Engineering fully exposed edge-plane sites on carbon-based electrodes for efficient water oxidation

doi:10.1016/S1872-2067(24)60018-5

Abstract

Abstract:

Endowing metal-free graphitic carbon electrodes with high electrocatalytic reactivity is a field of intense research, but remains elusive. Here, we introduce a prototypical edge-plane-site-specific engineering strategy on “herringbone” multi-walled carbon nanotubes by performing an intercalation-exfoliation and truncation process in molten inorganic salts. Controllable synthesis of the target H-MWCNTs-MS with fully exposed edge-plane sites on both the outer surface and inner channels was demonstrated. in-situ infrared spectroscopic study supports the theoretically energetic “edge-state” and identifies the reconstructed ketone/carboxyl-terminated edge sites under oxygen evolution reaction (OER) conditions. These oxygenated edge-plane sites boost charge redistribution and interlayer coupling, which essentially govern the synergistic catalysis, as evidenced by combined theoretical, electrokinetic, and H/D isotopic studies. Benefiting from the dense reactive sites and efficient electron tunneling, the H-MWCNTs-MS demonstrated impressive OER activity with an overpotential of 236 mV at a current density of 10 mA cm^‒2 in alkaline media, outperforming most state-of-the-art metal-free electrocatalysts reported to date. Furthermore, the catalyst displayed no noticeable degradation during 100 h of operation, indicating its potential for practical applications.

Key words: Multi-walled carbon nanotube, Edge-plane site, Oxygen evolution reaction, Molten salt, Electronic coupling

Jingya Guo, Wei Liu, Wenzhe Shang, Duanhui Si, Chao Zhu, Jinwen Hu, Cuncun Xin, Xusheng Cheng, Songlin Zhang, Suchan Song, Xiuyun Wang, Yantao Shi. Engineering fully exposed edge-plane sites on carbon-based electrodes for efficient water oxidation[J]. Chinese Journal of Catalysis, 2024, 60: 272-283.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60018-5

https://www.cjcatal.com/EN/Y2024/V60/I5/272

Figures/Tables 5

Fig. 1. (a) Side (left) and top (right) views of the atomic structure model of the stepped graphite surface (zigzag edge termination). Top view of the calculated differential charge density diagram, revealing obvious electron density redistribution centered at the edge-plane sites (yellow: electron accumulation; cyan: electron depletion). Calculated C 2p density of states at the zigzag edge (b) and in the basal plane (c).

Fig. 2. (a) Schematic illustration of the MS-mediated pyrolysis strategy for the target H-MWCNTs-MS. Representative TEM (b,c) and HAADF-STEM (d) images of the H-MWCNTs-MS. (e) C K-edge NEXAFS spectra of the H-MWCNTs-MS and H-MWCNTs. (f) HAADF intensity line profiles showing the interlayer spacing between the stacked graphene layers in the H-MWCNTs-MS and H-MWCNTs. (g) Raman spectra of the H-MWCNTs-MS and H-MWCNTs. The Raman spectra were deconvoluted using a multipeak Voigt fit.

Fig. 3. (a) Polarization curves of the H-MWCNTs-MS in 1 mol L?1 KOH for the first several runs on a glassy carbon electrode (GCE). (b) In situ ATR-SEIRAS spectra of the H-MWCNTs-MS during positive potential steps. All potentials are referred to the RHE scale. (c) C K-edge NEXAFS and (d) O 1s XPS spectrum of H-MWCNTs-MS/AR.

Fig. 4. (a) OER polarization curves and Tafel slopes (inset) of the H-MWCNTs-MS in Fe-free KOH electrolytes of various concentrations (0.5, 0.75, 1.0, 1.5 and 2 mol L?1). (b) Linear fitting plot of the potentials at a current density of 1 mA cm?2 versus the logarithm of [OH?]. (c) LSV curves for H-MWCNTs-MS in 1 mol L?1 KOH and KOD. (d) Determination of the H/D isotope effect by comparing the current densities in 1 mol L?1 KOH and KOD at the same overpotentials. Charge density difference diagrams on ketone- (e) and carboxyl- (f) group terminated structures (yellow: electron accumulation, cyan: electron depletion). (g) DFT-calculated free energy diagram for the ketone-terminated H-MWCNTs-MS. The displayed structures show the DFT-optimized atomic configuration details. C, O, and H atoms are shown in gray, red and white, respectively. (h) Overview of the electrostatic potential at the surface of the ketone-terminated H-MWCNTs-MS (with *O intermediate chemisorption). Positive and negative charges are drawn in red and blue, respectively.

Fig. 5. Electrochemical OER performance. Polarization curves (a) and corresponding Tafel slopes (b) on carbon cloth (CC) electrode. (c) EIS Nyquist plots. (d) Current normalized by the BET surface area for activity comparison. (e) Faraday efficiency testing of the H-MWCNTs-MS using the RRDE technique (schematic shown in the inset) in N2-saturated 1 mol L?1 KOH solution. The O2 evolution from the H-MWCNTs-MS at a constant current of 220 μA is reduced at the Pt ring at a constant potential of 0.4 V vs. RHE. (f) Long-term chronopotentiometry test of H-MWCNTs-MS in 1 mol L?1 KOH at current densities of 10, 50, 100 mA cm?2 (upper), at a specific current density of 1000 mA cm?2 (below) on NF electrode.

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