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Nano Research 2023, 16(8): 10756-10762 https://doi.org/10.1007/s12274-023-5755-2
Research Article | Issue | Published: 15 June 2023

Atomically precise coreless AuCu bimetallic nanoclusters for Ullmann C–O coupling

Show Author's Information Yapei Yun1,§,  Lin Li1,§,  Manman Zhou1,  Meng Li1,  Ningning Sun1,  Haifeng Li1,  Shan Jin1,  Chunshan Zuo2( ),  Hongting Sheng1( ),  Manzhou Zhu1( )
School of Materials Science and Engineering, Anhui Province Key Laboratory of Chemistry for Inorganic/Organic Hybrid Functionalized Materials, Institutes of Physical Science and Information Technology, Department of Chemistry and Center for Atomic Engineering of Advanced Materials, Key Laboratory of Structure and Functional Regulation of Hybrid Materials of the Ministry of Education, Anhui University, Hefei 230601, China
College of Pharmaceutical and Chemical Enginnering, Huanghuai University, Zhumadian 463000, China

§ Yapei Yun and Lin Li contributed equally to this work.

Keywords:
bimetallic catalysts, coreless nanoclusters, metal synergy, Ullmann C–O coupling
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Nanocatalysts
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Yun Y, Li L, Zhou M, et al. Atomically precise coreless AuCu bimetallic nanoclusters for Ullmann C–O coupling. Nano Research, 2023, 16(8): 10756-10762. https://doi.org/10.1007/s12274-023-5755-2
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Abstract Full text Electronic supplementary material About this article

Bimetallic nanocluster with atomic precision has gained widespread attention due to its unique synergism. The coreless Au4Cu5 bimetallic nanoclusters were selected as models to explore the relationship between their microstructure and performance, and compare with the coreless monometallic nanoclusters, core–shell nanoclusters, and single atom catalyst (SAC). The experimental results show that the coreless bimetallic nanocluster catalyst Au4Cu5/activated carbon (AC) exhibits high activity and stability in the Ullmann C–O coupling reaction, much higher than coreless monometallic nanoclusters (Au11/AC and Cu11/AC), core–shell nanoclusters (Au25/AC, Cu25/AC, and Au1Cu24/AC), and single atom catalysts (Au SAC and Cu SAC). Moreover, the coreless Au4Cu5/AC catalyst efficiently catalyzed the Ullmann C–O coupling of benzyl alcohol for the first time. This structure–activity relationship was successfully extended to other coreless bimetallic systems, such as Au4Cu4/AC nanocluster, and it is expected to provide new insights for the design of bimetallic catalysts with well-defined performance.


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Electronic supplementary material
About this article

Atomically precise coreless AuCu bimetallic nanoclusters for Ullmann C–O coupling

Show Author's information Yapei Yun1,§, Lin Li1,§, Manman Zhou1, Meng Li1, Ningning Sun1, Haifeng Li1, Shan Jin1, Chunshan Zuo2( ), Hongting Sheng1( ), Manzhou Zhu1( )
School of Materials Science and Engineering, Anhui Province Key Laboratory of Chemistry for Inorganic/Organic Hybrid Functionalized Materials, Institutes of Physical Science and Information Technology, Department of Chemistry and Center for Atomic Engineering of Advanced Materials, Key Laboratory of Structure and Functional Regulation of Hybrid Materials of the Ministry of Education, Anhui University, Hefei 230601, China
College of Pharmaceutical and Chemical Enginnering, Huanghuai University, Zhumadian 463000, China

§ Yapei Yun and Lin Li contributed equally to this work.

Abstract

Bimetallic nanocluster with atomic precision has gained widespread attention due to its unique synergism. The coreless Au4Cu5 bimetallic nanoclusters were selected as models to explore the relationship between their microstructure and performance, and compare with the coreless monometallic nanoclusters, core–shell nanoclusters, and single atom catalyst (SAC). The experimental results show that the coreless bimetallic nanocluster catalyst Au4Cu5/activated carbon (AC) exhibits high activity and stability in the Ullmann C–O coupling reaction, much higher than coreless monometallic nanoclusters (Au11/AC and Cu11/AC), core–shell nanoclusters (Au25/AC, Cu25/AC, and Au1Cu24/AC), and single atom catalysts (Au SAC and Cu SAC). Moreover, the coreless Au4Cu5/AC catalyst efficiently catalyzed the Ullmann C–O coupling of benzyl alcohol for the first time. This structure–activity relationship was successfully extended to other coreless bimetallic systems, such as Au4Cu4/AC nanocluster, and it is expected to provide new insights for the design of bimetallic catalysts with well-defined performance.

Keywords: bimetallic catalysts, coreless nanoclusters, metal synergy, Ullmann C–O coupling

References(46)

[1]

Jin, R. C.; Li, G.; Sharma, S.; Li, Y. W.; Du, X. S. Toward active-site tailoring in heterogeneous catalysis by atomically precise metal nanoclusters with crystallographic structures. Chem. Rev. 2021, 121, 567–648.
DOI Google Scholar
[2]

Chakraborty, I.; Pradeep, T. Atomically precise clusters of noble metals: Emerging link between atoms and nanoparticles. Chem. Rev. 2017, 117, 8208–8271.
DOI Google Scholar
[3]

Sun, Y. N.; Cai, X.; Hu, W. G.; Liu, X.; Zhu, Y. Electrocatalytic and photocatalytic applications of atomically precise gold-based nanoclusters. Sci. China Chem. 2021, 64, 1065–1075.
DOI Google Scholar
[4]

Du, Y. X.; Sheng, H. T.; Astruc, D.; Zhu. M. Z. Atomically precise noble metal nanoclusters as efficient catalysts: A bridge between structure and properties. Chem. Rev. 2020, 120, 526–622.
DOI Google Scholar
[5]

Liu, X.; Astruc, D. Atomically precise copper nanoclusters and their applications. Coord. Chem. Rev. 2018, 359, 112–126.
DOI Google Scholar
[6]

Kawawaki, T.; Kataoka, Y.; Hirata, M.; Iwamatsu, Y.; Hossain, S.; Negishi, Y. Toward the creation of high-performance heterogeneous catalysts by controlled ligand desorption from atomically precise metal nanoclusters. Nanoscale Horiz. 2021, 6, 409–448.
DOI Google Scholar
[7]

Meng, G.; Cao, H. J.; Wei, T. R.; Liu, Q.; Fu, J. T.; Zhang, S. S.; Luo, J.; Liu, X. J. Highly dispersed Ru clusters toward an efficient and durable hydrogen oxidation reaction. Chem. Commun. 2022, 58, 11839–11842.
DOI Google Scholar
[8]

Liu, W. X.; Feng, J. X.; Wei, T. R.; Liu, Q.; Zhang, S. S.; Luo, Y.; Luo, J.; Liu, X. J. Active-site and interface engineering of cathode materials for aqueous Zn-gas batteries. Nano Res. 2023, 16, 2325–2346.
DOI Google Scholar
[9]

Gao, S. S.; Wei, T. R.; Sun, J. Q.; Liu, Q.; Ma, D.; Liu, W. X.; Zhang, S. S.; Luo, J.; Liu, X. J. Atomically dispersed metal-based catalysts for Zn-CO2 batteries. Small Struct. 2022, 3, 2200086.
DOI Google Scholar
[10]

Zhang, W. Q.; Qin, X. H.; Wei, T. R.; Liu, Q.; Luo, J.; Liu, X. J. Single atomic cerium sites anchored on nitrogen-doped hollow carbon spheres for highly selective electroreduction of nitric oxide to ammonia. J. Colloid Interface Sci. 2023, 638, 650–657.
DOI Google Scholar
[11]

Chai, J. S.; Yang, S.; Lv, Y.; Chong, H. B.; Yu, H. Z.; Zhu, M. Z. Exposing the delocalized Cu–S π bonds on the Au24Cu6(SPhtBu)22 nanocluster and its application in ring-opening reactions. Angew. Chem., Int. Ed. 2019, 58, 15671–15674.
DOI Google Scholar
[12]

Sun, L. L.; Yun, Y. P.; Sheng, H. T.; Du, Y. X.; Ding, Y. M.; Wu, P.; Li, P.; Zhu, M. Z. Rational encapsulation of atomically precise nanoclusters into metal–organic frameworks by electrostatic attraction for CO2 conversion. J. Mater. Chem. A 2018, 6, 15371–15376.
DOI Google Scholar
[13]

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.
DOI Google Scholar
[14]

Liu, Y. Y.; Chai, X. Q.; Cai, X.; Chen, M. Y.; Jin, R. C.; Ding, W. P.; Zhu, Y. Central doping of a foreign atom into the silver cluster for catalytic conversion of CO2 toward C–C bond formation. Angew. Chem., Int. Ed. 2018, 57, 9775–9779.
DOI Google Scholar
[15]

Sun, L. L.; Shen, K. Q.; Sheng, H. T.; Yun, Y. P.; Song, Y. B.; Pan, D. H.; Du, Y. X.; Yu, H. Z.; Chen, M. Y.; Zhu, M. Z. Au-Ag synergistic effect in CF3-ketone alkynylation catalyzed by precise nanoclusters. J. Catal. 2019, 378, 220–225.
DOI Google Scholar
[16]

Chen, S.; Higaki, T.; Ma, H. D.; Zhu, M. Z.; Jin, R. C.; Wang, G. L. Inhomogeneous quantized single-electron charging and electrochemical-optical insights on transition-sized atomically precise gold nanoclusters. ACS Nano 2020, 14, 16781–16790.
DOI Google Scholar
[17]

Tang, J.; Liu, C.; Zhu, C. Y.; Sun, K. J.; Wang, H.; Yin, W.; Xu, C. T.; Li, Y.; Wang, W. G.; Wang, L. et al. High-nuclearity and thiol protected core–shell [Cu75(S-Adm)32]2+: Distorted octahedra fixed to Cu15 core via strong cuprophilic interactions. Nanoscale 2023, 15, 2843–2848.
DOI Google Scholar
[18]

Li, S. T.; Nagarajan, A. V.; Du, X. S.; Li, Y. W.; Liu, Z. Y.; Kauffman, D. R.; Mpourmpakis, G.; Jin, R. C. Dissecting critical factors for electrochemical CO2 reduction on atomically precise Au nanoclusters. Angew. Chem., Int. Ed. 2022, 61, e202211771.
DOI Google Scholar
[19]

Zhou, Y.; Liao, L. W.; Zhuang, S. L.; Zhao, Y.; Gan, Z. B.; Gu, W. M.; Li, J.; Deng, H. T.; Xia, N.; Wu, Z. K. Traceless removal of two kernel atoms in a gold nanocluster and its impact on photoluminescence. Angew. Chem., Int. Ed. 2021, 60, 8668–8672.
DOI Google Scholar
[20]

Bootharaju, M. S.; Lee, S.; Deng, G. C.; Malola, S.; Baek, W.; Häkkinen, H.; Zheng, N. F.; Hyeon, T. Ag44(EBT)26(TPP)4 nanoclusters with tailored molecular and electronic structure. Angew. Chem., Int. Ed. 2021, 60, 9038–9044.
DOI Google Scholar
[21]

Zhou, M. M.; Jin, S.; Wei, X.; Yuan, Q. Q.; Wang, S. X.; Du, Y. X.; Zhu, M. Z. Reversible Cu-S motif transformation and Au4 distortion via thiol ligand exchange engineering. J. Phys. Chem. C 2020, 124, 7531–7538.
DOI Google Scholar
[22]

Yu, W.; Hu, D. Q.; Xiong, L.; Li, Y. F.; Kang, X.; Chen, S.; Wang, S. X.; Pei, Y.; Zhu, M. Z. Isomer structural transformation in Au-Cu alloy nanoclusters: Water ripple-like transfer of thiol ligands. Part. Part. Syst. Charact. 2019, 36, 1800494.
DOI Google Scholar
[23]

Hua, Y.; Huang, J. H.; Shao, Z. H.; Luo, X. M.; Wang, Z. Y.; Liu, J. Q.; Zhao, X. L.; Chen, X. Y.; Zang, S. Q. Composition-dependent enzyme mimicking activity and radiosensitizing effect of bimetallic clusters to modulate tumor hypoxia for enhanced cancer therapy. Adv. Mater. 2022, 34, 2203734.
DOI Google Scholar
[24]

Zhang, T. S.; Fei, W. W.; Li, N.; Zhang, Y.; Xu, C.; Luo, Q. Q.; Li, M. B. Open nitrogen site-induced kinetic resolution and catalysis of a gold nanocluster. Nano Lett. 2023, 23, 235–242.
DOI Google Scholar
[25]

Liu, L.; Nevado, C. Diaryl ether formation merging photoredox and nickel catalysis. Organometallics 2021, 40, 2188–2193.
DOI Google Scholar
[26]

Singh, V. V.; Singh, A. K. Nanoflowers of Cu1.8S: Free and decorated on graphene oxide (GO-Cu1.8S) as efficient and recyclable catalysts for C–O coupling. ACS Appl. Nano Mater. 2018, 1, 2164–2174.
DOI Google Scholar
[27]

Muto, K.; Okita, T.; Yamaguchi, J. Transition-metal-catalyzed denitrative coupling of nitroarenes. ACS Catal. 2020, 10, 9856–9871.
DOI Google Scholar
[28]

Wang, Y. B.; Guo, X. N.; Lü, M. Q.; Zhai, Z. Y.; Wang, Y. Y.; Guo, X. Y. Cu2O/SiC as efficient catalyst for Ullmann coupling of phenols with aryl halides. Chin. J. Catal. 2017, 38, 658–664.
DOI Google Scholar
[29]

Gorginpour, F.; Zali-Boeini, H. Synergistic effect of copper nanocrystals-nanoparticles incorporated in a porous organic polymer for the Ullmann C–O coupling reaction. Mol. Catal. 2021, 504, 111460.
DOI Google Scholar
[30]

Begum, T.; Mondal, M.; Borpuzari, M. P.; Kar, R.; Gogoi, P. K.; Bora, U. Palladium-on-carbon-catalyzed coupling of nitroarenes with phenol: Biaryl ether synthesis and evidence of an oxidative-addition-promoted mechanism. Eur. J. Org. Chem. 2017, 16, 3244–3248.
DOI Google Scholar
[31]

Du, Y. Y.; Yao, F.; Tuo, Y.; Cai, M. Z. Highly efficient heterogeneous copper-catalysed O-arylation of phenols by nitroarenes leading to diaryl ethers. J. Chem. Res. 2017, 41, 725–729.
DOI Google Scholar
[32]

Maity, T.; Bhunia, S.; Das, S.; Koner, S. Heterogeneous O-arylation of nitroarenes with substituted phenols over a copper immobilized mesoporous silica catalyst. RSC Adv. 2016, 6, 33380–33386.
DOI Google Scholar
[33]

Zhao, J. B.; Jin, R. C. Heterogeneous catalysis by gold and gold-based bimetal nanoclusters. Nano Today 2018, 18, 86–102.
DOI Google Scholar
[34]

Li, G.; Liu, C.; Lei, Y.; Jin, R. C. Au25 nanocluster-catalyzed Ullmann-type homocoupling reaction of aryl iodides. Chem. Commun. 2012, 48, 12005–12007.
DOI Google Scholar
[35]

Li, G.; Abroshan, H.; Liu, C.; Zhuo, S.; Li, Z. M.; Xie, Y.; Kim, H. J.; Rosi, N. L.; Jin, R. C. Tailoring the electronic and catalytic properties of Au25 nanoclusters via ligand engineering. ACS Nano 2016, 10, 7998–8005.
DOI Google Scholar
[36]

Das, A. K.; Mukherjee, S.; R, S. S.; Nair, A. S.; Bhandary, S.; Chopra, D.; Sanyal, D.; Pathak, B.; Mandal, S. Defects engineering on ceria and C–C coupling reactions using [Au11(PPh3)7I3] nanocluster: A combined experimental and theoretical study. ACS Nano 2020, 14, 16681–16688.
DOI Google Scholar
[37]

Liu, L. L.; Song, Y. B.; Chong, H. B.; Yang, S.; Xiang, J.; Jin, S.; Kang, X.; Zhang, J.; Yu, H. Z.; Zhu, M. Z. Size-confined growth of atom-precise nanoclusters in metal–organic frameworks and their catalytic applications. Nanoscale 2016, 8, 1407–1412.
DOI Google Scholar
[38]

Li, H.; Zhai, H. S.; Zhou, C. J.; Song, Y. B.; Ke, F.; Xu, W. W.; Zhu, M. Z. Atomically precise copper cluster with intensely near-infrared luminescence and its mechanism. J. Phys. Chem. Lett. 2020, 11, 4891–4896.
DOI Google Scholar
[39]

Zhu, M. Z.; Lanni, E.; Garg, N.; Bier, M. E.; Jin, R. C. Kinetically controlled, high-yield synthesis of Au25 clusters. J. Am. Chem. Soc. 2008, 130, 1138–1139.
DOI Google Scholar
[40]

Chen, A. L.; Kang, X.; Jin, S.; Du, W. J.; Wang, S. X.; Zhu, M. Z. Gram-scale preparation of stable hydride M@Cu24 (M = Au/Cu) nanoclusters. J. Phys. Chem. Lett. 2019, 10, 6124–6128.
DOI Google Scholar
[41]

Mishra, D.; Aldeek, F.; Lochner, E.; Palui, G.; Zeng, B. R.; Mackowski, S.; Mattoussi, H. Aqueous growth of gold clusters with tunable fluorescence using photochemically modified lipoic acid-based ligands. Langmuir, 2016, 32, 6445–6458.
DOI Google Scholar
[42]

Negishi, Y.; Nobusada, K.; Tsukuda, T. Glutathione-protected gold clusters revisited: Bridging the gap between gold(I)-thiolate complexes and thiolate-protected gold nanocrystals. J. Am. Chem. Soc. 2005, 127, 5261–5270.
DOI Google Scholar
[43]

Pieta, I. S.; Kadam, R. G.; Pieta, P.; Mrdenovic, D.; Nowakowski, R.; Bakandritsos, A.; Tomanec, O.; Petr, M.; Otyepka, M.; Kostecki, R. et al. The hallmarks of copper single atom catalysts in direct alcohol fuel cells and electrochemical CO2 fixation. Adv. Mater. Interfaces 2021, 8, 2001822.
DOI Google Scholar
[44]

Wei, S. J.; Li, A.; Liu, J. C.; Li, Z.; Chen, W. X.; Gong, Y.; Zhang, Q. H.; Cheong, W. C.; Wang, Y.; Zheng, L. R. et al. Direct observation of noble metal nanoparticles transforming to thermally stable single atoms. Nat. Nanotechnol. 2018, 13, 856–861.
DOI Google Scholar
[45]

Ma, S. H.; Han, Z.; Leng, K. Y.; Liu, X. J.; Wang, Y.; Qu, Y. T.; Bai, J. B. Ionic exchange of metal–organic frameworks for constructing unsaturated copper single-atom catalysts for boosting oxygen reduction reaction. Small 2020, 16, 2001384.
DOI Google Scholar
[46]

Fang, Y. P.; Bao, K.; Zhang, P.; Sheng, H. T.; Yun, Y. P.; Hu, S. X.; Astruc, D.; Zhu, M. Z. Insight into the mechanism of the CuAAC reaction by capturing the crucial Au4Cu4-π-alkyne intermediate. J. Am. Chem. Soc. 2021, 143, 1768–1772.
DOI Google Scholar
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Publication history
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Acknowledgements

Publication history

Received: 04 March 2023
Revised: 10 April 2023
Accepted: 18 April 2023
Published: 15 June 2023
Issue date: August 2023

Copyright

© Tsinghua University Press 2023

Acknowledgements

Acknowledgements

We acknowledge financial support by the National Natural Science Foundation of China (Nos. 21972001 and 21871001), Natural Science Foundation of Anhui Province (No. 2008085MB37), and Anhui University.

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