Flux Synthesis, Optical and Photocatalytic Properties of n-type Sn2TiO4: Hydrogen and Oxygen Evolution under Visible Light

Boltersdorf, Jonathan; Sullivan, Ian; Shelton, Timothy L.; Wu, Zongkai; Gray, Matthew; Zoellner, Brandon; Osterloh, Frank E.; Maggard, Paul A.

doi:10.1021/acs.chemmater.6b02003

Title: Flux Synthesis, Optical and Photocatalytic Properties of n-type Sn₂TiO₄: Hydrogen and Oxygen Evolution under Visible Light

Journal Article · Mon Nov 14 00:00:00 EST 2016 · Chemistry of Materials

DOI:https://doi.org/10.1021/acs.chemmater.6b02003· OSTI ID:1534436

Boltersdorf, Jonathan ^[1]; Sullivan, Ian ^[1]; Shelton, Timothy L. ^[2]; Wu, Zongkai ^[2]; Gray, Matthew ^[3]; Zoellner, Brandon ^[1];

^[2];

^[1]

North Carolina State Univ., Raleigh, NC (United States)
Univ. of California, Davis, CA (United States)
Allegheny College, Meadville, PA (United States)

Here, the n-type Sn₂TiO₄ phase was synthesized using flux methods and found to have one of the smallest visible-light bandgap sizes known that also maintains suitable conduction and valence band energies for driving photocatalytic water-splitting reactions. The Sn₂TiO₄ phase was synthesized using either a SnCl₂ flux or a SnCl₂/SnF₂ peritectic flux in a 2:1 flux-to-precursor ratio heated at 600 and 400 °C for 24 h, respectively. The two types of salt fluxes resulted in large rod-shaped particles at 600 °C and smaller tetragonal prism-shaped particles at 400 °C. Surface photovoltage spectroscopy measurements produced a negative photovoltage under illumination >1.50 eV, which confirmed electrons as the majority charge carriers and ~1.50 eV as the effective band gap. Mott–Schottky measurements at pH 9.0 showed the conduction (–0.54 V vs NHE) and valence band (+1.01 V vs NHE) positions meet the critical thermodynamic requirements for total water splitting. The Sn₂TiO₄ particles were deposited and annealed as polycrystalline films on FTO slides, and exhibited photoanodic currents in aqueous solutions under visible-light irradiation. The Sn₂TiO₄ particles were also suspended in aqueous methanol solutions and irradiated with visible and ultraviolet light. The larger rod-shaped Sn₂TiO₄ particles had the higher rates of photocatalytic hydrogen production (~11.6 μmol H₂ h^–1) in comparison to the smaller tetragonal prism-shaped Sn₂TiO₄ particles (~3.4 μmol H₂ h^–1). Conversely, for photocatalytic oxygen production, the rates for the smaller tetragonal prism-shaped particles in aqueous AgNO₃ solution were slightly higher (~16.3 μmol O₂ h^–1) than for the larger rod-shaped particles (~11.9 μmol O₂ h^–1). Apparent quantum yields of 0.995% and 0.0098% were measured for O₂ and H₂ production, respectively, under 435 nm light.

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Research Organization:: Univ. of California, Davis, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC); National Science Foundation (NSF); State of North Carolina

Grant/Contract Number:: SC0015329

OSTI ID:: 1534436

Journal Information:: Chemistry of Materials, Vol. 28, Issue 24; ISSN 0897-4756

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 56 works

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