Exploiting the synergistic catalytic effects of CoPi nanostructures on Zr-doped highly ordered TiO2 nanotubes for efficient solar water oxidation

Photoelectrochemical (PEC) catalysis offers promising strategies for sustainable development. This study demonstrated the synergistic catalytic behavior of ZrO2 and a cobalt phosphate on anodized TiO2 nanotubes (TNTs), which significantly enhanced the PEC performance for visible-light-driven water splitting reactions. The sequential addition of ZrO2/CoPi-decorated TNTs was performed via electrodeposition and photoassisted electrodeposition. The substitution of Zr4+ by Ti4 can lead to the creation of oxygen vacancies, enabling electron trapping, reducing charge recombination, and thereby enhancing the charge transfer efficiency. Further, in the case of TNTs/ZrO2/CoPi photoanode, the CoPi WOC functioned as a hole-transfer relay to promote the water-splitting reaction. Specifically, incorporating ZrO2/CoPi rushes the surface reaction kinetics of TNTs and considerably improves charge transfer efficiency (ηCT = 90%), photocurrent density (0.86 mA/cm2 at 1.23 VRHE) and durability were obtained. Further, the mechanistic examination by impedance measurements showed the enhanced charge transfer, and surface conductivity for prepared materials. The proposed method can be widely used to develop electrodes made of other materials to produce solar fuels

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

Bulletin of the Kyushu Imperial University Forests

In recent years, microfluidic chips have proven ideal tools for biochemical analysis, which, however, demands a unique and compatible plasma separation scheme. Various research groups have established continuous flow separation methods in microfluidic devices; however, they have worked with relatively small dimension microchannels (similar to the blood cell diameter). The present work demonstrates separation of plasma by utilizing the hydrodynamic separation techniques in microchannels with size of the order of mm. The separation process exploits the phenomenon, which is very similar to that of plasma skimming explained under Zweifach-Fung bifurcation law. The present experiments demonstrates for, the first time, that applicability of the Zweifach-Fung bifurcation law can be extended to dimensions much higher than the suspended particle size. The T-microchannel device (comprising perpendicularly connected blood and plasma channels) were micro-fabricated using conventional PDMS micro-molding techniques. Three variables (feed hematocrit, main channel width, and flow rate distributions) were identified as the important parameters which define the device's efficiency for the blood plasma separation. A plasma separation efficiency of 99.7 % was achieved at a high flow ratio. Novel concepts of 2-stage or multiple plasma channel designs are also proposed to yield high separation efficiency with undiluted blood. The possible underlying principle causing plasma separation (viz. aggregation and shear thinning) are investigated in detail as part of this work. The results are significant because they show nearly 100 % separations in microchannels which are much easier to fabricate than previously designed device

Bifunctional Electrocatalyst of Low-Symmetry Mesoporous Titanium Dioxide Modified with Cobalt Oxide for Oxygen Evolution and Reduction Reactions

Hybrids of low-symmetry (disordered) mesoporous titanium dioxide modified with different weight ratios of cobalt oxide nanoparticles (Co3O4(x)/lsm-TiO2) are prepared using a one-pot self-assembly surfactant template. The physicochemical characterization of Co3O4(x)/lsm-TiO2 hybrids by scanning and transmission electron microscopy, X-ray diffraction, N2 adsorption–desorption isotherms, and X-ray photoelectron spectroscopy confirm the successful incorporation of cobalt oxide nanoparticles (2–3 nm in diameter) with preservation of the highly mesoporous structure of titanium dioxide substrate. Among these mesoporous hybrids, the ~3.0 wt.% Co3O4/lsm-TiO2 exhibits the best performance toward both the oxygen evolution (OER) and reduction (ORR) reactions in alkaline solution. For the OER, the hybrid shows oxidation overpotential of 348 mV at 10 mA cm−2, a turnover frequency (TOF) of 0.034 s−1, a Tafel slope of 54 mV dec−1, and mass activity of 42.0 A g−1 at 370 mV. While for ORR, an onset potential of 0.84 V vs. RHE and OER/ORR overpotential gap (ΔE) of 0.92 V are achieved which is significantly lower than that of commercial Pt/C, hexagonal mesoporous, and bulk titanium dioxide analogous. The Co3O4/lsm-TiO2 hybrid demonstrates significantly higher long-term durability than IrO2. Apparently, such catalytic activity performance originates from the synergetic effect between Co3O4 and TiO2 substrate, in addition to higher charge carrier density and the presence of disordered mesopores which provide short ions diffusion path during the electrocatalytic process

Boosting the Photoelectrochemical Water Oxidation Performance of TiO2 Nanotubes by Surface Modification Using Silver Phosphate

Photoelectrocatalytic approaches are fascinating options for long-lasting energy storage through the transformation of solar energy into electrical energy or hydrogen fuel. Herein, we report a facile method of fabricating a composite electrode of well-aligned TiO2 nanotubes (TNTs) decorated with photodeposited silver phosphate (Ag3PO4) nanoparticles. Assessment of the optical, physiochemical and photoelectrochemical features demonstrated that the fabricated TNTs/Ag3PO4 films showed a substantially boosted photocurrent response of 0.74 mA/cm2, almost a 3-fold enrichment in comparison with the pure TNTs. Specifically, the applied bias photon-to-current efficiency of the fabricated TNTs/Ag3PO4 composite electrode was 2.4-fold superior to that of the pure TNTs electrode. In these TNTs/Ag3PO4 photoanodes, the introduction of Ag3PO4 over TNTs enhanced light absorption and improved charge transfer and surface conductivity. The developed process can be generally applied to designing and developing efficient contact interfaces between photoanodes and numerous cocatalysts

Boosting the Photoelectrochemical Water Oxidation Performance of TiO₂ Nanotubes by Surface Modification Using Silver Phosphate

Photoelectrocatalytic approaches are fascinating options for long-lasting energy storage through the transformation of solar energy into electrical energy or hydrogen fuel. Herein, we report a facile method of fabricating a composite electrode of well-aligned TiO2 nanotubes (TNTs) decorated with photodeposited silver phosphate (Ag3PO4) nanoparticles. Assessment of the optical, physiochemical and photoelectrochemical features demonstrated that the fabricated TNTs/Ag3PO4 films showed a substantially boosted photocurrent response of 0.74 mA/cm2, almost a 3-fold enrichment in comparison with the pure TNTs. Specifically, the applied bias photon-to-current efficiency of the fabricated TNTs/Ag3PO4 composite electrode was 2.4-fold superior to that of the pure TNTs electrode. In these TNTs/Ag3PO4 photoanodes, the introduction of Ag3PO4 over TNTs enhanced light absorption and improved charge transfer and surface conductivity. The developed process can be generally applied to designing and developing efficient contact interfaces between photoanodes and numerous cocatalysts

Enhanced Electrocatalytic Oxygen Reduction Reaction of TiO₂ Nanotubes by Combining Surface Oxygen Vacancy Engineering and Zr Doping

This work examines the cooperative effect between Zr doping and oxygen vacancy engineering in anodized TiO2 nanotubes (TNTs) for enhanced oxygen reduction reactions (ORRs). Zr dopant and annealing conditions significantly affected the electrocatalytic characteristics of grown TNTs. Zr doping results in Zr4+ substituted for Ti4+ species, which indirectly creates oxygen vacancy donors that enhance charge transfer kinetics and reduce carrier recombination in TNT bulk. Moreover, oxygen vacancies promote the creation of unsaturated Ti3+(Zr3+) sites at the surface, which also boosts the ORR interfacial process. Annealing at reductive atmospheres (e.g., H2, vacuum) resulted in a larger increase in oxygen vacancies, which greatly enhanced the ORR activity. In comparison to bare TNTs, Zr doping and vacuum treatment (Zr:TNT–Vac) significantly improved the conductivity and activity of ORRs in alkaline media. The finding also provides selective hydrogen peroxide production by the electrochemical reduction of oxygen