Proposed mechanisms for water oxidation by Photosystem II and nanosized manganese oxides.

Plants, algae and cyanobacteria capture sunlight, extracting electrons from H2O to reduce CO2 into sugars while releasing O2 in the oxygenic photosynthetic process. Because of the important role of water oxidation in artificial photosynthesis and many solar fuel systems, understanding the structure and function of this unique biological catalyst forms a requisite research field. Herein the structure of the water-oxidizing complex and its ligand environment are described with reference to the 1.9Å resolution X-ray-derived crystallographic model of the water-oxidizing complex from the cyanobacterium Thermosynechococcus vulcanus. Proposed mechanisms for water oxidation by Photosystem II and nanosized manganese oxides are also reviewed and discussed in the paper.

Improvement of photocatalytic ammonia production of cobalt ferrite nanoparticles utilizing microporous ZSM-5 type ferrisilicate zeolite.

The development of decarbonized synthesis approaches is a critical step in the fabrication of ammonia, an indispensable chemical and a potential carbon-neutral energy carrier. In this regard, the photocatalytic production technology has gained ample attention as a sustainable alternative to energy-intensive and environmentally detrimental Haber-Bosch process. Here, we present cobalt ferrite nanoparticles supported on microporous ZSM-5 type ferrisilicate zeolite as a desirable novel photocatalyst for the ammonia generation. The zeolite introduced as a microporous support increasing the catalytically active sites. A straightforward one-pot sol-gel method was used to synthesize cobalt ferrite (CoFe2O4) and CoFe2O4/ferrisilicate (CF/FS) nanocomposites with various weight percentages (10, 25 and 50%) of CoFe2O4. The photocatalytic performances of the samples in the production of ammonia were investigated under visible light irradiation. The highest rate of NH4+ production (484.74 µmol L-1 h-1) was achieved using the CF50%/FS photocatalyst. The distribution of < 50 nm-sized CoFe2O4 nanoparticles on the surface of the zeolite, as demonstrated by TEM images, and extensive BET surface areas are presented as convincing evidences for the improved photocatalytic activity paticularly in CF50%/FS photocatalyst.

Nitrate removal study of synthesized nano γ-alumina and magnetite-alumina nanocomposite adsorbents prepared by various methods and precursors.

The challenges in water treatment include the need for efficient removal of pollutants like nitrate, which poses significant environmental and health risks. Alumina's significance lies in its proven effectiveness as an adsorbent for nitrate removal due to its high surface area and affinity for nitrate ions. This study delves into the synthesis of differen nano-sized γ-alumina (γA1-5) employing diverse precursors and methods, including nepheline syenite, lime, aluminum hydroxide, precipitation, and hydrothermal processes at varying reaction times. Simultaneously, magnetite (Fe3O4) nanoparticles and magnetite/γ-alumina nanocomposites (Fn/γA5) were synthesized using the co-precipitation method with varying weight ratios (n). Our primary objective was to optimize γ-alumina synthesis by comparing multiple methods, shedding light on the influence of different precursors and sources. Hence, a comprehensive adsorption study was conducted to assess the materials' efficacy in nitrate removal. This study fills gaps in the literature, providing a novel perspective through the simultaneous assessment of magnetite/alumina nanocomposites and pure alumina performance. Structural and morphological properties were studied employing XRD, FT-IR, FESEM, EDX, XRD, and VSM techniques. The conducted experiments for γA5, F5/γA5, and F10/γA5 nanocomposites showcased the optimum pH of 5 and contact time of 45 min for all samples. The influence of nitrate's initial concentration on the removal percentage was investigated with initial concentrations of 10 ppm, 50 ppm, and 100 ppm. γA5, F5/γA5 and F10/γA5 nanocomposites had 17.3%, 55%, and 70% at 10 ppm, 18%, 55.16%, and 74% at 50 ppm, and 8.6%, 53.1%, and 63%, respectively. The results highlighted that F10/γA5 can be used as a remarkable adsorbent for wastewater treatment purposes.

Epoxy-matrix polyaniline/p-phenylenediamine-functionalised graphene oxide coatings with dual anti-corrosion and anti-fouling performance.

This research work reports on the anti-corrosion and anti-fouling properties of epoxy (E) coatings reinforced with polyaniline (PANI)/p-phenylenediamine-functionalised graphene oxide (PGO) composites. The mass ratio of graphene oxide/p-phenylenediamine in any PGO was assumed to be 1 : 1, but different PANI-PGO composites containing various loadings of PGO were prepared. An ultrasonic-assisted in situ polymerization method was employed to produce PANI-PGO at low temperature (0 °C). Several analytical and microscopical techniques, i.e., Fourier-transfer infrared (FTIR) spectroscopy, X-ray diffraction (XRD), and field emission scanning electron microscopy (FESEM), were used to confirm that PANI-PGO composites were successfully synthesized. The epoxy-based coatings (E/PANI-PGO (x), x = 0.05-0.4 g) were applied by brushing them onto carbon steel substrates, which exhibited dual anti-corrosion and anti-fouling performance. Electrochemical impedance spectroscopy (EIS) results show that E/PANI-PGO (0.2) has the highest corrosion resistance (8.87 × 106 Ω cm2) after 192 h of immersion in 3.5 wt% NaCl amongst all the coatings compared with neat epoxy (1.00 × 104 Ω cm2) and E/PANI (6.82 × 103 Ω cm2). Efficient antifouling performance at the macroscopic level under simulated marine conditions was observed for the epoxy-based PANI-PGO coatings with a range of PGO compositions, in particular for the 0.1 and 0.2 g PGO coatings.

Microwave-Assisted Auto-Combustion Synthesis of Binary/Ternary Co x Ni1-x Ferrite for Electrochemical Hydrogen and Oxygen Evolution.

Enormous efforts have been dedicated to engineering low-cost and efficient electrocatalysts for both hydrogen evolution and oxygen evolution reactions (HER and OER, respectively). For this, the current contribution reports the successful synthesis of binary/ternary metal ferrites (Co x Ni1-x Ferrite; x = 0.0, 0.1, 0.3, 0.5, 0.7, and 1.0) by a simple one-step microwave technique and subsequently discusses its chemical and electrochemical properties. The X-ray diffraction analysis substantiated the phase purity of the as-obtained catalysts with various compositions. Additionally, the morphology of the nanoparticles was identified via transmission electron microscopy. Further, the vibrating sample magnetometer justified the ferromagnetic character of the as-prepared products. The electrochemical measurements revealed that the as-prepared materials required the overpotentials of 422-600 and 419-467 mV for HER and OER, respectively, to afford current densities of 10 mA cm-2. In the general sense, Ni cation substitution with Co influenced favorably toward both HER and OER. Among all synthesized electrocatalysts, Co0.9Ni0.1Ferrite displayed the highest performance in terms of OER in 1 M KOH solution, which is related to the synergistic effect of multiple parameters including the optimal substitution amount of Co, the highest Brunauer-Emmett-Teller surface area, the smallest particle size among all samples (26.71 nm), and the lowest charge transfer resistance. The successful synthesis of ternary ferrites carried out for the first time via a microwave-assisted auto-combustion route opens up a new path for their applications in renewable energy technologies.

Electrochemical water oxidation by simple manganese salts.

Recently, it has been great efforts to synthesize an efficient water-oxidizing catalyst. However, to find the true catalyst in the harsh conditions of the water-oxidation reaction is an open area in science. Herein, we showed that corrosion of some simple manganese salts, MnCO3, MnWO4, Mn3(PO4)2 · 3H2O, and Mn(VO3)2 · xH2O, under the water-electrolysis conditions at pH = 6.3, gives an amorphous manganese oxide. This conversion was studied with X-ray absorption spectroscopy (XAS), as well as, scanning electron microscopy (SEM), Energy-dispersive X-ray spectroscopy (EDXS), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), spectroelectrochemistry and electrochemistry methods. When using as a water-oxidizing catalyst, such results are important to display that long-term water oxidation can change the nature of the manganese salts.