Millisecond-timescale electrodeposition of platinum atom-doped molybdenum oxide as an efficient electrocatalyst for hydrogen evolution reaction

doi:10.1007/s11706-022-0606-8

Front. Mater. Sci.

2022, Vol. 16

Issue (3) : 220606 https://doi.org/10.1007/s11706-022-0606-8

RESEARCH ARTICLE

Millisecond-timescale electrodeposition of platinum atom-doped molybdenum oxide as an efficient electrocatalyst for hydrogen evolution reaction

Yi XIAO^1,², Wenxue SHANG^2,³, Jiyuan FENG², Airu YU^2,⁴, Lu CHEN^1,², Liqiu ZHANG²(

), Hongxia SHEN², Qiong CHENG², Lichun LIU^1,^2,^3,⁴(

), Song BAI¹(

)

¹. College of Chemistry and Life Sciences, Zhejiang Normal University, Jinhua 321000, China
². College of Biological, Chemical Sciences and Engineering & Nanotechnology Research Institute, Jiaxing University, Jiaxing 314000, China
³. College of Petroleum Engineering, Liaoning Petrochemical University, Fushun 113000, China
⁴. College of Chemistry, Jilin Normal University, Changchun 130103, China

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Abstract

We present a straightforward method for one-pot electrodeposition of platinum atoms-doped molybdenum oxide (Pt·MoO_3−x) films and show their superior electrocatalytic activity in the hydrogen evolution reaction (HER). A ~15-nm-thick Pt·MoO_3−x film was prepared by one-pot electrodeposition at −0.8 V for 1 ms. Due to considerably different solute concentrations, the content of Pt atoms in the electrodeposited composite electrocatalyst is low. No Pt crystals or islands were observed on the flat Pt·MoO_3−x films, indicating that Pt atoms were homogeneously dispersed within the MoO_3−x thin film. The catalytic performance and physicochemical features of Pt·MoO_3−x as a HER electrocatalyst were characterized. The results showed that our Pt·MoO_3−x film exhibits 23- and 11-times higher current density than Pt and MoO_3−x electrodeposited individually under the same conditions, respectively. It was found that the dramatic enhancement in the HER performance was principally due to the abundant oxygen defects. The use of the developed one-pot electrodeposition and doping method can potentially be extended to various catalytically active metal oxides or hydroxides for enhanced performance in various energy storage and conversion applications.

Keywords platinum molybdenum oxide electrodeposition hydrogen evolution reaction doping electrocatalyst

Corresponding Author(s): Liqiu ZHANG,Lichun LIU,Song BAI

Issue Date: 21 September 2022

Cite this article:

Yi XIAO,Wenxue SHANG,Jiyuan FENG, et al. Millisecond-timescale electrodeposition of platinum atom-doped molybdenum oxide as an efficient electrocatalyst for hydrogen evolution reaction[J]. Front. Mater. Sci., 2022, 16(3): 220606.

URL:

https://academic.hep.com.cn/foms/EN/10.1007/s11706-022-0606-8
https://academic.hep.com.cn/foms/EN/Y2022/V16/I3/220606

Scheme1 Schematic illustration of electrodeposition of the Pt-doped MoO_3?x film from a mixed solution containing a high concentration of (NH₄)₆Mo₇O₂₄ and an extremely low concentration of H₂PtCl₆.

Fig.1 (a) LSV curves featuring reduction potentials of 100 mmol·L^?1 (NH₄)₆Mo₇O₂₄·4H₂O and 20 mmol·L^?1 H₂PtCl₆ at a scan rate of 100 mV·s^?1. (b) Cross-sectional SEM image of the Pt·MoO_3?x film obtained by 100-ms long electrodeposition from a mixture containing 100 mmol·L^?1 (NH₄)₆Mo₇O₂₄·4H₂O and 10 μmol·L^?1 H₂PtCl₆. Inset: SEM image of the Pt·MoO_3?x film with 1-ms electrodeposition.

Fig.2 (a) Cyclic voltammograms for polycrystalline Au substrate, Pt, MoO_3?x, and Pt·MoO_3?x in 1 mol·L^?1 KOH (Pt and MoO_3?x were electrodeposited separately under the same conditions that were used for the electrodeposition of Pt·MoO_3?x). (b) Current enhancement factor f = I(C_n+1)/I(C_n) for electrocatalytic hydrogen evolution plotted as a function of the H₂PtCl₆ concentration at ?0.3 V in LSV at 50 mV·s^?1. f refers to the HER current ratio at ?0.3 V using Pt·MoO_3?x electrodeposited with a concentration and a neighboring lower concentration of H₂PtCl₆ in 0.1 mol·L^?1 (NH₄)₆Mo₇O₂₄·4H₂O.

Fig.3 (a) HAADF-TEM image of the Pt·MoO_3?x film. Insets: film thickness ~15 nm (upper right) and electron diffraction (lower right). (b)(c)(d) Elemental mappings of the Pt·MoO_3?x film for Mo, O, and Pt. (e) Electron diffraction spectrum. (f) EDS result for the Pt·MoO_3?x film.

Fig.4 (a) Linear sweep voltammograms on three different electrodes recorded at a scan rate of 50 mV·s^?1. Inset: enhancement of current on the Pt·MoO_3?x electrocatalyst vs. pure electrodeposited Pt and MoO_3?x at different overpotentials. (b) Tafel slopes. (c) Electrochemical impedance spectra: Nyquist plot (0.01 Hz?1 MHz). Lower inset: analog circuit (R_s, solution resistance; R_ct, charge transfer resistance; W, Warburg resistance; Q, imperfect capacitor). (d) Chronoamperometry curves at ?0.4 V. The electrolyte used in each test was 0.1 mol·L^?1 KOH.

Fig.5 XPS spectra of (a) Mo 3d and (b) O 1s for MoO_3?x and Pt·MoO_3?x films.

Fig.6 (a) Electron paramagnetic resonance spectra and (b) Raman spectra for MoO_3?x and Pt·MoO_3?x films.

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