Integration of theory prediction and experimental electrooxidation of glycerol on NiCo2O4 nanosheets

doi:10.1016/S1872-2067(23)64585-1

Abstract

Abstract:

Electrocatalytic refinery of low-value biomass-based glycerol into value-added chemicals formic acid (FA) is an attractive alternative to traditional thermochemical refineries. However, constructing non-precious catalysts with abundant active hydroxyl (OH*) is the main obstacle to the electrocatalytic glycerol oxidation reaction (EGOR). Herein, we combine density functional theory (DFT) and experiments to investigate EGOR over the finely constructed NiCo₂O₄ nanosheets. DFT results firstly indicate that the NiCo₂O₄ nanosheets exhibit the highly hydroxylated (311)-OH* surface with the lowest Gibbs free energy, which significantly improves the electrochemical reaction kinetics and can achieve desirable FA yield by adjusting the adsorption energy of the adsorption intermediate. Following the theoretical prediction, ultrathin NiCo₂O₄ nanosheets (~1.70 nm) are fabricated by a facile electrodeposition method with sufficient OH* on the surface. The charge-transfer resistance of NiCo₂O₄ nanosheets in EGOR is only 0.94 Ω and the anode power consumption can be reduced by up to 320 mV at 10 mA cm^-2, keeping the high glycerol conversion (89%) and FA selectivity (70%) during the 120-h stability test. DFT calculations and experimental tools (e.g., multi-potential step experiments, operational electrochemical impedance spectroscopy) confirm that OH* in-situ generated on the thin nanosheets structure is essential in facilitating charge transfer between catalysts and adsorbed molecules to enhance C-C bond cleavage. This work offers a guideline for the rational design of robust catalysts for the selective upgrading of biomass-derived chemicals.

Key words: Density functional theory prediction, active hydroxyl, Electrochemical oxidation, Glycerol, NiCo₂O₄ nanosheets

Yan Duan, Mifeng Xue, Bin Liu, Man Zhang, Yuchen Wang, Baojun Wang, Riguang Zhang, Kai Yan. Integration of theory prediction and experimental electrooxidation of glycerol on NiCo₂O₄ nanosheets[J]. Chinese Journal of Catalysis, 2024, 57: 68-79.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(23)64585-1

https://www.cjcatal.com/EN/Y2024/V57/I2/68

Figures/Tables 7

Fig. 1. (a) The top view and side views of NiCo2O4 (220) and NiCo2O4 (311) surface. (b) Gibbs free-energy diagram of the EGOR process over NiCo2O4 (220) and NiCo2O4 (311) surfaces and the corresponding structures are shown in Fig. S3. The Gibbs free-energy diagram of the EGOR and OER processes over NiCo2O4 (311) (c) and NiCo2O4 (311)-OH* (d) surface and the corresponding structure of intermediates are shown in Figs. S4 and S5.

Fig. 2. Synthesis process and morphological characterization of NiCo2O4 catalyst: (a) Schematic diagram; (b) SEM; (c) the corresponding EDX mapping; (d) AFM; (e) TEM; (f) HR-TEM; (g) SAED.

Fig. 3. Internal atomic structure analysis of NiCo2O4 nanosheets catalyst: XPS spectra of Ni 2p (a) and Co 2p (b). XANES spectra of Ni K-edge (c) and Co K-edge (d). Fourier-transformed EXAFS spectra of Ni R-space (e) and Co R-space (f). (g) Wavelet-EXAFS maps of the Ni atom environment with the standard substrate of NiO and the Co atom environment with the standard substrate of Co2O3, deeper color meant greater intensity.

Fig. 4. Electrochemical characterization analysis of NiCo2O4 nanosheets electrode: (a) Comparison of the LSV curves without (OER) and within (EGOR) 0.1 mol L-1 glycerol in 1.0 mol L-1 KOH solution at a scan rate of 5 mV s?1 with 60% iR-corrected. (b) The corresponding Tafel slope. (c) Nyquist plots of impedances. (d) The comparison of electric double layer capacitance (Cdl) values corresponding to CV curves with different scan rates (2-20 mV s-1) in OER and EGOR. (e) Ring current on an RRDE at the ring potential of 0.40 VRHE in OER and EGOR. Hold 200 s at 0 μA current and 200 s at 200 μA current. (f) The comparison at 10 mA cm-2 between this work and previously reported data.

Fig. 5. Products analysis and cycle stability testing. (a) The evolution of product concentration and glycerol conversion as a function of electrolysis time at 1.42 VRHE in 0.1 mol L-1 glycerol-KOH mixture. (b) The selectivity of different products after electrolyzing as a function of electrolysis time and the overall Faradaic efficiency. (c) Stability test for EGOR at the potential of 1.42 VRHE for 5 cycles. After each test, replace the electrode surface with deionized water and a new electrolyte (0.1 mol L-1 glycerol-KOH mixture). (d) Glycerol conversion rate and overall Faradaic efficiency of each cycle test.

Fig. 6. Mechanism analysis. (a) Multi-potential step experimental results. (b) EPR spectroscopic analysis of NiCo2O4 nanosheets electrode in 0 and 0.1 mol L-1 glycerol-KOH mixture at 1.42 VRHE. Bode plots of OER (c) and EGOR (d). (e) The scheme of the relationship between structure-activity-potential.

Fig. 7. Schematic diagram of the main reaction pathways for glycerol oxidation to FA on a simplified model of NiCo2O4.

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Integration of theory prediction and experimental electrooxidation of glycerol on NiCo₂O₄ nanosheets

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