CeO2的形貌对CuO/CeO2催化剂CO2加氢制甲醇性能的影响

doi:10.16085/j.issn.1000-6613.2021-1977

化工进展 ›› 2022, Vol. 41 ›› Issue (8): 4213-4223.DOI: 10.16085/j.issn.1000-6613.2021-1977

CeO₂的形貌对CuO/CeO₂催化剂CO₂加氢制甲醇性能的影响

张嘉琪¹^,²(), 林丽娜¹^,², 高文桂¹^,²^,³(), 祝星²^,³

^1.昆明理工大学冶金与能源工程学院，云南昆明 650093
^2.昆明理工大学省部共建复杂有色金属资源清洁利用国家重点实验室，云南昆明 650093
^3.冶金节能减排教育部工程研究中心，云南昆明 650093

收稿日期:2021-09-06 修回日期:2021-11-18 出版日期:2022-08-25 发布日期:2022-08-22
通讯作者: 高文桂
作者简介:张嘉琪（1997—），女，硕士研究生，研究方向为能源催化。E-mail：382732828@qq.com。
基金资助:
省部共建复杂有色金属资源清洁利用国家重点实验室自主课题(CNMRCUTS2009);国家重点研发计划(2018YFB0605402-02)

Effect of CeO₂ morphology on the performance of CuO/CeO₂ catalyst for CO₂ hydrogenation to methanol

ZHANG Jiaqi¹^,²(), LIN Lina¹^,², GAO Wengui¹^,²^,³(), ZHU Xing²^,³

^1.Faculty of Metallurgy and Energy Engineering, Kunming University of Science and Technology, Kunming 650093, Yunnan, China
^2.State Key Laboratory for Clean Utilization of Complex Nonferrous Metal Resources, Kunming University of Science and Technology, Kunming 650093, Yunnan, China
^3.Engineering Research Center of Ministry of Education for Energy Conservation and Emission Reduction in Metallurgy, Kunming 650093, Yunnan, China

Received:2021-09-06 Revised:2021-11-18 Online:2022-08-25 Published:2022-08-22
Contact: GAO Wengui

摘要/Abstract

摘要：

采用水热法制备CeO₂纳米颗粒（W-CeO₂）、CeO₂纳米片（S-CeO₂）、CeO₂纳米棒（B-CeO₂）及CeO₂纳米八面体（O-CeO₂），用浸渍法负载相同质量分数的铜形成CuO/CeO₂催化剂。通过扫描电镜（SEM）、高分辨透射电子显微镜（TEM）、X射线衍射（XRD）、拉曼光谱（Raman）、自动吸附分析仪（BET）、H₂程序升温还原（H₂-TPR）、N₂O滴定等表征技术对催化剂进行表征，并在可控温控压的固定床石英管反应器中对催化剂的催化性能进行评价。研究了不同形貌CuO/CeO₂催化剂对CO₂加氢制备甲醇的影响；结果表明，CuO/CeO₂催化剂的催化活性存在明显的形貌依赖性，催化剂的暴露晶面、比表面积、表面碱性位点、表面氧缺陷的差异均会对CO₂转化率、甲醇选择性和产率产生影响。其中，不同形貌CeO₂优先暴露晶面的活性顺序为S-CeO₂（{100}+{110}）>W-CeO₂{100}>B-CeO₂{111}≈O-CeO₂{111}，暴露晶面活性越高，催化剂表面氧缺陷越多，CuO-CeO₂间相互作用越强，则催化活性越好。当为CuO/S-CeO₂时，催化剂表面中碱性位点最多，催化剂比表面积为88.8m²/g，铜分散度为19.2%，CO₂转化率为6.56%，甲醇选择性和收率为96.3%和0.063g/(g_cat·h)，催化活性最好，由活性评价试验得转化率由高到低依次为S-CeO₂>B-CeO₂>W-CeO₂>O-CeO₂，可知CeO₂形貌差异会决定CuO/CeO₂催化剂的物化性能和催化活性，从而提升对不同形貌CuO/CeO₂催化剂催化CO₂加氢制甲醇的基础认识。

关键词: CeO₂形貌, 催化剂, 二氧化碳, 加氢, 甲醇

Abstract:

CeO₂ nanoparticles(W-CeO₂), CeO₂ nanosheets(S-CeO₂), CeO₂ nanorods(B-CeO₂) and CeO₂nano-octahedra(O-CeO₂) were firstly prepared by hydrothermal method, and then CuO/CeO₂ catalysts with fixed copper mass fraction were obtained by impregnation method. The catalysts were characterized by scanning electron microscopy (SEM), high-resolution transmission electron microscopy (TEM), X-ray diffraction (XRD), Raman spectroscopy (Raman), automated adsorption analyzer (BET), H₂ programmed temperature rise reduction (H₂-TPR), N₂O titration and other characterization techniques, and their catalytic performance was assessed in a fixed bed quartz tube reactor with controlled temperature and pressure. The effects of the CuO/CeO₂ catalyst morphology on the methanol production by CO₂ hydrogenation were investigated. The catalytic activity of the CuO/CeO₂catalysts showed a strong dependence on their morphology, and the factors of the exposed crystalline surface, specific surface area, surface basic sites and surface oxygen defects of the catalysts all affected the CO₂ conversion, methanol selectivity and the yield. Among them, the order of the activity of the preferentially exposed crystalline surfaces of CeO₂ with different morphologies is S-CeO₂({100}+{110})>W-CeO₂{100}>B-CeO₂{111}≈ O-CeO₂{111}). The higher the activity of the exposed crystalline surfaces, the more oxygen defects on the catalyst surface, and the stronger the CuO/CeO₂ interactions, the better the catalytic activity. Regarding CuO/S-CeO₂, it had the most basic sites on the surface with a specific surface area of 88.8m²/g and copper dispersion of 19.2%, giving the best catalytic activity of CO₂ conversion 6.56%, methanol selectivity 96.3% and yield 0.063g/(g_cat·h). The activity evaluation tests showed the conversion rates of the catalysts were in the order of S-CeO₂>B-CeO₂>W-CeO₂>O-CeO₂, which indicates that the CeO₂ morphology could determine the physical and chemical properties and the catalytic activity of the CuO/CeO₂ catalysts.

Key words: CeO₂ morphology, catalyst, carbon dioxide, hydrogenation, methanol

中图分类号:

O643.3

张嘉琪, 林丽娜, 高文桂, 祝星. CeO₂的形貌对CuO/CeO₂催化剂CO₂加氢制甲醇性能的影响[J]. 化工进展, 2022, 41(8): 4213-4223.

ZHANG Jiaqi, LIN Lina, GAO Wengui, ZHU Xing. Effect of CeO₂ morphology on the performance of CuO/CeO₂ catalyst for CO₂ hydrogenation to methanol[J]. Chemical Industry and Engineering Progress, 2022, 41(8): 4213-4223.

图/表 11

图1 CeO2的SEM图

a1~a3—S-CeO2；b1~b3—B-CeO2；c1~c3—O-CeO2

图2 不同形貌CuO/CeO2催化剂的TEM图a1、b1、c1、d1、a2、b2、c2、d2—不同形貌CeO2的TEM图；a3、b3、c3、d3—不同形貌CuO/CeO2催化剂经H2还原后的TEM图

图3 不同形貌CuO/CeO2催化剂的XRD图

图4 拉曼表征谱图

表1 载体及催化剂的比表面积、氧空位浓度比

CeO₂载体	S_BET/m²·g^-1	ID/IF_2g	CuO/CeO₂催化剂	S_BET/m²·g^-1	ID/IF_2g
W-CeO₂	66.9	0.035	CuO/W-CeO₂	76.4	0.126
S-CeO₂	79.2	0.056	CuO/S-CeO₂	88.8	0.284
B-CeO₂	114.1	0.048	CuO/B-CeO₂	122.2	0.154
O-CeO₂	35.8	0.026	CuO/O-CeO₂	43.5	0.067

图5 不同形貌CuO/CeO2催化剂N2吸脱附曲线

图6 载体及催化剂H2-TPR谱图

表2 不同温度下催化剂H2-TPR还原峰数据

催化剂	α		β
催化剂	面积/mV·℃	T_max/℃	面积/mV·℃	T_max/℃
CuO/W-CeO₂	5200	323	16820	390	0.236
CuO/S-CeO₂	3200	311	10256	358	0.238
CuO/B-CeO₂	5395	428	18202	470	0.229
CuO/O-CeO₂	3143	312	11824	372	0.210

图7 不同形貌CuO/CeO2催化剂CO2-TPD谱图

表3 不同形貌CuO/CeO2催化剂碱性位点分布表

催化剂	弱碱性位点	中碱性位点	强碱性位点	总位点
CuO/W-CeO₂	1220	902	30	2152
CuO/S-CeO₂	1126	1835	35	2996
CuO/B-CeO₂	250	986	11	1247
CuO/O-CeO₂	55	579	24	658

表4 不同形貌CuO/CeO2催化剂的CO2催化评价表

催化剂	$X C O 2$ /%	$S C H 3 O H$ /%	S_CO/%	$W C H 3 O H$ /%	D_Cu/%
CuO/W-CeO₂	5.47	99.04	0.96	5.42	15.8
CuO/S-CeO₂	8.56	96.30	3.70	8.24	19.2
CuO/B-CeO₂	6.01	98.09	1.91	5.90	17.4
CuO/O-CeO₂	3.97	99.99	0.01	3.97	11.9

表4 不同形貌CuO/CeO2催化剂的CO2催化评价表

催化剂	$X C O 2$ /%	$S C H 3 O H$ /%	S_CO/%	$W C H 3 O H$ /%	D_Cu/%
CuO/W-CeO₂	5.47	99.04	0.96	5.42	15.8
CuO/S-CeO₂	8.56	96.30	3.70	8.24	19.2
CuO/B-CeO₂	6.01	98.09	1.91	5.90	17.4
CuO/O-CeO₂	3.97	99.99	0.01	3.97	11.9

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CeO₂的形貌对CuO/CeO₂催化剂CO₂加氢制甲醇性能的影响

Effect of CeO₂ morphology on the performance of CuO/CeO₂ catalyst for CO₂ hydrogenation to methanol

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