Manipulating the electronic state of ruthenium to boost highly selective electrooxidation of ethylene to ethylene glycol in acid

doi:10.1016/S1872-2067(24)60024-0

Abstract

Abstract:

Electrochemical oxidation of ethylene is a novel approach to manufacture valuable ethylene glycol (EG), which is an important raw material in organic chemical industry. However, the poor EG selectivity and expensive additional purification costs hinder this method from being practically used. In this work, ultrafine iridium-ruthenium (IrRu) alloy nanoparticles are synthesized through the precipitation-reduction method and their electrocatalytic performance towards ethylene oxidation to EG has been comprehensively studied. Near 100% selectivity is achieved with a EG yield of 60.62 mmol g_Ru^-1 h^-1 at 1.475 V on an optimal Ir_0.54Ru_0.46 catalyst. OH-stripping, in-situ electrochemical attenuated total internal reflectance Fourier transform infrared spectra and DFT calculation reveal that the introduction of Ir can modulate the electronic structure and d-band center so as to endow the Ru with the mild binding energy with the key intermediates and small energy barrier for *HOCH₂CH₂OH desorption, thereby enhancing the EG generation. Simultaneously, the high energy barrier for the overoxidation of the *CH₂CH₂OH renders the EG formation thermodynamically favorable, thus realizing the near 100% EG selectivity. This work provides a new understanding for the high-selectivity electrosynthesis of high-value-added oxides.

Key words: Ethylene electrooxidation, Ethylene glycol, High selectivity, IrRu alloy, Electronic structure1. Introduction

Jie Wang, Yihe Chen, Yuda Wang, Hao Zhao, Jinyu Ye, Qingqing Cheng, Hui Yang. Manipulating the electronic state of ruthenium to boost highly selective electrooxidation of ethylene to ethylene glycol in acid[J]. Chinese Journal of Catalysis, 2024, 60: 376-385.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60024-0

https://www.cjcatal.com/EN/Y2024/V60/I5/376

Figures/Tables 4

Fig. 1. Synthetic scheme and characterization of Ir-Ru NPs. (a) Schematic illustration of the synthetic process. (b) XRD patterns of Ir0.57Ru0.43, Ir0.54Ru0.46, Ir0.46Ru0.54 and Ru NPs. TEM image (c) and alloy nanoparticle size distribution (d) of Ir0.54Ru0.46 NPs. Aberration STEM image (e), SAED pattern (f) and elemental mapping (g) for Ir0.54Ru0.46 NPs. (h) High-resolution XPS spectra of Ru 3p3/2. Normalized XANES (i) and R-space of the EXAFS spectra (j) of Ir0.57Ru0.43, Ir0.54Ru0.46, Ir0.46Ru0.54, Ir foil, and Ru foil at the Ru K-edge.

Fig. 2. Catalytic performance of IrRu alloy NPs and Ru NPs toward ethylene to EG in 50 mL 0.1 mol L-1 HClO4. CVs (a) and LSVs (b) of Ir0.54Ru0.46 NPs in N2- and ethylene-saturated electrolyte. Yield rates of EG (c), TOF (d) and FEEG (e) at the potentials from 1.400 to 1.475 V. (f) Nyquist plots of different catalysts (The inset is equivalent circuit, where Rs, Rc, Cc, Cdl and Rct represent electrolyte resistance, contact resistance, contact capacitance, Double-layer capacitance and charge transfer resistance, respectively). (g) Selectivity of EG at a potential range from 1.400 to 1.475 V. (h) Durability test for Ir0.54Ru0.46 NPs. (i) EG productivity rate at 1.45 V during the 12 h electrolysis.

Fig. 3. (a) EG yielding and corresponding FEEG in the presence of 100 mmol methanol or 100 mmol p-benzoquinone of Ir0.54Ru0.46 NPs catalysts, respectively. (b) Desorption of OH on Ir0.46Ru0.54 NPs, Ir0.54Ru0.46 NPs, Ir0.57Ru0.43 NPs. CV curves with the scan rate of 50 mV?s?1. (c) VBS of Ir0.57Ru0.43, Ir0.54Ru0.46, Ir0.46Ru0.54, and Ru NPs catalysts measured by XPS. (d) Electrochemical in situ ATR-FTIR spectra of ethylene oxidation on Ir0.54Ru0.46 NPs at different potentials (0.1-1.4 V) in ethylene-saturated 0.1 mol L-1 HClO4 solution. (e) Schematic diagram of electrooxidation of ethylene to EG on IrRu alloy.

Fig. 4. Theoretical calculations for ethylene oxidation. (a) Calculation model for Ru NPs and Ir0.54Ru0.46 NPs. (b) Charge transfer between Ir and Ru atoms in Ir0.54Ru0.46 NPs. (c) P-DOS for Ru NPs and Ir0.54Ru0.46 NPs. (d) Free energy diagram on Ru NPs and Ir0.54Ru0.46 NPs (pathway I: C2H4 → HOCH2CH2OH, pathway II: C2H4 → HOCH2COOH).

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