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Research Article

Revealing efficient catalytic performance of N-CuOx for aerobic oxidative coupling of aliphatic alkynes: A Langmuir–Hinshelwood reaction mechanism

Jun Tang1, Bowen Jiao1, Wei Chen2( ), Fei Ruan1, Fengfeng Li1, Peixin Cui3( ), Chao Wan1, Minh Ngoc Ha1,4, Van Noi Nguyen4, Qingping Ke1( )
College of Chemistry and Chemical Engineering, Anhui University of Technology, Maanshan 243002, China
Key Laboratory of Carbon Materials of Zhejiang Province, College of Chemistry and Materials Engineering, Wenzhou University, Wenzhou 325035, China
Key Laboratory of Soil Environment and Pollution Remediation, Institute of Soil Science, the Chinese Academy of Sciences, Nanjing 210008, China
VNU Key Laboratory of Advanced Material for Green Growth, VNU University of Science, Vietnam National University, Hanoi 100000, Vietnam
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Graphical Abstract

An N doped copper oxides (N-CuOx), synthesized with hydrothermal method, has been successfully employed as excellent catalyst for homo/cross-coupling of aliphatic alkynes to 1,3-conjugated diynes.

Abstract

Oxidative couplings of aliphatic alkynes are crucial for the production of naturally occurring 1,3-diynes. Herein we report the novel approach for effective synthesis of unsaturated coordinated N doped copper oxides (N-CuOx) catalyst, and uncover that N-CuOx catalyst as an additive-free and cost-effective heterogeneous catalyst has highly catalytic performance for directly oxidative coupling of aliphatic alkynes. The key to achieve efficient oxidative coupling of aliphatic alkynes is the synergistic effect of N species and uncoordinated O/Cu species caused by N dopants, which undergoes the Langmuir–Hinshelwood reaction mechanism. The N-CuOx catalyst displays ~ 89.1% yield for hexadeca-7,9-diyne under mild conditions and stable reusability (5 cycles), showing significant advances compared with the traditionally copper oxides. These findings highlight the heteroatom dopants that provide a new methodology for designing efficient copper catalysts in synthesis of naturally occurring 1,3-diynes.

Keywords

N doped copper oxides (N-CuOx) straight chain alkyneshomo-couplingadditive-free1,3-diynes

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References

1

Hohmann, C.; Schneider, K.; Bruntner, C.; Irran, E.; Nicholson, G.; Bull, A. T.; Jones, A. L.; Brown, R.; Stach, J. E. M.; Goodfellow, M. et al. Caboxamycin, a new antibiotic of the benzoxazole family produced by the deep-sea strain Streptomyces sp. NTK 937. J. Antibiot. 2009, 62, 99–104.
Crossref Google Scholar
2

Hu, J. P.; Liang, Z. F.; Shen, K. C.; Xie, L.; Zhang, H.; Huang, C. Q.; Huang, Y. B.; Huang, H.; Tang, J. X.; Jiang, Z. et al. Identifying the convergent reaction path from predesigned assembled structures: Dissymmetrical dehalogenation of Br2Py on Ag (111). Nano Res. 2021, 14, 4704–4713.
Crossref Google Scholar
3

Rida, S. M.; Ashour, F. A.; El-Hawash, S. A. M.; ElSemary, M. M.; Badr, M. H.; Shalaby, M. A. Synthesis of some novel benzoxazole derivatives as anticancer, anti-HIV-1 and antimicrobial agents. Eur. J. Med. Chem. 2005, 40, 949–959.
Crossref Google Scholar
4

Han, S.; Kim, H. S.; Zhang, M. S.; Xia, Y. Z.; Lee, S. Ni/Cu-catalyzed decarboxylative addition of alkynoic acids to terminal alkynes for the synthesis of gem-1,3-enynes. Org. Lett. 2019, 21, 5426–5431.
Crossref Google Scholar
5

Knutson, P. C.; Fredericks, H. E.; Ferreira, E. M. Synthesis of 1,3-diynes via cadiot-chodkiewicz coupling of volatile, in situ generated bromoalkynes. Org. Lett. 2018, 20, 6845–6849.
Crossref Google Scholar
6

Shi Shun, A. L. K.; Tykwinski, R. R. Synthesis of naturally occurring polyynes. Angew. Chem., Int. Ed. 2006, 45, 1034–1057.
Crossref Google Scholar
7

Bédard, A. C.; Collins, S. K. Phase separation as a strategy toward controlling dilution effects in macrocyclic Glaser–Hay couplings. J. Am. Chem. Soc. 2011, 133, 19976–19981.
Crossref Google Scholar
8

Ren, P.; Li, Q. L.; Song, T.; Yang, Y. Facile fabrication of the Cu-N-C catalyst with atomically dispersed unsaturated Cu-N2 active sites for highly efficient and selective Glaser–Hay coupling. ACS Appl. Mater. Interfaces 2020, 12, 27210–27218.
Crossref Google Scholar
9

Chen, J. F.; Li, C. K. Cobalt-catalyzed gem-cross-dimerization of terminal alkynes. ACS Catal. 2020, 10, 3881–3889.
Crossref Google Scholar
10

Chen, Z.; Shen, R. G.; Chen, C.; Li, J. P.; Li, Y. D. Synergistic effect of bimetallic PdAu nanocrystals on oxidative alkyne homocoupling. Chem. Commun. 2018, 54, 13155–13158.
Crossref Google Scholar
11

Liu, L. C.; Matsushita, T.; Concepción, P.; Leyva-Pérez, A.; Corma, A. Facile synthesis of surface-clean monodispersed CuOx nanoparticles and their catalytic properties for oxidative coupling of alkynes. ACS Catal. 2016, 6, 2211–2221.
Crossref Google Scholar
12

Biswas, S.; Mullick, K.; Chen, S. Y.; Kriz, D. A.; Shakil, M. D.; Kuo, C. H.; Angeles-Boza, A. M.; Rossi, A. R.; Suib, S. L. Mesoporous copper/manganese oxide catalyzed coupling of alkynes: Evidence for synergistic cooperative catalysis. ACS Catal. 2016, 6, 5069–5080.
Crossref Google Scholar
13

Zhang, R. X.; Chen, Y.; Ding, M. H.; Zhao, J. Heterogeneous Cu catalyst in organic transformations. Nano Res. 2022, 15, 2810–2833.
Crossref Google Scholar
14

Zhang, S. L.; Liu, X. Y.; Wang, T. Q. An efficient copper-catalyzed homocoupling of terminal alkynes to give symmetrical 1,4-disubstituted 1,3-diynes. Adv. Synth. Catal. 2011, 353, 1463–1466.
Crossref Google Scholar
15

Ye, X. H.; Peng, H. H.; Wei, C. Y.; Yuan, T.; Wojtas, L.; Shi, X. D. Gold-catalyzed oxidative coupling of alkynes toward the synthesis of cyclic conjugated diynes. Chem 2018, 4, 1983–1993.
Crossref Google Scholar
16

Harcken, C.; Brückner, R.; Rank, E. Total syntheses of (−)-grandinolide and (−)-sapranthin by the sharpless asymmetric dihydroxylation of methyl trans-3-pentenoate: Elucidation of the stereostructure of (−)-sapranthin. Chem. Eur. J. 1998, 4, 2342–2352.
Crossref
17
Barrero A. F. Herrador M. M. Akssira M. Arteaga P. Romera J. L. Lignans and polyacetylenes from Bupleurumacutifolium J. Nat. Prod 1999 62 946 948 10.1021/np980445p

Barrero, A. F.; Herrador, M. M.; Akssira, M.; Arteaga, P.; Romera, J. L. Lignans and polyacetylenes from Bupleurumacutifolium. J. Nat. Prod 1999, 62, 946–948.
Crossref Google Scholar
18

Ding, Y. Q.; Wu, Q. Q.; Lin, B.; Guo, Y. L.; Guo, Y.; Wang, Y. S.; Wang, L.; Zhan, W. C. Superior catalytic activity of a Pd catalyst in methane combustion by fine-tuning the phase of ceria-zirconia support. Appl. Catal. B: Environ. 2020, 266, 118631.
Crossref Google Scholar
19

Li, F. F.; Tang, J.; Ke, Q. P.; Guo, Y.; Ha, M. N.; Wan, C.; Lei, Z. P.; Gu, J.; Ling, Q.; Nguyen, V. N. et al. Investigation into enhanced catalytic performance for epoxidation of styrene over LaSrCoxFe2−xO6 double perovskites: The role of singlet oxygen species promoted by the photothermal effect. ACS Catal. 2021, 11, 11855–11866.
Crossref Google Scholar
20

Jing, H. Y.; Liu, W.; Zhao, Z. Y.; Zhang, J. W.; Zhu, C.; Shi, Y. T.; Wang, D. S.; Li, Y. D. Electronics and coordination engineering of atomic cobalt trapped by oxygen-driven defects for efficient cathode in solar cells. Nano Energy 2021, 89, 106365.
Crossref Google Scholar
21

Liu, H.; Jia, W. L.; Yu, X.; Tang, X.; Zeng, X. H.; Sun, Y.; Lei, T. Z.; Fang, H. Y.; Li, T. Y.; Lin, L. Vitamin C-assisted synthesized Mn-Co oxides with improved oxygen vacancy concentration: Boosting lattice oxygen activity for the air-oxidation of 5-(hydroxymethyl)furfural. ACS Catal. 2021, 11, 7828–7844.
Crossref Google Scholar
22

Tang, J.; Cao, Y. L.; Ruan, F.; Li, F. F.; Jin, Y. X.; Ha, M. N.; Han, X. Y.; Ke, Q. P. New approach for controllable synthesis of N-MnOx microflowers and their superior catalytic performance for benzoxazole synthesis. Ind. Eng. Chem. Res. 2020, 59, 9408–9413.
Crossref Google Scholar
23

Jin, Y. X.; Li, F. F.; Cui, P. X.; Yang, Y.; Ke, Q. P.; Ha, M. N.; Zhan, W. C.; Ruan, F.; Wan, C.; Lei, Z. et al. Jahn–Teller distortion assisted interstitial nitrogen engineering: Enhanced oxygen dehydrogenation activity of N-doped MnxCo3−xO4 hierarchical micro-nano particles. Nano Res. 2021, 14, 2637–2643.
Crossref Google Scholar
24

Ke, Q. P.; Jin, Y. X.; Ruan, F.; Ha, M. N.; Li, D. D.; Cui, P. X.; Cao, Y. L.; Wang, H.; Wang, T. T.; Nguyen, V. N. et al. Boosting the activity of catalytic oxidation of 5-hydroxymethylfurfural to 2,5-diformylfuran over nitrogen-doped manganese oxide catalysts. Green Chem. 2019, 21, 4313–4318.
Crossref Google Scholar
25

Ruan, F.; Li, F. F.; Dong, Z. P.; Ke, Q. P.; Jin, Y. X.; Zhan, W. C.; Ha, M. N.; Tang, J. Enhanced activity for aerobic oxidative of alcohols over manganese oxides stimulated with interstitial nitrogen doping. Green Synth. Catal. 2021, 2, 38–44.
Crossref Google Scholar
26

Xiao, X. X.; Xu, Y.; Bhavanarushi, S.; Liu, B.; Lv, X. M. Selective C-C coupling of terminal alkynes under an air atmosphere without base over Cu-Nx-C catalysts. New J. Chem. 2020, 44, 20993–20998.
Crossref Google Scholar
27

Liu, A. N.; Liu, L. C.; Cao, Y.; Wang, J. M.; Si, R.; Gao, F.; Dong, L. Controlling dynamic structural transformation of atomically dispersed CuOx species and influence on their catalytic performances. ACS Catal. 2019, 9, 9840–9851.
Crossref Google Scholar
28

Balčytis, A.; Ryu, M.; Seniutinas, G.; Juodkazytė, J.; Cowie, B. C. C.; Stoddart, P. R.; Zamengo, M.; Morikawa, J.; Juodkazis, S. Black-CuO: Surface-enhanced Raman scattering and infrared properties. Nanoscale 2015, 7, 18299–18304.
Crossref Google Scholar
29

Liu, J. H.; Zhang, T. K.; Wang, Z. C.; Dawson, G.; Chen, W. Simple pyrolysis of urea into graphitic carbon nitride with recyclable adsorption and photocatalytic activity. J. Mater. Chem. 2011, 21, 14398–14401.
Crossref Google Scholar
30

Li, J. J.; Zan, W. Y.; Kang, H. X.; Dong, Z. P.; Zhang, X. M.; Lin, Y. X.; Mu, Y. W.; Zhang, F. W.; Zhang, X. M.; Gu, J. Graphitic-N highly doped graphene-like carbon: A superior metal-free catalyst for efficient reduction of CO2. Appl. Catal. B: Environ. 2021, 298, 120510.
Crossref Google Scholar
31

Zhang, X. R.; Wang, Y. Q.; Wang, K.; Huang, Y. L.; Lyu, D. D.; Yu, F.; Wang, S. B.; Tian, Z. Q.; Shen, P. K.; Jiang, S. P. Active sites engineering via tuning configuration between graphitic-N and thiophenic-S dopants in one-step synthesized graphene nanosheets for efficient water-cycled electrocatalysis. Chem. Eng. J. 2021, 416, 129096.
Crossref Google Scholar
32

Su, Y. H.; Jiang, H. L.; Zhu, Y. H.; Yang, X. L.; Shen, J. H.; Zou, W. J.; Chen, J. D.; Li, C. Z. Enriched graphitic N-doped carbon-supported Fe3O4 nanoparticles as efficient electrocatalysts for oxygen reduction reaction. J. Mater. Chem. A 2014, 2, 7281–7287.
Crossref Google Scholar
33

Peng, S. J.; Gong, F.; Li, L. L.; Yu, D. S.; Ji, D. X.; Zhang, T. R.; Hu, Z.; Zhang, Z. Q.; Chou, S. L.; Du, Y. H. et al. Necklace-like multishelled hollow spinel oxides with oxygen vacancies for efficient water electrolysis. J. Am. Chem. Soc. 2018, 140, 13644–13653.
Crossref Google Scholar
34

Gao, Q. Q.; Dai, Y. Q.; Li, C. B.; Yang, L. G.; Li, X. C.; Cui, C. J. Correlation between oxygen vacancies and dopant concentration in Mn-doped ZnO nanoparticles synthesized by co-precipitation technique. J. Alloys Compd. 2016, 684, 669–676.
Crossref Google Scholar
35

Chaabane, L.; Beyou, E.; Luneau, D.; Baouab, M. H. V. Functionalization of graphene oxide sheets with magnetite nanoparticles for the adsorption of copper ions and investigation of its potential catalytic activity toward the homocoupling of alkynes under green conditions. J. Catal. 2020, 388, 91–103.
Crossref Google Scholar
36

Alonso, F.; Yus, M. Heterogeneous catalytic homocoupling of terminal alkynes. ACS Catal. 2012, 2, 1441–1451.
Crossref Google Scholar
37

Yuan, Y. Y.; Wang, Y. Q.; Zhuang, G. L.; Li, Q. Y.; Yang, F. L.; Wang, X. J.; Han, X. G. Supporting a Cu@In2O3 core–shell structure on N-doped graphitic carbon cuboctahedral cages for efficient photocatalytic homo-coupling of terminal alkynes. J. Mater. Chem. A 2021, 9, 24909–24914.
Crossref Google Scholar
38

Zhu, Y.; Deng, N.; Feng, M. Q.; Liu, P. On the comparable activity in plasmonic photocatalytic and thermocatalytic oxidative homocoupling of alkynes over prereduced copper ferrite. Chin. J. Catal. 2019, 40, 1505–1515.
Crossref Google Scholar
39

Li, X. D.; Xie, X.; Sun, N.; Liu, Y. H. Gold-catalyzed cadiot-chodkiewicz-type cross-coupling of terminal alkynes with alkynyl hypervalent iodine reagents: Highly selective synthesis of unsymmetrical 1,3-diynes. Angew. Chem., Int. Ed. 2017, 56, 6994–6998.
Crossref Google Scholar
40

Yin, W. Y.; He, C.; Chen, M.; Zhang, H.; Lei, A. W. Nickel-catalyzed oxidative coupling reactions of two different terminal alkynes using O2 as the oxidant at room temperature: Facile syntheses of unsymmetric 1,3-diynes. Org. Lett. 2009, 11, 709–712.
Crossref Google Scholar
41

Peng, H. H.; Xi, Y. M.; Ronaghi, N.; Dong, B. L.; Akhmedov, N. G.; Shi, X. D. Gold-catalyzed oxidative cross-coupling of terminal alkynes: Selective synthesis of unsymmetrical 1,3-diynes. J. Am. Chem. Soc. 2014, 136, 13174–13177.
Crossref Google Scholar
42

Chakraborty, D.; Nandi, S.; Mullangi, D.; Haldar, S.; Vinod, C. P.; Vaidhyanathan, R. Cu/Cu2O nanoparticles supported on a phenol-pyridyl COF as a heterogeneous catalyst for the synthesis of unsymmetrical diynes via Glaser–Hay coupling. ACS Appl. Mater. Interfaces 2019, 11, 15670–15679.
Crossref Google Scholar
43

Xu, H.; Wu, K. Y.; Tian, J.; Zhu, L.; Yao, X. Q. Recyclable Cu/C3N4 composite catalysed homo- and cross-coupling of terminal alkynes under mild conditions. Green Chem. 2018, 20, 793–797.
Crossref Google Scholar
44

Sheldon, R. A.; Downing, R. S. Heterogeneous catalytic transformations for environmentally friendly production. Appl. Catal. A: Gen. 1999, 189, 163–183.
Crossref Google Scholar
45

Li, H. X.; Liu, L. Short-term effects of polyethene and polypropylene microplastics on soil phosphorus and nitrogen availability. Chemosphere 2022, 291, 132984.
Crossref Google Scholar
46

Shen, H.; Wu, W.; Wang, Z. Y.; Wu, W. Z.; Yuan, Y.; Feng, Y. L. Effect of modified layered double hydroxide on the flammability of intumescent flame retardant PP nanocomposites. J. Appl. Polym. Sci. 2021, 138, 51187.
Crossref Google Scholar
47

Zhan, J.; Huang, H. G.; Yu, H. Y.; Zhang, X. Z.; Zheng, Z. C.; Wang, Y. D.; Liu, T.; Li, T. X. The combined effects of Cd and Pb enhanced metal binding by root cell walls of the phytostabilizer Athyrium wardii (Hook. ). Environ. Pollut. 2020, 258, 113663.
Crossref Google Scholar
48
Zhu, J. Y.; Hu, J. H.; Hu, Q.; Zhang, X. Y.; Ushakova, E. V.; Liu, K. K.; Wang, S. X.; Chen, X.; Shan, C. X.; Rogach, A. L. et al. White light afterglow in carbon dots achieved via synergy between the room-temperature phosphorescence and the delayed fluorescence. Small, in press, https://doi.org/10.1002/smll.202105415.
49

Wang, B. L.; Jin, C. X.; Shao, S. J.; Yue, Y. X.; Zhang, Y. T.; Wang, S. S.; Chang, R. Q.; Zhang, H. F.; Zhao, J.; Li, X. N. Electron-deficient Cu site catalyzed acetylene hydrochlorination. Green Energy Environ. 2022, 18, 2105415.
Crossref Google Scholar
50

Di, J. Q.; Zhang, M.; Chen, Y. X.; Wang, J. X.; Geng, S. S.; Tang, J. Q.; Zhang, Z. H. Copper anchored on phosphorus g-C3N4 as a highly efficient photocatalyst for the synthesis of N-arylpyridin-2-amines. Green Chem. 2021, 23, 1041–1049.
Crossref Google Scholar
Nano Research
Volume 15 Issue 7,
July 2022
Pages 6076-6083
DOI: 10.1007/s12274-022-4323-5
Cite this article:
Tang J, Jiao B, Chen W, et al. Revealing efficient catalytic performance of N-CuOx for aerobic oxidative coupling of aliphatic alkynes: A Langmuir–Hinshelwood reaction mechanism. Nano Research, 2022, 15(7): 6076-6083. https://doi.org/10.1007/s12274-022-4323-5
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Received: 11 February 2022
Revised: 12 March 2022
Accepted: 13 March 2022
Published: 06 May 2022
© Tsinghua University Press 2022
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