富空穴CoSi合金无溶剂无碱醇氧化

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

催化学报 ›› 2023, Vol. 48: 175-184.DOI: 10.1016/S1872-2067(23)64418-3

富空穴CoSi合金无溶剂无碱醇氧化

赵志月^a^,¹, 蒋志伟^a^,¹, 黄一哲^a, Mebrouka Boubeche^b, Valentina G. Matveeva^c, Hector F. Garces^d, 罗惠霞^b, 严凯^a^,^*()

^a中山大学环境科学与工程学院, 广东广州510006, 中国
^b中山大学材料与工程学院, 光电材料与技术国家重点实验室, 广东广州510006, 中国
^c特维尔国立技术大学生物技术与化学系, 俄罗斯
^d布朗大学工程学院, 美国

收稿日期:2022-11-28 接受日期:2023-02-14 出版日期:2023-05-18 发布日期:2023-04-20
通讯作者: * 电子信箱: yank9@mail.sysu.edu.cn (严凯).
作者简介:第一联系人：
¹共同第一作者
基金资助:
国家自然科学基金(21776324);国家自然科学基金(22078374);广州市科技计划项目(202206010145)

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

Zhiyue Zhao^a^,¹, Zhiwei Jiang^a^,¹, Yizhe Huang^a, Mebrouka Boubeche^b, Valentina G. Matveeva^c, Hector F. Garces^d, Huixia Luo^b, Kai Yan^a^,^*()

^aSchool of Environmental Science and Engineering, Sun Yat-Sen University, Guangzhou 510006, Guangdong, China
^bState Key Laboratory of Optoelectronic Materials and Technologies, School of Materials Science and Engineering, Sun Yat-Sen University, Guangzhou 510006, Guangdong, China
^cDepartment of Biotechnology and Chemistry, Tver State Technical University, Tver 170026, Tver, Russian
^dSchool of Engineering, Brown University, Providence 02912, Rhode Island, USA

Received:2022-11-28 Accepted:2023-02-14 Online:2023-05-18 Published:2023-04-20
Contact: * E-mail: yank9@mail.sysu.edu.cn (K. Yan).
About author:First author contact:
¹Contributed equally to this work.
Supported by:
National Natural Science Foundation of China(21776324);National Natural Science Foundation of China(22078374);Scientific and Technological Planning Project of Guangzhou, China(202206010145)

摘要/Abstract

摘要：

醇类化合物选择性氧化为醛、酸和酯在工业应用中是一类重要的化学反应. 按照绿色化学的要求, 无溶剂、无外加碱源, 以分子氧为氧化剂, 对醇类氧化反应提出了重要挑战, 特别是无溶剂氧化醇制备酯类化学品. 因此开发高效催化剂应用于无溶剂醇氧化成为研究热点. 目前Pd基贵金属催化剂应用于醇的无溶剂氧化已取得一定进展, 但贵金属的稀缺性限制了其工业应用. 由于碱性环境可以有效促进醇的氧化, 但碱性物质的添加可能导致反应体系的二次污染. 此外, Co基非贵金属催化剂可以有效无溶剂氧化醇, 但稳定性一般. 因此, 合成高活性高稳定性催化剂用于醇类化合物的无溶剂选择性氧化是重要的科学问题.
本文采用电弧熔炼法可控制备半金属CoSi合金(AM-CoSi), 在无溶剂无碱条件下将其应用于六种芳香醇的选择性氧化. 采用X射线吸收精细结构谱、电子顺磁共振和球差扫描透射电镜对AM-CoSi催化剂进行结构表征, 发现其以钴硅合金的形式存在, 具有Co空穴和Si空穴, 并且以Si空穴为主. 反应结果表明, 使用AM-CoSi催化剂在220 °C可完全转化苯甲醇, 并以70%的产率得到苯甲酸苄酯(BBE), 使用无缺陷CoSi合金, 只得到9.5%的BBE, 说明Si空穴存在可以高效的转化苯甲醇并高产率得到BBE. 此外, 通过调控反应温度, 使用AM-CoSi无溶剂氧化六种芳香醇(带有不同吸电子基团和供电子基团)可高选择性得到对应的醛, 选择性高达84%以上. 中间体反应实验结果表明, AM-CoSi催化剂具有很好的酯化催化活性, 苯甲醇首先氧化成苯甲醛, 再氧化成苯甲酸, 然后苯甲酸与苯甲醇发生酯化反应生成BBE. 采用单组分合金成分和无空穴CoSi合金(S-CoSi)进行催化剂对比实验, 发现合金结构和空穴有利于苯甲醇的氧化. 设计无空穴CoSi合金、Co空穴CoSi合金和Si空穴CoSi合金三种催化剂模型, 并利用密度泛函理论计算模拟苯甲醇在这三种模型上的氧化路径, 结果表明, CoSi合金结构促进醇的转化, Si空穴有利于BBE的产生. 综上, 本文将为其他半金属合金催化剂的合成和应用提供了新思路.

关键词: 半金属合金, 醇氧化, 无溶剂, 空穴, 密度泛函理论计算

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

赵志月, 蒋志伟, 黄一哲, Mebrouka Boubeche, Valentina G. Matveeva, Hector F. Garces, 罗惠霞, 严凯. 富空穴CoSi合金无溶剂无碱醇氧化[J]. 催化学报, 2023, 48: 175-184.

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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图/表 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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富空穴CoSi合金无溶剂无碱醇氧化

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

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