Covalently Bonded Ni Sites in Black Phosphorene with Electron Redistribution for Efficient Metal-Lightweighted Water Electrolysis

doi:10.1007/s40820-024-01331-6

Abstract

Abstract:

The metal-lightweighted electrocatalysts for water splitting are highly desired for sustainable and economic hydrogen energy deployments, but challengeable. In this work, a low-content Ni-functionalized approach triggers the high capability of black phosphorene (BP) with hydrogen and oxygen evolution reaction (HER/OER) bifunctionality. Through a facile in situ electro-exfoliation route, the ionized Ni sites are covalently functionalized in BP nanosheets with electron redistribution and controllable metal contents. It is found that the as-fabricated Ni-BP electrocatalysts can drive the water splitting with much enhanced HER and OER activities. In 1.0 M KOH electrolyte, the optimized 1.5 wt% Ni-functionalized BP nanosheets have readily achieved low overpotentials of 136 mV for HER and 230 mV for OER at 10 mA cm⁻². Moreover, the covalently bonding between Ni and P has also strengthened the catalytic stability of the Ni-functionalized BP electrocatalyst, stably delivering the overall water splitting for 50 h at 20 mA cm⁻². Theoretical calculations have revealed that Ni-P covalent binding can regulate the electronic structure and optimize the reaction energy barrier to improve the catalytic activity effectively. This work confirms that Ni-functionalized BP is a suitable candidate for electrocatalytic overall water splitting, and provides effective strategies for constructing metal-lightweighted economic electrocatalysts.

Key words: Black phosphorus, Water electrolysis, Electrocatalyst, Electron redistribution, Covalent functionalization

Wenfang Zhai, Ya Chen, Yaoda Liu, Yuanyuan Ma, Paranthaman Vijayakumar, Yuanbin Qin, Yongquan Qu, Zhengfei Dai. Covalently Bonded Ni Sites in Black Phosphorene with Electron Redistribution for Efficient Metal-Lightweighted Water Electrolysis[J]. Nano-Micro Letters, 2024, 16(1): 115-.

Wenfang Zhai, Ya Chen, Yaoda Liu, Yuanyuan Ma, Paranthaman Vijayakumar, Yuanbin Qin, Yongquan Qu, Zhengfei Dai. [J]. Nano-Micro Letters, 2024, 16(1): 115-.

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Figures/Tables 5

Fig. 1 Synthesis method and microstructures for Ni-functionalized BP. a Synthetic scheme for Ni-BP-6. b SEM image of bulk BP. Characterizations of BP NSs: c SEM, d AFM, e TEM, and f HRTEM images. TEM characterizations of Ni-BP-6: g TEM, h HRTEM, and i EDS mapping images

Fig. 2 Chemical states and XANES analyses of Ni-functionalized BP. a Raman spectra. b XPS survey of samples. c P 2p XPS profiles of BP NSs, Ni-BP-3, Ni-BP-6, and Ni-BP-9. d Ni 2p XPS profiles of BP NSs, Ni-BP-3, Ni-BP-6, and Ni-BP-9. e XANES spectra for Ni-BP-6, NiO, and Ni foil. f Ni K-edge EXAFS spectra in R space. g Wavelet transform for the k³-weighted EXAFS signal for Ni-BP-6

Fig. 3 Electrochemical performances of Ni-BP-6 at 1.0 M KOH. a OER LSV curves, b Corresponding Tafel plots. c OER i-t curve. d HER LSV curves, e Corresponding Tafel plots. f HER i-t curve. g Polarization curves of overall water splitting (OWS) based on Ni-BP-6||Ni-BP-6 and Pt/C||RuO₂ couples. h Catalyst durability for OWS for 50 h. i Comparison of the OWS voltages at 10 mA cm⁻² with recently reported OWS bifunctional catalysts

Fig. 4 a Postmortem structural analyses after stability tests. a 2D in situ Raman intensity map of Ni-BP-6. Characterizations of Ni-BP-6 after stability test: b TEM, c HRTEM, d EDS mapping. e SAED pattern, f XRD pattern, g XPS surveys, h P 2p XPS profile, and i Ni 2p XPS profile of Ni-BP-6 after stability test

Fig. 5 Theoretical profiles for the BP NSs and Ni-BP-6 structures. The band structure of a BP NSs, b Ni-BP-6. c DOS of Ni-BP-6. d Schematic work function diagram (top) of BP NSs and Ni₄. And proposed OER and HER process (bottom) of Ni-BP-6. The brown and blue balls represent P and Ni atoms. e The electron localization function mapping on the (001) surface of Ni-BP-6. The red/blue colors refer to positive/negative charged areas, respectively. f The free energy diagram of the OER process on BP NSs and Ni-BP-6 at U = 0 V. Insets show the optimized structures with the adsorption of oxygen-containing intermediates during OER process of Ni-BP-6. g Hydrogen adsorption Gibbs free energy of different catalysts. The insets from left to right show the BP NSs and Ni-BP-6 with the adsorption of hydrogen. h H₂O adsorption model and energy of BP NSs and Ni-BP-6. The insets from left to right show the BP NSs and Ni-BP-6 with the adsorption of H₂O. i Humidity sensing performances of BP NSs, Ni-BP-3, Ni-BP-6, and Ni-BP-9 at 60%RH. Inset is the sensor electrode structure

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