(Yb1-xGdx)2SO4(OH)2F2的合成、结构及亚开尔文温区磁热效应★

doi:10.6023/A26060187

化学学报 ›› 2026, Vol. 84 ›› Issue (8): 1231-1235.DOI: 10.6023/A26060187 上一篇下一篇

研究论文

(Yb_1-_xGd_x)₂SO₄(OH)₂F₂的合成、结构及亚开尔文温区磁热效应^★

丁书颖^b, 付名扬^c, 吴若彤^a, 孟银杉^c, 徐侨飞^a^,^b^,^*(), 庄桂林^b, 刘涛^c^,^*(), 龙腊生^a^,^*()

^a 厦门大学化学化工学院化学系表界面化学全国重点实验室厦门 361005
^b 安徽师范大学化学与分子科学学院化学与分子科学学院芜湖 241002
^c 大连理工大学化工学院智能材料化工前沿科学中心精细化工全国重点实验室大连 116024

投稿日期:2026-06-08 发布日期:2026-07-10
作者简介:
^★“纪念兰州大学化学学科创建80周年”专辑
基金资助:
国家自然科学基金(22527801); 安徽师范大学博士启动基金(903762604)

Synthesis, Structure, and Sub-Kelvin Magnetocaloric Effect of (Yb_1-_xGd_x)₂SO₄(OH)₂F₂^★

Shuying Ding^b^,^†, Mingyang Fu^c^,^†, Ruotong Wu^a, Yinshan Meng^c, Qiaofei Xu^a^,^b^,^*(), Guilin Zhuang^b, Tao Liu^c^,^*(), Lasheng Long^a^,^*()

^a State Key Laboratory of Physical Chemistry of Solid Surfaces and Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China
^b College of Chemistry and Molecular Sciences, Anhui Normal University, Wuhu 241002, China
^c State Key Laboratory of Fine Chemicals, Frontier Science Center for Smart Materials, School of Chemical Engineering, Dalian University of Technology, Dalian 116024, China

Received:2026-06-08 Published:2026-07-10
Contact: *E-mail: qfxu@ahnu.edu.cn; liutao@dlut.edu.cn; lslong@xmu.edu.cn
About author:
†Ding, Shuying & Fu, Mingyang contributed equally to this work.
^★For the VSI “Celebration of 80th Anniversary of Chemistry in Lanzhou University”
Supported by:
National Natural Science Foundation of China(22527801); Doctoral Research Start-up Fund of Anhui Normal University(903762604)

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1. Supporting Information-A26060187.pdf(895KB)

摘要/Abstract

基于磁热效应的绝热去磁制冷技术是实现亚开尔文温区的重要途径之一, 其无需依赖³He资源或重力环境, 具有高效、可靠等优势. 然而, 目前该技术的发展仍受到高性能磁制冷材料匮乏的限制, 理想的超低温磁制冷材料需要同时具备大的磁熵变、低的磁有序温度以及优异的化学稳定性. 本工作中, 合成并系统研究了一种新型镱基氟羟基硫酸盐框架材料Yb₂SO₄(OH)₂F₂ (1)及其Gd掺杂衍生物(Yb_0.9Gd_0.1)₂SO₄(OH)₂F₂ (2)和(Yb_0.7Gd_0.3)₂SO₄(OH)₂F₂ (3). 结构分析表明, 该系列化合物由Yb配位多面体通过F^-和SO₄^2-桥联形成的致密三维框架结构. 磁化率和热容测试结果表明: 三种化合物均表现出弱反铁磁相互作用, 并且磁有序出现在1 K以下温区. 值得注意的是, Gd的引入不仅显著提高了体系的磁熵, 而且进一步降低了磁有序温度, 实现了磁密度增加与磁有序温度降低的协同优化. 得益于这一特征, 化合物3在0~2 T磁场变化下表现出约 100 mJ•cm^-3•K^-1的最大磁熵变, 约为铁铵矾的2倍, 并超过铬钾矾的2倍. 研究结果表明, 通过Gd掺杂实现磁密度优化是提升超低温磁热性能的有效策略, 同时也表明氟羟基硫酸盐框架材料是一类极具潜力的绝热去磁制冷候选材料.

关键词: 亚开尔文温区, 绝热去磁制冷, 稀土材料, 磁热效应

Adiabatic demagnetization refrigeration based on the magnetocaloric effect represents an efficient route to achieving sub-Kelvin temperatures without relying on scarce ³He resources or gravity-dependent cooling systems. However, the development of this technology remains limited by the lack of high-performance refrigerants that simultaneously exhibit large magnetic entropy changes, low magnetic ordering temperatures and good chemical stability. Herein, we report a new ytterbium fluorohydroxysulfate framework, Yb₂SO₄(OH)₂F₂ (1), together with its Gd-substituted analogues, (Yb_0.9Gd_0.1)₂SO₄(OH)₂F₂ (2) and (Yb_0.7Gd_0.3)₂SO₄(OH)₂F₂ (3). Structural analysis reveals a dense three-dimensional framework assembled from interconnected Yb-centered polyhedra linked by fluoride and sulfate groups. Magnetic susceptibility and heat-capacity measurements indicate weak antiferromagnetic interactions and low magnetic ordering temperatures below 1 K. Notably, Gd substitution significantly enhances the magnetic entropy while simultaneously suppressing the ordering temperature, resulting in an unusual combination of increased magnetic density and reduced magnetic ordering. Consequently, 3 exhibits a maximum magnetic entropy change of 100 mJ•cm^-3•K^-1 under 2 T, nearly twice that of ferric ammonium alum and more than twice that of chromic potassium alum. These results demonstrate that magnetic-density optimization through Gd incorporation is an effective strategy for enhancing sub-Kelvin magnetocaloric performance and establish fluorohy-droxysulfate frameworks as promising candidates for adiabatic demagnetization refrigeration.

Key words: sub-kelvin temperatures, adiabatic demagnetization refrigeration, rare-earth materials, magnetocaloric effect

引用此文

丁书颖, 付名扬, 吴若彤, 孟银杉, 徐侨飞, 庄桂林, 刘涛, 龙腊生. (Yb_1-_xGd_x)₂SO₄(OH)₂F₂的合成、结构及亚开尔文温区磁热效应^★[J]. 化学学报, 2026, 84(8): 1231-1235.

Shuying Ding, Mingyang Fu, Ruotong Wu, Yinshan Meng, Qiaofei Xu, Guilin Zhuang, Tao Liu, Lasheng Long. Synthesis, Structure, and Sub-Kelvin Magnetocaloric Effect of (Yb_1-_xGd_x)₂SO₄(OH)₂F₂^★[J]. Acta Chimica Sinica, 2026, 84(8): 1231-1235.

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图/表 4

Figure 1. (a) Asymmetric unit in 1; (b) triangular units formed by three neighboring Yb3+; (c) the hexanuclear {Yb6} unit; (d) the zigzag infinite one-dimensional chain; (e) the 3D framework of 1.

Figure 2. Curie-Weiss fitting at 2—10 K for 1—3.

Figure 3. (a) Experimental heat capacity (Cp) normalized to the gas constant (R) of 3; (b) temperature dependence of the zero-field magnetic heat capacity (Cm) in 1—3; (c) temperature dependence of the experimental magnetic entropy Sm in 3 under 0 T and 2 T; (d) the calculated -ΔSm values of 3 under 2 T.

Refrigerants	T₀/K	-ΔS_max (2 T)/(mJ•cm^-3•K^-1)	Ref.
KYb₃F₁₀	<0.05	133	[22]
Gd_0.1Yb_0.9F₃	0.18	197	[18]
K(Gd_0.1Yb_0.9)₃F₁₀	<0.05	142	[20]
LiGd_0.1Yb_0.9F₄	0.085	136	[19]
Yb₃Ga₅O₁₂	0.054, 0.18	116	[23]
1	0.65	54	This work
2	0.60	74
3	0.55	100
KBaYb(BO₃)₂	0.009	61	[14]
NaYbP₂O₇	—	57	[15]
YbPt₂Sn	0.25	93	[5]
YbNi₄Mg	0.3	71	[24]
YbNi_1.6Sn(8T)	0.14	131	[25]
YbCu_4.6Au_0.4	—	43	[25]
(NH₄)Fe(SO₄)₂•12H₂O	26	52	[26]
CrK(SO₄)₂•12H₂O	9	41	[26]

Table 1. Magnetic ordering temperature (T0) and maximum magnetic entropy changes (-ΔSmax) under 2 T of selected Yb-based refrigerants

参考文献 26

[1]	Jordan, C.; Bernhardt, J.; Rahamim, J.; Kirichenko, A.; Bharadwaj, K.; Fry-Bouriaux, L.; Somoroff, A.; Porsch, K.; Tsai, K.-T.; Walter, J.; Weis, A.; Yu, M.-J.; Renzullo, M.; Javelle, J.; Checkley, C.; Mukhanov, O.; Yohannes, D.; Vernik, I.; Han, S.-J. Nat. Electron. 2026, 9, 287. doi: 10.1038/s41928-026-01576-6
[2]	Wang, Z.; Rea, N.; Bao, T.; Kaplan, D. L.; Lenc, E.; Wadiasingh, Z.; Hare, J.; Zic, A.; Anumarlapudi, A.; Bera, A.; Beniamini, P.; Cooper, A. J.; Clarke, T. E.; Deller, A. T.; Dawson, J. R.; Glowacki, M.; Hurley-Walker, N.; McSweeney, S. J.; Polisensky, E. J.; Peters, W. M.; Younes, G.; Bannister, K. W.; Caleb, M.; Dage, K. C.; James, C. W.; Kasliwal, M. M.; Karambelkar, V.; Lower, M. E.; Mori, K.; Ocker, S. K.; Pérez-Torres, M.; Qiu, H.; Rose, K.; Shannon, R. M.; Taub, R.; Wang, F.; Wang, Y.; Zhao, Z.; Bhat, N. D. R.; Dobie, D.; Driessen, L. N.; Murphy, T.; Jaini, A.; Deng, X.; Jahns-Schindler, J. N.; Lee, Y. W. J.; Pritchard, J.; Tuthill, J.; Thyagarajan, N. Nature 2025, 642, 583. doi: 10.1038/s41586-025-09077-w
[3]	Shu, M.; Xu, X.; Xi, N.; He, M.; Xiang, J.; Qu, G.; Khalyavin, D.; Manuel, P.; Nakamura, J. G.; Jiao, J.; Liu, Y.; Wu, G.; Guo, K.; Zhao, H.; Xu, W.; Duan, Q.; Zhong, R.; Wang, X.; Han, Y.; Ling, L.; Sun, X.; Song, D.; Gao, Y.; Wang, Z.; Chen, X.; Qian, T.; Jia, S.; Du, H.; Su, G.; Li, W.; Ma, J.; Qu, Z. Nature 2026, 651, 61. doi: 10.1038/s41586-026-10144-z
[4]	Xiang, J.; Zhang, C.; Gao, Y.; Schmidt, W.; Schmalzl, K.; Wang, C.-W.; Li, B.; Xi, N.; Liu, X.-Y.; Jin, H.; Li, G.; Shen, J.; Chen, Z.; Qi, Y.; Wan, Y.; Jin, W.; Li, W.; Sun, P.; Su, G. Nature 2024, 625, 270. doi: 10.1038/s41586-023-06885-w
[5]	Jang, D.; Gruner, T.; Steppke, A.; Mitsumoto, K.; Geibel, C.; Brando, M. Nat. Commun. 2015, 6, 8680. doi: 10.1038/ncomms9680
[6]	Yang, Y.; Zhang, Q.-C.; Pan, Y.-Y.; Long, L.-S.; Zheng, L.-S. Chem. Commun. 2015, 51, 7317. doi: 10.1039/C5CC01254F
[7]	Palacios, E.; Rodríguez-Velamazán, J. A.; Evangelisti, M.; McIntyre, G. J.; Lorusso, G.; Visser, D.; De Jongh, L. J.; Boatner, L. A. Phys. Rev. B 2014, 90, 214423. doi: 10.1103/PhysRevB.90.214423
[8]	Chen, Y.-C.; Qin, L.; Meng, Z.-S.; Yang, D.-F.; Wu, C.; Fu, Z.; Zheng, Y.-Z.; Liu, J.-L.; Tarasenko, R.; Orendáč, M.; Prokleška, J.; Sechovský, V.; Tong, M.-L. J. Mater. Chem. A 2014, 2, 9851. doi: 10.1039/C4TA01646G
[9]	Lorusso, G.; Sharples, J. W.; Palacios, E.; Roubeau, O.; Brechin, E. K.; Sessoli, R.; Rossin, A.; Tuna, F.; McInnes, E. J. L.; Collison, D.; Evangelisti, M. Adv. Mater. 2013, 25, 4653. doi: 10.1002/adma.v25.33
[10]	Mo, Z.; Jiang, J.; Tian, L.; Xie, H.; Li, Y.; Zheng, X.; Zhang, L.; Gao, X.; Li, Z.; Liu, G.; Li, L.; Shen, J. J. Am. Chem. Soc. 2025, 147, 14684. doi: 10.1021/jacs.5c02997
[11]	Manvell, A. S.; Dunstan, M. A.; Gracia, D.; Hrubý, J.; Kubus, M.; McPherson, J. N.; Palacios, E.; Weihe, H.; Hill, S.; Schnack, J.; Evangelisti, M.; Pedersen, K. S. J. Am. Chem. Soc. 2025, 147, 7597. doi: 10.1021/jacs.4c17003
[12]	Xu, N.; Chen, W.; Ding, Y.-S.; Zheng, Z. J. Am. Chem. Soc. 2024, 146, 9506. doi: 10.1021/jacs.4c01372
[13]	Wang, Y.; Xiang, J.; Zhang, L.; Gong, J.; Li, W.; Mo, Z.; Shen, J. J. Am. Chem. Soc. 2024, 146, 3315. doi: 10.1021/jacs.3c12158
[14]	Tokiwa, Y.; Bachus, S.; Kavita, K.; Jesche, A.; Tsirlin, A. A.; Gegenwart, P. Commun. Mater. 2021, 2, 42. doi: 10.1038/s43246-021-00142-1
[15]	Telang, P.; Treu, T.; Klinger, M.; Tsirlin, A. A.; Gegenwart, P.; Jesche, A. Phys. Rev. B 2025, 111, 064431. doi: 10.1103/PhysRevB.111.064431
[16]	Bag, R.; Ennis, M.; Liu, C.; Dissanayake, S. E.; Shi, Z.; Liu, J.; Balents, L.; Haravifard, S. Phys. Rev. B 2021, 104, L220403. doi: 10.1103/PhysRevB.104.L220403
[17]	Schmidt, B.; Sichelschmidt, J.; Ranjith, K. M.; Doert, T.; Baenitz, M. Phys. Rev. B 2021, 103, 214445. doi: 10.1103/PhysRevB.103.214445
[18]	Xu, Q.-F.; Chen, M.-T.; Wu, R.-T.; Long, L.-S.; Zheng, L.-S. J. Am. Chem. Soc. 2024, 146, 20116. doi: 10.1021/jacs.4c04258
[19]	Xu, Q.; Zhao, P.; Chen, M.; Wu, R.; Dai, W.; Long, L.; Zheng, L. Adv. Mater. 2025, 37, 2414226. doi: 10.1002/adma.v37.11
[20]	Xu, Q.; Zhao, P.; Chen, M.-T.; Wu, R.-T.; Dai, W.; Long, L.-S.; Zheng, L. Ind. Chem. Mater. 2026, 10.1039.D6IM00032K.
[21]	Zhang, Y.; Na, Y.; Liu, X.; Xiang, J.; Chen, F.; Li, H.-F.; Sun, P.; Zhou, S.; Zhang, X.; Li, L. Nat. Commun. 2026, 17, 1554. doi: 10.1038/s41467-025-68278-z
[22]	Xu, Q.-F.; Liu, X.-Y.; Wu, R.-T.; Fu, M.-Y.; Chen, M.-T.; Xiang, J.-S.; Meng, Y.-S.; Liu, T.; Sun, P.-J.; Long, L.-S.; Zheng, L.-S. J. Am. Chem. Soc. 2025, 147, 27089. doi: 10.1021/jacs.5c10483
[23]	Paixao Brasiliano, D. A.; Duval, J.-M.; Marin, C.; Bichaud, E.; Brison, J.-P.; Zhitomirsky, M.; Luchier, N. Cryogenics 2020, 105, 103002. doi: 10.1016/j.cryogenics.2019.103002
[24]	Shimura, Y.; Watanabe, K.; Taniguchi, T.; Osato, K.; Yamamoto, R.; Kusanose, Y.; Umeo, K.; Fujita, M.; Onimaru, T.; Takabatake, T. J. Appl. Phys. 2022, 131, 013903. doi: 10.1063/5.0064355
[25]	Gruner, T.; Chen, J.; Jang, D.; Banda, J.; Geibel, C.; Brando, M.; Grosche, F. M. Commun. Mater. 2024, 5, 63. doi: 10.1038/s43246-024-00494-4
[26]	Vilches, O. E.; Wheatley, J. C. Phys. Rev. 1966, 148, 509. doi: 10.1103/PhysRev.148.509

(Yb_1-_xGd_x)₂SO₄(OH)₂F₂的合成、结构及亚开尔文温区磁热效应^★

Synthesis, Structure, and Sub-Kelvin Magnetocaloric Effect of (Yb_1-_xGd_x)₂SO₄(OH)₂F₂^★

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