In situ X-ray Absorption Spectroscopy Characterization of Copper Valence State in Cu-Zn/SiO2 Catalyst

doi:10.6023/A18010036

Acta Chim. Sinica ›› 2018, Vol. 76 ›› Issue (8): 639-643.DOI: 10.6023/A18010036 Previous Articles Next Articles

Article

X-射线吸收谱原位表征Cu-Zn/SiO₂催化剂Cu价态

贾臻龙^a, 涂云宝^a, 王建强^a, Frenkel Anatoly I.^b, 杨为民^a, 刘仲能^a, 许中强^a

a 中国石油化工股份有限公司上海石油化工研究院上海 201208;
b Yeshiva University, Physics Department, New York, NY10016, United States

投稿日期:2018-01-18 发布日期:2018-06-13
通讯作者: 王建强, 杨为民 E-mail:wangjq.sshy@sinopec.com;yangwm.sshy@sinopec.com
基金资助:
中国石油化工科技开发有限公司与美国叶史瓦大学国际合作项目资助.

In situ X-ray Absorption Spectroscopy Characterization of Copper Valence State in Cu-Zn/SiO₂ Catalyst

Jia Zhenlong^a, Tu Yunbao^a, Wang Jianqiang^a, Frenkel Anatoly I.^b, Yang Weimin^a, Liu Zhongneng^a, Xu Zhongqianga^a

a Sinopec Shanghai Research Institute of Petrochemical Technology, Shanghai 201208;
b Physics Department, Yeshiva University, New York, NY 10016, United States

Received:2018-01-18 Published:2018-06-13
Contact: 10.6023/A18010036 E-mail:wangjq.sshy@sinopec.com;yangwm.sshy@sinopec.com
Supported by:
Project supported by the international cooperation project between China Petrochemical Technology Co., Ltd. and Yeshiva University.

1. In situ X-ray Absorption Spectroscopy Characterization of Copper Valence State in Cu-Zn/SiO₂ Catalyst.PDF(811KB)

Abstract

The valence states of copper-based catalyst are still controversial for whether Cu⁺ exists or even dominates the corresponding catalysis performance, especially for the catalyst prepared by unconventional method. For example, Cu/SiO₂ catalyst prepared by deposition-precipitation exhibits different ratio of Cu⁰ and Cu⁺ in the literatures. Zinc-doping Cu/SiO₂ catalyst is primarily chosen for carbonyl hydrogenation. Additionally, the copper catalysts employed in the industrial reactor require a doping of zinc for catalyst stability and relatively low temperature reduction, which makes the valence states of copper catalyst under working conditions even more complicated. In this paper, copper phyllosilicate, 15 wt% Cu-5.0 wt% Zn/SiO₂, was prepared by ammonia evaporation method with the following procedures:(1) complexation of Cu/Zn to silicasol by mixing of an amount of copper ammonia solution (0.5 mol/L) and zinc ammonia solution (0.5 mol/L) with silicasol (5%, SiO₂) for 5 h at room temperature, and then decomposition of metal ammonia under 95℃; (2) dried, crushed and calcined at 450℃ for 4 h. The Cu/SiO₂ catalyst precursor without the addition of zinc was prepared with the same procedures as Cu-Zn catalyst precursor. The valence states of copper catalyst of Cu-Zn/SiO₂ and Cu/SiO₂ catalyst during hydrogen reduction in the temperature range of 20℃ to 350℃ has been studied by in situ X-ray absorption spectroscopy characterization under the atmosphere of 10% H₂ in He, 50 mL/min. Valence state composition was analyzed by using Linear Combination Fitting (LCF) method based on X-ray Absorption Near Edge Spectroscopy (XANES) spectra, which indicated:(1) the reduction degree of Cu²⁺ to Cu⁰ is increased with the addition of zinc; (2) Cu⁺ occurred and mainly existed at low reduction temperature (<250℃) with a low concentration, but it diminished completely at high reduction temperature; (3) Cu⁰ could be the active center for hydrogenation of methyl acetate to ethanol.

Key words: Cu/SiO₂, Cu-Zn/SiO₂, methyl acetate, ethanol, XANES

Cite this article

Jia Zhenlong, Tu Yunbao, Wang Jianqiang, Frenkel Anatoly I., Yang Weimin, Liu Zhongneng, Xu Zhongqianga. In situ X-ray Absorption Spectroscopy Characterization of Copper Valence State in Cu-Zn/SiO₂ Catalyst[J]. Acta Chim. Sinica, 2018, 76(8): 639-643.

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X-射线吸收谱原位表征Cu-Zn/SiO₂催化剂Cu价态

In situ X-ray Absorption Spectroscopy Characterization of Copper Valence State in Cu-Zn/SiO₂ Catalyst

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X-射线吸收谱原位表征Cu-Zn/SiO2催化剂Cu价态