Quenching to optimize the crystalline/amorphous ratio of CoPS nanorods for hydrazine-assisted total water decomposition at ampere-level current density

doi:10.1016/S1872-2067(24)60044-6

Abstract

Abstract:

Directional construction of crystalline/amorphous (c/a)-phosphosulfide heterostructures with exceptional intrinsic activity through a facile strategy is challenging. In this study, we synthesized q-CoPS nanorods with a unique c/a-CoPS core-shell heterostructure through the ‘gas-phase phosphorus vulcanization-quenching’ treatment. This work also innovatively masters the regulation of the initial quenching temperature to alter the c/a ratio of the CoPS nanorods. Surprisingly, with increasing initial quenching temperature, the area of the amorphous CoPS shell gradually increases. Density functional theory calculations reveal that the Co sites at the c/a-heterointerface, as the difunctional c/a-interface active site, effectively optimize the kinetics of the hydrogen evolution reaction (HER) and hydrazine oxidation reaction (HzOR). As anticipated, q-CoPS/CF requires an overpotential of only 90 mV at a current density of 1000 mA cm^-2 for the alkaline HER, which is much lower than that required using the state-of-the-art Pt/C catalyst. Additionally, q-CoPS/CF achieves a current density of 1000 mA cm^-2 at only 0.06 V in the HzOR. Overall, this work proposes an efficient strategy for developing a bifunctional electrocatalyst with a unique c/a-heterostructure to address future energy needs.

Key words: q-CoPS, c/a-heterostructures, Quenching, Hydrogen evolution reaction, Hydrazine oxidation reaction

Xiao Chen, Yunmei Du, Yu Yang, Kang Liu, Jinling Zhao, Xiaodan Xia, Lei Wang. Quenching to optimize the crystalline/amorphous ratio of CoPS nanorods for hydrazine-assisted total water decomposition at ampere-level current density[J]. Chinese Journal of Catalysis, 2024, 62: 265-276.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60044-6

https://www.cjcatal.com/EN/Y2024/V62/I7/265

Figures/Tables 6

Fig. 1. Morphology and structural characterization of CoPS/CF and q-CoPS/CF. (a) Schematic illustration of the synthesis process; (b,c) SEM images; (d,e) TEM images; (f,g) HRTEM images; (h) HAADF-STEM and the corresponding EDX mapping images.

Fig. 2. Structure characterization. Total XPS spectra (a) and S 2p (b), Co 2p (c), and P 2p (d) XPS spectra.

Fig. 3. HER performance in 1.0 mol L-1 KOH. (a) Polarization curves. (b) Overpotentials at a current density of 10, 100, and 500 mA cm-2. (c) Tafel slopes of different catalysts obtained from the polarization curves in (a). (d) Nyquist plots. (e) Dependence of the average capacitive currents on scan rate. (f) Comparison of η10 of recently reported noble metal-based electrocatalysts for the HER.

Fig. 4. HzOR performance of q-CoPS/CF and its counterparts in alkaline solution. (a) LSV curves of the HzOR and OER. (b) HzOR and OER overpotential at 10-500 mA cm?2. (c) LSV curves. (d) Overpotential at 10, 100, 1000, and 2000 mA cm?2. (e) Tafel slopes. (f) Nyquist plots. (g) Comparison of overpotentials at 10 mA cm?2 of the recently reported catalysts. (h) Multi-steps chronopotentiometry curves for q-CoPS/CF tested at different current densities.

Fig. 5. (a) Model diagram of a-CoPS and c-CoPS structures of the q-CoPS catalyst. (b) ΔGH* of Co at the a-CoPS site, c-CoPS site, and c/a-interface. (c) ΔG of Co at the a-CoPS site, c-CoPS site, and c/a-interface. (d) ΔGH* and (e) ΔG on the Co, P, and S sites.

Fig. 6. OHzS performance of q-CoPS/CF ‖ q-CoPS/CF and the counterparts in alkaline solution. (a) LSV curves of q-CoPS for OHzS and OWS. (b) Overpotential of q-CoPS for OHzS and OWS at 10-500 mA cm?2. (c) LSV curves. (d) Multi-step chronopotentiometry curves for q-CoPS/CF ‖ q-CoPS/CF tested at different current densities. (e) Solar energy-driven OHzS and OWS in q-CoPS/CF ‖ q-CoPS/CF. (f) Comparison of the overpotentials at 10 mA cm?2 of the recently reported catalysts.

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