Electronic modification of Ni active sites by W for selective benzylamine oxidation and concurrent hydrogen production

doi:10.1016/S1872-2067(23)64596-6

Abstract

Abstract:

We present self-supporting W-doped Ni₂P nanosheet arrays, serving as bifunctional catalysts for selective electrooxidation of benzylamine (BA) to high-value benzonitrile (BN), while simultaneously promoting hydrogen production. The assembled W-Ni₂P/NF||W-Ni₂P/NF (NF: nickel foam) electrolyzer requires a voltage of only 1.41 V to achieve a current density of 10 mA cm^‒2 in alkaline solution containing 25 mmol L^‒1 BA, exhibiting an impressive Faradaic efficiency 95% for benzonitrile synthesis. In-situ Raman and FTIR spectroscopies identify catalytically active NiOOH centers and key catalytic intermediates. X-ray absorption spectroscopy (XAS) and theoretical calculations suggest that W acts as electron attractors on adjacent Ni atoms, forming an electron-deficient Ni domain that promotes the adsorption and activation of -NH₂ group, leading to efficient dehydrogenation into C≡N bonds. The doped W also optimizes the adsorption of hydrogen (ΔG_H*) on Ni₂P, thus promote the hydrogen evolution. This work highlights the electronic modification of Ni active sites as a key factor for bifunctional electrocatalysis in selective nitrile electrosynthesis and concurrent hydrogen evolution.

Key words: Bifunctional electrocatalyst, Selective oxidation, Benzonitrile electrosynthesis, Dehydrogenation, Hydrogen evolution reaction

Zhentao Tu, Xiaoyang He, Xuan Liu, Dengke Xiong, Juan Zuo, Deli Wu, Jianying Wang, Zuofeng Chen. Electronic modification of Ni active sites by W for selective benzylamine oxidation and concurrent hydrogen production[J]. Chinese Journal of Catalysis, 2024, 58: 146-156.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(23)64596-6

https://www.cjcatal.com/EN/Y2024/V58/I3/146

Figures/Tables 9

Scheme 1. Illustration of the current industrial route for benzonitrile synthesis and their wide applications.

Scheme 2. Schematic illustration for synthesis of bifunctional W-Ni2P/NF nanoarray electrocatalysts and selective oxidation of benzylamine.

Fig. 1. SEM images of Ni2P (a,b) and W-Ni2P (c,d) at low and high magnifications. TEM (e) and HRTEM (f) images of W-Ni2P. (g) Elemental mapping images of Ni, P and W on W-Ni2P.

Fig. 2. (a) XRD patterns of W-Ni2P and Ni2P. XPS spectra for W 4f (b), P 2p (c), and Ni 2p (d). Ni K-edge XANES spectra (e) and R space Fourier transform EXAFS spectra (f) of Ni foil, NiO, Ni2P, and W-Ni2P. (g) Wavelet transform plots of Ni foil, NiO, Ni2P, and W-Ni2P.

Fig. 3. HER polarization curves (a) and Tafel plots (b) for various catalysts in 1.0 mol L?1 KOH solution. (c) Nyquist plots of various catalysts at an overpotential of 110 mV; the inset shows the equivalent circuit diagram. (d) CV curves for W-Ni2P at scan rates from 20 to 120 mV s-1. (e) Cdl values of various catalysts. (f) j-t curve of W-Ni2P and LSV curves before and after 3000 CV scan cycles.

Fig. 4. (a) LSV curves of W-Ni2P in 1.0 mol L?1 KOH with and without 25 mmol L?1 BA. (b) Potential comparison of BAOR and OER at different current densities. LSV curves (c) and Tafel plots (d) for W-Ni2P, Ni2P, W-Ni LDH, Ni LDH and RuO2 in 1.0 mol L?1 KOH containing 25 mmol L?1 BA. (e) 1H NMR spectra for BA and its oxidation products during electrolysis. (f) 1H NMR local magnification from 7.0 to 8 δ. (g) 13C NMR spectra for BA and its oxidation products during electrolysis. (h) Nyquist plots of various catalysts at an overpotential of 110 mV; the inset shows the equivalent circuit diagram. (i) j-t curve (inset) of W-Ni2P and LSV curves before and after stability test.

Fig. 5. Potential dependent, in-situ Raman spectra at W-Ni2P in 1.0 mol L?1 KOH without (a) and with (b) 25 mmol L?1 BA. (c) In-situ Raman spectra at 1.45 V after addition of 25 mmol L?1 BA. (d) In-situ FTIR spectra of W-Ni2P at different applied potentials for the BAOR. (e) In-situ FTIR spectra of W-Ni2P at different times following (d) at the open circuit potential.

Fig. 6. (a) Schematic diagram of a two-electrode electrolyzer with W-Ni2P as the anode and cathode. Polarization curves (b) and comparison of cell voltages (c) for different current densities achieved at W-Ni2P electrodes in 1.0 mol L-1 KOH with and without 25 mmol L-1 BA. (d) Chronopotentiometric curves of BA oxidation at W-Ni2P at 20 mA cm-2 in 1.0 mol L-1 KOH containing 25 mmol L-1 BA; the inset illustrates the change in voltage before and after electrolysis. (e) Optical photo of a HER||BAOR electrolytic cell powered by a small solar cell.

Fig. 7. Theoretical models of W-Ni2P (a), Ni2P (b), W-Ni2P@W-NiOOH (c) and Ni2P@NiOOH (d). (e) The free energy diagram of HER on the W-Ni2P and Ni2P. (f) The partial density of states (PDOS) of W-Ni2P and Ni2P. (g) Benzylamine adsorption energy on W-Ni2P@W-NiOOH and Ni2P@NiOOH. (h) Electron density difference at the W-Ni2P@W-NiOOH interface. (i) The free energy diagram of BAOR on the W-Ni2P and Ni2P.

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