Mild polarization electric field in ultra-thin BN-Fe-graphene sandwich structure for efficient nitrogen reduction

doi:10.1016/S1872-2067(24)60114-2

Abstract

Abstract:

The electrocatalytic N₂ reduction reaction (NRR) is expected to supersede the traditional Haber-Bosch technology for NH₃ production under ambient conditions. The activity and selectivity of electrochemical NRR are restricted to a strong polarized electric field induced by the catalyst, correct electron transfer direction, and electron tunneling distance between bare electrode and active sites. By coupling the chemical vapor deposition method with the poly(methyl methacylate)-transfer method, an ultrathin sandwich catalyst, i.e., Fe atoms (polarized electric field layer) sandwiched between ultrathin (within electron tunneling distance) BN (catalyst layer) and graphene film (conducting layer), is fabricated for electrocatalytic NRR. The sandwich catalyst not only controls the transfer of electrons to the BN surface in the correct direction under applied voltage but also suppresses hydrogen evolution reaction by constructing a neutral polarization electric field without metal exposure. The sandwich electrocatalyst NRR system achieve NH₃ yield of 8.9 μg h^-1 cm^-2 and Faradaic Efficiency of 21.7%. The N₂ adsorption, activation, and polarization electric field changes of three sandwich catalysts (BN-Fe-G, BN-Fe-BN, and G-Fe-G) during the electrocatalytic NRR are investigated by experiments and density functional theory simulations. Driven by applied voltage, the neutral polarized electric field induced by BN-Fe-G leads to the high activity of electrocatalytic NRR.

Key words: Ultra-thin BN, Fe doping, BN-Fe-graphene, Mild polarization electric field, Nitrogen reduction reaction

Ziyuan Xiu, Wei Mu, Xin Zhou, Xiaojun Han. Mild polarization electric field in ultra-thin BN-Fe-graphene sandwich structure for efficient nitrogen reduction[J]. Chinese Journal of Catalysis, 2024, 65: 126-137.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60114-2

https://www.cjcatal.com/EN/Y2024/V65/I10/126

Figures/Tables 6

Fig. 1. (a) Enlarged optical microscopy images of the BN film. AFM data of the as-grown BN (b) and BN-Fe-G heterostructure (c). (d) KPFM image of BN-Fe-G heterostructure. The blue and green dashed lines represent BN and Fe-G edges, respectively. (e) The potential variation along the red line and yellow line of KPFM image.

Fig. 2. (a) Raman spectra of the as-grown samples of BN, G, and the BN-Fe-G vertical heterostructure. (b) The fine Raman spectra of the BN-Fe-G vertical heterostructure at the range of 1300-1450 cm?1. (c) Raman spectroscopy optical microscopy imaging of BN-Fe-G over 100 μm × 100 μm. (d) Raman signal distribution of IG/I2D heterogeneous structures over a large area in Fig. 2(c). XPS spectra of BN-Fe-G composites working electrodes: (e) survey; (f) C 1s; (g) Fe 2p; (h) B 1s; (i) N 1s.

Fig. 3. (a) LSV curves in the Ar- and N2-saturated 0.1 mol L-1 HCl. (b) I-t results of BN-Fe-G at five applied voltages. Inset: enlarged I-t results of -0.2 and -0.3 V vs. RHE. (c) Indophenol blue chromogenic UV-vis spectra of NH3 obtained at five potentials. (d) NH3 yield and FE of BN-Fe-G at five potentials. (e) NH3 yield of BN-Fe-G, BN (two layers)-Fe-G, and BN (three layers)-Fe-G at -0.3 V vs. RHE. (f) Quantitative 1H-NMR analysis of BN-Fe-G immerge in 0.1 mol L-1 HCl fed by 15N2 and 14N2 after 10 h electrocatalytic N2 fixation at -0.3 V vs. RHE. (g) NH3 amount after electrolysis of -0.3 V vs. RHE for 2 h under different experimental conditions. (h) Cyclic testing of NH3 yield and FE. (i) The charge current density of BN-Fe-G, Fe-G, G, and BN varies with the scanning rate.

Fig. 4. (a) Schematic illustration of in-situ ATR-FTIR measurement. (b) In situ ATR-FTIR spectra of BN-Fe-G at different time. In situ ATR-FTIR spectra (c) and the corresponding contour image of BN-Fe-G at different applied potentials (d). (e) Peak area of ATR-FTIR spectra at 1539 cm?1. (f) Schematic illustration of the hydrogenation mechanism from N2 to NH3.

Fig. 5. The geometry (top) of G-Fe-G (a), BN-Fe-BN (b), and BN-Fe-G (c) sandwich systems and partial charge densities 0.2 eV below the Fermi level (middle and bottom). The total state density and projected state density of different sandwich systems G-Fe-G (d), BN-Fe-BN (e) and BN-Fe-G (f). The equivalent face value of the middle panel is set to 0.003 e ??3, and the Fermi level of the bottom panel is set to 0. The difference of electron density of nitrogen adsorbed by BN-Fe-G under different applied electric fields. The yellow and blue areas represent electron accumulation and consumption, respectively, with isosurface value equivalent of 0.0004 e ??3. N2 dipole moment of 0 V ??1 (g), 0.2 V ??1 (h), and 0.5 V ??1 (i).

Fig. 6. Work function of BN (a), Fe-G (b), and BN-Fe-G (c). (d) Partial DOS of B and N2 before and after N2 reduction. (e) Free energy and structural changes of the distal and alternate paths for NRR over BN-Fe-G.

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