Lewis酸碱调控镧掺杂氧化锌催化CO<sub>2</sub>转化制碳酸乙烯酯

杜昌元; 苏倩; 许振洋; 付梦倩; 贾松岩; 董丽

doi:10.19906/j.cnki.JFCT.2023060

Lewis酸碱调控镧掺杂氧化锌催化CO₂转化制碳酸乙烯酯

doi: 10.19906/j.cnki.JFCT.2023060

杜昌元^{1, 2,},
苏倩^2,,
许振洋^2,,
付梦倩^2,,
贾松岩^1, ,,
董丽^2, ,

1.
沈阳化工大学, 化学工程学院, 辽宁沈阳 110142
2.
中国科学院过程工程研究所, 离子液体清洁过程北京市重点实验室, 北京 100190

基金项目: 国家自然科学基金 (22178356, 22078329, 21890763)资助

详细信息

通讯作者:
jiasongyan@126.com

Tel: 13810430696, E-mail: ldong@ipe.ac.cn

中图分类号: O643.36
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- 被引次数: 0
出版历程
- 收稿日期: 2023-07-18
- 修回日期: 2023-08-14
- 录用日期: 2023-08-14
- 网络出版日期: 2023-09-18

Lewis acid-base modulated lanthanum-doped zinc oxide catalyzed CO₂ conversion to ethylene carbonate

DU Chang-yuan^{1, 2
,},
SU Qian^2
,,
XU Zhen-yang^2
,,
FU Meng-qian^2
,,
JIA Song-yan^{1
, ,},
DONG Li^{2
, ,}

1.
College of Chemical Engineering, Shenyang University of Chemical Technology, Shenyang, 110142, China
2.
Beijing Key Laboratory of Ionic Liquid Clean Process, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China

Funds: The project was supported by National Natural Science Foundation of China (22178356, 22078329, 21890763).

摘要

摘要: 温室气体CO₂的大量排放引发了全球变暖和生态环境破坏等问题。如何将CO₂作为资源有效利用，并创造经济效益在近年来备受关注。本文以CO₂和乙二醇(EG)合成碳酸乙烯酯(EC)为目标，设计合成一系列La掺杂ZnO催化剂，可对ZnO表面Lewis酸碱性位点调控，并在无助剂条件下研究了催化剂活性。La-ZnO-1%-550 ℃具有最好的催化活性，在130 ℃、4 MPa CO₂、1 h条件下，EG的转化率为0.54%，EC的时空收率和选择性分别为7.326 mmol·h⁻¹∙g⁻¹和99%，并具有良好的稳定性。结合对催化剂的晶体结构、形貌和表面酸碱性等分析，结果显示：La均匀分布在ZnO中空纳米片中，经过550 ℃煅烧的La掺杂ZnO的表面具有最多的Lewis酸碱性位点，催化剂的催化活性随中强Lewis酸碱性位点增多而升高。
- CO₂ /
- ZnO /
- 碳酸乙烯酯 /
- Lewis酸碱催化
Abstract: The massive emission of the greenhouse gas CO₂ has caused problems such as global warming and ecological damage. How to effectively utilize CO₂ as a resource and create economic benefits has attracted much attention in recent years. In this paper, a series of La-doped ZnO catalysts were designed and synthesized targeting the synthesis of ethylene carbonate (EC) from CO₂ and ethylene glycol (EG), which could modulate the Lewis acid-base sites on the ZnO surface, and the catalyst activity was investigated under additive-free conditions. La-ZnO-1%-550 ℃ had the best catalytic activity with 0.54% conversion of EG, 7.326 mmol∙h⁻¹∙g⁻¹ and 99% space-time yield and selectivity of EC at 130 ℃, 4 MPa CO₂, and 1 h with good stability. Combined with the analysis of the crystal structure, morphology and surface acid-base of the catalysts, the results showed that La was uniformly distributed in the ZnO hollow nanosheets, and the surface of the La-doped ZnO calcined at 550 ℃ had the most Lewis acid-base sites, and the catalytic activity of the catalysts increased with the increase of moderate to strong Lewis acid-base sites.
- co₂ /
- zno /
- ethylene carbonate /
- lewis acid-base catalysis

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图 1 CO₂与乙二醇合成碳酸乙烯酯

Figure 1 Synthesis of Ethylene Carbonate by CO₂ and Ethylene Glycol

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图 2 催化剂的(a)XRD和(b)FT-IR图

Figure 2 (a) XRD and (b) FT-IR images of the catalysts

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图 3 (a)和(b)为La-ZnO-1%-550 ℃的SEM图；(c)，(d)，(e)和(f)为La-ZnO-1%-550 ℃的EDS元素分布图

Figure 3 (a) and (b) are SEM images of La-ZnO-1%-550 ℃; (c), (d), (e) and (f) are EDS elemental distribution maps of La-ZnO-1%-550 ℃

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图 4 催化剂的(a)Zn2p，(b)La3d，(c)O1s的XPS图

Figure 4 XPS images of (a) Zn2p, (b) La3d, (c) O1s of the catalysts

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图 5 催化剂的(a)Py-IR， (b)NH₃-TPD和(c)CO₂-TPD图

Figure 5 (a) Py-IR, (b) NH₃-TPD and (c) CO₂-TPD images of the catalysts

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图 6 EC时空收率与催化剂的中强Lewis酸(a)碱(b)位点数量之间的关系

Figure 6 Relationship between EC space-time yield and the number of moderate to strong Lewis acid (a) base (b) sites of the catalyst

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图 7 (a)反应温度，(b)反应压力和(c)催化剂用量对EG和CO₂合成EC的影响

Figure 7 Effects of (a) reaction temperature, (b) reaction pressure and (c) catalyst dosage on EC synthesis by EG and CO₂

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图 8 (a)La-ZnO-1%-550 ℃的循环使用性能，使用前后La-ZnO-1%-550 ℃的(b)XRD和(c)FT-IR图

Figure 8 (a) Cycling performance of La-ZnO-1%-550 ℃, (b) XRD and (c)FT-IR images for before and after used La-ZnO-1%-550 ℃

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表 1 催化剂的各种状态氧的占比和La占Zn的比例(mol)

Table 1 The proportion of oxygen in various states of the catalyst and the proportion of La to Zn (mol)

Catalysts	O_L/(%)	O_V/(%)	O_C/(%)	La/Zn/(%)
ZnO-550 ℃	19.28	54.53	26.20	0.0
La-ZnO-1%-450 ℃	24.43	66.44	9.13	1.2
La-ZnO-1%-550 ℃	26.76	58.02	15.18	1.1
La-ZnO-1%-700 ℃	19.96	69.19	10.85	1.1

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表 2 Py-IR和TPD结果定量酸碱位点数量

Table 2 Number of acid-base sites quantified by Py-IR and TPD

Catalysts	Acid/(mmol∙g⁻¹)		Base/(mmol∙g⁻¹)		B/L acid
Catalysts	Weak	Moderate	Weak	Moderate	B/L acid
ZnO-550 ℃	0.0352	0.0992	0.0504	0.0747	0.0424
La-ZnO-1%-450 ℃	0.0921	0.1425	0.0836	0.1263	0.0582
La-ZnO-1%-550 ℃	0.0816	0.3786	0.0785	0.2316	0.0315
La-ZnO-1%-700 ℃	0.0965	0.2718	0.0671	0.1759	0.0894

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表 3 不同催化剂的催化活性

Table 3 Catalytic activity of different catalysts

Catalysts	C_EG/%	STY_EC/ mmol∙h⁻¹∙g⁻¹	S_EC/%
---	0	0	0
ZnO-550 ℃	0.16	1.141	99
Ce-ZnO-1%-550 ℃	0.11	0.970	99
Ni-ZnO-1%-550 ℃	0.07	0.446	99
Co-ZnO-1%-550 ℃	0.28	1.995	99
La-ZnO-1%-550 ℃	0.64	4.711	99
La-ZnO-1%-450 ℃	0.23	1.651	99
La-ZnO-1%-700 ℃	0.32	2.864	99
CeO₂-ZrO₂^a[4]	1.33	1.330	100
Reaction conditions: 150 mmol EG, 0.1 g catalyst, 130 ℃, 4 MPa CO₂ and 2 h
^a100 mmol EG, 120 mmol acetonitrile (dehydrating agent), 0.5 g CeO₂-ZrO₂, 150 ℃, 3.5 MPa CO₂ and 2 h

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表 4 反应时间对合成EC的影响

Table 4 Effect of reaction time on the synthesis of EC

Reaction time/h	C_EG/%	STY_EC/mmol∙h⁻¹∙g⁻¹	S_EC/%
0.5	0.31	8.461	99
1	0.54	7.326	99
2	0.64	4.511	99
Reaction conditions: 150 mmol EG, 0.1 g La-ZnO-1%-550 ℃, 130 ℃ and 4 MPa CO₂

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