Inverse Decoration of ZnO on Small-Sized Cu/Sio<sub>2</sub> with Controllable Cu-ZnO Interaction for CO<sub>2</sub> Hydrogenation to Produce Methanol

注册 English

Inverse Decoration of ZnO on Small-Sized Cu/Sio₂ with Controllable Cu-ZnO Interaction for CO₂ Hydrogenation to Produce Methanol

Hanlin Lyu , Bing Hu , Guoliang Liu , Xinlin Hong , Lin Zhuang

Citation: Lyu Hanlin, Hu Bing, Liu Guoliang, Hong Xinlin, Zhuang Lin. Inverse Decoration of ZnO on Small-Sized Cu/Sio₂ with Controllable Cu-ZnO Interaction for CO₂ Hydrogenation to Produce Methanol[J]. Acta Physico-Chimica Sinica, 2020, 36(11): 1911008-0. doi: 10.3866/PKU.WHXB201911008 shu

shu

ZnO逆修饰小尺寸Cu/SiO₂催化剂及其在CO₂加氢制甲醇中的应用

吕翰林 ^1, ,
胡兵 ^2, ,
刘国亮 ^2, ,
洪昕林 ^{2,
,} ,
庄林 ^{1,2,
,}

1.
武汉大学高等研究院，武汉 430072
2.
武汉大学化学与分子科学学院，武汉 430072

通讯作者: 洪昕林, hongxl@whu.edu.cn
庄林, lzhuang@whu.edu.cn

基金项目:
国家自然科学基金 21872106

中央高校基本科研业务费专项资金 2042019kf0019

国家自然科学基金(21872106, 21603244), 中央高校基本科研业务费专项资金(2042019kf0019)资助项目

国家自然科学基金 21603244

摘要: Cu-ZnO催化剂广泛应用于CO₂还原制甲醇，但是如何构建具备强金属-载体相互作用、粒径可控的Cu-ZnO催化剂仍然富有挑战性。本文发展了一种利用高比表面硅酸铜前驱物合成小粒径且组分相互作用可控的Cu-ZnO/SiO₂催化剂的方法，制备得到一系列ZnO含量不同的Cu-ZnO/SiO₂催化剂，并对其CO₂加氢制甲醇的催化活性进行系统考察。发现在523 K的条件下，甲醇选择性由未加入ZnO的20%提高至ZnO含量为14%时的67%。催化剂活性与ZnO含量之间呈现火山型关系，在ZnO含量为7%，温度为543 K，H₂/CO₂压力为4.5 MPa时，甲醇时空产率(STY)最优，为244 g·kg^-1·h^-1。此外，本文探究了催化剂中Cu与ZnO的协同效应，发现ZnO可以显著增强Cu的催化活性，但过量ZnO的引入会使Cu颗粒粒径增长，降低催化剂中的总反应位点数，进而影响催化剂催化活性。

关键词:

English

Inverse Decoration of ZnO on Small-Sized Cu/Sio₂ with Controllable Cu-ZnO Interaction for CO₂ Hydrogenation to Produce Methanol

Lyu Hanlin ^1, ,
Hu Bing ^2, ,
Liu Guoliang ^2, ,
Hong Xinlin ^{2,
,} ,
Zhuang Lin ^{1,2,
,}

1.
Institute for Advanced Studies, Wuhan University, Wuhan 430072, P. R. China
2.
College of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430072, P. R. China

Corresponding author: Hong Xinlin, hongxl@whu.edu.cn Zhuang Lin, lzhuang@whu.edu.cn

Received Date: 04 November 2019
Revised Date: 15 December 2019
Available Online: 15 November 2020
Fund Project:
the National Natural Science Foundation of China 21872106

the Fundamental Research Funds for the Central Universities, China 2042019kf0019

This work is financially supported by the National Natural Science Foundation of China (21872106, 21603244) and the Fundamental Research Funds for the Central Universities, China (2042019kf0019)

the National Natural Science Foundation of China 21603244

Abstract: Cu-ZnO is broadly used as a catalyst in CO₂ reduction to produce methanol, but fabricating small-sized Cu-ZnO catalysts with strong Cu-ZnO interactions remains a challenge. In this work, a simple, low-cost method is proposed to synthesize small-sized Cu-ZnO/SiO₂ with high activity and controllable Cu-ZnO interactions derived from copper silicate nanotubes. A series of Cu-ZnO/SiO₂ samples with different amounts of ZnO were prepared. The activities of the as-prepared catalysts for methanol synthesis were tested, and the results revealed a volcano relationship with the weight fraction of ZnO. At 523 K, the methanol selectivity increased from 20% to 67% when 14% ZnO was added to the Cu/SiO₂ catalyst, while the conversion of CO₂ increased first and then decreased with the addition of ZnO. The optimum space time yield (STY) of 244 g·kg^-1·h^-1 was obtained on C-SiO₂-7%ZnO at 543 K under 4.5 MPa H₂/CO₂. Furthermore, the synergistic effect of Cu and ZnO was studied by high resolution transmission electron microscopy (HRTEM), powder X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), in situ diffuse-reflectance infrared Fourier transform spectroscopy (DRIFTS), and temperature-programmed reduction (TPR) analyses. The HRTEM images showed that the Cu particles come in contact with ZnO more frequently with increased addition of ZnO, indicating that the catalysts with higher ZnO contents have a greater probability of formation of the Cu-ZnO interface, which promotes the catalytical activity of Cu-ZnO/SiO₂. Meanwhile, the HRTEM images, XRD patterns, and TPR results showed that the addition of excess ZnO leads to an increase in the size of the Cu particles, which in turn decreases the total number of active sites and further degrades the activity of the catalysts. The activation energy (E_a) for methanol synthesis and reverse water gas shift (RWGS) was calculated based on the results of the catalytical test. With the addition of ZnO, E_a for methanol synthesis decreased from 72.5 to 34.8 kJ·mol^-1, while that for RWGS increased from 61.3 to 102.7 kJ·mol^-1, illustrating that ZnO promotes the synergistic effect of Cu-ZnO. The results of XPS and in situ DRIFTS showed that the amount of Cu⁺ species decreases with the addition of ZnO, indicating that the Cu-ZnO interface serves as the active site. The Cu surface area and the turnover frequency (TOF) of methanol were calculated based on the H₂-TPR curves. The TOF of methanol on the Cu-ZnO/SiO₂ catalysts at 543 K increased from 1.5 × 10^-3 to 3.9 × 10^-3 s^-1 with the addition of ZnO, which further confirmed the promotion effect of the Cu-ZnO interface on the methanol synthesis. This study provides a method to construct Cu-ZnO interfaces based on copper silicate and to investigate the influence of ZnO on Cu-ZnO/SiO₂ catalysts.

Key words:

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