Scalable synthesis of ultra-small Ru2P@Ru/CNT for efficient seawater splitting

doi:10.1016/S1872-2067(21)64012-3

Abstract

Abstract:

In this study, an ultra-fast and simple solvent-free microwave method was successfully demonstrated using a series of ultra-small (~2.5 nm) surfactant-free Ru₂P@Ru/CNT heterostructures for the first time. The structure has a high-density Ru component and Ru₂P component interface, which accelerates the hydrogen evolution reaction (HER). The prepared Ru₂P@Ru/CNT demonstrated excellent catalytic effects for the HER in alkaline media and real seawater. The experimental results indicate that ratio-optimized Ru₂P@Ru/CNT (Ru₂P:Ru = 66:34) requires only 23 and 29 mV to reach 10 mA cm^-2in 1.0 mol/L KOH and real seawater, respectively. These values are 10 and 24 mV lower than those of commercial Pt/C in 1.0 mol/L KOH (33 mV) and real seawater (53 mV), respectively, making it among the best non-Pt HER reported in the literature. Additionally, the TOF of Ru₂P@Ru/CNT in alkaline freshwater and seawater were 13.1 and 8.5 s^-1, respectively. These exceed the corresponding values for Pt/C, indicating that the catalyst has excellent intrinsic activity. The high current activity of Ru₂P@Ru/CNT in 1.0 mol/L KOH was explored, and only 77 and 104 mV were required to reach 500 and 1000 mA cm^-2, respectively. After 100 h of durability testing, the catalyst retained excellent catalytic and structural stability in low current density, high current density, and seawater.

Key words: Ultra-small nanoparticles, Phosphide, Multi-interface, Solvent-free microwave method, Seawater splitting

Dan Zhang, Hongfu Miao, Xueke Wu, Zuochao Wang, Huan Zhao, Yue Shi, Xilei Chen, Zhenyu Xiao, Jianping Lai, Lei Wang. Scalable synthesis of ultra-small Ru₂P@Ru/CNT for efficient seawater splitting[J]. Chinese Journal of Catalysis, 2022, 43(4): 1148-1155.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(21)64012-3

https://www.cjcatal.com/EN/Y2022/V43/I4/1148

Figures/Tables 5

Fig. 1. (a) The SEM image of Ru2P@Ru/CNT; (b) TEM image of Ru2P@Ru/CNT; (c) HRTEM image of Ru2P@Ru/CNT; (d) Nanoparticle size distribution of Ru2P@Ru/CNT; (e) XRD pattern of Ru2P@Ru/CNT; line scan image (f) and HAADF-STEM (g) with corresponding elemental mapping images of Ru2P@Ru/CNT.

Fig. 2. (a) High resolution XPS spectra of P 2p in Ru2P/CNT and Ru2P@Ru/CNT; (b) High resolution XPS spectra of Ru 3p spectra in Ru/CNT and Ru2P@Ru/CNT; (c) High resolution XPS spectra of Ru 3d in Ru/CNT and Ru2P@Ru/CNT.

Fig. 3. (a) HER polarization curves of Ru/CNT, Pt/C Ru2P/CNT and Ru2P@Ru/CNT catalysts in N2-saturated 1.0 mol/L KOH solution; (b) Comparison of overpotential at 10 mA cm-2; (c) Tafel plots obtained from the polarization curves in (a); (d) Exchange current density obtained from (c); (e) The potential dependent TOF curves of Ru/CNT, Pt/C Ru2P/CNT and Ru2P@Ru/CNT catalysts; (f) Polarization curves for Ru2P@Ru/CNT catalyst before and after 10000 cycles.

Fig. 4. (a) Polarization curves for Ru2P@Ru/CNT, Ru2P/CNT, Ru/CNT and CC in 1.0 mol/L KOH solution; (b) Polarization curves for Ru2P@Ru/CNT before and after 10000 cycles; (c) Durability evaluation via chronoamperometry test at η = 77 mV of Ru2P@Ru/CNT for 150 h; (d) Theoretical and experimental results of H2 production of Ru2P@Ru/CNT.

Fig. 5. (a) HER polarization curves of Ru/CNT, Pt/C Ru2P/CNT and Ru2P@Ru/CNT catalysts in 1.0 mol/L KOH + 0.5 mol/L NaCl solution; (b) Comparison of overpotential at 10 mA cm-2in 1.0 mol/L KOH + 0.5 mol/L NaCl solution; (c) HER polarization curves of Ru/CNT, Pt/C Ru2P/CNT and Ru2P@Ru/CNT catalysts in 1.0 mol/L KOH + seawater; (d) Comparison of overpotential at 10 mA cm-2in 1.0 mol/L KOH + seawater; (e) HER polarization curves of Ru2P@Ru/CNT in 1.0 mol/L KOH, 1.0 mol/L KOH + 0.5 mol/L NaCl and 1.0 mol/L KOH + seawater; (f) Comparison of overpotential at 10 mA cm-2in 1.0 mol/L KOH, 1.0 mol/L KOH + 0.5 mol/L NaCl and 1.0 mol/L KOH + seawater.

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Scalable synthesis of ultra-small Ru₂P@Ru/CNT for efficient seawater splitting

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