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In Situ Shape Change of Au Nanoparticles on TiO₂ by CdS Photodeposition: Its Near-Field Enhancement Effect on Photoinduced Electron Injection from CdS to TiO₂.

ABSTRACT: Hemisphere-like gold nanoparticles (NPs) were loaded on TiO₂ (Au/TiO₂) by the deposition-precipitation method. Subsequent photodeposition of CdS on the Au surface of Au/TiO₂ at 50 °C yields Au(core)-CdS(shell) hybrid quantum dots with a heteroepitaxial (HEPI) junction on TiO₂ (Au@#CdS/TiO₂), whereas nonHEPI Au@CdS/TiO₂ was formed by CdS photodeposition at 25 °C. In the HEPI system, the shape of the Au core changes to an angular shape, whereas it remains in a hemisphere-like shape in the nonHEPI system. The hot photodeposition technique was applied to the Au NP-loaded mesoporous TiO₂ nanocrystalline film (Au/mp-TiO₂). Using Au@CdS/mp-TiO₂ and Au@#CdS/mp-TiO₂ as the photoanodes, two-electrode quantum dot-sensitized photoelectrochemical cells were fabricated for hydrogen (H₂) generation from water, and the performances of the cells were evaluated under illumination of simulated sunlight. In the photocurrent and the rate of H₂ evolution, the Au@#CdS/mp-TiO₂ photoanode cell surpasses the CdS/mp-TiO₂ and Au@CdS/mp-TiO₂ ones. Three-dimensional finite-difference time-domain calculations for the model systems indicated that the angular shape Au core generates an intense electric field at the corners and edges, extending the electric field distribution over the Au core-CdS shell interface. The striking shape effect on the cell performances can originate from the promotion of the CdS excitation and charge separation due to the near-field enhancement by the deformed Au core.

SUBMITTER: Fujishima M

PROVIDER: S-EPMC6644424 | biostudies-literature | 2018 Jun

REPOSITORIES: biostudies-literature

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In Situ Shape Change of Au Nanoparticles on TiO2 by CdS Photodeposition: Its Near-Field Enhancement Effect on Photoinduced Electron Injection from CdS to TiO2.

Fujishima Musashi M Ikeda Takuya T Akashi Ryo R Tada Hiroaki H

ACS omega 20180606 6

Hemisphere-like gold nanoparticles (NPs) were loaded on TiO2 (Au/TiO2) by the deposition-precipitation method. Subsequent photodeposition of CdS on the Au surface of Au/TiO2 at 50 °C yields Au(core)-CdS(shell) hybrid quantum dots with a heteroepitaxial (HEPI) junction on TiO2 (Au@#CdS/TiO2), whereas nonHEPI Au@CdS/TiO2 was formed by CdS photodeposition at 25 °C. In the HEPI system, the shape of the Au core changes to an angular sh ...[more]

PMID: 31458797

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Project description:ObjectiveAlthough photoelectrochemical (PEC) water splitting heralds the emergence of the hydrogen economy, the need for external bias and low efficiency stymies the widespread application of this technology. By coupling water splitting (in a PEC cell) to a microbial fuel cell (MFC) using Escherichia coli as the biocatalyst, this work aims to successfully demonstrate a sustainable hybrid PEC-MFC platform functioning solely by biocatalysis and solar energy, at zero bias. Through further chemical modification of the photo-anode (in the PEC cell) and biofilm (in the MFC), the performance of the hybrid system is expected to improve in terms of the photocurrent generated and hydrogen evolved.MethodsThe hybrid system constitutes the interconnected PEC cell with the MFC. Both PEC cell and MFC are typical two-chambered systems housing the anode and cathode. Au-TiO2 hollow spheres and conjugated oligoelectrolytes were synthesised chemically and introduced to the PEC cell and MFC, respectively. Hydrogen evolution measurements were performed in triplicates.ResultsThe hybrid PEC-MFC platform generated a photocurrent density of 0.35?mA/cm2 (~70× enhancement) as compared with the stand-alone P25 standard PEC cell (0.005?mA/cm2) under one-sun illumination (100?mW/cm2) at zero bias (0?V vs. Pt). This increase in photocurrent density was accompanied by continuous H2 production. No H2 was observed in the P25 standard PEC cell whereas H2 evolution rate was ~3.4??mol/h in the hybrid system. The remarkable performance is attributed to the chemical modification of E. coli through the incorporation of novel conjugated oligoelectrolytes in the MFC as well as the lower recombination rate and higher photoabsorption capabilities in the Au-TiO2 hollow spheres electrode.ConclusionsThe combined strategy of photo-anode modification in PEC cells and chemically modified MFCs shows great promise for future exploitation of such synergistic effects between MFCs and semiconductor-based PEC water splitting.

Dataset Information

In Situ Shape Change of Au Nanoparticles on TiO₂ by CdS Photodeposition: Its Near-Field Enhancement Effect on Photoinduced Electron Injection from CdS to TiO₂.

Publications

In Situ Shape Change of Au Nanoparticles on TiO<sub>2</sub> by CdS Photodeposition: Its Near-Field Enhancement Effect on Photoinduced Electron Injection from CdS to TiO<sub>2</sub>.

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