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Free-Standing Electrospun W-Doped BiVO4 Porous Nanotubes for the Efficient Photoelectrochemical Water Oxidation.

ABSTRACT: While bismuth vanadate (BiVO4) has emerged as a promising photoanode in solar water splitting, it still suffers from poor electron-hole separation and electron transport properties. Therefore, the development of BiVO4 nanomaterials that enable performing high charge transfer rate at the interface and lowering charge recombination is urgent needed. Herein, cobalt borate (Co-B) nanoparticle arrays anchored on electrospun W-doped BiVO4 porous nanotubes (BiV0.97W0.03O4) was prepared for photoelectrochemical (PEC) water oxidation. One-dimensional, free-standing and porousBiV0.97W0.03O4/Co-B nanotubes was synthesized through electrospun and electrodeposition process. BiV0.97W0.03O4/Co-B arrays exhibit a unique self-supporting core-shell structure with rough porous surface, providing abundant conductive cofactor (W) and electrochemically active sites (Co) exposed to the electrolyte. When applied to PEC water oxidation. BiV0.97W0.03O4/Co-B modified FTO electrode displays high incident photon-to-current conversion efficiency (IPCE) of 33% at 405 nm (at 1.23 V vs. RHE) and its photocurrent density is about 4 times to the pristine nanotube. The higher PEC water oxidation properties of BiV0.97W0.03O4/Co-B porous nanotubes may be attributed to the effectively suppress the electron-hole recombination at electrolyte interface due to its self-supporting core-shell structure, the high electrocatalytic activity of Co and the good electrical conductivity of BiV0.97W0.03O4 arrays. This work offers a simple preparation strategy for the integrated Co-B nanoparticle with BiV0.97W0.03O4 nanotube, demonstrating the synergistic effect of co-catalysts for PEC water oxidation.

SUBMITTER: Yuan X

PROVIDER: S-EPMC7192020 | biostudies-literature | 2020

REPOSITORIES: biostudies-literature

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Free-Standing Electrospun W-Doped BiVO4 Porous Nanotubes for the Efficient Photoelectrochemical Water Oxidation.

Yuan Xiuhua X Sun Xia X Zhou Huawei H Zeng Suyuan S Liu Bingxin B Li Xia X Liu Dong D

Frontiers in chemistry 20200423

While bismuth vanadate (BiVO4) has emerged as a promising photoanode in solar water splitting, it still suffers from poor electron-hole separation and electron transport properties. Therefore, the development of BiVO4 nanomaterials that enable performing high charge transfer rate at the interface and lowering charge recombination is urgent needed. Herein, cobalt borate (Co-B) nanoparticle arrays anchored on electrospun W-doped BiVO4 porous nanotubes (BiV0.97 ...[more]

PMID: 32391331

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Project description:Layered double hydroxides (LDHs) are an ideal platform to host catalytic metal centers for water oxidation (WO) owing to the high accessibility of water to the interlayer region, which makes all centers potentially reachable and activated. Herein, we report the syntheses of three iridium-doped zinc-aluminum LDHs (Ir-LDHs) nanomaterials (1-3, with about 80 nm of planar size and a thickness of 8 nm as derived by field emission scanning electron microscopy and powder X-ray diffraction studies, respectively), carried out in the confined aqueous environment of reverse micelles, through a very simple and versatile procedure. These materials exhibit excellent catalytic performances in WO driven by NaIO4 at neutral pH and 25 °C, with an iridium content as low as 0.5 mol % (∼0.8 wt %), leading to quantitative oxygen yields (based on utilized NaIO4, turnover number up to ∼10,000). Nanomaterials 1-3 display the highest ever reported turnover frequency values (up to 402 min-1) for any heterogeneous and heterogenized catalyst, comparable only to those of the most efficient molecular iridium catalysts, tested under similar reaction conditions. The boost in activity can be traced to the increased surface area and pore volume (>5 times and 1 order of magnitude, respectively, higher than those of micrometric materials of size 0.3-1 μm) estimated for the nanosized particles, which guarantee higher noble metal accessibility. X-ray absorption spectroscopy (XAS) studies suggest that 1-3 nanomaterials, as-prepared and after catalysis, contain a mixture of isolated, single octahedral Ir(III) sites, with no evidence of Ir-Ir scattering from second-nearest neighbors, excluding the presence of IrO2 nanoparticles. The combination of the results obtained from XAS, elemental analysis, and ionic chromatography strongly suggests that iridium is embedded in the brucite-like structure of LDHs, having four hydroxyls and two chlorides as first neighbors. These results demonstrate that nanometric LDHs can be successfully exploited to engineer efficient WOCs, minimizing the amount of iridium used, consistent with the principle of the noble-metal atom economy.

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Free-Standing Electrospun W-Doped BiVO4 Porous Nanotubes for the Efficient Photoelectrochemical Water Oxidation.

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Free-Standing Electrospun W-Doped BiVO<sub>4</sub> Porous Nanotubes for the Efficient Photoelectrochemical Water Oxidation.

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