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Nd掺杂对Ce基催化剂用于CO2与CH3OH直接合成DMC的影响
Effects of Nd doping on direct synthesis of DMC with CO2 and CH3OH catalyzed by Ce-based catalysts
- 低碳化学与化工 2025: 1-12.
- 作者机构：
1.华东理工大学 化工学院 大型工业反应器工程教育部工程研究中心，上海 200237
2.华东理工大学 煤液化气化及高效低碳利用全国重点实验室，上海 200237
- 作者简介：
沈怡婷（1998—），硕士研究生，研究方向为低碳化工，E-mail：isabelshen@126com。
钱炜鑫（1983—），博士，副教授，研究方向为低碳化工，E-mail：wxqian@ecust.edu.cn。
- 基金信息：国家自然科学基金(22178113);中央高校基本科研业务费专项资金(JKA01231712;JKCA1241202)
DOI：10.12434/j.issn.2097-2547.20250026
中图分类号： TQ426收稿日期：2025-01-16，
修回日期：2025-02-26，
网络出版日期：2025-06-09，
- 稿件说明：
移动端阅览
沈怡婷,张海涛,马宏方等.Nd掺杂对Ce基催化剂用于CO2与CH3OH直接合成DMC的影响[J].低碳化学与化工,
SHEN Yiting,ZHANG Haitao,MA Hongfang,et al.Effects of Nd doping on direct synthesis of DMC with CO2 and CH3OH catalyzed by Ce-based catalysts[J].Low-Carbon Chemistry and Chemical Engineering,
沈怡婷,张海涛,马宏方等.Nd掺杂对Ce基催化剂用于CO2与CH3OH直接合成DMC的影响[J].低碳化学与化工, DOI：10.12434/j.issn.2097-2547.20250026.
SHEN Yiting,ZHANG Haitao,MA Hongfang,et al.Effects of Nd doping on direct synthesis of DMC with CO2 and CH3OH catalyzed by Ce-based catalysts[J].Low-Carbon Chemistry and Chemical Engineering, DOI：10.12434/j.issn.2097-2547.20250026.
摘要
二氧化碳（CO
2
）与甲醇（CH
3
OH）直接合成碳酸二甲酯（DMC），是目前最具环保优势的DMC合成方法之一。Ce基催化剂常用于CO
2
与CH
3
OH直接合成DMC反应，但CeO
2
存在热稳定性不足和活性位点有限等问题。以六水硝酸钕（NdN
3
O
9
·6H
2
O）作为助剂，采用共沉淀法制备了一系列Nd掺杂Ce基催化剂。催化剂的结构经ICP-OES、XRD、HR-TEM和XPS等表征，并研究了催化剂的催化性能。结果表明，适当的Nd掺杂量（质量分数）对优化催化剂的比表面积、氧空位密度和酸碱性位点数量有积极作用。其中，Nd掺杂量为5%的催化剂（5% Nd
2
O
3
-CeO
2
）具有最大的氧空位密度、较多的中酸性位点和最多的弱碱性位点。在CH
3
OH用量为23.74 g、2-氰基吡啶用量为36.44 g、5% Nd
2
O
3
-CeO
2
用量为200 mg、温度为140 ℃和压力为1.2 MPa的条件下反应2 h，5% Nd
2
O
3
-CeO
2
的CH
3
OH转化率为27.35%，DMC选择性为77.72%，DMC产量为392.90 mmol/g。在温度为140 ℃、压力为1.2 MPa、CH
3
OH用量为23.74 g、5% Nd
2
O
3
-CeO
2
用量为200 mg和反应时间为2 h的条件下，5% Nd
2
O
3
-CeO
2
经过4次循环反应后，其催化性能仍优于CeO
2
。
Abstract
The direct synthesis of dimethyl carbonate (DMC) with carbon dioxide (CO
2
) and methanol (CH
3
OH) is currently one of the most environmentally advantageous methods for DMC production. Ce based catalysts are commonly used in direct synthesis of DMC with CO
2
and CH
3
OH
but CeO
2
suffers from issues such as insufficient thermal stability and limited active sites. Using neodymium nitrate hexahydrate (NdN
3
O
9
·6H
2
O) as the promoter
a series of Nd-doped Ce-based catalysts were prepared by co-precipitation method. The structures of catalysts were characterized by ICP-OES
XRD
HR-TEM
and XPS
etc.
and their catalytic performances were investigated. The results show that the appropriate Nd doping amount (mass fraction) can positively optimize the catalyst’s specific surface area
oxygen vacancy density and the number of acid-base sites. Among them
the catalyst with Nd doping amount of 5% (5% Nd
2
O
3
-CeO
2
) has the highest oxygen vacancy density
m
ore medium-strong acid sites
and the most weak base sites. Under the reaction conditions of CH
3
OH dosage of 23.74 g
2-cyanopyridine dosage of 36.44 g
5% Nd
2
O
3
-CeO
2
dosage of 200 mg
temperature of 140 °C and pressure of 1.2 MPa for 2 h
5% Nd
2
O
3
-CeO
2
achieves CH
3
OH conversion rate of 27.35%
DMC selectivity of 77.72% and DMC yield of 392.90 mmol/g. After four cycles under the conditions of temperature of 140 °C
pressure of 1.2 MPa
CH
3
OH dosage of 23.74 g
5% Nd
2
O
3
-CeO
2
dosage of 200 mg and reaction time of 2 h
the catalytic performance of 5% Nd
2
O
3
-CeO
2
remains superior to that of CeO
2
.
关键词
Keywords
references
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