Pd和Hg共掺杂的金属纳米团簇HgPdAu23(PET)18★

doi:10.6023/A23030078

摘要/Abstract

异金属原子引入原子精确的金属纳米团簇是调控团簇物理化学性质的有效手段, 目前报道的异金属原子掺杂团簇大多数是单个金属原子掺入金属团簇中形成的二元金属纳米团簇, 而两个异金属原子同时掺入同一个金属团簇中形成三元金属纳米团簇的报道较少. 本工作中, 我们报道了Pd和Hg双原子同时掺入Au₂₅(PET)₁₈(PET=苯乙硫醇)团簇中形成HgPdAu₂₃(PET)₁₈新团簇, 推测了Pd和Hg在三元金属团簇中最可能的位置, 即Pd位于三元金属团簇的内核中心, 而Hg原子位于三元金属团簇内核的表面. 不同金属种类以及不同的掺杂位置导致了三元金属团簇HgPdAu₂₃(PET)₁₈具有不同于原始团簇Au₂₅(PET)₁₈和二元金属团簇PdAu₂₄(PET)₁₈和HgAu₂₄(PET)₁₈的电子构型. 本研究为双金属异原子掺入金属纳米团簇的精准制备提供了新的思路.

关键词: 金属团簇, 异原子, 掺杂, 结构

The introduction of heteroatoms into metal nanoclusters is an effective strategy to regulate the physical and chemical properties of clusters. Most of the doped clusters reported are binary metal nanoclusters via one metal heteroatom doping into a metal nanocluster, while the preparation and properties of ternary metal nanoclusters via two heteroatoms doping into a metal nanocluster are rarely studied. In this work, we report the Pd and Hg co-doped ternary metal nanocluster HgPdAu₂₃(PET)₁₈(PET=2-phenylethanethiol) using the Au₂₅(PET)₁₈ nanocluster as an ideal template that can be viewed as a Au₁₃ icosahedral core protected by the exterior 12 Au atoms as a shell. The structural framework of the HgPdAu₂₃(PET)₁₈ nanocluster is similar to that of its parent Au₂₅(PET)₁₈ nanocluster, determined by single-crystal X-ray crystallography and electrospray ionization mass spectroscopy (ESI-MS), which shows a 13-atom icosahedral core and a 12-atom shell capped by 18 thiolate ligands. It indicated that the doping strategy might destroy the total structure (core plus surface) of the parent nanocluster, which will offer an excited opportunity for the correlation of the structure with properties of the doped nanoclusters. More notably, the possible doping location of the Pd and Hg atoms in the HgPdAu₂₃(PET)₁₈ nanocluster can be determined by the combination of single-crystal X-ray crystallography and nuclear magnetic resonance (NMR) spectroscopy (i.e., ¹H NMR and two-dimentional NMR). It is suggested that the Pd atom is possibly located on the center of the icosahedron of the HgPdAu₂₃(PET)₁₈ nanocluster, while the Hg atom is possibly located on the surface of the icosahedron of the HgPdAu₂₃(PET)₁₈ nanocluster. The electronic configuration of HgPdAu₂₃(PET)₁₈ nanocluster is distinct from those of the parent Au₂₅(PET)₁₈ and one-metal doped PdAu₂₄(PET)₁₈ and HgAu₂₄(PET)₁₈ nanoclusters, which can be implied by the X-ray photoelectron spectroscopy (XPS) and UV-Vis absorption spectroscopy. This study provides a new design rule for the two-metal-heteroatom doped nanoclusters.

Key words: nanocluster, heteroatoms, doping, structure

引用此文

张玉莹, 蔡潇, 胡维刚, 李光俊, 祝艳. Pd和Hg共掺杂的金属纳米团簇HgPdAu₂₃(PET)₁₈^★[J]. 化学学报, 2023, 81(7): 703-708.

Yuying Zhang, Xiao Cai, Weigang Hu, Guangjun Li, Yan Zhu. Pd and Hg Atoms Co-doped HgPdAu₂₃(PET)₁₈ Nanocluster^★[J]. Acta Chimica Sinica, 2023, 81(7): 703-708.

导出引用 EndNote|Reference Manager|ProCite|BibTeX|RefWorks

分享此文

图/表 7

图1. (a) HgPdAu23(PET)18团簇的质谱图; (b) Au25(PET)18、PdAu24(PET)18、HgAu24(PET)18和HgPdAu23(PET)18的Au 4f X射线光电子能谱图; (c) PdAu24(PET)18和HgPdAu23(PET)18的Pd 3d X射线光电子能谱图; (d) HgAu24(PET)18和HgPdAu23(PET)18的Hg 4f X射线光电子能谱图

Figure 1. (a) Electrospray mass data of HgPdAu23(PET)18 cluster; (b) Au 4f XPS spectra of Au25(PET)18, PdAu24(PET)18, HgAu24(PET)18 and HgPdAu23(PET)18; (c) Pd 3d XPS spectra of PdAu24(PET)18 and HgPdAu23(PET)18; (d) XPS Hg 4f spectra of HgAu24(PET)18 and HgPdAu23(PET)18

图2. Au25(PET)18、PdAu24(PET)18、HgAu24(PET)18和HgPdAu23(PET)18纳米团簇的晶体结构图 (颜色标注: 绿色代表Au, 紫红色代表Pd, 蓝色代表Hg, 黄色代表硫; C和H原子均省略)

Figure 2. Crystal structures of Au25(PET)18, PdAu24(PET)18, HgAu24(PET)18 and HgPdAu23(PET)18 nanoclusters (Color code: green=Au, magenta=Pd, blue=Hg, yellow=sulfur; C and H atoms are omitted)

图3. HgAu24(PET)18和HgPdAu23(PET)18团簇在δ 2.80~3.80范围的核磁共振波谱图

Figure 3. 1H NMR spectra of HgAu24(PET)18 and HgPdAu23(PET)18 clusters in the range of δ 2.80~3.80

图4. HgPdAu23(PET)18团簇的二维核磁共振波谱图(H-H COSY)

Figure 4. Two-dimensional NMR spectra (H-H COSY) of HgPdAu23(PET)18 cluster

图5. HgPdAu23(PET)18团簇的二维核磁共振谱图(HMQC)

Figure 5. Two-dimensional NMR spectra (HMQC) of HgPdAu23(PET)18 cluster

	[Au₂₅]^－	[PdAu₂₄]⁰	[HgAu₂₄]⁰	[HgPdAu₂₃]⁰
M_core—M_shell/nm	0.2759~0.2789	0.2738~0.2798	0.2779~0.2805	0.2771~0.2796
Averaged value/nm	0.2774	0.2778	0.2792	0.2781
SD^a/nm	0.0011	0.0023	0.0010	0.0008
M_shell—M_shell/nm	0.2789~0.2947	0.2745~0.3223	0.2810~0.3023	0.2792~0.3013
Averaged value/nm	0.2918	0.2921	0.2937	0.2925
SD/nm	0.0063	0.0163	0.0071	0.0072

表1. Au25(PET)18、PdAu24(PET)18、HgAu24(PET)18和HgPdAu23(PET)18团簇晶体结构的相关参数

Table 1. Crystal structure parameters of Au25(PET)18, PdAu24(PET)18, HgAu24(PET)18 and HgPdAu23(PET)18 clusters

图6. (a) Au25; (b) PdAu24; (c) HgAu24和(d) HgPdAu23团簇的紫外-可见吸收光谱

Figure 6. UV-Vis spectra of (a) Au25, (b) PdAu24, (c) HgAu24 and (d) HgPdAu23 clusters

参考文献 30

[1]	Carrillo A. J.; Serra J. M. Catalysis 2021, 11, 741.
[2]	Senapati S.; Ahmad A.; Khan M. I.; Sastry M.; Kumar R. Small 2010, 1, 517. doi: 10.1002/(ISSN)1613-6829
[3]	Sugano Y.; Shiraishi Y.; Tsukamoto D.; Ichikawa S.; Tanaka S.; Hirai T. Angew. Chem., Int. Ed. 2013, 52, 5295. doi: 10.1002/anie.201301669
[4]	Chao W.; Sheng P.; Chan R.; Sun S. Small 2010, 5, 567. doi: 10.1002/smll.v5:5
[5]	Li D. Q.; Zhang Z. Q.; Zang P. Y.; Ma Y. W.; Wu Q.; Yang L. J.; Chen Q.; Wang X. Z.; Hu Z. Acta Chim. Sinica 2016, 74, 587. (in Chinese) doi: 10.6023/A16040196
	(黎聃勤, 张志琦, 臧鹏远, 马延文, 吴强, 杨立军, 陈强, 王喜章, 胡征, 化学学报, 2016, 74, 587.)
[6]	Zhang Y. F.; Park S. J. J. Catal. 2017, 355, 1. doi: 10.1016/j.jcat.2017.08.007
[7]	Jin Y. L.; Qin W.; Jiang Y.; Wang M.; Yao J. L.; Huang J.; Gu R. A. Acta Chim. Sinica 2008, 66, 2494. (in Chinese)
	(金毅亮, 秦维, 蒋芸, 王梅, 姚建林, 黄洁, 顾仁敖, 化学学报, 2008, 66, 2494.)
[8]	Zhu C. Z.; Guo S. J.; Dong S. J. Adv. Mater. 2012, 24, 2326. doi: 10.1002/adma.201104951
[9]	Fan X. Y.; Zhuang Q. C.; Wei G. Z.; Ke F. S.; Huang L.; Dong Q. F.; Sun S. G. Acta Chim. Sinica 2009, 67, 1547. (in Chinese)
	(樊小勇, 庄全超, 魏国祯, 柯福生, 黄令, 董全峰, 孙世刚, 化学学报, 2009, 67, 1547.)
[10]	Yamazoe S.; Kurashige W.; Nobusada K.; Negishi Y.; Tsukuda T. J. Phys. Chem. C 2014, 118, 25284. doi: 10.1021/jp5085372
[11]	Negishi Y.; Munakata K.; Ohgake W.; Nobusada K. J. Phys. Chem. Lett. 2012, 3, 2209. doi: 10.1021/jz300892w
[12]	Cai X.; Saranya G.; Shen K. Q.; Chen M. Y.; Si R.; Ding W. P.; Zhu Y. Angew. Chem., Int. Ed. 2019, 58, 9964. doi: 10.1002/anie.v58.29
[13]	Wang S. X.; Song Y. B.; Jin S.; Liu X.; Zhang J.; Pei Y.; Meng X. M.; Chen M.; Li P.; Zhu M. Z. J. Am. Chem. Soc. 2015, 137, 4018. doi: 10.1021/ja511635g
[14]	Bhat S.; Baksi A.; Mudedla S. K.; Natarajan G.; Subramanian V.; Pradeep T. J. Phys. Chem. Lett. 2017, 8, 2787. doi: 10.1021/acs.jpclett.7b01052
[15]	Walsh A. G.; Zhang P. J. Phys. Chem. Lett. 2021, 12, 257. doi: 10.1021/acs.jpclett.0c03252
[16]	Sels A.; Salassa G.; Pollitt S.; Guglieri C.; Rupprechter G.; Barrabés N.; Bürgi T. J. Phys. Chem. C 2017, 121, 10919. doi: 10.1021/acs.jpcc.6b12066
[17]	Nasaruddin R. R.; Hülsey M. J.; Xie J. P. Mol. Catal. 2022, 518, 112095.
[18]	Chen Q.; Qin Z. X.; Liu S.; Zhu M. C.; Li G.J. Chem. Phys. C 2021, 154, 164308.
[19]	Kang X.; Li Y. W.; Zhu M. Z.; Jin R. C. Chem. Soc. Rev. 2020, 49, 6443. doi: 10.1039/C9CS00633H
[20]	Qin Z. X.; Zhao D.; Zhao L.; Xiao Q.; Wu T. T.; Zhang J. W.; Wan C. Q.; Li G. Nanoscale Adv. 2019, 1, 2529. doi: 10.1039/C9NA00234K
[21]	Panapitiya G.; Wang H.; Chen Y. X.; Hussain E.; Jin R. C.; Lewis J. P. Phys. Chem. Chem. Phys. 2018, 20, 13747. doi: 10.1039/C7CP07295C
[22]	Kwak K.; Choi W.; Tang Q.; Kim M.; Lee Y.; Jiang D. E.; Lee D. Nat. Chem. 2017, 8, 14723.
[23]	Lu Y. Z.; Zhang C. M.; Li X. K.; Frojd A. R.; Xing W.; Clayborne A. Z.; Chen W. Nano Energy 2018, 50, 316. doi: 10.1016/j.nanoen.2018.05.052
[24]	Li S.; Alfonso D.; Nagarajan A. V.; House S. D.; Yang J. C.; Kauffman D. R.; Mpourmpakis G.; Jin R. C. ACS Catal. 2020, 10, 12011. doi: 10.1021/acscatal.0c02266
[25]	Yang S.; Wang S. X.; Jin S.; Chen S.; Sheng H. T.; Zhu M. Z. Nanoscale 2015, 7, 10005. doi: 10.1039/C5NR01965F
[26]	Suyama M.; Takano S.; Tsukuda T. J. Phys. Chem. C 2020, 124, 23923. doi: 10.1021/acs.jpcc.0c06765
[27]	Bootharaju M. S.; Sinatraa L.; Bakr O. M. Nanoscale 2016, 8, 17333. doi: 10.1039/C6NR06353E
[28]	Fei W. W.; Antonello S.; Dainese T.; Dolmella A.; Lahtinen M.; Rissanen K.; Venzo A.; Maran F. J. Am. Chem. Soc. 2019, 141, 16033. doi: 10.1021/jacs.9b08228
[29]	Zhu M. Z.; Lanni E.; Garg N.; Bier M. E.; Jin R. C. J. Am. Chem. Soc. 2008, 130, 1138. doi: 10.1021/ja0782448
[30]	Takano S.; Ito S.; Tsukuda T. J. Am. Chem. Soc. 2019, 141, 15994. doi: 10.1021/jacs.9b08055

Pd和Hg共掺杂的金属纳米团簇HgPdAu₂₃(PET)₁₈^★

Pd and Hg Atoms Co-doped HgPdAu₂₃(PET)₁₈ Nanocluster^★

RichHTML

PDF

补充材料

可视化

摘要/Abstract

引用此文

分享此文

图/表 7

参考文献 30

相关文章 15

编辑推荐

相关统计

本文评价

[1]	刘洋, 高丰琴, 马占营, 张引莉, 李午戊, 侯磊, 张小娟, 王尧宇. 一例钴基金属有机框架化合物活化过氧单硫酸盐高效降解水中亚甲基蓝研究[J]. 化学学报, 2024, 82(2): 152-159.
[2]	张凯, 武晓君. 具有室温铁磁性的二维Janus钛硫属化物^★[J]. 化学学报, 2023, 81(9): 1142-1147.
[3]	张正初, 熊炜, 吕华. α-螺旋聚氨基酸交联的水凝胶的制备和材料特性^★[J]. 化学学报, 2023, 81(9): 1113-1119.
[4]	杨蓉婕, 周璘, 苏彬. 基于共价有机框架修饰电极的维生素A和C的选择性检测^★[J]. 化学学报, 2023, 81(8): 920-927.
[5]	崔国庆, 胡溢玚, 娄颖洁, 周明霞, 李宇明, 王雅君, 姜桂元, 徐春明. CO₂加氢制醇类催化剂的设计制备及性能研究进展[J]. 化学学报, 2023, 81(8): 1081-1100.
[6]	胡立伟, 刘宪虎, 刘春太, 宋延林, 李明珠. 光子晶体结构色材料的自组装制备与应用^★[J]. 化学学报, 2023, 81(7): 809-819.
[7]	刘振宇, 饶俊峰, 祝守加, 王兵洋, 余帆, 冯全友, 解令海. 溶液加工型自主体热活化延迟荧光材料的研究进展[J]. 化学学报, 2023, 81(7): 820-835.
[8]	刘佳, 陈光海, 陈轶群, 江杰涛, 肖霄, 吴强, 杨立军, 王喜章, 胡征. 碳热还原活化扩孔提升介观结构碳纳米笼超级电容器性能^★[J]. 化学学报, 2023, 81(7): 709-716.
[9]	刘嘉文, 林玮璜, 王惟嘉, 郭学益, 杨英. Cu_1.94S-SnS纳米异质结的合成及其光催化降解研究[J]. 化学学报, 2023, 81(7): 725-734.
[10]	梁雪峰, 荆剑, 冯昕, 赵勇泽, 唐新员, 何燕, 张立胜, 李慧芳. 共价有机框架COF66/COF366的电子结构: 从单体到二维平面聚合物[J]. 化学学报, 2023, 81(7): 717-724.
[11]	陈剑, 蔡卓尔, 焦淑琳, 张祥, 胡进忠, 刘敏, 孙伯旺, 花秀妮. 一种热响应介电开关型零维有机-无机杂化材料: (C₃H₆NH₂)₂CoCl₄[J]. 化学学报, 2023, 81(5): 480-485.
[12]	贾洋刚, 陈诗洁, 邵霞, 程婕, 林娜, 方道来, 冒爱琴, 李灿华. 高性能无钴化钙钛矿型高熵氧化物负极材料的制备及储锂性能研究[J]. 化学学报, 2023, 81(5): 486-495.
[13]	蒋江民, 郑欣冉, 孟雅婷, 贺文杰, 陈亚鑫, 庄全超, 袁加仁, 鞠治成, 张校刚. 氟氮共掺杂多孔碳纳米片的制备及其储钾性能研究[J]. 化学学报, 2023, 81(4): 319-327.
[14]	宁聪聪, 杨倩, 毛阿敏, 唐梓嘉, 金燕, 胡宝山. 石墨烯纳米带的可控制备研究进展[J]. 化学学报, 2023, 81(4): 406-419.
[15]	赵政嘉, 刘康, 郭燕, 于吉攀, 石伟群. 超铀金属有机化学研究进展[J]. 化学学报, 2023, 81(11): 1633-1641.