纳米CeO2的制备及其在CO2合成聚碳酸酯中的活性

doi:10.15541/jim20240304

无机材料学报 ›› 2025, Vol. 40 ›› Issue (1): 70-76.DOI: 10.15541/jim20240304 CSTR: 32189.14.10.15541/jim20240304

纳米CeO₂的制备及其在CO₂合成聚碳酸酯中的活性

马俊杰¹(), 杨钰莹¹, 高名扬¹, 齐冰杰¹, 吴玉龙¹^,², 黄雪莉¹, 黄河¹()

1.新疆大学化工学院, 省部共建碳基能源资源化学与利用国家重点实验室, 乌鲁木齐 830017
2.清华大学核能与新能源技术研究院, 北京 100084

收稿日期:2024-06-21 修回日期:2024-08-26 出版日期:2025-01-20 网络出版日期:2024-09-02
通讯作者: 黄河, 副教授. E-mail: xjuhuanghe@xju.edu.cn
作者简介:马俊杰(2002-), 男, 本科. E-mail: 2165471663@qq.com
基金资助:
中央引导地方科技发展专项(ZYYD2022C16);新疆维吾尔自治区重大科技专项(2022A01002-1);新疆大学大学生创新训练计划项目(XJU-SRT-22018)

Preparation and Activity of CeO₂ Nanoparticles in Synthesis of Polycarbonates from CO₂

MA Junjie¹(), YANG Yuying¹, GAO Mingyang¹, QI Bingjie¹, WU Yulong¹^,², HUANG Xueli¹, HUANG He¹()

1. State Key Laboratory of Chemistry and Utilization of Carbon Based Energy Resources, School of Chemical Engineering and Technology, Xinjiang University, Urumqi 830017, China
2. Institute of Nuclear and New Energy Technology, Tsinghua University, Beijing 100084, China

Received:2024-06-21 Revised:2024-08-26 Published:2025-01-20 Online:2024-09-02
Contact: HUANG He, associate professor. E-mail: xjuhuanghe@xju.edu.cn
About author:MA Junjie (2002-), male, undergraduate. E-mail: 2165471663@qq.com
Supported by:
Special Project of Central Guiding Local Science and Technology Development(ZYYD2022C16);Major Science and Tecnology Special Project of Xinjiang Uygur Autonomous Region(2022A01002-1);Xinjiang University Student Innovation Training Program Project(XJU-SRT-22018)

摘要/Abstract

摘要：

CO₂和二醇直接聚合制备碳酸酯是一种绿色高效的CO₂应用途径, CeO₂在该反应体系中表现出良好的催化性能。本研究以NaOH为沉淀剂, 采用水热法制备纳米CeO₂催化剂, 探究了焙烧温度(500、600、700 ℃)和不同类型表面活性剂(阳离子、阴离子和非离子型)对CeO₂结构和性质的影响规律。当焙烧温度为600 ℃时, CeO₂结晶度良好且缺陷位点数量超过其他焙烧温度制得样品。各类表面活性剂(阳离子、阴离子和非离子型)能有效提高CeO₂表面氧空位浓度, 25 ℃下的CO₂吸收量最高可达0.532 mmol/g。基于以上研究, 将制备的一系列CeO₂催化剂应用于CO₂和二醇一步法合成聚碳酸酯的反应中, 可有效提高反应体系的转化率和选择性。结果表明, 不同焙烧温度和表面活性剂制备的CeO₂的催化活性存在显著差异。以十六烷基三甲基溴化铵(CTAB)作为表面活性剂, 在600 ℃下焙烧得到的CeO₂显示出最高的催化活性和选择性(1,6-己二醇转化率为91.0%, 聚(6-羟基己基)碳酸酯选择性为76.6%)。CeO₂优异的催化活性以及高产率主要归因于其良好的结构、丰富的缺陷位点和高的CO₂吸收能力。

关键词: 纳米CeO₂, 缺陷位点, 表面活性剂, CO₂转化, 二醇, 聚碳酸酯

Abstract:

Direct polymerization of CO₂ with diols for synthesis of carbonates represents a sustainable and efficient approach for CO₂ utilization, in which CeO₂ exhibits favorable catalytic properties in the reaction system. In this study, nanometer-sized CeO₂ catalysts were synthesized via a hydrothermal method utilizing NaOH as precipitating agent. The effects of sintering temperatures (500, 600, and 700 ℃) and surfactants (cationic, anionic, and nonionic) on structural and physicochemical properties of CeO₂ were thoroughly investigated. When the sintering temperature was 600 ℃, CeO₂ displayed an optimal crystallinity and a higher concentration of defect sites compared to the other temperatures. The surfactants significantly increased oxygen vacancy concentration on the surface of CeO₂, leading to a maximum CO₂ uptake of 0.532 mmol/g at 25 ℃. Building upon these findings, a series of synthesized CeO₂ catalysts were applied in the one-step synthesis of polycarbonate from CO₂ and diol, resulting in significant improvements in both conversion and selectivity within the reaction system. The results demonstrated that catalytic activities of CeO₂ prepared at various sintering temperatures with different surfactants displayed notable differences. Notably, the CeO₂ catalyst sintered with cetyltrimethylammonium bromide (CTAB) as the surfactant at 600 ℃ exhibited the highest catalytic activity and selectivity, achieving a conversion of 91.0% for 1,6-hexanediol and a selectivity of 76.6% for poly(6-hydroxyhexyl) carbonate. The outstanding catalytic performance of CeO₂ with the high yield can be primarily attributed to its favorable structural characteristics, abundant defect sites, and high CO₂ uptake capacity.

Key words: CeO₂ nanoparticle, defect site, surfactant, CO₂ conversion, diol, polycarbonate

中图分类号:

TQ133

马俊杰, 杨钰莹, 高名扬, 齐冰杰, 吴玉龙, 黄雪莉, 黄河. 纳米CeO₂的制备及其在CO₂合成聚碳酸酯中的活性[J]. 无机材料学报, 2025, 40(1): 70-76.

MA Junjie, YANG Yuying, GAO Mingyang, QI Bingjie, WU Yulong, HUANG Xueli, HUANG He. Preparation and Activity of CeO₂ Nanoparticles in Synthesis of Polycarbonates from CO₂[J]. Journal of Inorganic Materials, 2025, 40(1): 70-76.

图/表 15

图1 样品的XRD谱图

Fig. 1 XRD patterns of samples

表1 样品的物理化学性质

Table 1 Physicochemical properties of samples

Sample	Average particle size/nm	Relative crystallinity/%	I_D/I_F2g
CeO₂-500	8.3	74.3	0.029
CeO₂-600	11.7	81.4	0.036
CeO₂-700	15.8	82.9	0.014
CTAB-CeO₂	10.0	82.6	0.045
SDS-CeO₂	10.5	80.1	0.039
PEG-CeO₂	9.3	76.5	0.024

图2 样品的微观形貌表征

Fig. 2 Micro-morphological characterization of samples (a-c) SEM images of (a) CeO2-500, (b) CeO2-600 and (c) CeO2-700; (d-e) TEM images of (d) CeO2-600 and (e) CTAB-CeO2; (f) HRTEM image of CeO2-600

图3 样品的N2吸脱附等温线及孔径分布

Fig. 3 Isothermal N2 adsorption and desorption curves and pore size distribution of samples

图4 样品的Raman谱图

Fig. 4 Raman spectra of samples

图5 CeO2-600和CTAB-CeO2的XPS谱图

Fig. 5 XPS spectra of CeO2-600 and CTAB-CeO2 (a) Ce3d; (b) O1s

图6 样品的CO2-TPD曲线

Fig. 6 CO2-TPD curves of samples

表2 CO2和1,6-HDO在CeO2催化剂上反应的测试结果

Table 2 Test results of reaction of CO2 and 1,6-HDO on CeO2 catalysts

Sample	C/%	S/%	Y/%	M_n/(g·mol^-1)	D_p
CeO₂-500	86.4	67.1	58.0	982	6
CeO₂-600	88.9	74.5	66.3	1171	8
CeO₂-700	85.6	5.9	5.1	1153	8
CTAB-CeO₂	91.0	76.6	69.7	1333	9
SDS-CeO₂	90.5	76.1	68.9	1108	8
PEG-CeO₂	88.8	43.3	38.5	1169	8

图7 低聚物产率Y与样品ID/IF2g的关系

Fig. 7 Oligomer yield Y versus ID/IF2g of samples

表S1 样品的比表面积、孔容和平均孔径

Table S1 Specific surface area, pore volume, and average pore size of samples

Sample	S_BET/(m²·g^-1)	Proe volume/ (cm³·g^-1)	Average pore size/nm
CeO₂-500	118	0.76	27.91
CeO₂-600	113	0.80	28.27
CeO₂-700	42	0.30	31.26
CTAB-CeO₂	119	0.92	30.39

表S2 样品的CO2-TPD测试数据分析

Table S2 Analysis of CO2-TPD test data of samples

Sample	Peak number	Temperature at maximum/℃	Quantity/ (mmol·g^-1)
CeO₂-500	2	116.6	0.214
CeO₂-500	2	269.8	0.104
CeO₂-600	1	156.6	0.403
CeO₂-700	1	137.3	0.288
CTAB-CeO₂	1	146.3	0.532

表S3 CTAB-CeO2的稳定性测试

Table S3 Stability test of CTAB-CeO2

Number of reaction	1	2	3
1,6-HDO conversion/%	91.0	88.9	86.3

图S1 不同表面活性剂制备的样品的XRD谱图

Fig. S1 XRD patterns of samples prepared with different surfactants

图S2 不同表面活性剂制备的样品的Raman谱图

Fig. S2 Raman spectra of samples prepared with different surfactants

图S3 CeO2-500上产物的1H NMR谱图

Fig. S3 1H NMR spectrum of the product on CeO2-500

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纳米CeO₂的制备及其在CO₂合成聚碳酸酯中的活性

Preparation and Activity of CeO₂ Nanoparticles in Synthesis of Polycarbonates from CO₂

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