AI Chat Paper
Note: Please note that the following content is generated by AMiner AI. SciOpen does not take any responsibility related to this content.
{{lang === 'zh_CN' ? '文章概述' : 'Summary'}}
{{lang === 'en_US' ? '中' : 'Eng'}}
Chat more with AI
Powered by AMiner. Clicking this button will take you away from SciOpen.
Home Nano Research Article
Article Link
Cite
EndNote(RIS) BibTeX
Collect
Submit Manuscript
Show Outline
Outline
Show full outline
Hide outline
Outline
Show full outline
Hide outline
Research Article

Three-stage alloying of [Ag44(p-MBA)30]4− cluster with [Au2(p-NTP)2Cl]−

Baoyu Huang, Xiaomei Zhao, Yong Pei( )
Department of Chemistry, Key Laboratory of Environmentally Friendly Chemistry and Applications of Ministry of Education, Key Laboratory for Green Organic Synthesis and Application of Hunan Province, Xiangtan University, Xiangtan 411105, China
Show Author Information

Graphical Abstract

The density functional theory (DFT) calculation results demonstrated that the metal exchange proceeded via different mechanisms at different reaction stages. In reaction stages I and II, the metal exchange proceeded via formation of a dianionic [Ag44(p-MBA)30]4−-[Au2(p-NTP)2Cl]− intermediate and then broke and recombined with the ligand-shell. In stage III, the diffusion of Au(I) to icosahedral Ag12-core (stage III) proceeded via a motif catalyzed heterometal atom diffusion mechanism.

Abstract

Precise control of alloying sites has long been a challenge, yet little has been achieved in the atomic-level manipulation of metallic nanomaterials. This study reported a three-stage metal and motif exchange mechanism of alloying reaction of an atomically precise ligand-protected [Ag44(p-MBA)30]4− (p-MBA = para-mercaptobenzoic acid) cluster with [Au2(p-NTP)2Cl]− (p-MBA = para-mercaptobenzoic acid). During the first stage (Stage I), an exchange of ligand-shell metal atoms took place. During the second stage (Stage II), the motif exchanged on the [AuAg43(p-MBA)30]4− cluster. During the third stage (Stage III), the Au(I) atom in the ligand-shell was swapped with a Ag(0) atom of the icosahedral Ag12-core. The density functional theory (DFT) calculation results demonstrated that the metal exchange proceeded via different mechanisms at the different reaction stages. In reaction Stages I and II, the metal exchange proceeded via formation of a dianionic [Ag44(p-MBA)30]4−-[Au2(p-NTP)2Cl]− intermediate and then broke and recombined with the ligand-shell. In Stage III, the diffusion of the Au(I) to icosahedral Ag12-core (Stage III) was proceeded via a motif catalyzed heterometal atom diffusion mechanism. We hope that this work will provide a new perspective for the precise control of alloy position in alloyed nanomaterials.

Keywords

metal clusteralloying mechanismdensity functional theory (DFT) calculationsmetal exchange

Electronic Supplementary Material

Download File(s)
12274_2022_4364_MOESM1_ESM.pdf (1.5 MB)

References

1

Lin, X. Z.; Ma, W. G.; Sun, K. J.; Sun, B.; Fu, X. M.; Ren, X. Q.; Liu, C.; Huang, J. H. [AuAg26(SR)18S]− nanocluster: Open shell structure and high faradaic efficiency in electrochemical reduction of CO2 to CO. J. Phys. Chem. Lett. 2021, 12, 552–557.
Crossref Google Scholar
2

Qin, Z. X.; Sharma, S.; Wan, C. Q.; Malola, S.; Xu, W. W.; Häkkinen, H.; Li, G. A. Homoleptic alkynyl-ligated [Au13Ag16L24]3− cluster as a catalytically active eight-electron superatom. Angew. Chem., Int. Ed. 2021, 60, 970–975.
Crossref Google Scholar
3

Cai, X.; Saranya, G.; Shen, K. Q.; Chen, M. Y.; Si, R.; Ding, W. P.; Zhu, Y. Reversible switching of catalytic activity by shuttling an atom into and out of gold nanoclusters. Angew. Chem., Int. Ed. 2019, 58, 9964–9968.
Crossref Google Scholar
4

Wu, Z. L.; Mullins, D. R.; Allard, L. F.; Zhang, Q. F.; Wang, L. S. CO Oxidation over ceria supported Au22 nanoclusters: Shape effect of the support. Chin. Chem. Lett. 2018, 29, 795–799.
Crossref Google Scholar
5

Song, Y. B.; Li, Y. W.; Zhou, M.; Liu, X.; Li, H.; Wang, H.; Shen, Y. H.; Zhu, M. Z.; Jin, R. C. Ultrabright Au@Cu14 nanoclusters: 71.3% phosphorescence quantum yield in non-degassed solution at room temperature. Sci. Adv. 2021, 7, eabd2091.
Crossref Google Scholar
6

Liu, X.; Saranya, G.; Huang, X. Y.; Cheng, X. L.; Wang, R.; Chen, M. Y.; Zhang, C. F.; Li, T.; Zhu, Y. Ag2Au50(PET)36 nanocluster: Dimeric assembly of Au25(PET)18 enabled by silver atoms. Angew. Chem., Int. Ed. 2020, 59, 13941–13946.
Crossref Google Scholar
7

Xie, Y. S.; Zhang, N.; Tang, Z. R.; Anpo, M.; Xu, Y. J. Tip-grafted Ag-ZnO nanorod arrays decorated with Au clusters for enhanced photocatalysis. Catal. Today 2020, 340, 121–127.
Crossref Google Scholar
8

Posha, B.; Nambiar, S. R.; Sandhyarani, N. Gold atomic cluster mediated electrochemical aptasensor for the detection of lipopolysaccharide. Biosens. Bioelectron. 2018, 101, 199–205.
Crossref Google Scholar
9

Zhou, R. H.; Li, Y. Q.; Tian, Y. Y.; Sun, Q.; Deng, P. C.; Wu, L.; Hou, X. D. Simple fluorescence sensing of extreme acidity based on inner filter effect of ascorbic acid to fluorescent Au nanoclusters. Nanoscale 2017, 9, 10167–10172.
Crossref Google Scholar
10

Zheng, K. Y.; Xie, J. P. Composition-dependent antimicrobial ability of full-spectrum AuxAg25-x alloy nanoclusters. ACS Nano 2020, 14, 11533–11541.
Crossref Google Scholar
11

Zhang, P.; Zhai, J.; Gao, X. Y.; Zhao, H. K.; Su, W. Y.; Zhao, L. N. Targeted peptide-Au cluster binds to epidermal growth factor receptor (EGFR) in both active and inactive states: A clue for cancer inhibition through dual pathways. Sci. Bull. 2018, 63, 349–355.
Crossref Google Scholar
12

Zhang, H.; Liu, H.; Tian, Z. Q.; Lu, D.; Yu, Y.; Cestellos-Blanco, S.; Sakimoto, K. K.; Yang, P. D. Bacteria photosensitized by intracellular gold nanoclusters for solar fuel production. Nat. Nanotechnol. 2018, 13, 900–905.
Crossref Google Scholar
13

Wei, X.; Kang, X.; Duan, T. F.; Li, H.; Wang, S. X.; Pei, Y.; Zhu, M. Z. [Au16Ag43H12(SPhCl2)34]5−: An Au-Ag alloy nanocluster with 12 hydrides and its enlightenment on nanocluster structural evolution. Inorg. Chem. 2021, 60, 11640–11647.
Crossref Google Scholar
14

Zou, X. J.; Li, Y. F.; Jin, S.; Kang, X.; Wei, X.; Wang, S. X.; Meng, X. M.; Zhu, M. Z. Doping copper atoms into the nanocluster kernel: Total structure determination of [Cu30Ag61(SAdm)38S3](BPh4). J. Phys. Chem. Lett. 2020, 11, 2272–2276.
Crossref Google Scholar
15

Qin, Z. X.; Zhang, J. W.; Wan, C. Q.; Liu, S.; Abroshan, H.; Jin, R. C.; Li, G. Atomically precise nanoclusters with reversible isomeric transformation for rotary nanomotors. Nat. Commun. 2020, 11, 6019.
Crossref Google Scholar
16

Higaki, T.; Liu, C.; Morris, D. J.; He, G. Y.; Luo, T. Y.; Sfeir, M. Y.; Zhang, P.; Rosi, N. L.; Jin, R. C. Au130−xAgx nanoclusters with non-metallicity: A drum of silver-rich sites enclosed in a marks-decahedral cage of gold-rich sites. Angew. Chem., Int. Ed. 2019, 58, 18798–18802.
Crossref Google Scholar
17

Li, Y. F.; Zhou, M. M.; Jin, S.; Xiong, L.; Yuan, Q. Q.; Du, W. J.; Pei, Y.; Wang, S. X.; Zhu, M. Z. Total structural determination of [Au1Ag24(Dppm)3(SR)17]2+ comprising an open icosahedral Au1Ag12 core with six free valence electrons. Chem. Commun. 2019, 55, 6457–6460.
Crossref Google Scholar
18

Wan, X. K.; Cheng, X. L.; Tang, Q.; Han, Y. Z.; Hu, G. X.; Jiang, D. E.; Wang, Q. M. Atomically precise bimetallic Au19Cu30 nanocluster with an icosidodecahedral Cu30 shell and an alkynyl-Cu interface. J. Am. Chem. Soc. 2017, 139, 9451–9454.
Crossref Google Scholar
19

Bootharaju, M. S.; Kozlov, S. M.; Cao, Z.; Harb, M.; Maity, N.; Shkurenko, A.; Parida, M. R.; Hedhili, M. N.; Eddaoudi, M.; Mohammed, O. F. et al. Doping-induced anisotropic self-assembly of silver icosahedra in [Pt2Ag23Cl7(PPh3)10] nanoclusters. J. Am. Chem. Soc. 2017, 139, 1053–1056.
Crossref Google Scholar
20

Liu, X.; Yao, G.; Cheng, X. L.; Xu, J. Y.; Cai, X.; Hu, W. G.; Xu, W. W.; Zhang, C. F.; Zhu, Y. Cd-driven surface reconstruction and photodynamics in gold nanoclusters. Chem. Sci. 2021, 12, 3290–3294.
Crossref Google Scholar
21

Qin, Z. X.; Hu, S.; Han, W. H.; Li, Z. W.; Xu, W. W.; Zhang, J. J.; Li, G. Tailoring optical and photocatalytic properties by single-Ag-atom exchange in Au13Ag12(PPh3)10Cl8 nanoclusters. Nano Res. 2022, 15, 2971–2976.
Crossref Google Scholar
22

Fei, W. W.; Antonello, S.; Dainese, T.; Dolmella, A.; Lahtinen, M.; Rissanen, K.; Venzo, A.; Maran, F. Metal doping of Au25(SR)18− clusters: Insights and hindsights. J. Am. Chem. Soc. 2019, 141, 16033–16045.
Crossref Google Scholar
23

Yan, N.; Liao, L. W.; Yuan, J. Y.; Lin, Y. J.; Weng, L. H.; Yang, J. L.; Wu, Z. K. Bimetal doping in nanoclusters: Synergistic or counteractive? Chem. Mater. 2016, 28, 8240–8247.
Crossref Google Scholar
24

Jin, S.; Zhou, M. M.; Kang, X.; Li, X. W.; Du, W. J.; Wei, X.; Chen, S.; Wang, S. X.; Zhu, M. Z. Three-dimensional octameric assembly of icosahedral M13 units in [Au8Ag57(Dppp)4(C6H11S)32Cl2]Cl and its [Au8Ag55(Dppp)4(C6H11S)34][BPh4]2 derivative. Angew. Chem., Int. Ed. 2020, 59, 3891–3895.
Crossref Google Scholar
25

Niihori, Y.; Kikuchi, Y.; Kato, A.; Matsuzaki, M.; Negishi, Y. Understanding ligand-exchange reactions on thiolate-protected gold clusters by probing isomer distributions using reversed-phase high-performance liquid chromatography. ACS Nano 2015, 9, 9347–9356.
Crossref Google Scholar
26

Du, W. J.; Jin, S.; Xiong, L.; Chen, M.; Zhang, J.; Zou, X. J.; Pei, Y.; Wang, S. X.; Zhu, M. Z. Ag50(Dppm)6(SR)30 and its homologue AuAg50−x(Dppm)6(SR)30 alloy nanocluster: Seeded growth, structure determination, and differences in properties. J. Am. Chem. Soc. 2017, 139, 1618–1624.
Crossref Google Scholar
27

Chen, T.; Yang, S.; Chai, J. S.; Song, Y. B.; Fan, J. Q.; Rao, B.; Sheng, H. T.; Yu, H. Z.; Zhu, M. Z. crystallization-induced emission enhancement: A novel fluorescent Au-Ag bimetallic nanocluster with precise atomic structure. Sci. Adv. 2017, 3, e1700956.
Crossref Google Scholar
28

Wang, Z.; Senanayake, R.; Aikens, C. M.; Chen, W. M.; Tung, C. H.; Sun, D. Gold-doped silver nanocluster [Au3Ag38(SCH2Ph)24X5]2− (X = Cl or Br). Nanoscale 2016, 8, 18905–18911.
Crossref Google Scholar
29

Bootharaju, M. S.; Kozlov, S. M.; Cao, Z.; Harb, M.; Parida, M. R.; Hedhili, M. N.; Mohammed, O. F.; Bakr, O. M.; Cavallo, L.; Basset, J. -M. Directversus ligand-exchange synthesis of [PtAg28(BDT)12(TPP)4]4− Nanoclusters: Effect of a single-atom dopant on the optoelectronic and chemical properties. Nanoscale 2017, 9, 9529–9536.
Crossref Google Scholar
30

Dou, X. Y.; Yuan, X.; Yao, Q. F.; Luo, Z. T.; Zheng, K. Y.; Xie, J. P. Facile synthesis of water-soluble Au25−xAgx nanoclusters protected by mono- and bi-thiolate ligands. Chem. Commun. 2014, 50, 7459–7462.
Crossref Google Scholar
31

Wang, X Y.; Wang, S. S.; Qian, S. Y.; Liu, N. W.; Dou, X. Y.; Yuan, X. Mechanistic insights into the two-phase synthesis of heteroleptic Au nanoclusters. Nanoscale 2021, 13, 3512–3518.
Crossref Google Scholar
32

Dou, X. Y.; Wang, X. Y.; Qian, S. Y.; Liu, N. W.; Yuan, X. From understanding the roles of tetraoctylammonium bromide in the two-phase brust-schiffrin method to tuning the size of gold nanoclusters. Nanoscale 2020, 12, 19855–19860.
Crossref Google Scholar
33

Yang, S.; Chai, J. S.; Song, Y. B.; Fan, J. Q.; Chen, T.; Wang, S. X.; Yu, H. Z.; Li, X. W.; Zhu, M. Z. In situ two-phase ligand exchange: A new method for the synthesis of alloy nanoclusters with precise atomic structures. J. Am. Chem. Soc. 2017, 139, 5668–5671.
Crossref Google Scholar
34

Das, A.; Li, T.; Nobusada, K.; Zeng, C. J.; Rosi, N. L.; Jin, R. C. Nonsuperatomic [Au23(SC6H11)16]− nanocluster featuring bipyramidal Au15 kernel and trimeric Au3(SR)4 motif. J. Am. Chem. Soc. 2013, 135, 18264–18267.
Crossref Google Scholar
35

Kang, X.; Wei, X.; Wang, S. X.; Zhu, M. Z. An insight, at the atomic level, into the polarization effect in controlling the morphology of metal nanoclusters. Chem. Sci. 2021, 12, 11080–11088.
Crossref Google Scholar
36

Pan, P. Y.; Zhou, C. J.; Li, H.; Zhu, C.; Chen, C.; Kang, X.; Zhu, M. Z. Reversible transformation between Au14Ag8 and Au14Ag4 nanoclusters. Nanoscale 2021, 13, 17162–17167.
Crossref Google Scholar
37

Kang, X.; Huang, L.; Liu, W.; Xiong, L.; Pei, Y.; Sun, Z. H.; Wang, S. X.; Wei, S. Q.; Zhu, M. Z. Reversible nanocluster structure transformation between face-centered cubic and icosahedral isomers. Chem. Sci. 2019, 10, 8685–8693.
Crossref Google Scholar
38

Sels, A.; Salassa, G.; Pollitt, S.; Guglieri, C.; Rupprechter, G.; Barrabés, N.; Bürgi, T. Structural investigation of the ligand exchange reaction with rigid dithiol on doped (Pt, Pd)Au25 Clusters. J. Phys. Chem. C 2017, 121, 10919–10926.
Crossref Google Scholar
39

Kothalawala, N.; Kumara, C.; Ferrando, R.; Dass, A. Au144−xPdx(SR)60 nanomolecules. Chem. Commun. 2013, 49, 10850–10852.
Crossref Google Scholar
40

Kumara, C.; Dass, A. (AuAg)144(SR)60 alloy nanomolecules. Nanoscale 2011, 3, 3064–3067.
Crossref Google Scholar
41

Neumaier, M.; Baksi, A.; Weis, P.; Schneider, E. K.; Chakraborty, P.; Hahn, H.; Pradeep, T.; Kappes, M. M. Kinetics of intercluster reactions between atomically precise noble metal clusters [Ag25(DMBT)18]− and [Au25(PET)18]− in room temperature solutions. J. Am. Chem. Soc. 2021, 143, 6969–6980.
Crossref Google Scholar
42

Baksi, A.; Schneider, E. K.; Weis, P.; Chakraborty, I.; Fuhr, O.; Lebedkin, S.; Parak, W. J.; Kappes, M. M. Linear size contraction of ligand protected Ag29 clusters by substituting Ag with Cu. ACS Nano 2020, 14, 15064–15070.
Crossref Google Scholar
43

Khatun, E.; Chakraborty, P.; Jacob, B. R.; Paramasivam, G.; Bodiuzzaman, M.; Dar, W. A.; Pradeep, T. Intercluster reactions resulting in silver-rich trimetallic nanoclusters. Chem. Mater. 2020, 32, 611–619.
Crossref Google Scholar
44

Krishnadas, K. R.; Ghosh, A.; Baksi, A.; Chakraborty, I.; Natarajan, G.; Pradeep, T. Intercluster reactions between Au25(SR)18 and Ag44(SR)30. J. Am. Chem. Soc. 2016, 138, 140–148.
Crossref Google Scholar
45

Krishnadas, K. R.; Baksi, A.; Ghosh, A.; Natarajan, G.; Pradeep, T. Manifestation of geometric and electronic shell structures of metal clusters in intercluster reactions. ACS Nano 2017, 11, 6015–6023.
Crossref Google Scholar
46

Chakraborty, I.; Pradeep, T. Atomically precise clusters of noble metals: Emerging link between atoms and nanoparticles. Chem. Rev. 2017, 117, 8208–8271.
Crossref Google Scholar
47

Li, Y. W.; Zhou, M.; Jin, R. C. Programmable metal nanoclusters with stomic precision. Adv. Mater. 2021, 33, 2006591.
Crossref Google Scholar
48

Kawawaki, T.; Imai, Y.; Suzuki, D.; Kato, S.; Kobayashi, I.; Suzuki, T.; Kaneko, R.; Hossain, S.; Negishi, Y. Atomically precise alloy nanoclusters. Chem. Eur. J. 2020, 26, 16150–16193.
Crossref Google Scholar
49

Kang, X.; Li, Y. W.; Zhu, M. Z.; Jin, R. C. Atomically precise alloy nanoclusters: Syntheses, structures, and properties. Chem. Soc. Rev. 2020, 49, 6443–6514.
Crossref Google Scholar
50

Pillay, M. N.; Van Zyl, W. E.; Liu, C. W. A construction guide for high-nuclearity (≥ 50 metal atoms) coinage metal clusters at the nanoscale: Bridging molecular precise constructs with the bulk material phase. Nanoscale 2020, 12, 24331–24348.
Crossref Google Scholar
51

Bootharaju, M. S.; Joshi, C. P.; Parida, M. R.; Mohammed, O. F.; Bakr, O. M. Templated atom-precise galvanic synthesis and structure elucidation of a [Ag24Au(SR)18]− nanocluster. Angew. Chem., Int. Ed. 2016, 128, 934–938.
Crossref Google Scholar
52

Zheng, K. Y.; Fung, V.; Yuan, X.; Jiang, D. E.; Xie, J. P. Real time monitoring of the dynamic intracluster diffusion of single gold atoms into silver nanoclusters. J. Am. Chem. Soc. 2019, 141, 18977–18983.
Crossref Google Scholar
53

Zhang, B.; Safonova, O. V.; Pollitt, S.; Salassa, G.; Sels, A.; Kazan, R.; Wang, Y. M.; Rupprechter, G.; Barrabés, N.; Bürgi, T. On the mechanism of rapid metal exchange between thiolate-protected gold and gold/silver clusters: A time-resolved in situ XAFS study. Phys. Chem. Chem. Phys. 2018, 20, 5312–5318.
Crossref Google Scholar
54

Yao, Q. F.; Feng, Y.; Fung, V.; Yu, Y.; Jiang, D. E.; Yang, J.; Xie, J. P. Precise control of alloying sites of bimetallic nanoclusters via surface motif exchange reaction. Nat. Commun. 2017, 8, 1555.
Crossref Google Scholar
55

Yang, H. Y.; Wang, Y.; Huang, H. Q.; Gell, L.; Lehtovaara, L.; Malola, S.; Häkkinen, H.; Zheng, N. F. All-thiol-stabilized Ag44 and Au12Ag32 nanoparticles with single-crystal structures. Nat. Commun. 2013, 4, 2422.
Crossref Google Scholar
56

Gell, L.; Häkkinen, H. Theoretical analysis of the M12Ag32(SR)404− and X@M12Ag32(SR)304− nanoclusters (M = Au, Ag; X = H, Mn). J. Phys. Chem. C 2015, 119, 10943–10948.
Crossref Google Scholar
57

Morera-Boado, C.; Hidalgo, F.; Noguez, C. Stability and electronic charge compensation of [Ag44−xAux(SR)30]4− clusters. J. Phys. Chem. C 2019, 123, 26633–26643.
Crossref Google Scholar
58

Tang, L.; Kang, X.; Wang, X. Y.; Zhang, X. H.; Yuan, X.; Wang, S. X. Dynamic metal exchange between a metalloid silver cluster and silver(I) thiolate. Inorg. Chem. 2021, 60, 3037–3045.
Crossref Google Scholar
59

Desireddy, A.; Conn, B. E.; Guo, J.; Yoon, B.; Barnett, R. N.; Monahan, B. M.; Kirschbaum, K.; Griffith, W. P.; Whetten, R. L.; Landman, U. et al. Ultrastable silver nanoparticles. Nature 2013, 501, 399–402.
Crossref Google Scholar
60

Perdew, J. P.; Burke, K.; Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 1996, 77, 3865–3868.
Crossref Google Scholar
61

Delley, B. An all-electron numerical method for solving the local density functional for polyatomic molecules. J. Chem. Phys. 1990, 92, 508–517.
Crossref Google Scholar
62

Delley, B. From molecules to solids with the DMol3 approach. J. Chem. Phys. 2000, 113, 7756–7764.
Crossref Google Scholar
63

Perdew, J. P.; Levy, M. Physical content of the exact Kohn-sham orbital energies: Band gaps and derivative discontinuities. Phys. Rev. Lett. 1983, 51, 1884–1887.
Crossref Google Scholar
64

Bučko, T.; Lebègue, S.; Hafner, J.; Ángyán, J. G. Tkatchenko-scheffler Van der Waals correction method with and without self-consistent screening applied to solids. Phys. Rev. B. 2013, 87, 064110.
Crossref Google Scholar
65

Yang, H. Y.; Wang, Y.; Yan, J. Z.; Chen, X.; Zhang, X.; Häkkinen, H.; Zheng, N. F. Structural evolution of atomically precise thiolated bimetallic [Au12+nCu32(SR)30+n]4−(n= 0, 2, 4, 6) Nanoclusters. J. Am. Chem. Soc. 2014, 136, 7197–7200.
Crossref Google Scholar
Nano Research
Volume 15 Issue 8,
August 2022
Pages 7742-7751
DOI: 10.1007/s12274-022-4364-9
Cite this article:
Huang B, Zhao X, Pei Y. Three-stage alloying of [Ag44(p-MBA)30]4− cluster with [Au2(p-NTP)2Cl]−. Nano Research, 2022, 15(8): 7742-7751. https://doi.org/10.1007/s12274-022-4364-9
Topics:
Density functional theory

863

Views

0

Crossref

0

Web of Science

0

Scopus

0

CSCD

Altmetrics
Received: 03 February 2022
Revised: 22 March 2022
Accepted: 25 March 2022
Published: 31 May 2022
© Tsinghua University Press 2022
Return