Pd插层NbSe2化合物的制备、晶体结构和电学性质研究

doi:10.15541/jim20190125

无机材料学报 ›› 2020, Vol. 35 ›› Issue (4): 505-510.DOI: 10.15541/jim20190125

所属专题： 2020年能源材料论文精选(三) :太阳能电池、热电材料及其他

• 研究快报 • 上一篇

Pd插层NbSe₂化合物的制备、晶体结构和电学性质研究

黄冲^1,²,赵伟¹(),王东¹,卜克军^1,²,王思顺¹,黄富强^1,³()

1. 中国科学院上海硅酸盐研究所, 高性能陶瓷和超微结构国家重点实验室, 上海 200050
2. 中国科学院大学, 北京 100049
3. 北京大学化学与分子工程学院, 北京分子科学国家实验室与稀土材料化学及应用国家重点实验室, 北京 100871

收稿日期:2019-03-26 修回日期:2019-04-30 出版日期:2020-04-20 网络出版日期:2019-06-17
作者简介:黄冲(1994-), 男, 硕士研究生. E-mail: huangchong@student.sic.ac.cn

Synthesis, Crystal Structure, and Electrical Conductivity of Pd-intercalated NbSe₂

HUANG Chong^1,²,ZHAO Wei¹(),WANG Dong¹,BU Kejun^1,²,WANG Sishun¹,HUANG Fuqiang^1,³()

1. State Key Laboratory of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China
2. University of Chinese Academy of Sciences, Beijing 100049, China
3. State Key Laboratory of Rare Earth Materials Chemistry and Applications and Beijing National Laboratory for Molecular Sciences, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China

Received:2019-03-26 Revised:2019-04-30 Published:2020-04-20 Online:2019-06-17
Supported by:
National Key Research and Development Program(2016YFB0901600);Science and Technology Commission of Shanghai(16JC1401700);Science and Technology Commission of Shanghai(16ZR1440500);National Natural Science Foundation of China(Y93GJ11101);The Key Research Program of Chinese Academy of Sciences(QYZDJ-SSW-JSC013);The Key Research Program of Chinese Academy of Sciences(KGZD-EW-T06);CAS Center for Excellence in Superconducting Electronics, and Youth Innovation Promotion Association CAS

摘要/Abstract

摘要：

通过固相反应法合成一系列插层化合物Pd_xNbSe₂ (x=0~0.17)。它们与2H-NbSe₂相同, 属于六方晶格, 空间群为P6₃/mmc。Pd占据NbSe₂层间的八面体空位。随着Pd含量的增加, 晶格常数c线性增大, 而a几乎不变。X射线单晶衍射结果表明, Pd_0.17NbSe₂的晶格常数为a=b=0.34611(2) nm, c=1.27004(11) nm。每个Pd原子与六个Se原子键合形成[PdSe₆]八面体来连接相邻的Nb-Se层, 使晶体结构变得更加稳定, 从而提高化合物的热稳定性。电学测试表明, 随着Pd含量的增加, Pd_xNbSe₂的剩余电阻比减小。此外, 超导转变温度也随着Pd含量的增加而下降, 说明Pd的引入不利于NbSe₂的超导态。

关键词: Pd_xNbSe₂, 过渡金属硫族化合物, 晶体结构, 超导

Abstract:

New intercalated compounds Pd_xNbSe₂ (x=0-0.17) were synthesized via solid-state reaction. They possess the parent structure of 2H-NbSe₂ and crystalize in the hexagonal space group of P6₃/mmc. The intercalated Pd occupies the octahedral position in the van der Waals gaps of 2H-NbSe₂. Unit cell parameter c increases linearly with the Pd content, while a is nearly unchanged. The lattice parameter of Pd_0.17NbSe₂ (a=b=0.34611(2) nm, c= 1.27004(11) nm) is identified by single crystal X-ray diffraction. The intercalated Pd stabilizes the crystal structure of NbSe₂ by connecting the adjacent Nb-Se layers with [PdSe₆] octahedra and leads to the enhanced thermostability in air. Temperature dependence of electric resistivity reveals that the residual resistivity ratio of Pd_xNbSe₂ monotonically decreases with addition of the intercalated Pd content. The decreased superconducting critical temperature of Pd_xNbSe₂ indicates the suppression effect of Pd intercalation on the superconductivity in the host NbSe₂.

Key words: Pd_xNbSe₂, transition metal dichalcogenide, crystal structure, superconducting

中图分类号:

O782

黄冲,赵伟,王东,卜克军,王思顺,黄富强. Pd插层NbSe₂化合物的制备、晶体结构和电学性质研究[J]. 无机材料学报, 2020, 35(4): 505-510.

HUANG Chong,ZHAO Wei,WANG Dong,BU Kejun,WANG Sishun,HUANG Fuqiang. Synthesis, Crystal Structure, and Electrical Conductivity of Pd-intercalated NbSe₂[J]. Journal of Inorganic Materials, 2020, 35(4): 505-510.

图/表 11

参考文献 24

[1]	TAN CHAO-LIANG, CAO XIE-HONG, WU XUE-JUN , et al. Recent advances in ultrathin two-dimensional nanomaterials. Chemical Reviews, 2017,117(9):6225-6331.
[2]	GOPALAKRISHNAN D, LEE A, THANGAVEL N K , et al. Facile synthesis of electrocatalytically active NbS₂ nanoflakes for an enhanced hydrogen evolution reaction. Sustainable Energy & Fuels, 2018,2(1):96-102.
[3]	JIN HUAN-YU, GUO CHUN-XIAN, LIU XIN , et al. Emerging two-dimensional nanomaterials for electrocatalysis. Chemical Reviews, 2018,118(13):6337-6408.
[4]	WANG REN-YAN, GAN LIN, ZHAI TIAN-YOU . ReX₂ (X=S, Se): a new opportunity for development of two-dimensional anisotropic materials. Journal of Inorganic Materials, 2019,34(1):1-16.
[5]	ZHAO DE-RUI, ZHAI YING-JIAO, LI JIN-HUA , et al. Preparation and properties of glucose biosensor based on flower-like MoS₂ micrometer material. Journal of Inorganic Materials, 2016,31(2):153-158.
[6]	CHIA X, AMBROSI A, LAZAR P , et al. Electrocatalysis of layered group 5 metallic transition metal dichalcogenides (MX₂, M=V, Nb, and Ta; X = S, Se, and Te). Journal of Materials Chemistry A, 2016,4(37):14241-14253.
[7]	SIPOS B, KUSMARTSEVA A F, AKRAP A , et al. From Mott state to superconductivity in 1T-TaS₂. Nature Materials, 2008,7(12):960-965.
[8]	LUO HUI-XIA, STRYCHALSKA-NOWAK J, LI JUN , et al. S-shaped suppression of the superconducting transition temperature in Cu-intercalated NbSe₂. Chemistry of Materials, 2017,29(8):3704-3712.
[9]	WANG MENG-JING, WILLIAMS D, LAHTI G , et al. Chemical intercalation of heavy metal, semimetal, and semiconductor atoms into 2D layered chalcogenides. 2D Materials, 2018,5(4):045005.
[10]	HAO QIAO-YAN, WANG DA-KE, ZHU BAI-CHUAN ,et al. Facile synthesis, structure and physical properties of 3R-A_xNbS₂(A=Li, Na). Journal of Alloys and Compounds, 2016,663:225-229.
[11]	PRODAN A, MARINKOVIC V, ROJSEK M , et al. The surface superstructures in niobium disulfide and diselenide intercalated by Cu, Co and Fe. Surface Science, 2001,476(1):71-77.
[12]	HUGHES T A, KEVAN S D, COX D E , et al. Synthesis of superlattices of intercalated transition metal dichalcogenides. Journal of the American Chemical Society, 2000,122(37):8910-8915.
[13]	LIAN CHAO-SHENG, SI CHEN, WU JIAN , et al. First-principles study of Na-intercalated bilayer NbSe₂: suppressed charge-density wave and strain-enhanced superconductivity. Physical Review B, 2017,96(23):235426.
[14]	WANG DONG, WANG XIN, LU YUE , et al. Atom-scale dispersed palladium in a conductive Pd_0.1TaS₂ lattice with a unique electronic structure for efficient hydrogen evolution. Journal of Materials Chemistry A, 2017,5(43):22618-22624.
[15]	BHOI D, KHIM S, NAM W , et al. Interplay of charge density wave and multiband superconductivity in 2H-Pd_xTaSe₂. Scientific Reports, 2016,6:24068.
[16]	MOMMA K, IZUMI F . VESTA 3 for three-dimensional visualization of crystal, volumetric and morphology data. Journal of Applied Crystallography, 2011,44(6):1272-1276.
[17]	MAREZIO M, DERNIER P, MENTH A , et al. The crystal structure of NbSe₂ at 15 K. Journal of Solid State Chemistry, 1972,4(3):425-429.
[18]	HAMIDANI A, BENNECER B, ZANAT K . Structural and electronic properties of the pseudo-binary compounds PdX₂ (X=P, S and Se). Journal of Physics and Chemistry of Solids, 2010,71(1):42-46.
[19]	ZHAO BEN-LIANG, HUANG JIAN, FU QI , et al. MoS₂/NbSe₂ hybrid nanobelts for enhanced hydrogen evolution. Journal of The Electrochemical Society, 2016,163(6):H384-H387.
[20]	HALASYAMANI P S, O'HARE D . Synthesis and characterization of Se₄Nb₂O₁₃: a new ternary Se⁴⁺-Nb⁵⁺-oxide with monoselenite and diselenite groups . Chemistry of Materials, 1998,10(2):646-649.
[21]	BU KE-JUN, HUANG JIAN, LUO MENG-JIA , et al. Observation of high Seebeck coefficient and low thermal conductivity in [SrO]- intercalated CuSbSe₂ compound. Chemistry of Materials, 2018,30(16):5539-5543.
[22]	WANG QIN-CHAO, MENG JING-KE, YUE XIN-YANG , et al. Tuning P2-structured cathode material by Na-site Mg substitution for Na-Ion batteries. Journal of the American Chemical Society, 2019,141(2):840-848.
[23]	NAIK I, RASTOGI A K . Transport properties of 2H-NbSe₂: effect of Ga-intercalation. Physica B: Condensed Matter, 2010,405(3):955-957.
[24]	HAUDER J J, ROBBINS M, DISALVO F J . Effect of 3d impurities on the superconducting transition temperature of the layered compound NbSe₂. Physical Review B, 1973,8(3):1038-1042.

Chemical formula	Pd_0.17NbSe₂
M_r/(g∙mol^-1)	269.03
Crystal system	Hexagonal, P6₃/mmc
a, c/nm	0.34611(2), 1.27004(11)
V/nm³	0.13176(2)
Z	2
Radiation type	Mo Kα, λ=0.071073 nm
Crystal color	Black
ρ_c/(g∙cm^-3)	6.781
µ/mm^-1	32.93
Crystal size/mm³	0.01×0.01×0.003
Diffractometer	Bruker D8 QUEST
T_min, T_max	0.494, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	1480, 121, 103
R_int	0.053
(sinθ/λ)_max/nm^-1	7.55
R₁, wR₂, S^a	0.019, 0.035, 1.14
No. of reflections	121
No. of parameters	9

Chemical formula	Pd_0.17NbSe₂
M_r/(g∙mol^-1)	269.03
Crystal system	Hexagonal, P6₃/mmc
a, c/nm	0.34611(2), 1.27004(11)
V/nm³	0.13176(2)
Z	2
Radiation type	Mo Kα, λ=0.071073 nm
Crystal color	Black
ρ_c/(g∙cm^-3)	6.781
µ/mm^-1	32.93
Crystal size/mm³	0.01×0.01×0.003
Diffractometer	Bruker D8 QUEST
T_min, T_max	0.494, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	1480, 121, 103
R_int	0.053
(sinθ/λ)_max/nm^-1	7.55
R₁, wR₂, S^a	0.019, 0.035, 1.14
No. of reflections	121
No. of parameters	9

Atom	Wyck. Site	x	y	z	U_iso* or U_eq/nm²	Occ.
Nb	2b	0	1	1/4	0.000075(2)	1
Se	4f	1/3	2/3	0.38104(5)	0.0000736(17)	1
Pd	2a	0	1	1/2	0.000059(11)	0.171(3)

Atom	Wyck. Site	x	y	z	U_iso* or U_eq/nm²	Occ.
Nb	2b	0	1	1/4	0.000075(2)	1
Se	4f	1/3	2/3	0.38104(5)	0.0000736(17)	1
Pd	2a	0	1	1/2	0.000059(11)	0.171(3)

	U₁₁/nm²	U₂₂/nm²	U₃₃/nm²	U₁₂/nm²
Nb	0.000074(3)	0.000074(3)	0.000075(4)	0.0000372(13)
S	0.000064(2)	0.000064(2)	0.000094(3)	0.0000318(10)
Pd	0.000062(13)	0.000062(13)	0.000052(19)	0.000031(7)

Pd插层NbSe₂化合物的制备、晶体结构和电学性质研究

Synthesis, Crystal Structure, and Electrical Conductivity of Pd-intercalated NbSe₂

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 11

参考文献 24

相关文章 15

编辑推荐

Metrics

本文评价

Bond	Distance/nm	Bond	Distance/nm
Nb1—Se2ⁱ	0.26006(4)	Se2—Pd3^viii	0.25051(4)
Nb1—Se2ⁱⁱ	0.26006(4)	Se2—Nb1^viii	0.26006(4)
Nb1—Se2ⁱⁱⁱ	0.26006(4)	Se2—Nb1^vii	0.26006(4)
Nb1—Se2^iv	0.26006(4)	Pd3—Se2^ix	0.25051(4)
Nb1—Se2	0.26006(4)	Pd3—Se2^iv	0.25051(4)
Nb1—Se2^v	0.26006(4)	Pd3—Se2^x	0.25051(4)
Nb1—Pd3^vi	0.31751(3)	Pd3—Se2ⁱ	0.25051(4)
Nb1—Pd3	0.31751(3)	Pd3—Se2^xi	0.25051(4)
Se2—Pd3^vii	0.25051(4)	Pd3—Nb1^xi	0.31751(3)
Se2—Pd3	0.25051(4)
Bond	Angle/(°)	Bond	Angle/(°)
Se2ⁱ—Nb1—Se2ⁱⁱ	134.813 (8)	Pd3^viii—Se2—Nb1	133.822 (3)
Se2ⁱ—Nb1—Se2ⁱⁱⁱ	79.58 (2)	Nb1^viii—Se2—Nb1	83.434 (16)
Se2ⁱⁱ—Nb1—Se2ⁱⁱⁱ	83.434 (16)	Pd3^vii—Se2—Nb1^vii	76.881 (6)
Se2ⁱ—Nb1—Se2^iv	83.434 (16)	Pd3—Se2—Nb1^vii	133.822 (3)
Se2ⁱⁱ—Nb1—Se2^iv	79.58 (2)	Pd3^viii—Se2—Nb1^vii	133.822 (3)
Se2ⁱⁱⁱ—Nb1—Se2^iv	134.813 (7)	Nb1^viii—Se2—Nb1^vii	83.434 (16)
Se2ⁱ—Nb1—Se2	83.433 (16)	Nb1—Se2—Nb1^vii	83.434 (16)
Se2ⁱⁱ—Nb1—Se2	134.812 (7)	Se2—Pd3—Se2^ix	92.612 (17)
Se2ⁱⁱⁱ—Nb1—Se2	134.812 (8)	Se2—Pd3—Se2^iv	87.388 (17)
Se2^iv—Nb1—Se2	83.433 (16)	Se2^ix—Pd3—Se2^iv	180.0
Se2ⁱ—Nb1—Se2^v	134.812 (8)	Se2—Pd3—Se2^x	92.612 (17)
Se2ⁱⁱ—Nb1—Se2^v	83.434 (16)	Se2^ix—Pd3—Se2^x	87.388 (17)
Se2ⁱⁱⁱ—Nb1—Se2^v	83.434 (16)	Se2^iv—Pd3—Se2^x	92.612 (17)
Bond	Angle/(°)	Bond	Angle/(°)
Se2^iv—Nb1—Se2^v	134.812 (8)	Se2—Pd3—Se2ⁱ	87.388 (17)
Se2—Nb1—Se2^v	79.58 (2)	Se2^ix—Pd3—Se2ⁱ	92.612 (17)
Se2ⁱ—Nb1—Pd3^vi	129.790 (11)	Se2^iv—Pd3—Se2ⁱ	87.388 (17)
Se2ⁱⁱ—Nb1—Pd3^vi	50.210 (11)	Se2^x—Pd3—Se2ⁱ	180.0
Se2ⁱⁱⁱ—Nb1—Pd3^vi	50.210 (11)	Se2—Pd3—Se2^xi	180.0
Se2^iv—Nb1—Pd3^vi	129.790 (11)	Se2^ix—Pd3—Se2^xi	87.388 (17)
Se2—Nb1—Pd3^vi	129.790 (11)	Se2^iv—Pd3—Se2^xi	92.612 (17)
Se2^v—Nb1—Pd3^vi	50.210 (11)	Se2^x—Pd3—Se2^xi	87.388 (17)
Se2ⁱ—Nb1—Pd3	50.210 (11)	Se2ⁱ—Pd3—Se2^xi	92.612 (17)
Se2ⁱⁱ—Nb1—Pd3	129.790 (11)	Se2—Pd3—Nb1	52.909 (12)
Se2ⁱⁱⁱ—Nb1—Pd3	129.790 (11)	Se2^ix—Pd3—Nb1	127.092 (12)
Se2^iv—Nb1—Pd3	50.210 (11)	Se2^iv—Pd3—Nb1	52.908 (12)
Se2—Nb1—Pd3	50.210 (11)	Se2^x—Pd3—Nb1	127.092 (12)
Se2^v—Nb1—Pd3	129.790 (11)	Se2ⁱ—Pd3—Nb1	52.908 (12)
Pd3^vi—Nb1—Pd3	180.0	Se2^xi—Pd3—Nb1	127.091 (12)
Pd3^vii—Se2—Pd3	87.388 (17)	Se2—Pd3—Nb1^xi	127.091 (12)
Pd3^vii—Se2—Pd3^viii	87.388 (17)	Se2^ix—Pd3—Nb1^xi	52.908 (12)
Pd3—Se2—Pd3^viii	87.388 (17)	Se2^iv—Pd3—Nb1^xi	127.092 (12)
Pd3^vii—Se2—Nb1^viii	133.822 (2)	Se2^x—Pd3—Nb1^xi	52.908 (12)
Pd3—Se2—Nb1^viii	133.822 (3)	Se2ⁱ—Pd3—Nb1^xi	127.092 (12)
Pd3^viii—Se2—Nb1^viii	76.881 (6)	Se2^xi—Pd3—Nb1^xi	52.909 (12)
Pd3^vii—Se2—Nb1	133.822 (2)	Nb1—Pd3—Nb1^xi	180.0
Pd3—Se2—Nb1	76.881 (6)

[1]	赵伟, 徐阳, 万颖杰, 蔡天逊, 穆金潇, 黄富强. 金属氰胺化合物的结构、合成及电化学储能应用[J]. 无机材料学报, 2022, 37(2): 140-151.
[2]	彭帆, 曾毅. 利用菊池衍射花样鉴定晶体结构的方法研究[J]. 无机材料学报, 2021, 36(11): 1193-1198.
[3]	李淑芳,赵爽,周潇,李满荣. Zn_3-_xMn_xTeO₆的晶体结构与吸收光谱和磁性研究[J]. 无机材料学报, 2020, 35(8): 895-901.
[4]	李淑芳, 赵爽, 李满荣. 助熔剂法合成钨氧氯化合物Li₂₃CuW₁₀O₄₀Cl₅[J]. 无机材料学报, 2020, 35(7): 834-838.
[5]	曾祥雄, 杨进超, 左联, 杨奔奔, 秦峻, 彭志航. Li/Ce/La共掺杂对CaBi₂Nb₂O₉陶瓷晶体结构及电学性能的影响[J]. 无机材料学报, 2019, 34(4): 379-386.
[6]	罗志永, 廖楚剑, 蔡传兵, 刘志勇, 李敏娟, 鲁玉明. 氩离子刻蚀对TFA-MOD法YBa₂Cu₃O_7-_x薄膜性能的影响研究[J]. 无机材料学报, 2019, 34(12): 1279-1284.
[7]	黄龙, 丁士华, 张晓云, 严欣堪, 李超, 朱惠. Li₂O-B₂O₃-SiO₂玻璃相对BaAl₂Si₂O₈结构及微波介电性能的影响[J]. 无机材料学报, 2019, 34(10): 1091-1096.
[8]	周鑫, 马垒, 刘涛, 郭永斌, 王岛, 董培林. Si₃N₄/FePd/Si₃N₄薄膜的晶体结构和磁性能研究[J]. 无机材料学报, 2018, 33(8): 909-913.
[9]	左珺凉, 赵跃, 吴蔚, 储静远, 张智巍, 洪智勇, 金之俭. 无氟MOD法制备YBCO超导薄膜工艺中物相的演变过程[J]. 无机材料学报, 2018, 33(7): 773-778.
[10]	孟凡斌, 马晓帆, 张炜, 吴光恒, 张玉洁. Mn和Fe掺杂对尖晶石氧化物Co₂MnO₄结构和磁性的影响[J]. 无机材料学报, 2017, 32(6): 609-614.
[11]	王晴晴, 史坚, 李焕英, 陈晓峰, 潘尚可, 卞建江, 任国浩. Cs₂LiYCl₆:Ce闪烁晶体的光学及闪烁性能[J]. 无机材料学报, 2017, 32(2): 175-179.
[12]	淡猛, 张骞, 钟云倩, 周莹. 不同晶相MnS制备及光解H₂S制氢性能研究[J]. 无机材料学报, 2017, 32(12): 1308-1314.
[13]	杨志胜, 柯蔚芳, 王艳香, 黄丽群, 郭平春, 朱华. 杂化钙钛矿(HOC₂H₄NH₃)₂CuCl₄的制备与表征[J]. 无机材料学报, 2017, 32(10): 1063-1067.
[14]	张瑶, 丁士华, 刘杨琼, 段绍英, 肖鹏, 韩林材. Ba_1-_xMg_xAl₂Si₂O₈晶体结构与微波介电性能的研究[J]. 无机材料学报, 2017, 32(1): 91-95.
[15]	刘鑫, 熊杰, 张飞, 赵晓辉, 赵睿鹏, 陶伯万. Ba源配比对MOCVD法制备YBCO薄膜性能的影响研究[J]. 无机材料学报, 2014, 29(3): 275-278.