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Enhancing the ethynylation performance of CuO-Bi2O3 nanocatalysts by tuning Cu-Bi interactions and phase structures

Enhancing the ethynylation performance of CuO-Bi2O3 nanocatalysts by tuning Cu-Bi interactions and phase structures
Enhancing the ethynylation performance of CuO-Bi2O3 nanocatalysts by tuning Cu-Bi interactions and phase structures

Catalytic systems consisting of copper oxide and bismuth oxide are commonly employed for the industrial production of 1,4-butynediol (BD) through ethynylation. However, few studies have investigated the influence mechanism of Bi for these Cu-based catalysts. Herein, a series of nanostructured CuO-Bi2O3 catalysts were prepared by co-precipitation followed by calcination at different temperatures. The obtained catalysts were applied to the ethynylation reaction. The textural and crystal properties of the catalysts, their reduction behavior, and the interactions between copper and bismuth species, were found to strongly depend on temperature. When calcined at 600C, strong interactions between Cu and Bi in the CuO phase facilitated the formation of highly dispersed active cuprous sites and stabilized the Cu+ valency, resulting in the highest BD yield. Bi2O3 was completely absent when calcined at 700C, having been converted into the spinel CuBi2O4 phase. Spinel Cu2+ was released gradually to form active Cu+ species over eight catalytic cycles, which continuously replenished the decreasing activity resulting from the formation of metallic Cu and enhanced catalytic stability. Moreover, the positive correlation between the in-situ-formed surface Cu+ ions and BD yield suggests that the amount of Cu+ ions is the key factor for ethynylation of formaldehyde to BD on the as prepared CuO-Bi2O3 catalysts. Based on these results and the literature, we propose an ethynylation reaction mechanism for CuO-based catalysts and provide a simple design strategy for highly efficient catalytic CuO-Bi2O3 systems, which has considerable potential for industrial applications.

Calcination temperature, Cuo-bi2o3, Ethynylation, Interactions, Spinel cu2+
2073-4344
1-18
Wang, Zhipeng
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Niu, Zhuzhu
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Hao, Quanai
00e67874-c1c3-4599-97fb-12dd0db17277
Ban, Lijun
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Li, Haitao
fb97792b-c451-4886-9f27-ca5a76ff46f1
Zhao, Yongxiang
ad91486b-c15f-4cd0-a380-0ba4f8c8d546
Jiang, Zheng
bcf19e78-f5c3-48e6-802b-fe77bd12deab
Wang, Zhipeng
7fe43ce8-1394-49c0-8bfc-efa77d744952
Niu, Zhuzhu
4a69223e-c950-481c-85d6-729ab96787a1
Hao, Quanai
00e67874-c1c3-4599-97fb-12dd0db17277
Ban, Lijun
469ced11-0d2d-4ecc-9e4f-5317439c51a9
Li, Haitao
fb97792b-c451-4886-9f27-ca5a76ff46f1
Zhao, Yongxiang
ad91486b-c15f-4cd0-a380-0ba4f8c8d546
Jiang, Zheng
bcf19e78-f5c3-48e6-802b-fe77bd12deab

Wang, Zhipeng, Niu, Zhuzhu, Hao, Quanai, Ban, Lijun, Li, Haitao, Zhao, Yongxiang and Jiang, Zheng (2019) Enhancing the ethynylation performance of CuO-Bi2O3 nanocatalysts by tuning Cu-Bi interactions and phase structures. Catalysts, 9 (1), 1-18, [35]. (doi:10.3390/catal9010035).

Record type: Article

Abstract

Catalytic systems consisting of copper oxide and bismuth oxide are commonly employed for the industrial production of 1,4-butynediol (BD) through ethynylation. However, few studies have investigated the influence mechanism of Bi for these Cu-based catalysts. Herein, a series of nanostructured CuO-Bi2O3 catalysts were prepared by co-precipitation followed by calcination at different temperatures. The obtained catalysts were applied to the ethynylation reaction. The textural and crystal properties of the catalysts, their reduction behavior, and the interactions between copper and bismuth species, were found to strongly depend on temperature. When calcined at 600C, strong interactions between Cu and Bi in the CuO phase facilitated the formation of highly dispersed active cuprous sites and stabilized the Cu+ valency, resulting in the highest BD yield. Bi2O3 was completely absent when calcined at 700C, having been converted into the spinel CuBi2O4 phase. Spinel Cu2+ was released gradually to form active Cu+ species over eight catalytic cycles, which continuously replenished the decreasing activity resulting from the formation of metallic Cu and enhanced catalytic stability. Moreover, the positive correlation between the in-situ-formed surface Cu+ ions and BD yield suggests that the amount of Cu+ ions is the key factor for ethynylation of formaldehyde to BD on the as prepared CuO-Bi2O3 catalysts. Based on these results and the literature, we propose an ethynylation reaction mechanism for CuO-based catalysts and provide a simple design strategy for highly efficient catalytic CuO-Bi2O3 systems, which has considerable potential for industrial applications.

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Accepted/In Press date: 25 December 2018
e-pub ahead of print date: 1 January 2019
Published date: 2 January 2019
Keywords: Calcination temperature, Cuo-bi2o3, Ethynylation, Interactions, Spinel cu2+

Identifiers

Local EPrints ID: 427477
URI: http://eprints.soton.ac.uk/id/eprint/427477
ISSN: 2073-4344
PURE UUID: 0e15e812-d01b-4941-99a0-bc6c46c18560
ORCID for Zheng Jiang: ORCID iD orcid.org/0000-0002-7972-6175

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Date deposited: 18 Jan 2019 17:30
Last modified: 07 Oct 2020 02:04

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Contributors

Author: Zhipeng Wang
Author: Zhuzhu Niu
Author: Quanai Hao
Author: Lijun Ban
Author: Haitao Li
Author: Yongxiang Zhao
Author: Zheng Jiang ORCID iD

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