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CuO-BiO/MgAlO催化剂的简便一锅法合成及其在甲醛乙炔化反应中的性能

Facile one-pot synthesis of CuO-BiO/MgAlO catalyst and its performance in the ethynylation of formaldehyde.

作者信息

Guan Gang, Ma Fengyun, Luo Ping, Zhang Xiaolin, Li Xiaoding, Li Guangxing

机构信息

College of Chemistry and Chemical Engineering, Xinjiang University, Urumqi, Xinjiang, 830046, PR China.

Hubei Research Institute of Chemistry, Jianghan University, Wuhan, 430056, PR China.

出版信息

Heliyon. 2024 Sep 27;10(19):e38721. doi: 10.1016/j.heliyon.2024.e38721. eCollection 2024 Oct 15.

DOI:10.1016/j.heliyon.2024.e38721
PMID:39397931
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC11470502/
Abstract

The CuO-BiO/MgAlO catalyst was synthesized via one-pot synthesis and used to catalyze formaldehyde (HCHO) ethynylation. Coprecipitation using Cu, Bi, Mg, and Al nitrates and NaOH generated Cu and Bi oxides and spinel MgAlO phase. The catalyst precursor was calcined at 450 °C. The catalytic performance of CuO-BiO/MgAlO in the synthesis of 1,4-butynediol via HCHO ethynylation was investigated. The presence of a new spinel phase enhanced the acid-base properties on the catalyst surface and prevented the aggregation of CuO particles. These properties resulted in improved CuO dispersion during calcination and CuO particle growth suppression, affording smaller CuO crystals. The MgAlO support facilitated the reduction of Cu to Cu and formation of abundant active species during the reaction. The catalyst exhibited abundant weakly basic, fewer strongly basic, and least acidic sites, which facilitated the adsorption of HCHO and acetylene. The catalytic performance of CuO-BiO/MgAlO demonstrated 97 % conversion and 80 % selectivity after the online monitoring of the ethynylation reaction for 6 h. The leaching of Cu during the reaction, as analyzed by inductively coupled plasma spectroscopy, was extremely low. Moreover, conversion and selectivity did not substantially change after eight cycles. In addition, the catalyst exhibited superior activity and long-term stability in the ethynylation reaction.

摘要

通过一锅法合成了CuO-BiO/MgAlO催化剂,并将其用于催化甲醛(HCHO)乙炔化反应。使用硝酸铜、铋、镁和铝以及氢氧化钠进行共沉淀,生成了铜和铋的氧化物以及尖晶石MgAlO相。将催化剂前驱体在450℃下煅烧。研究了CuO-BiO/MgAlO在通过HCHO乙炔化合成1,4-丁炔二醇中的催化性能。新的尖晶石相的存在增强了催化剂表面的酸碱性质,并防止了CuO颗粒的聚集。这些性质导致煅烧过程中CuO分散性提高,抑制了CuO颗粒生长,得到了更小的CuO晶体。MgAlO载体促进了反应过程中Cu还原为Cu并形成大量活性物种。该催化剂表现出丰富的弱碱性位点、较少的强碱性位点和最少的酸性位点,有利于HCHO和乙炔的吸附。在对乙炔化反应进行6小时的在线监测后,CuO-BiO/MgAlO的催化性能显示出97%的转化率和80%的选择性。通过电感耦合等离子体光谱分析,反应过程中Cu的浸出极低。此外,经过八个循环后,转化率和选择性没有显著变化。此外,该催化剂在乙炔化反应中表现出优异的活性和长期稳定性。

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本文引用的文献

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Effects of a forming process on the properties and structure of RANEY®-Ni catalysts for the hydrogenation of 1,4-butenediol.成型工艺对用于1,4 - 丁烯二醇加氢的阮内镍催化剂的性能和结构的影响。
RSC Adv. 2020 Feb 5;10(10):5516-5524. doi: 10.1039/c9ra10200k. eCollection 2020 Feb 4.
2
Walter Reppe Revival - Identification and Genesis of Copper Acetylides Cu C as Active Species in Ethynylation Reactions.沃尔特·雷佩复兴——乙炔化反应中作为活性物种的乙炔铜Cu₂C的鉴定与起源
Chemistry. 2021 Dec 6;27(68):16834-16839. doi: 10.1002/chem.202101932. Epub 2021 Aug 1.
3
Ethynylation of Formaldehyde over CuO/SiO Catalysts Modified by Mg Species: Effects of the Existential States of Mg Species.
镁物种改性的CuO/SiO催化剂上甲醛的乙炔化反应:镁物种存在状态的影响
Nanomaterials (Basel). 2019 Aug 7;9(8):1137. doi: 10.3390/nano9081137.
4
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Nanomaterials (Basel). 2019 Jun 1;9(6):842. doi: 10.3390/nano9060842.