Synthesis, Structure, and Sub-Kelvin Magnetocaloric Effect of (Yb1-xGdx)2SO4(OH)2F2★

doi:10.6023/A26060187

Acta Chimica Sinica ›› 2026, Vol. 84 ›› Issue (8): 1231-1235.DOI: 10.6023/A26060187 Previous Articles Next Articles

Article

(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
通讯作者: 徐侨飞, 刘涛, 龙腊生
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: Qiaofei Xu, Tao Liu, Lasheng Long
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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Abstract

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

Cite this article

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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Fig. & Tab. 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

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(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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