Masaki Ujihara

Significantly stronger ROS and OER activities of FeSA950NC suggest the significant roles of V _N and sp ³ -carbon defects with coordinately unsaturated Fe–N ₂ sites in improving its catalytic performance.

A high-temperature pyrolysis-controlled coordination reconstruction resulted in a single-Ni-atom structure with a Ni–N_x–C structural unit (x = N atom coordinated to Ni). Pyrolysis of Ni-phen@ZIF-8-RF at 700 °C resulted in NiNP-NC-700 with predominantly Ni nanoparticles. Upon elevating the pyrolysis temperature from 700 to 900 °C, a coordination reconstruction offers Ni–N_x atomic sites in NiSA-NC-900. A combined investigation with X-ray absorption spectroscopy, X-ray photoelectron spectroscopy, and soft X-ray L₃-edge spectroscopy suggests the stabilization of low-valent Ni^δ+ (0 < δ < 2) in the Ni–N–C structural units. The oxygen evolution reaction (OER) is a key process during water splitting in fuel cells. However, OER is a thermodynamically uphill reaction with multi-step proton-coupled electron transfer and sluggish kinetics, due to which there is a need for a catalyst that can lower the OER overpotentials. The adsorption energy of a multi-step reaction on a single metal atom with coordination unsaturation tunes the adsorption of each oxygenated intermediate. The promising OER activity of the NiSA-NC-900/NF anode on nickel foam was followed by the overall water splitting (OWS) using using NiSA-NC-900/NF as anode and Pt coil as the cathodic counterpart, wherein a cell potential of 1.75 V at 10 mA cm⁻² was achieved. The cell potential recorded with Pt(−)/(+)NiSA-NC-900/NF was much lower than that obtained for other cells, i.e., Pt(−)/NF and NF(−)/(+)NF, which enhances the potentials of low-valent NiSAs for insightful understanding of the OER. At a constant applied potential of 1.61 V (vs. RHE) for 12 h, an small increase in current for initial 0.6 h followed by a constant current depicts the fair stability of catalyst for 12 h. Our results offer an insightful angle into the OER with a coordinatively reconstructed single-Ni-atom structure at lower valency (<+2).

Mixed and core–shell WO₃/TiO₂exhibited different photocatalytic activities due to their surface charges and charge separation behaviors.

For effective supercapacitors, we developed a process involving chemical bath deposition, followed by electrochemical deposition and calcination, to produce WO₃/SnO₂ nanocomposite electrodes. In aqueous solutions, the hexagonal WO₃ microspheres were first chemically deposited on a carbon cloth, and then tin oxides were uniformly electrodeposited. The synthesized WO₃/SnO₂ nanocomposite was characterized by XRD, XPS, SEM, and EDX techniques. Electrochemical properties of the WO₃/SnO₂ nanocomposite were analyzed by cyclic voltammetry, galvanostatic charge-discharge tests, and electrochemical impedance spectroscopy in an aqueous solution of Na₂SO₄ with/without the redox-active electrolyte K₃Fe(CN)₆. K₃Fe(CN)₆ exhibited a synergetic effect on the electrochemical performance of the WO₃/SnO₂ nanocomposite electrode, with a specific capacitance of 640 F/g at a scan rate of 5 mV/s, while that without K₃Fe(CN)₆ was 530 F/g. The WO₃/SnO₂ nanocomposite catalyzed the redox reactions of [Fe(CN)₆]³/[Fe(CN)₆]⁴⁻ ions, and the [Fe(CN)₆]³⁻/[Fe(CN)₆]⁴⁻ ions also promoted redox reactions of the WO₃/SnO₂ nanocomposite. A symmetrical configuration of the nanocomposite electrodes provided good cycling stability (coulombic efficiency of 99.6% over 2000 cycles) and satisfied both energy density (60 Whkg⁻¹) and power density (540 Wkg⁻¹) requirements. Thus, the WO₃/SnO₂ nanocomposite prepared by this simple process is a promising component for a hybrid pseudocapacitor system with a redox-flow battery mechanism.

Graphene oxide (GO), single-walled carbon nanohorn (CNHox), and nitrogen-doped CNH (N-CNH) were functionalized with fluorinated poly(ethylene glycol) (F-PEG) and/or with a fluorinated dendrimer (F-DEN) to prepare a series of assembled nanocomposites (GO/F-PEG, CNHox/F-PEG, N-CNH/F-PEG, N-CNH/F-DEN, and N-CNH/F-DEN/F-PEG) that provide effective multisite O2 reservoirs. In all cases, the O2 uptake increased with time and saturated after 10-20 min. When graphitic carbons (GO and CNHox) were coated with F-PEG, the O2 uptake doubled. The O2 loading was slightly higher in N-CNH compared to CNHox. Notably, coating N-CNH with F-DEN or F-PEG, or with both F-DEN and F-PEG, was more effective. The best performance was obtained with the N-CNH/F-DEN/F-PEG nanocomposite. The O2 uptake kinetics and mechanisms were analyzed in terms of the Langmuir adsorption equation based on a multibinding site assumption. This allowed the precise determination of multiple oxygen binding sites, including on the graphitic structure and in the dendrimer, F-DEN, and F-PEG. After an initial rapid, relatively limited release, the amount of O2 trapped in the nanomaterials remained high (> 95%). This amount was marginally lower for the functionalized composites, but the oxygen stored was reserved for longer times. Finally, it is shown that these systems can generate singlet oxygen after irradiation by a light-emitting diode, and this production correlates with the amount of O2 loaded. Thus, it was anticipated that the present nanocomposites hierarchically assembled from components with different characters and complementary affinities for oxygen can be useful as O(2 )reservoirs for singlet oxygen generation to kill bacteria and viruses and to perform photodynamic therapy.