Study of the formation features of Pt(0) nanoparticles at the interface of nickel-aqueous solution of reagents under sild conditions and their electrocatalytic properties in hydrogen evolution reaction during water electrolysis in an alkaline medium

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Abstract

The article explores the features of Pt(0) nanoparticle formation at the interface of nickel-aqueous solution of reagents and a similar interface containing nanoflakes of Co(OH)2. The synthesis was carried out under Successive Ionic Layers Deposition (SILD) conditions, and solutions of Na2PtCl6, CoCl2, and NaBH4 were used as the reagents. Pt(0) nanolayers were produced on the nickel surface using Na2PtCl6 and NaBH4 solutions, and for Co(OH)2 nanolayers CoCl2 and NaBH4 solutions were used. Structural chemical studies of the samples synthesized were performed by HRTEM, FESEM, EDX, SAED, XPS, FT-IR, and Raman spectroscopy. It was shown that Pt(0) nanolayers consist of separate nanoparticles, while Co(OH)2 nanolayers consist of nanoflakes. The main attention in the work is paid to the formation features of Pt(0) nanoparticles on a nickel surface to which a nanolayer of Co(OH)2 was previously applied. The study of the electrocatalytic properties of such samples in the hydrogen evolution reaction (HER) during water electrolysis in the alkaline medium showed that the best properties are exhibited by nanoparticles synthesized after 20–40 SILD cycles and on nickel substrates with Co(OH)2 nanolayers applied in advance. Also, it was found that among these samples the best properties are displayed by those containing Co(OH)2 layers synthesized after 5 SILD cycles. One of the best examples of this series was obtained from 40 SILD cycles and is characterized by the overpotential value at 29 mV of current density at 10 mA/cm2, the Tafel slope value at 29.5 mV/dec, and high stability of these values at multiple cycle potential. It is noted that the Pt(0) nanoparticles synthesized after 40 SILD cycles are 4–8 nm in size and are located on the surface of the nanoflakes at a distance of about 10 nm from each other for the nickel foam sample, on the surface of which a Co(OH)2 nanolayer was synthesized as a result of 5 SILD cycles. These features contribute to the formation of a set of Pt(0) nanoparticle contact points with the surface of Co(OH)2 nanoflakes, which determines the high electrocatalytic activity and stability of properties of such structures.

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About the authors

M. V. Kaneva

Institute of Chemistry, Saint Petersburg State University

Email: v.tolstoy@spbu.ru
Russian Federation, Saint Petersburg

L. B. Gulina

Institute of Chemistry, Saint Petersburg State University

Email: v.tolstoy@spbu.ru
Russian Federation, Saint Petersburg

V. P. Tolstoy

Institute of Chemistry, Saint Petersburg State University

Author for correspondence.
Email: v.tolstoy@spbu.ru
Russian Federation, Saint Petersburg

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Supplementary files

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2. Fig. 1. Schematic representation of the sequence of substrate treatments in reagent solutions and water during 1 IN cycle.

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3. Fig. 2. Electron micrographs obtained by SEM with a magnification of ×250 of Pt(0) nanoparticles synthesized by the SI method on the nickel surface as a result of 20 (a) and 40 (b) processing cycles.

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4. Fig. 3. FTIR spectrum (a) and Raman spectrum (b) of a Co(OH)2 nanolayer synthesized on nickel as a result of 20 SI cycles.

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5. Fig. 4. Series of electron micrographs obtained by the SEM method with magnification of ×100, ×250 and ×500 times of multilayers on the nickel surface synthesized by the SI method as a result of 5 cycles of treatment with CoCl2 and NaBH4 solutions and subsequent 5–40 cycles of treatment using Na2PtCl6 and NaBH4 solutions. a) 5Co(OH)2-5Pt sample, b) 5Co(OH)2-20Pt, c) 5Co(OH)2-40Pt.

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6. Fig. 5. TEM electron micrographs of nanoparticles synthesized by the SI method on the nickel surface as a result of 5 cycles of treatment with CoCl2 and NaBH4 solutions and 5–40 cycles of treatment with Na2PtCl6 and NaBH4 solutions. a) sample 5Co(OH)2-5Pt, b) 5Co(OH)2-20Pt, c) 5Co(OH)2-40Pt, d) electron diffraction pattern of sample 5Co(OH)2-40Pt.

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7. Fig. 6. Energy-dispersive X-ray spectrum (a) and X-ray photoelectron spectra of 4f-electrons of Pt(0) (b), 1s-electrons of O (c) and 2p-electrons of Co (d) of a sample synthesized by the SI method using the 5Co(OH)2-40Pt program.

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8. Fig. 7. Polarization curves (a) and Tafel slope values ​​(b) in the RVW for PN electrodes with nCo(OH)2-mPt multilayers synthesized by the SI method. 1 – sample 5Co(OH)2-5Pt, 2 – 5Co(OH)2-10Pt, 3 – 5Co(OH)2-20Pt, 4 – 5Co(OH)2-40Pt, 5 – 5Co(OH)2-60Pt.

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9. Fig. 8. Polarization curves (a) and Tafel slope values ​​(b) in the RVW for the PN electrode with Pt(0) nanoparticles synthesized as a result of 40 SI cycles (1) and the 5Co(OH)2-40Pt electrode (2). The changes in the polarization curves in the RVW of these electrodes after 500-fold potential cycling are shown in the figure (c).

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Note

Публикуется по материалам IX Всероссийской конференции с международным участием “Топливные элементы и энергоустановки на их основе”, Черноголовка, 2022.


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