Facile synthesis of CoSi alloy catalysts with rich vacancies for base- and solvent-free aerobic oxidation of aromatic alcohols

doi:10.1016/S1872-2067(23)64418-3

Abstract

Abstract:

The rational design and green synthesis of low-cost, robust, and efficient catalysts for the selective oxidation of various alcohols are highly challenging. Herein, we report a fast and solvent-free arc-melting (AM) method to controllably synthesize a semimetallic CoSi alloy catalyst (denoted as AM-CoSi) that is efficient in the base- and solvent-free oxidation of six types of aromatic alcohols. X-ray absorption fine structure analysis, electron paramagnetic resonance spectroscopy, and aberration-corrected high angle annular dark field scanning transmission electron microscopy confirmed the successful synthesis of AM-CoSi with abundant Si vacancies (Si_v). The as-prepared CoSi alloy catalysts exhibit an order of magnitude greater activity in the oxidation of a model reactant, benzyl alcohol (BAL) to benzyl benzoate (BBE), compared with their mono-counterparts, and provide 70% yield of BBE, the highest yield reported to date. Experimental results and density functional theory calculations suggest that the CoSi alloy structure improves the BAL conversion and that Si vacancy is the main contributor to the generation of BBE, based on which a potential reaction pathway is rationally proposed. Furthermore, the CoSi alloy maintains high stability and also exhibits high activity in the selective oxidation of various alcohols with different functional groups. This work demonstrates for the first time that semimetallic CoSi alloys can be robust catalysts for the green oxidation of various alcohols and proviedes a vast opportunity for the rational design and application of other semimetal alloy catalysts.

Key words: Semimetal alloy, Alcohols oxidation, Solvent-free, Vacancy, Density functional theory calculation

Zhiyue Zhao, Zhiwei Jiang, Yizhe Huang, Mebrouka Boubeche, Valentina G. Matveeva, Hector F. Garces, Huixia Luo, Kai Yan. Facile synthesis of CoSi alloy catalysts with rich vacancies for base- and solvent-free aerobic oxidation of aromatic alcohols[J]. Chinese Journal of Catalysis, 2023, 48: 175-184.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(23)64418-3

https://www.cjcatal.com/EN/Y2023/V48/I5/175

Figures/Tables 7

Fig. 1. (a) Schematic of the synthesis of the AM-CoSi alloy through arc melting. (b) HR-TEM image of the AM-CoSi alloy. (c) Point defects (inset shows the image intensity line profile corresponding to the white dotted line). (d) Line defects (inset shows the image intensity line profiles corresponding to the areas enclosed in blue and red rectangles). (e) Plane defects; AC HAADF-STEM (f) and ACTEM (g) images of the AM-CoSi alloy.

Fig. 2. Structural characterization of the AM-CoSi catalyst by XAFS spectroscopy: experimental Co K-edge XANES profiles (a) and Fourier-transformed magnitude (b) of the experimental Co K-edge EXAFS signal of the AM-CoSi alloy and reference samples (Co foil, Co3O4, and S-CoSi). (c) Wavelet transform (WT) for the k3-weighted EXAFS signals of the AM-CoSi alloy. (d) Corresponding EXAFS R-space fitting curve of the AM-CoSi alloy.

Fig. 3. (a) Scheme of the selective oxidation of BAL over the AM-CoSi catalyst. Effect of time on the solvent-free aerobic oxidation of BAL over AM-CoSi at 140 °C (b) and 220 °C (c) under 5 bar O2. The effect of O2 pressure in the solvent-free aerobic oxidation of BAL over AM-CoSi at 140 °C for 6 h (d) and at 220 °C for 24 h (e). Product distributions of the oxidation of BAL over different catalysts at 140 °C for 6 h under 5 bar O2 (f) and at 220 °C for 24 h under 9 bar O2 (g). Reaction conditions: 3 mL of BAL, 10 mg of the catalyst.

Table 1 Solvent-free aerobic oxidation of various alcohols over the AM-CoSi catalyst.

Entry	Conversion (%)	Selectivity (%)	Yield (%)
1	54.8	84.7	46.4
2	52.6	97.3	51.2
3	42.5	88.3	37.5
4	30.2	92.5	27.9
5	54.3	95.4	51.8
6	32.2	99.6	32.1

Fig. 4. (a) Reusability of the AM-CoSi alloy catalyst for 5 cycles. XRD patterns (b) and Co 2p XPS profiles (c) of AM-CoSi before and after the reaction. (d) HR-TEM image of the spent AM-CoSi alloy catalyst (inset shows the image intensity line profiles corresponding to the white dotted line).

Fig. 5. DFT-calculated conformations of the adsorption states of BAL on CovSi (a), CoSiv (b), and S-CoSi (c).

Fig. 6. Reaction energy profiles for the formation of BAD and BBE on the (200) crystal planes of S-CoSi (a) and CoSiv (b). Route 1: conversion of BAL to BAD; Route 2: conversion of BAL to BBE.

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