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Transient Behavior of Ni@NiO _x Functionalized SrTiO₃ in Overall Water Splitting.

ABSTRACT: Transients in the composition of Ni@NiO _x core-shell co-catalysts deposited on SrTiO₃ are discussed on the basis of state-of-the-art continuous analysis of photocatalytic water splitting, and post-XPS and TEM analyses. The formation of excessive hydrogen (H₂:O₂ ? 2) in the initial stages of illumination demonstrates oxidation of Ni(OH)₂ to NiOOH (nickel oxyhydroxide), with the latter catalyzing water oxidation. A disproportionation reaction of Ni and NiOOH, yielding Ni(OH)₂ with residual embedded Ni, occurs when illumination is discontinued, which explains repetitive transients in (excess) hydrogen and oxygen formation when illumination is reinitiated.

SUBMITTER: Han K

PROVIDER: S-EPMC5384480 | biostudies-literature | 2017 Mar

REPOSITORIES: biostudies-literature

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Transient Behavior of Ni@NiO x Functionalized SrTiO3 in Overall Water Splitting.

Han Kai K Kreuger Tomas T Mei Bastian B Mul Guido G

ACS catalysis 20170124 3

Transients in the composition of Ni@NiO x core-shell co-catalysts deposited on SrTiO3 are discussed on the basis of state-of-the-art continuous analysis of photocatalytic water splitting, and post-XPS and TEM analyses. The formation of excessive hydrogen (H2:O2 ≫ 2) in the initial stages of illumination demonstrates oxidation of Ni(OH)2 to NiOOH (nickel oxyhydroxide), with the latter catalyzing water oxidation. A disproportionation re ...[more]

PMID: 28405491

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Project description:By photodeposition of CrOx on SrTiO3-based semiconductors doped with aliovalent Mg(II) and functionalized with Ni/NiOx catalytic nanoparticles (economically significantly more viable than commonly used Rh catalysts), an increase in apparent quantum yield (AQYs) from ∼10 to 26% in overall water splitting was obtained. More importantly, deposition of CrOx also significantly enhances the stability of Ni/NiO nanoparticles in the production of hydrogen, allowing sustained operation, even in intermittent cycles of illumination. In situ elemental analysis of the water constituents during or after photocatalysis by inductively coupled plasma mass spectrometry/optical emission spectrometry shows that after CrOx deposition, dissolution of Ni ions from Ni/NiOx-Mg:SrTiO3 is significantly suppressed, in agreement with the stabilizing effect observed, when both Mg dopant and CrOx are present. State-of-the-art electron microscopy and energy-dispersive X-ray spectroscopy (EDX) and electron energy-loss spectroscopy (EELS) analyses demonstrate that upon preparation, CrOx is photodeposited in the vicinity of several, but not all, Ni/NiOx particles. This implies the formation of a Ni-Cr mixed metal oxide, which is highly effective in water reduction. Inhomogeneities in the interfacial contact, evident from differences in contact angles between Ni/NiOx particles and the Mg:SrTiO3 semiconductor, likely affect the probability of reduction of Cr(VI) species during synthesis by photodeposition, explaining the observed inhomogeneity in the spatial CrOx distribution. Furthermore, by comparison with undoped SrTiO3, Mg-doping appears essential to provide such favorable interfacial contact and to establish the beneficial effect of CrOx. This study suggests that the performance of semiconductors can be significantly improved if inhomogeneities in interfacial contact between semiconductors and highly effective catalytic nanoparticles can be resolved by (surface) doping and improved synthesis protocols.

Dataset Information

Transient Behavior of Ni@NiO _x Functionalized SrTiO₃ in Overall Water Splitting.

Publications

Transient Behavior of Ni@NiO <sub><i>x</i></sub> Functionalized SrTiO<sub>3</sub> in Overall Water Splitting.

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