and Fourier transform infrared spectroscopy techniques reveal the Hg(II) removal mechanism. The DHLA@Fe3O4 nanoclusters show a high removal efficiency of 99.2 % with a maximum Hg(II) removal capacity of 140.84 mg g-1. A kinetic study shows that the adsorption equilibrium is rapidly reached within 60 min and follows a pseudo second-order kinetic model. The adsorption and separation system can be readily recycled using an external magnet when the separation occurs within 10 s. We have studied the effect of various factors on the adsorption process, including pH, concentration, dosage, and temperature. The newly synthesized superparamagnetic DHLA@Fe3O4 nanoclusters open a new path for further development of the medical, catalysis, and environmental fields.

Biosynthesized Highly Stable Au/C Nanodots: Ideal Probes for the Selective and Sensitive Detection of Hg2+ Ions.

The enormous ongoing industrial development has caused serious water pollution which has become a major crisis, particularly in developing countries. Among the various water pollutants, non-biodegradable heavy metal ions are the most prevalent. Thus, trace-level detection of these metal ions using a simple technique is essential. To address this issue, we have developed a fluorescent probe of Au/C nanodots (GCNDs-gold carbon nanodots) using an eco-friendly method based on an extract from waste onion leaves (Allium cepa-red onions). The leaves are rich in many flavonoids, playing a vital role in the formation of GCNDs. Transmission electron microscopy (TEM) and Scanning transmission electron microscopy-Energy-dispersive X-ray spectroscopy (STEM-EDS) elemental mapping clearly indicated that the newly synthesized materials are approximately 2 nm in size. The resulting GCNDs exhibited a strong orange fluorescence with excitation at 380 nm and emission at 610 nm. The GCNDs were applied as a fluorescent probe for the detection of Hg2+ ions. They can detect ultra-trace concentrations of Hg2+ with a detection limit of 1.3 nM. The X-ray photoelectron spectroscopy results facilitated the identification of a clear detection mechanism. We also used the new probe on a real river water sample. The newly developed sensor is highly stable with a strong fluorescent property and can be used for various applications such as in catalysis and biomedicine.

Bio-inspired self-propelled diatom micromotor by catalytic decomposition of H2O2 under low fuel concentration.

Recently, active bubble-propelled micromotors have attracted great attention for fuel applications. However, for generating bubble-propelled micromotors, additional catalysts, such as Pt, Ag, and Ru, are required. These catalysts are expensive, toxic, and highly unstable for broad applications. To overcome these issues, in this study, we present an innovative methodology for the preparation of self-propelled motor machines using naturally occurring diatom frustules. This natural diatom motor shows effective motion in the presence of a very low concentration (0.8%) of H2O2 as a fuel at pH 7. Due to the unique 3D anisotropic shape of the diatom, the self-propelled motor exhibited unidirectional motion with a speed of 50 µm s-1 and followed pseudo first-order kinetics. It was found that a trace amount of iron oxide (Fe2O3) in the diatom was converted into Fe3O4, which can act as a catalyst to achieve the facile decomposition of H2O2. Interestingly, "braking" of the unidirectional motion was observed upon treatment with EDTA, which blocked the catalytically active site. These results illustrate that diatom catalytic micromotors have opened a new era in the field of catalysis and bioengineering applications.

Highly Sensitive Electrochemical Sensor for Anticancer Drug by a Zirconia Nanoparticle-Decorated Reduced Graphene Oxide Nanocomposite.

Because of their large surface area and conductivity, some inorganic materials have emerged as good candidates for the trace-level detection of pharmaceutical drugs. In the present work, we demonstrate the detection of an anticancer drug (regorafenib, REG) by using an electrochemical sensor based on a nanocomposite material. We synthesized a zirconia-nanoparticle-decorated reduced graphene oxide composite (ZrO2/rGO) using a one-pot hydrothermal method. Reduction of the graphene oxide supports of the Zr2+ ions with hydrazine hydrate helped in preventing the agglomeration of the zirconia nanoparticles and in obtaining an excellent electrocatalytic response of the nanostructure ZrO2/rGO-based electrochemical sensor. Structural and morphological characterization of the nanostructure ZrO2/rGO was performed using various analytical methods. A novel regorafenib (REG) electrochemical sensor was fabricated by immobilizing the as-prepared nanostructure ZrO2/rGO on to a glassy carbon electrode (GCE). The resulting ZrO2/rGO/GCE could be used for the rapid and selective determination of REG in the presence of ascorbic acid and uric acid. The ZrO2/rGO/GCE showed a linear response for the REG analysis in the dynamic range 11-343 nM, with a remarkable lower detection limit and limit of quantifications of 17 and 59 nM, respectively. The newly developed sensor was used for the accurate determination of REG in both serum samples and pharmaceutical formulations, with satisfactory results.

Bioinspired 2D-Carbon Flakes and Fe3O4 Nanoparticles Composite for Arsenite Removal.

Development of carbon-based materials has received tremendous attention owing to their multifunctional properties. Biomaterials often serve as an inspiration for the preparation of new carbon materials. Herein, we present a facile synthesis of a new bioinspired graphene oxide-like 2D-carbon flake (CF) using a natural resource, waste onion sheathing (Allium cepa). The 2D-CF was further decorated with crystalline Fe3O4 nanoparticles for applications. Superparamagnetic Fe3O4 nanoparticles (7 nm) were well-dispersed on the surface of the 2D-CF, which was characterized by X-ray diffractometry, X-ray photoelectron spectroscopy, Raman spectrometry, and transmission electron microscopy. Batch As(III) adsorption experiments showed that aqueous arsenic ions strongly adsorbed to the Fe3O4@2D-CF composite. The adsorption capacity of the Fe3O4@2D-CF composite for As(III) was 57.47 mg g(-1). The synergetic effect of both graphene oxide-like 2D-CF and Fe3O4 nanoparticles aided in excellent As(III) adsorption. An As(III) ion adsorption kinetics study showed that adsorption was very fast at the initial stage, and equilibrium was reached within 60 min following a pseudo-second-order rate model. Owing to the excellent superparamagnetic properties (52.6 emu g(-1)), the Fe3O4@2D-CF composite exhibited superb reusability with the shortest recovery time (28 s) among reported materials. This study indicated that Fe3O4@2D-CF composites can be used for practical applications as a global economic material for future generations.

Surfactant-free green synthesis of Fe3O4 nanoparticles capped with 3,4-dihydroxyphenethylcarbamodithioate: stable recyclable magnetic nanoparticles for the rapid and efficient removal of Hg(II) ions from water.

Mercury is considered one of the most notorious global pollutants due to its high toxicity and widespread use in industry. Although many materials have been developed for the removal of mercury for water purification, most of these materials are difficult to reuse, which may lead to an increase in the mercury handling expense. Therefore, new sustainable materials that can be easily recycled and are highly efficient for the removal of mercury are required. Herein, we report the surfactant-free green synthesis of Fe3O4 magnetic nanoparticles (MNPs) using a watermelon (Citrullus lanatus) rind extract. The Fe3O4 MNPs were further functionalized with 3,4-dihydroxyphenethylcarbamodithioate (DHPCT) and applied to the removal of Hg(ii). Evaluation of the mercury removal efficiency and the amount adsorbed by DHPCT@Fe3O4 MNPs demonstrated a high Hg(ii) removal efficiency (98%) with a maximum Hg(ii) adsorption capacity of 52.1 mg g(-1). Systematic studies of the adsorption mechanism and selectivity suggest that the soft ligand (DHPCT) can preferentially coordinate with the soft metal ion (Hg(ii)) resulting in selective mercury removal. The developed DHPCT@Fe3O4 MNPs were readily recycled several times using an external magnet by exploiting their ferromagnetic character, without a significant decline in the Hg(ii) removal efficiency. This study provides a new insight into the preparation of a highly efficient adsorbent for Hg(ii) removal by an eco-friendly method.

Core-Shell Ferromagnetic Nanorod Based on Amine Polymer Composite (Fe3O4@DAPF) for Fast Removal of Pb(II) from Aqueous Solutions.

Heavy metal ion removal from wastewater constitutes an important issue in the water treatment industry. Although a variety of nanomaterials have been developed for heavy metal removal via adsorption, the adsorption capacity, removal efficiency, and material recyclability still remain a challenge. Here, we present novel Fe3O4@DAPF core-shell ferromagnetic nanorods (CSFMNRs) for the removal of Pb(II) from aqueous solutions; they were prepared by the facile surface modification of twin-like ferromagnetic Fe3O4 nanorods using a 2,3-diaminophenol and formaldehyde (DAPF)-based polymer. The crystallinity and structure of the Fe3O4 nanorods were confirmed via X-ray diffraction (XRD). Transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS) revealed the core-shell morphology and composition of the materials. Pb(II) removal using the prepared Fe3O4@DAPF CSFMNRs was assessed, and comparable adsorption capacities (83.3 mg g(-1)) to the largest value were demonstrated. A thermodynamic study of the adsorption clearly indicated that the adsorption was exothermic and spontaneous. Due to the ferromagnetic properties with a high saturation magnetization value (56.1 emu g(-1)) of the nanorods, the nanorods exhibited excellent reusability with one of the fastest recovery times (25 s) among reported materials. Therefore, the Fe3O4@DAPF CSFMNRs can serve as recyclable adsorbent materials and as an alternative to commonly used sorbent materials for the rapid removal of heavy metals from aqueous solutions.