稀土离子掺杂调控MIL-101的电子结构促进电催化氮还原反应

杨童卉; 岳嵩; 公伟伟; 王仁卿; 胡伟达; 刘小磐; 高朋召; 覃航; 郭文明; 肖汉宁

doi:10.19976/j.cnki.43-1448/TF.2024033

粉末冶金材料科学与工程 >

2024 , Vol. 29 >Issue 3: 231 - 245

DOI: https://doi.org/10.19976/j.cnki.43-1448/TF.2024033

工艺技术

稀土离子掺杂调控MIL-101的电子结构促进电催化氮还原反应

杨童卉 ,
岳嵩 ,
公伟伟 ,
王仁卿 ,
胡伟达 ,
刘小磐 ,
高朋召 ,
覃航 ,
郭文明 ,
肖汉宁

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1.湖南大学材料科学与工程学院,长沙 410082;
2.湖南长远锂科股份有限公司,长沙 410205;
3.湖南工业大学醴陵陶瓷学院,株洲 412200;
4.湖南阳东电瓷电气股份有限公司,株洲 412205

收稿日期: 2024-04-10

修回日期: 2024-06-10

网络出版日期: 2024-08-12

基金资助

中央引导地方科技发展基金(2023ZYQ004); 湖南省自然科学基金资助项目(2021JJ50036); 湖南省级重点研发计划(2023GK2083)

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Rare earth ion doping regulates the electronic structure of MIL-101 to promote electrocatalytic nitrogen reduction reaction

YANG Tonghui ,
YUE Song ,
GONG Weiwei ,
WANG Renqing ,
HU Weida ,
LIU Xiaopan ,
GAO Pengzhao ,
QIN Hang ,
GUO Wenming ,
XIAO Hanning

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1. College of Materials Science and Engineering, Hunan University, Changsha 410082, China;
2. Hunan Changyuan Lico Co., Ltd., Changsha 410205, China;
3. Liling Ceramic College, Hunan University of Technology, Zhuzhou 412200, China;
4. Hunan Yangdong Porcelain Insulators & Electric Co., Ltd., Zhuzhou 412205, China

Received date: 2024-04-10

Revised date: 2024-06-10

Online published: 2024-08-12

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摘要

电催化氮还原反应(electrocatalytic nitrogen reduction reaction, eNRR)被认为是在环境条件下生产低浓度$NH_{3}/NH_{4}^{+}$的有效策略,而设计合适的催化剂是高效驱动eNRR的关键。本研究采用水热法制备MIL-101催化剂,研究水热温度和Gd元素掺杂对MIL-101催化剂eNRR性能的影响。结果表明：150-MIL-101具有最高的结晶度及eNRR性能(氨产率为11.5 μg/(h·mg),法拉第效率为30.5%)。MIL-101-0.5Gd表面下凹,暴露了内部粗糙孔结构,催化剂表观活性提高,同时氧空位浓度的增加可优化催化剂的特性活性,其在0.1 mol/L LiClO₄电解质、-1.3 V电位下的氨产率和法拉第效率分别为16.7 μg/(h·mg)和37.6%,优于无掺杂150-MIL-101,且催化剂具有较好的长期稳定性。

关键词： 稀土离子; 缺陷工程; 电催化氮还原; 形貌控制; 电子转移促进

本文引用格式

杨童卉 , 岳嵩 , 公伟伟 , 王仁卿 , 胡伟达 , 刘小磐 , 高朋召 , 覃航 , 郭文明 , 肖汉宁 . 稀土离子掺杂调控MIL-101的电子结构促进电催化氮还原反应[J]. 粉末冶金材料科学与工程, 2024 , 29(3) : 231 -245 . DOI: 10.19976/j.cnki.43-1448/TF.2024033

Abstract

Electrocatalytic nitrogen reduction reaction (eNRR) is considered as an effective strategy for producing $NH_{3}/NH_{4}^{+}$ with low concentrations under environmental conditions, and designing appropriate catalysts is the key to efficiently driving eNRR. This study used a hydrothermal method to prepare MIL-101 catalyst and investigated the effects of hydrothermal temperature and Gd element doping on the eNRR performance of MIL-101 catalyst. The results show that 150-M-101 has the highest crystallinity and eNRR performance (NH₃ yield of 11.5 μg/(h·mg), Faraday efficiency of 30.5%). The surface of MIL-101-0.5Gd is concave, exposing the internal rough pore structure, improving the apparent activity of the catalyst. At the same time, the increase of oxygen vacancy concentration optimizes the characteristic activity of the catalyst, the NH₃ yield and Faraday efficiency at 0.1 mol/L LiClO₄ electrolyte and -1.3 V potential are 16.7 μg/(h·mg) and 37.6%, respectively, which are better than undoped 150-MIL-101. The catalyst also has good long-term stability.

Key words： rare earth ion; defective engineering; electrocatalytic nitrogen reduction; morphological control; electronic transfer promotion

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