Photoluminescence and Electrochemical Sensing of Atomically Precise Cu13 Cluster

doi:10.6023/A21050212

Abstract

Copper-based nanomaterials show widespread applications in the fields of luminescence and (bio)chemical sensing. Copper nanoclusters as a new class of nanomaterials have attracted extensive attention due to their atomic-level structure, but the syntheses of stable atom-precise copper clusters with good properties are still challenging. In this work, we have successfully prepared a novel mercaptoimidazole-stabilized copper(I) nanocluster: [Cu₁₃(SR)₁₂] NO₃ (Cu₁₃ NC, where RSH=2-mercaptobenzimidazole) by introducing the reducing agent (NaBH₄) in an acetonitrile-methanol solution of copper nitrate and RSH. The presence of NaBH₄ not only reduced Cu(II) to Cu(I) but also provided a reducing system to avoid the reversed oxidation. The structure and composition of Cu₁₃ NC have been collectively elucidated by X-ray crystallography and electrospray ionization mass spectrometry (ESI-MS). The metal framework of Cu₁₃ NC can be seen as three triangular bipyramids sharing one or two vertices, which are surrounded by 12 thiolate ligands as protecting agents through a simple bridging mode. Since the counterions in the crystal lattice are highly disordered and could not be located, the existence of NO₃^- has been confirmed by infrared spectroscopy and ESI-MS. Cu₁₃ NC exhibits good stability under ambient conditions and shows bright-red emission in the solid state (λ_em=627 nm). The long-life emission in the order of microseconds and large Stokes shift (≈280 nm) indicate that the luminescence of Cu₁₃ NC is a spin-forbidden triplet phosphorescence. The absolute quantum yield of the solid-state Cu₁₃ NC was calculated to be 1.36%. Meanwhile, there are two exposed copper atoms at each end of the structure, endowing Cu₁₃ with good electrochemical activity. The test confirmed that Cu₁₃ NC shows prompt response, and great selectivity in electrochemical detection of H₂O₂, making it a low-cost advanced H₂O₂ sensing material. This work provides an opportunity to investigate the structure-optical and electrochemical property relationship of copper clusters.

Key words: copper-thiolate cluster, atom-precise structure, photoluminescence, electrochemical sensing

Cite this article

Hao-Nan Qin, Zhao-Yang Wang, Shuang-Quan Zang. Photoluminescence and Electrochemical Sensing of Atomically Precise Cu₁₃ Cluster[J]. Acta Chimica Sinica, 2021, 79(8): 1037-1041.

Export EndNote|Reference Manager|ProCite|BibTeX|RefWorks

share this article

Fig. & Tab. 4

Figure 1. (a) Total structure of Cu13 NC; (b) Cu13S12 frame; (c) Cu13 core formed by three vertex-sharing triangular biconicals. Color codes: Cu, brown and orange; S, yellow; C, gray; N, blue. H atoms are omitted for clarity

Figure 2. ESI mass spectrum of Cu13 NC in positive mode. Inset: comparison of the calculated (red) and experimental (black) isotope distribution patterns

Figure 3. (a) The photo of solid Cu13 NC under natural light and UV light respectively; (b) excitation and emission spectra of Cu13 NC in solid state at 298 K; (c) PL decays of a solid state of Cu13 NC at 298 K; (d) solid-state UV-vis absorption spectrum of Cu13 NC

Figure 4. (a) CVs of the Cu13 NC clusters in 0.1 mol•L-1 PBS; (b) the amperometric i-t curve of the Cu13 NC upon successive addition of H2O2 recorded at –0.56 V; (c) the linear relationship between responding current and concentration of H2O2; (d) the amperometric responses recorded on alternate addition of interfering chemicals and H2O2 in 0.1 mol•L-1 PBS; the concentration is 1×10-3 mol•L-1

References 46

[1]	Jin, R.; Zeng, C.; Zhou, M.; Chen, Y. Chem. Rev. 2016, 116, 10346. doi: 10.1021/acs.chemrev.5b00703
[2]	Wan, X. K.; Cheng, X. L.; Tang, Q.; Han, Y. Z.; Hu, G.; Jiang, D. E.; Wang, Q. M. J. Am. Chem. Soc. 2017, 139, 9451. doi: 10.1021/jacs.7b04622
[3]	Shen, Y. L.; Jin, J. L.; Duan, G. X.; Xie, Y. P.; Lu, X. Acta Chim. Sinica 2020, 78, 1255. (in Chinese) doi: 10.6023/A20070317
	( 沈扬林, 金俊玲, 段光雄, 谢云鹏, 卢兴, 化学学报, 2020, 78, 1255.) doi: 10.6023/A20070317
[4]	Su, Y. M.; Wang, Z.; Schein, S.; Tung, C. H.; Sun, D. Nat. Commun. 2020, 11, 3316. doi: 10.1038/s41467-020-17198-1
[5]	Edwards, A. J.; Dhayal, R. S.; Liao, P. K.; Liao, J. H.; Chiang, M. H.; Piltz, R. O.; Kahlal, S.; Saillard, J. Y.; Liu, C. W. Angew. Chem. Int. Ed. 2014, 53, 7214. doi: 10.1002/anie.v53.28
[6]	Deng, G.; Malola, S.; Yan, J.; Han, Y.; Yuan, P.; Zhao, C.; Yuan, X.; Lin, S.; Tang, Z.; Teo, B. K.; Hakkinen, H.; Zheng, N. Angew. Chem. Int. Ed. 2018, 57, 3421. doi: 10.1002/anie.201800327
[7]	Zhu, M.; Qian, H.; Meng, X.; Jin, S.; Wu, Z.; Jin, R. Nano Lett. 2011, 11, 3963. doi: 10.1021/nl202288j
[8]	Han, Z.; Dong, X. Y.; Luo, P.; Li, S.; Wang, Z. Y.; Zang, S. Q.; Mak, T. C.W. Sci. Adv. 2020, 6,eaay0107.
[9]	Song, Y.; Weng, S.; Li, H.; Yu, H.; Zhu, M. Inorg. Chem. 2019, 58, 7136. doi: 10.1021/acs.inorgchem.9b00547
[10]	He, W. M.; Zhou, Z.; Han, Z.; Li, S.; Zhou, Z.; Ma, L. F.; Zang, S. Q. Angew. Chem. Int. Ed. 2021, 60, 8505. doi: 10.1002/anie.v60.15
[11]	Kang, X.; Zhu, M. Z. Chem. Soc. Rev. 2019, 48, 2422. doi: 10.1039/c8cs00800k pmid: 30838373
[12]	Liu, H.; Hong, G.; Luo, Z.; Chen, J.; Chang, J.; Gong, M.; He, H.; Yang, J.; Yuan, X.; Li, L.; Mu, X.; Wang, J.; Mi, W.; Luo, J.; Xie, J.; Zhang, X. D. Adv. Mater. 2019, 31,e1901015.
[13]	Tang, Q.; Lee, Y.; Li, D. Y.; Choi, W.; Liu, C. W.; Lee, D.; Jiang, D. E. J. Am. Chem. Soc. 2017, 139, 9728. doi: 10.1021/jacs.7b05591
[14]	Chen, Y.; Liu, C.; Tang, Q.; Zeng, C.; Higaki, T.; Das, A.; Jiang, D. E.; Rosi, N. L.; Jin, R. J. Am. Chem. Soc. 2016, 138, 1482. doi: 10.1021/jacs.5b12094
[15]	Wu, Z. Acta Phys.-Chim. Sin. 2017, 33, 1930. (in Chinese)
	( 伍志鲲, 物理化学学报, 2017, 33, 1930.)
[16]	Zhang, Y.; Wu, M.; Wu, M.; Guo, L.; Cao, L.; Wu, H.; Zhang, X. Acta Chim. Sinica 2018, 76, 709. (in Chinese) doi: 10.6023/A18060225
	( 张燕燕, 武明豪, 武明杰, 国林沛, 曹琳, 吴虹仪, 张雪宁, 化学学报, 2018, 76, 709.) doi: 10.6023/A18060225
[17]	Yan, J.; Su, H.; Yang, H.; Malola, S.; Lin, S.; Hakkinen, H.; Zheng, N. J. Am. Chem. Soc. 2015, 137, 11880. doi: 10.1021/jacs.5b07186
[18]	Liao, L.; Wang, C.; Zhuang, S.; Yan, N.; Zhao, Y.; Yang, Y.; Li, J.; Deng, H.; Wu, Z. Angew. Chem. Int. Ed. 2020, 59, 731. doi: 10.1002/anie.v59.2
[19]	Jin, F. M.; Dong, H. W.; Zhao, Y.; Zhuang, S. L.; Liao, L. W.; Yan, N.; Gu, W. M.; Zha, J.; Yuan, J. Y.; Li, J.; Deng, H. T.; Gan, Z. B.; Yang, J. L.; Wu, Z. K. Acta Chim. Sinica 2020, 78, 407. doi: 10.6023/A20040134
[20]	Wang, Z. Y.; Wang, M. Q.; Li, Y. L.; Luo, P.; Jia, T. T.; Huang, R. W.; Zang, S. Q.; Mak, T. C.W. J. Am. Chem. Soc. 2018, 140, 1069. doi: 10.1021/jacs.7b11338
[21]	Dai, L.; Qin, Q.; Wang, P.; Zhao, X.; Hu, C.; Liu, P.; Qin, R.; Chen, M.; Ou, D.; Xu, C.; Mo, S.; Wu, B.; Fu, G.; Zhang, P.; Zheng, N. Sci. Adv. 2017, 3, e1701069. doi: 10.1126/sciadv.1701069
[22]	Gawande, M. B.; Goswami, A.; Felpin, F. X.; Asefa, T.; Huang, X.; Silva, R.; Zou, X.; Zboril, R.; Varma, R. S. Chem. Rev. 2016, 116, 3722. doi: 10.1021/acs.chemrev.5b00482 pmid: 26935812
[23]	Guo, Y.; Cao, F.; Lei, X.; Mang, L.; Cheng, S.; Song, J. Nanoscale 2016, 8, 4852. doi: 10.1039/C6NR00145A
[24]	Iyengar, P.; Huang, J.; De Gregorio, G. L.; Gadiyar, C.; Buonsanti, R. Chem. Commun. 2019, 55, 8796. doi: 10.1039/C9CC02522G
[25]	Kas, R.; Kortlever, R.; Milbrat, A.; Koper, M. T.; Mul, G.; Baltrusaitis, J. Phys. Chem. Chem. Phys. 2014, 16, 12194. doi: 10.1039/C4CP01520G
[26]	Lan, Y.; Xie, Y.; Chen, J.; Hu, Z.; Cui, D. Chem. Commun. 2019, 55, 8068. doi: 10.1039/C9CC02891A
[27]	Alayon, E. M.C.; Nachtegaal, M.; Bodi, A.; van Bokhoven, J. A. ACS Catal. 2013, 4, 16. doi: 10.1021/cs400713c
[28]	Yang, L.; Kinoshita, S.; Yamada, T.; Kanda, S.; Kitagawa, H.; Tokunaga, M.; Ishimoto, T.; Ogura, T.; Nagumo, R.; Miyamoto, A.; Koyama, M. Angew. Chem. Int. Ed. 2010, 49, 5348. doi: 10.1002/anie.v49:31
[29]	Gao, X.; Lu, Y.; Liu, M.; He, S.; Chen, W. J. Mater. Chem. C 2015, 3, 4050. doi: 10.1039/C5TC00246J
[30]	Jia, X.; Li, J.; Han, L.; Ren, J.; Yang, X.; Wang, E. ACS Nano 2012, 6, 3311. doi: 10.1021/nn3002455
[31]	Jia, X.; Yang, X.; Li, J.; Li, D.; Wang, E. Chem. Commun. 2014, 50, 237. doi: 10.1039/C3CC47771A
[32]	Yang, Z.; Zhang, X.; Shi, Y.; Long, C.; Zhang, B.; Yan, S.; Chang, L.; Tang, Z. Acta Chim. Sinica 2020, 78, 980. (in Chinese) doi: 10.6023/A20050165
	( 杨忠杰, 张小飞, 施亚男, 隆昶, 张彬灏, 闫书豪, 常琳, 唐智勇, 化学学报, 2020, 78, 980.) doi: 10.6023/A20050165
[33]	Cook, A. W.; Jones, Z. R.; Wu, G.; Scott, S. L.; Hayton, T. W. J. Am. Chem. Soc. 2018, 140, 394. doi: 10.1021/jacs.7b10960
[34]	Han, B. L.; Liu, Z.; Feng, L.; Wang, Z.; Gupta, R. K.; Aikens, C. M.; Tung, C. H.; Sun, D. J. Am. Chem. Soc. 2020, 142, 5834. doi: 10.1021/jacs.0c01053
[35]	Nguyen, D.; Jones, Z. R.; Leto, D. F.; Wu, G.; Scott, S. L.; Hayton, T. W. Chem. Mater. 2016, 28, 8385. doi: 10.1021/acs.chemmater.6b03879
[36]	Xie, Y. -P.; Wen, J. -B.; Pan, C. -W.; Duan, G. -X.; Li, L. -Y.; Lu, X. Cryst. Growth Des. 2019, 19, 5791. doi: 10.1021/acs.cgd.9b00803
[37]	Yuan, P.; Chen, R.; Zhang, X.; Chen, F.; Yan, J.; Sun, C.; Ou, D.; Peng, J.; Lin, S.; Tang, Z.; Teo, B. K.; Zheng, L. S.; Zheng, N. Angew. Chem. Int. Ed. 2019, 58, 835. doi: 10.1002/anie.v58.3
[38]	Zhang, M. M.; Dong, X. Y.; Wang, Z. Y.; Li, H. Y.; Li, S. J.; Zhao, X.; Zang, S. Q. Angew. Chem. Int. Ed. 2020, 59, 10052. doi: 10.1002/anie.v59.25
[39]	Anzlovar, A.; Orel, Z. C.; Zigon, M. J. Eur. Ceram. Soc. 2007, 27, 987. doi: 10.1016/j.jeurceramsoc.2006.04.131
[40]	Wei, W.; Lu, Y.; Chen, W.; Chen, S. J. Am. Chem. Soc. 2011, 133, 2060. doi: 10.1021/ja109303z
[41]	Kawasaki, H.; Kosaka, Y.; Myoujin, Y.; Narushima, T.; Yonezawa, T.; Arakawa, R. Chem. Commun. 2011, 47, 7740. doi: 10.1039/c1cc12346g
[42]	Lu, Y.; Wei, W.; Chen, W. Chin. Sci. Bull. 2012, 57, 41. doi: 10.1007/s11434-011-4896-y
[43]	Khatun, E.; Bodiuzzaman, M.; Sugi, K. S.; Chakraborty, P.; Paramasivam, G.; Dar, W. A.; Ahuja, T.; Antharjanam, S.; Pradeep, T. ACS Nano 2019, 13, 5753. doi: 10.1021/acsnano.9b01189 pmid: 31017759
[44]	Han, H.; Yao, Y.; Bhargava, A.; Wei, Z.; Tang, Z.; Suntivitch, J.; Voznyy, O.; Robinson, R. D. J. Am. Chem. Soc. 2020, 142, 14495. doi: 10.1021/jacs.0c04764
[45]	Liu, M.; Liu, R.; Chen, W. Biosens. Bioelectron. 2013, 45, 206. doi: 10.1016/j.bios.2013.02.010
[46]	Xu, F.; Deng, M.; Li, G.; Chen, S.; Wang, L. Electrochim. Acta 2013, 88, 59. doi: 10.1016/j.electacta.2012.10.070

原子级结构精确Cu₁₃团簇的光致发光和电化学传感研究

Photoluminescence and Electrochemical Sensing of Atomically Precise Cu₁₃ Cluster

RichHTML

PDF

Supporting Info.

Knowledge

Abstract

Cite this article

share this article

Fig. & Tab. 4

References 46

Related Articles 15

Recommended Articles

Metrics

Comments

[1]	Huimin Chen, Long Wang, Pan Zhang, Xilin Bai, Guojun Zhou. Investigation on Photoluminescence and Mechanoluminescence of Single Tb^3＋-doped Intense Green Phosphor [J]. Acta Chimica Sinica, 2023, 81(7): 771-776.
[2]	Shaoqin Zhang, Meiqing Li, Zhongjun Zhou, Zexing Qu. Theoretical Study on the Multiple Resonance Thermally Activated Delayed Fluorescence Process [J]. Acta Chimica Sinica, 2023, 81(2): 124-130.
[3]	Huarun Liang, Haoxuan Ma, Xinrong Duan, Jie Yu, Haomin Wang, Shuo Li, Mengjia Zhu, Aibing Chen, Hui Zheng, Yingying Zhang. Flexible Electrochemical Sensors and Their Applications in Noninvasive Medical Detection^★ [J]. Acta Chimica Sinica, 2023, 81(10): 1402-1419.
[4]	Wentao Wang, Gaochong Zhao, Liu Yang, Yicheng Zhou, Liming Ding. Study on Multimodal Color-switching Anti-counterfeiting Based on Magnetically Responsive Photonic Crystals and Quantum Dots [J]. Acta Chimica Sinica, 2022, 80(12): 1576-1582.
[5]	Daolan Xu, Ying Yang, Wentao Fan, Zongbing He, Jiafeng Zou, Lei Feng, Man-Bo Li, Zhikun Wu. Single, Self-Born RP-Au-PR Motif Boosts 19-Fold Photoluminescence Quantum Yield of Metal Nanocluster [J]. Acta Chimica Sinica, 2022, 80(1): 1-6.
[6]	Jin Fengming, Dong Hongwei, Zhao Yan, Zhuang Shengli, Liao Lingwen, Yan Nan, Gu Wanmiao, Zha Jun, Yuan Jinyun, Li Jin, Deng Haiteng, Gan Zibao, Yang Jinlong, Wu Zhikun. Module Replacement of Gold Nanoparticles by a Pseudo-AGR Process [J]. Acta Chimica Sinica, 2020, 78(5): 407-411.
[7]	Xu Weigao, Zhao Yanyuan, Shen Chao, Zhang Jun, Xiong Qihua. Phonon-assisted Upconversion Photoluminescence in Monolayer MoSe₂ and WSe₂ [J]. Acta Chim. Sinica, 2015, 73(9): 959-964.
[8]	Shen Cheng, Zhang Jing, Shi Dongxia, Zhang Guangyu. Photoluminescence Enhancement in Monolayer Molybdenum Disulfide by Annealing in Air [J]. Acta Chim. Sinica, 2015, 73(9): 954-958.
[9]	Yu Xiaowen, Sheng Kaixuan, Chen Ji, Li Chun, Shi Gaoquan. Electrochemical Biosensing Based on Graphene Modified Electrodes [J]. Acta Chimica Sinica, 2014, 72(3): 319-332.
[10]	Wang Xi, Han Yide, Hao Suqin, Yu Jihong, Xu Ruren. Microwave Synthesis, Characterization and Properties of Lanthanide Phosphites Gd_xTb₂_-x(HPO₃)₃(H₂O)₂(0≤x≤2) [J]. Acta Chimica Sinica, 2012, 70(13): 1496-1500.
[11]	Zhang Jinli, Zhao Liping, Luo Xuan, Du Kai. Synthesis and Spectra Analyses of Eu(III) Binary Complexes with Polycarboxylic Acid [J]. Acta Chimica Sinica, 2012, 0(05): 679-682 .
[12]	DU Yan-Rong, JIAO Huan, HE Di-Ping. Hydrothermal Synthesis and Luminescence of AgGd_0.9Eu_0.1(WO₄)₂Phosphor [J]. Acta Chimica Sinica, 2011, 69(21): 2550-2554.
[13]	XIE Jin-Song, WU Qing-Sheng. One-pot Glycine-hydrothermal Fabrication of NdOHCO₃ Nanodisks and Their Three-dimensional Architectures with Luminescence Property [J]. Acta Chimica Sinica, 2011, 69(16): 1865-1873.
[14]	. Synthesis of Aligned ZnO Submicron Rod Arrays by Heating Zinc Foil Covered with ZnCl2 Solution [J]. Acta Chimica Sinica, 2009, 67(13): 1515-1522.
[15]	LI Li^1,2 ;YANG He-Qing*^,1 ;YU Jie ;JIAO Hua ZHANG Jian-Ying; ZHANG Rui-Gang; MA Jun-Hu^{1 . Controlled Synthesis and Photoluminescence of ZnO Nanosheet-based Microspheres and Layered assemblies [J]. Acta Chimica Sinica, 2008, 66(3): 335-342.}

原子级结构精确Cu13团簇的光致发光和电化学传感研究