低场固体核磁共振魔角旋转探头关键部件的研制

doi:10.11938/cjmr20253163

波谱学杂志 ›› 2026, Vol. 43 ›› Issue (1): 1-15.doi: 10.11938/cjmr20253163cstr: 32225.14.cjmr20253163

• 磁共振仪器与技术专栏 • 上一篇下一篇

低场固体核磁共振魔角旋转探头关键部件的研制

吴肇博¹^,^#, 王佳鑫²^,^#, 刘万震²^,³, 程鑫²^,³, 魏巍¹, 黄臻¹, 陈方²^,³, 张志²^,³^,^*(), 刘朝阳²^,³^,^§()

1.武汉轻工大学电气与电子工程学院，湖北武汉 430023
2.中国科学院精密测量科学与技术创新研究院，磁共振波谱与成像全国重点实验室，武汉磁共振中心，湖北武汉 430071
3.中国科学院大学，北京 100049

收稿日期:2025-04-27 出版日期:2026-03-05 在线发表日期:2025-05-20
通讯作者: *Tel: 027-87199686, E-mail: zhangzhi@apm.ac.cn;§Tel: 027-87198790, E-mail: chyliu@apm.ac.cn.
作者简介:第一联系人：
#共同第一作者
基金资助:
国家重点研发计划(2023YFE0113300);国家重点研发计划(2022YFF0707000);中国科学院基础与交叉前沿科研先导专项(XDB0540300);国家自然科学基金项目(22327901);国家自然科学基金项目(22374158);国家自然科学基金项目(22127801);中国科学院精密测量科学与技术创新研究院交叉培育项目(S21S4101)

Design and Development of Key Components for a Low-field Solid-state NMR Magic Angle Spinning (MAS) Probe

WU Zhaobo¹^,^#, WANG Jiaxin²^,^#, LIU Wanzhen²^,³, CHENG Xin²^,³, WEI Wei¹, HUANG Zhen¹, CHEN Fang²^,³, ZHANG Zhi²^,³^,^*(), LIU Chaoyang²^,³^,^§()

1. School of Electrical and Electronic Engineering, Wuhan Polytechnic University, Wuhan 430023, China
2. State Key Laboratory of Magnetic Resonance Spectroscopy and Imaging, National Center for Magnetic Resonance in Wuhan, Innovation Academy for Precision Measurement Science and Technology, Chinese Academy of Sciences, Wuhan 430071, China
3. University of Chinese Academy of Sciences, Beijing 100049, China

Received:2025-04-27 Published:2026-03-05 Online:2025-05-20
Contact: *Tel: 027-87199686, E-mail: zhangzhi@apm.ac.cn;§Tel: 027-87198790, E-mail: chyliu@apm.ac.cn.

摘要/Abstract

摘要：

高场固体核磁共振（NMR）技术具有高灵敏度和多核检测能力，但在研究锂离子电池之类的顺磁材料时，过渡金属离子（如Mn³⁺、Fe³⁺等）的强顺磁效应会导致高场下磁场不均匀、谱线展宽、信号衰减、无法魔角旋转（MAS）等问题．低场条件下，顺磁效应引起的磁场畸变显著减弱，为解决这些问题提供了可能．本文通过理论分析低场环境对顺磁物质研究的优势，研制了用于0.5 T Halbach磁体的低场固体MAS探头，并构建了一套完整的低场固体MAS谱仪．实验在12 kHz转速下采集到多种顺磁样品的⁷Li NMR信号，验证了自主研制的低场固体MAS技术在顺磁样品体系中的可行性．该方案解决了高场条件下自旋边带叠加和MAS失效的问题，为顺磁材料的NMR研究提供了新途径．

关键词: 固体核磁共振, 低场核磁共振, 魔角旋转（MAS）技术, 低场MAS, 射频线圈

Abstract:

High-field solid-state nuclear magnetic resonance (NMR) technology boasts high sensitivity and multi-nucleus detection capability. However, when studying paramagnetic materials like lithium-ion batteries, the strong paramagnetism of transition metal ions (such as Mn³⁺, Fe³⁺, etc.) leads to issues like magnetic field inhomogeneity, spectral line broadening, signal attenuation, and inability to perform magic-angle spinning (MAS) at high magnetic fields. Under low-field conditions, the magnetic field distortion induced by paramagnetic effects is significantly reduced, offering a potential solution to these problems. This paper presents a theoretical analysis of the advantages of low-field environments for studying paramagnetic substances. A low-field solid-state MAS probe for a 0.5 T Halbach magnet was developed. Furthermore, a complete low-field solid-state MAS spectrometer was constructed. In experiments, ⁷Li NMR signals of various paramagnetic samples were acquired at a spinning speed of 12 kHz, verifying the feasibility of the self-developed low-field solid-state MAS technology for paramagnetic samples. This approach addresses the problems of overlapping spin sidebands and MAS failure at high fields, providing a new pathway for NMR research on paramagnetic materials.

Key words: solid-state NMR, low-field NMR, magic angle spinning (MAS) technology, low-field MAS, radio frequency coil

中图分类号:

O482.53

吴肇博, 王佳鑫, 刘万震, 程鑫, 魏巍, 黄臻, 陈方, 张志, 刘朝阳. 低场固体核磁共振魔角旋转探头关键部件的研制[J]. 波谱学杂志, 2026, 43(1): 1-15.

WU Zhaobo, WANG Jiaxin, LIU Wanzhen, CHENG Xin, WEI Wei, HUANG Zhen, CHEN Fang, ZHANG Zhi, LIU Chaoyang. Design and Development of Key Components for a Low-field Solid-state NMR Magic Angle Spinning (MAS) Probe[J]. Chinese Journal of Magnetic Resonance, 2026, 43(1): 1-15.

图/表 18

图1

图2

图3

图4

图5

表1

图6

图7

图8

图9

图10

图11

图12

表2

图13

图14

图15

图16

参考文献 29

[1]	杨勇. 固态电化学[M]. 北京: 化学工业出版社, 2017.
[2]	PECHER O. Materials' methods: NMR in battery research[J]. Chem Mater, 2017, 29(1): 213-242. doi: 10.1021/acs.chemmater.6b03183
[3]	LOWE I J. Free induction decays of rotating solids[J]. Phys Rev Lett, 1959, 2(7): 285-287. doi: 10.1103/PhysRevLett.2.285
[4]	ANDREW E R, BRADBURY A, Eades R G. Removal of dipolar broadening of nuclear magnetic resonance spectra of solids by specimen rotation[J]. Nature, 1959, 183: 1802-1803. doi: 10.1038/1831802a0
[5]	Yu P, Xu Y J, WU Z Y, et al. A low-cost home-built NMR using Halbach magnet[J]. J Magn Reson, 2018, 294: 162-168. doi: S1090-7807(18)30191-5 pmid: 30055440
[6]	HALBACH K. Strong rare earth cobalt quadrupoles[J]. Bull APS, 1979, 24(2): 183-183.
[7]	LEE J N, ALDERMAN D W, JIN J Y. Cylindrical spinner and speed controller for magicangle spinning nuclear magnetic resonance[J]. Rev Sci Instrum, 1984, 55(4): 516-520. doi: 10.1063/1.1137783
[8]	SORENSEN M K, BAKHAREV O, JENSEN O, et al. Magic-angle spinning solid-state multinuclear NMR on low-field instrumentation[J]. J Magn Reson, 2014, 238: 20-25. doi: 10.1016/j.jmr.2013.10.015 pmid: 24291330
[9]	KLUG C A, SWIFT M W, MILLER J B, et al. High resolution solid state NMR in paramagnetic metal-organic frameworks[J]. Solid State Nucl Magn Reson, 2022, 120: 101811. doi: 10.1016/j.ssnmr.2022.101811
[10]	XU K, ALDUDAK F, PECHER O, et al. High resolution solid-state NMR on the desktop[J]. Solid State Nucl Magn Reson, 2023, 126: 101884. doi: 10.1016/j.ssnmr.2023.101884
[11]	YE C H, LI L Y, SUN B Q. High resolution mas NMR of solids by a routine spectrometer for liquids[J]. Chinese J Magn Reson, 1985, 2(3): 227-236.
[12]	YANG Y, SUN X Q, GU L L, et al. Advances in the application of high-resolution magic-angle spinning NMR spectroscopy[J]. Chemical World, 2009, 50(5): 308-311.
[13]	王佳鑫. 固体核磁共振探头魔角旋转单元的研制[D]. 北京: 中国科学院大学, 2019.
[14]	ZBOROWSKI M, SUN L, MOORE L R, et al. Continuous cell separation using novel magnetic quadrupole flow sorter[J]. J Magn Magn Mater, 1999, 194(1): 224-230. doi: 10.1016/S0304-8853(98)00581-2
[15]	LEONG S S, AHMAD Z, LOW S C, et al. Unified view of magnetic nanoparticle separation under magnetophoresis[J]. Langmuir, 2020, 36(28): 8033-8055. doi: 10.1021/acs.langmuir.0c00839 pmid: 32551702
[16]	SUN B Q, YE Z H. Inhomogeneous interactions of solids under MAS[J]. Acta Physica Sinica, 1986, 35(3): 329-337. doi: 10.7498/aps
	孙伯勤, 叶朝辉. 魔角旋转情形下固体的非均匀相互作用[J]. 物理学报, 1986, 35(3): 329-337.
[17]	ILOTT A J, JERSCHOW A. Aspects of NMR reciprocity and applications in highly conductive media[J]. Concepts Magn Reson Part A, 2019, 1(2): 21466.
[18]	YANG B L, HU H B, ZHOU J W, et al. DNP CP/MAS probe design and discussion of DNP experimental technique[J]. Chinese J Magn Reson, 1996, 13(2): 183-190.
	杨保联, 胡红兵, 周建威, 等. 固体高分辨DNP CP/MAS探头的研制及DNP实验技术的探讨[J]. 波谱学杂志, 1996, 13(2): 183-190.
[19]	HENNEL J W, KLINOWSKI J. Magic-angle spinning: a historical perspective[J]. Top Curr Chem, 2005, 246: 1-14. doi: 10.1007/b98646 pmid: 22160286
[20]	KENDRICK R D, WIND R A, YANNONI C S. A method of orienting the rotation axis of a spinning sample used in a nuclear magnetic resonance experiment, its synthesis and use: EP, 0051124B1[P]. 1984-12-05.
[21]	HILL H D W, HUBER U. Device and method for spinning a sample for NMR probes, its synthesis and use: EP, 0020085A1[P]. 1980-12-10.
[22]	DAUGAARD P, JAKOBSEN H J, LANGER V. High speed spinner for NMR spectrometer, its synthesis and use: EP, 0249383B1[P]. 1991-01-16.
[23]	GAO C, JUDGE P T, SESTI E L, et al. Four millimeter spherical rotors spinning at 28 kHz with double-saddle coils for cross polarization NMR[J]. J Magn Reson, 2019, 303: 1-6. doi: 10.1016/j.jmr.2019.03.006
[24]	BUSCHOW K H J, CAHN R, FLEMINGS M C, et al. Encyclopedia of materials: science and technology[M]. Amsterdam: Elsevier, 2001.
[25]	吴利杰. 超高速空气静压电主轴动态性能流固耦合分析[D]. 广州: 广东工业大学, 2014.
[26]	WANG F, LIU T W, XU Y J, et al. A miniaturised NMR RF probe design with external field-locking channel[J]. Chinese J Magn Reson, 2023, 40(3): 332-340.
	王峰, 刘庭伟, 徐雅洁, 等. 一种带外部锁场通道的小型化核磁共振射频探头设计[J]. 波谱学杂志, 2023, 40(3): 332-340. doi: 10.11938/cjmr20223044
[27]	袁毅. 面向10 MHz低场核磁共振仪器射频探头的研制[D]. 南京: 东南大学, 2022.
[28]	JIANG Y J, WOOLFENDEN W R, ALDERMAN D W, et al. Efficient stator/rotor assembly for magic-angle spinning NMR[J]. Rev Sci Instrum, 1987, 58(5): 755-758. doi: 10.1063/1.1139626
[29]	BERNSTEIN M A, KING K F, ZHOU X J. Handbook of MRI pulse sequences[M]. Amsterdam: Elsevier, 2004.

线圈匝数（N）	相对信噪比（SNR）	射频场均匀性（δ_均匀）	品质因数（Q）	综合性能（P）
4	3.43E-03	59%	2.89E+02	0.586
5	3.68E-03	69%	2.89E+02	0.732
6	3.80E-03	76%	2.83E+02	0.819
7	3.79E-03	80%	2.70E+02	0.815
8	3.65E-03	84%	2.48E+02	0.761

低场固体核磁共振魔角旋转探头关键部件的研制

Design and Development of Key Components for a Low-field Solid-state NMR Magic Angle Spinning (MAS) Probe

RichHTML

PDF

可视化

摘要/Abstract

引用本文

使用本文

图/表 18

参考文献 29

相关文章 15

编辑推荐

Metrics

本文评价

实验次数	轴承气压/kPa	驱动气压/kPa	转速/kHz
1	105	35	4
2	120	45	5
3	140	55	6
4	170	70	7
5	190	85	8
6	205	100	9
7	220	120	10
8	245	145	11
9	270	165	12
10	290	190	13
11	310	215	14

[1]	李科言, 程鑫, 陈俊飞, 曹丽, 黄臻, 刘朝阳. 用于低场NMR的低噪声前置放大器研制[J]. 波谱学杂志, 2025, 42(3): 321-333.
[2]	沈雪媛, 王瑞琛, 齐国栋, 徐君, 邓风. 原位固体核磁共振转子插件的设计及其在催化反应中的应用研究[J]. 波谱学杂志, 2025, 42(1): 13-21.
[3]	陈阳, 周萌, 李勇, 杨海军. 固体核磁共振样品制备系统的自主研制[J]. 波谱学杂志, 2024, 41(1): 77-86.
[4]	贺彩艳,肖宇情,李申慧,徐君,邓风. 固体NMR研究MOFs吸附和分离过程中的主客体相互作用[J]. 波谱学杂志, 2023, 40(2): 192-206.
[5]	董洪春,张志兰,王宁,唐丹丹,裘子慧,舒婕. 基于固体核磁共振多次交叉极化的定量检测优化技术[J]. 波谱学杂志, 2023, 40(2): 136-147.
[6]	师光辉,肖立志,廖广志,罗嗣慧,侯学理,卢亚普. 低场核磁共振仪器振铃抑制新方法及其电路实现[J]. 波谱学杂志, 2023, 40(1): 68-78.
[7]	覃瑞,王超,王强,胡敏,李金林,徐君,邓风. SSZ-13分子筛上甲醇转化过程中甲氧基物种的生成与活性研究[J]. 波谱学杂志, 2022, 39(4): 439-447.
[8]	曾姝, 徐舒涛, 魏迎旭, 刘中民. H-SSZ-13分子筛催化乙醇脱水制乙烯反应的原位固体核磁共振研究[J]. 波谱学杂志, 2022, 39(2): 123-132.
[9]	陈翰迪,孔海宇,赵侦超,张维萍. 固体核磁共振结合密度泛函理论计算研究SSZ-39分子筛的钠离子落位与铝分布[J]. 波谱学杂志, 2021, 38(4): 543-551.
[10]	杨文杰,黄骏. 基于固体核磁共振技术的固体酸结构、酸性及活性分析[J]. 波谱学杂志, 2021, 38(4): 460-473.
[11]	夏锡锋,张文静,林芝晔,柯晓康,温玉洁,王芳,陈俊超,彭路明. 氧化物纳米材料表面结构与性质的固体核磁共振波谱研究[J]. 波谱学杂志, 2021, 38(4): 533-542.
[12]	王永祥,王强,徐君,夏清华,邓风. 六氟硅酸铵后处理对H-ZSM-5分子筛酸性影响的固体NMR研究[J]. 波谱学杂志, 2021, 38(4): 514-522.
[13]	王子春,黄骏,姜怡娇. 五配位铝强化硅铝固体酸的固体核磁共振研究[J]. 波谱学杂志, 2021, 38(4): 552-570.
[14]	史朝为,石攀,田长麟. 非天然氨基酸在蛋白质动态特性核磁共振研究中的应用[J]. 波谱学杂志, 2021, 38(4): 523-532.
[15]	肖瑶,夏长久,易先锋,刘凤庆,刘尚斌,郑安民. 固体核磁共振技术在锡硅分子筛表征中的应用[J]. 波谱学杂志, 2021, 38(4): 571-584.

实验次数	轴承气压/kPa	驱动气压/kPa	转速/kHz
1	105	35	4
2	120	45	5
3	140	55	6
4	170	70	7
5	190	85	8
6	205	100	9
7	220	120	10
8	245	145	11
9	270	165	12
10	290	190	13
11	310	215	14

实验次数	轴承气压/kPa	驱动气压/kPa	转速/kHz
1	105	35	4
2	120	45	5
3	140	55	6
4	170	70	7
5	190	85	8
6	205	100	9
7	220	120	10
8	245	145	11
9	270	165	12
10	290	190	13
11	310	215	14