The preparation of CuM/SiO2 (M=Bi, Mg, Mn) catalysts applied in ethynylation of formaldehyde for 1,4‑butynediol synthesis: the positive interface effect of CuO and Bi2O3

IF 3.5 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Dalton Transactions Pub Date : 2024-11-11 DOI:10.1039/d4dt02616k

Jiali Chen, Guihua Yang, Feng Gao, Rui Wang

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引用次数: 0

Abstract

The ethynylation of formaldehyde reaction catalyzed by Cu-based catalysts is an important synthesis method for 1,4-butynediol relating to high value-added chemicals. In this work, a series of CuM/SiO2 ( M=Bi, Mg, Mn ) catalysts were prepared by a deposition-precipitation method and applied in the ethynylation reaction. The effects of different promoters ( Bi, Mg, Mn ) on the catalytic activity were investigated. The relationship between catalyst structure and performance is systematically studied using XRD, TEM, SEM mapping, N2 low- temperature adsorption/desorption, FT-IR, XPS, and TG-DTA characterization analysis. The results show that 30Cu2Bi/SiO2 exhibits the highest 1,4-butynediol yield (70%) and selectivity (97%) after the ethynylation reaction for 7 h. Furthermore, compared with the commercial catalyst, 30Cu2Bi/SiO2 shows similar cyclic stability, 47% yield, and 98% selectivity for 1,4-butynediol after 8 times about 60 h. It is attributed that small CuO particles are uniformly dispersed in 30Cu2Bi/SiO2 with the biggest specific surface area (446.37 m2/g). What’s more, the Cu-Bi interface existing in 30Cu2Bi/SiO2 plays an important role in stabilizing cuprous, not excessively reduced to metallic Cu. Therefore, during the ethynylation reaction, 30Cu2Bi/SiO2 has the most active Cu2C2 and the least polyacetylene by-products. In addition, the richest oxygen vacancies arose in 30Cu2Bi/SiO2 also contribute to the ethynylation of the formaldehyde reaction.

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用于甲醛乙炔化合成 1,4-丁炔二醇的 CuM/SiO2（M=Bi、Mg、Mn）催化剂的制备：CuO 和 Bi2O3 的正界面效应

铜基催化剂催化的甲醛乙炔化反应是与高附加值化学品相关的 1,4-丁炔二醇的重要合成方法。本研究采用沉积-沉淀法制备了一系列 CuM/SiO2 催化剂（M=Bi、Mg、Mn），并将其应用于乙炔化反应。研究了不同促进剂（Bi、Mg、Mn）对催化活性的影响。利用 XRD、TEM、SEM 图谱、N2 低温吸附/解吸、FT-IR、XPS 和 TG-DTA 表征分析系统地研究了催化剂结构与性能之间的关系。结果表明，在乙炔化反应 7 小时后，30Cu2Bi/SiO2 表现出最高的 1,4-丁炔二醇产率（70%）和选择性（97%）。此外，与商用催化剂相比，30Cu2Bi/SiO2 具有相似的循环稳定性，在 8 次约 60 小时的反应后，1,4-丁炔二醇的产率为 47%，选择性为 98%。此外，30Cu2Bi/SiO2 中存在的 Cu-Bi 界面在稳定亚铜方面起着重要作用，不会过度还原成金属铜。因此，在乙炔化反应过程中，30Cu2Bi/SiO2 具有最活跃的 Cu2C2 和最少的聚乙炔副产物。此外，30Cu2Bi/SiO2 中产生的最丰富的氧空位也有助于甲醛的乙炔化反应。

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来源期刊

Dalton Transactions 化学-无机化学与核化学

CiteScore

6.60

自引率

7.50%

发文量

1832

审稿时长

1.5 months

期刊介绍： Dalton Transactions is a journal for all areas of inorganic chemistry, which encompasses the organometallic, bioinorganic and materials chemistry of the elements, with applications including synthesis, catalysis, energy conversion/storage, electrical devices and medicine. Dalton Transactions welcomes high-quality, original submissions in all of these areas and more, where the advancement of knowledge in inorganic chemistry is significant.