Gray mesoporous SnO2 catalyst for CO2 electroreduction with high partial current density and formate selectivity.

The mesoporous metal oxide semiconductors exhibit unique chemical and physical characteristics, making them highly desirable for catalysis, electrochemistry, energy conversion, and energy storage applications. Here, we report the facial fabrication of mesoporous gray SnO2 (MGS) electrocatalysts employing an evaporation-induced co-assembly (EICA) approach, utilizing poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) triblock copolymers Pluronic P123 (PEO-PPO-PEO) triblock copolymer as a template for electrochemical CO2 reduction reaction (eCO2RR). By sustaining the co-assembly conditions and utilizing a thermal treatment technique based on carbon, gray mesoporous SnO2 materials with a high density of active sites and oxygen vacancies can be constructed. The MGS materials were employed in eCO2RR in a flow cell type, which exhibits excellent catalytic activity and selectivity toward formate with a high partial current density of -234 mA cm-2 and Faradaic efficiency (FE) of 93.60 % at -1.3 V vs. reversible hydrogen electrode (RHE). Interestingly, the mesoporous SnO2 with a 1.5 wt% ratio of Sn precursor to P123 surfactant (MS-1.5@350N-400A) electrode exhibits a high level of Faradaic efficiency (FE) of (98%) at a low overpotential of -0.6 VRHE, which is a seldom recorded performance for similar systems. A stable FE of 96 ± 1% was observed in the range of -0.6 to -1.2 VRHE, which is the result of a large surface area (184 m2/g) and a high number of active sites and oxygen vacancies within the mesostructured framework.

Enhanced electrocatalytic oxygen redox reactions of iron oxide nanorod films by combining oxygen vacancy formation and cobalt doping.

A synergistic effect of Co-doping and vacuum-annealing on electrochemical redox reactions of iron oxide films is demonstrated in the present work. In this research, a series of defect-rich iron oxy/hydroxide nanorod arrays: α-FeOOH, Fe2O3, and FeOx nanorod thin film catalysts were synthesized via a hydrothermal approach followed by thermal and vacuum treatments. Besides, a cobalt doping process was employed to prepare the thin film of Co-doped FeOx nanorods. The morphology, crystallinity, and electrochemical activities of Co-doped oxygen-deficient FeOx (Co-FeOx/FTO) show strong correlations with metal concentration and thermal treatments. The electrochemical measurements demonstrated that the as-deposited Co-doped FeOx NR catalyst could achieve a maximum OER current of 30 mA cm-2, which was six times greater than that recorded by as-deposited Co-doped FeOOH NR catalysts (5.7 mA cm-2) at 1.65 V vs. RHE, confirming the superior electrocatalytic OER activity at the as-deposited Co-doped FeOx NR catalyst after cobalt doping. It is believed that these results are attributed to two factors: the synergistic effect of Co doping and the defect-rich nature of FeOx nanorod catalysts that are used in sustainable energy systems.

Fabricated Gamma-Alumina-Supported Zinc Ferrite Catalyst for Solvent-Free Aerobic Oxidation of Cyclic Ethers to Lactones.

The aim of this work was to fabricate a new heterogeneous catalyst as zinc ferrite (ZF) supported on gamma-alumina (γ-Al2O3) for the conversion of cyclic ethers to the corresponding, more valuable lactones, using a solvent-free method and O2 as an oxidant. Hence, the ZF@γ-Al2O3 catalyst was prepared using a deposition-coprecipitation method, then characterized using TEM, SEM, EDS, TGA, FTIR, XRD, ICP, XPS, and BET surface area, and further applied for aerobic oxidation of cyclic ethers. The structural analysis indicated spherical, uniform ZF particles of 24 nm dispersed on the alumina support. Importantly, the incorporation of ZF into the support influenced its texture, i.e., the surface area and pore size were reduced while the pore diameter was increased. The product identification indicated lactone compound as the major product for saturated cyclic ether oxidation. For THF as a model reaction, it was found that the supported catalyst was 3.2 times more potent towards the oxidation of cyclic ethers than the unsupported one. Furthermore, the low reactivity of the six-membered ethers can be tackled by optimizing the oxidant pressure and the reaction time. In the case of unsaturated ethers, deep oxidation and polymerization reactions were competitive oxidations. Furthermore, it was found that the supported catalyst maintained good stability and catalytic activity, even after four cycles.

Bifunctional vanadium doped mesoporous Co3O4 on nickel foam towards highly efficient overall urea and water splitting in the alkaline electrolyte.

Developing more active and stable electrode materials for oxygen evolution reaction (OER) and urea oxidation reaction (UOR) is necessary for electrocatalytic water and urea oxidation which can be used to generate hydrogen. Here, a low-cost vanadium-doped mesoporous cobalt oxide on Ni foam (V/meso-Co/NF) electrodes are obtained via the grouping of an in-situ citric acid (CA)-assisted evaporation-induced self-assembly (EISA) method and electrophoretic deposition process, and work as highly efficient and long-lasting electrocatalytic materials for OER/UOR. In particular, V/meso-Co/NF electrodes require 329 mV overpotential to maintain a 50 mA/cm2, with exceptional long-term durability of 30 h. Interestingly, V/meso-Co/NF also exhibits excellent electrocatalytic UOR performance, reaching 50 and 100 mA/cm2 versus RHE at low potentials of 1.34 and 1.35 V, respectively. By employing the V/meso-Co/NF materials as both the anode and cathode, this urea electrolysis assembly V/meso-Co/NF-5 (+,-) reaches current densities of 100 mA cm-2 at 1.62 V in KOH/urea, which is nearly 340 mV lesser than classical water electrolysis. The V/meso-Co/NF-5 electrocatalysts also exhibit remarkable durability for electrocatalytic OERs and UORs. The obtained findings revealed that the synthesized V/meso-Co/NF might be a promising electrode materials for overall urea-rich wastewater management and H2 generation from wastewater.

Photoelectrochemical Performance of Strontium Titanium Oxynitride Photo-Activated with Cobalt Phosphate Nanoparticles for Oxidation of Alkaline Water.

Photoelectrochemical (PEC) solar water splitting is favourable for transforming solar energy into sustainable hydrogen fuel using semiconductor electrodes. Perovskite-type oxynitrides are attractive photocatalysts for this application due to their visible light absorption features and stability. Herein, strontium titanium oxynitride (STON) containing anion vacancies of SrTi(O,N)3-δ was prepared via solid phase synthesis and assembled as a photoelectrode by electrophoretic deposition, and their morphological and optical properties and PEC performance for alkaline water oxidation are investigated. Further, cobalt-phosphate (CoPi)-based co-catalyst was photo-deposited over the surface of the STON electrode to boost the PEC efficiency. A photocurrent density of ~138 µA/cm at 1.25 V versus RHE was achieved for CoPi/STON electrodes in presence of a sulfite hole scavenger which is approximately a four-fold enhancement compared to the pristine electrode. The observed PEC enrichment is mainly due to the improved kinetics of oxygen evolution because of the CoPi co-catalyst and the reduced surface recombination of the photogenerated carriers. Moreover, the CoPi modification over perovskite-type oxynitrides provides a new dimension for developing efficient and highly stable photoanodes in solar-assisted water-splitting reactions.

Facile Synthesis, Characterization, Photocatalytic Activity, and Cytotoxicity of Ag-Doped MgO Nanoparticles.

Due to unique physicochemical properties, magnesium oxide nanoparticles (MgO NPs) have shown great potential for various applications, including biomedical and environmental remediation. Moreover, the physiochemical properties of MgO NPs can be tailored by metal ion doping that can be utilized in photocatalytic performance and in the biomedical field. There is limited study on the photocatalytic activity and biocompatibility of silver (Ag)-doped MgO NPs. This study was planned for facile synthesis, characterization, and photocatalytic activity of pure and silver (Ag)-doped MgO NPs. In addition, cytotoxicity of pure and Ag-doped MgO NPs was assessed in human normal umbilical vein endothelial cells (HUVECs). Pure MgO NPs and Ag-doped (1, 2, 5, and 7.5 mol%) MgO NPs were prepared via a simple sol-gel procedure. X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared (FTIR), photoluminescence (PL), and X-ray photoelectron spectroscopy (XPS) were used to characterize the prepared samples. XRD results showed the preparation of highly crystalline NPs with no impurity peaks. TEM and SEM studies indicate smooth surfaces with almost spherical morphology of MgO NPs, and Ag-doping did not change the morphology. Elemental composition study suggested that Ag is uniformly distributed in MgO particles. Intensity of the PL spectra of MgO NPs decreased with increasing the concentration of Ag dopants. In comparison to pure MgO NPs, Ag-MgO NPs showed higher degradation of methylene blue (MB) dye under UV irradiation. The improved photocatalytic activity of Ag-MgO NPs was related to the effect of dopant concentration on reducing the recombination between electrons and holes. Cytotoxicity studies showed good biocompatibility of pure and Ag-doped MgO NPs with human normal umbilical vein endothelial cells (HUVECs). These results highlighted the potential of Ag-doped MgO NPs in environmental remediation.

Structure and electrochemical activity of nickel aluminium fluoride nanosheets during urea electro-oxidation in an alkaline solution.

An electrocatalyst of potassium nickel aluminium hexafluoride (KNiAlF6) nanosheets has been prepared using solid-phase synthesis at 900 °C. X-ray diffraction, scanning electron microscopy, and conductivity studies confirmed the formation of KNiAlF6 nanosheets having a cubic defect pyrochlore structure with an average thickness of 60-70 nm and conductivity of 1.297 × 103 S m-1. The electrochemical catalytic activity of the KNiAlF6 nanosheets was investigated for urea oxidation in alkaline solution. The results show that the KNiAlF6 nanosheets exhibit a mass activity of ∼395 mA cm-2 mg-1 at 1.65 V vs. HRE, a reaction activation energy of 4.02 kJ mol-1, Tafel slope of 22 mV dec-1 and an oxidation onset potential of ∼1.35 V vs. HRE which is a significant enhancement for urea oxidation when compared with both bulk Ni(OH)2 and nickel hydroxide-based catalysts published in the literature. Chronoamperometry and impedance analysis of the KNiAlF6 nanosheets reveal lower charge transfer resistance and long-term stability during the prolonged urea electro-oxidation process, particularly at 60 °C. After an extended urea electrolysis process, the structure and morphology of the KNiAlF6 nanosheets were significantly changed due to partial transformation to Ni(OH)2 but the electrochemical activity was sustained. The enhanced electrochemical surface area and the replacement of nickel in the lattice by aluminium make KNiAlF6 nanosheets highly active electrocatalysts for urea oxidation in alkaline solution.

Mesoporous Tungsten Trioxide Photoanodes Modified with Nitrogen-Doped Carbon Quantum Dots for Enhanced Oxygen Evolution Photo-Reaction.

Nanostructured photoanodes are attractive materials for hydrogen production via water photo-electrolysis process. This study focused on the incorporation of carbon quantum dots doped with nitrogen as a photosensitizer into mesoporous tungsten trioxide photoanodes (N-CQD/meso-WO3) using a surfactant self-assembly template approach. The crystal structure, composition, and morphology of pure and N-CQD- modified mesoporous WO3 photoanodes were investigated using scanning electron and transmission microscopy, X-ray diffraction, and X-ray photoelectron spectroscopy. Due to their high surface area, enhanced optical absorption, and charge-carrier separation and transfer, the resulting N-CQD/meso-WO3 photoanodes exhibited a significantly enhanced photocurrent density of 1.45 mA cm-2 at 1.23 V vs. RHE under AM 1.5 G illumination in 0.5 M Na2SO4 without any co-catalysts or sacrificial reagent, which was about 2.23 times greater than its corresponding pure meso-WO3. Moreover, the oxygen evolution onset potential of the N-CQD/meso-WO3 photoanodes exhibited a negative shift of 95 mV, signifying that both the charge-carrier separation and transfer processes were promoted.