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Research Article

Synergy of Fe-N4 and non-coordinated boron atoms for highly selective oxidation of amine into nitrile

Hong-Hui Wang1, Li-Bing Lv1, Shi-Nan Zhang1, Hui Su1, Guang-Yao Zhai1, Wei-Wei Lei2, Xin-Hao Li1( ), Jie-Sheng Chen1
School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, Shanghai 200240, China
Institute for Frontier Materials, Deakin University, Victoria 3216, Australia
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Abstract

The rational design of highly active and stable atomically dispersed M-X4 (M = Fe, Co, Ni, etc., X = C, N) -based catalysts holds promises for wide application in almost all realms of catalysis. Despite great effort in the construction of specific M-X4 centers, the possible effect of non-coordinated heteroatoms on the catalytic activity of metal centers has been rarely explored. Herein, we develop a new type of M-X4 catalyst composed of Fe-N4 centers and non-coordinated B heteroatoms (FeNC+B) and find the key role of non-coordinated B adjacent to Fe-N4 centers in tailoring their electron density and final catalytic selectivity. The experimental and theoretical results demonstrated that non-coordinated boron atoms could decrease the electron density of Fe-N4 centers to a suitable level and thus boost the selective production of nitriles from amine oxidation by depressing the formation of imines due to the flattened energy barrier of the reversible conversion of imines back to amines. As a reusable heterocatalyst, the state-of-the-art FeNC+B catalyst provides a turn-over frequency (TOF) value of 21.6 molbenzonitrile·molFe-1·h-1 (100 °C), outpacing that of bench-marked nonnoble-metal-based homogeneous catalyst by a factor of 3.4.

Keywords

atomically dispersed catalystFe-N4non-coordinated boronselective oxidationnitrile

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References

[1]
Wang, Y.; Mao, J.; Meng, X. G.; Yu, L.; Deng, D. H.; Bao, X. H. Catalysis with two-dimensional materials confining single atoms: Concept, design, and applications. Chem. Rev. 2019, 119, 1806-1854.
Crossref Google Scholar
[2]
Byon, H. R.; Suntivich, J.; Shao-Horn, Y. Graphene-based non-noble-metal catalysts for oxygen reduction reaction in acid. Chem. Mater. 2011, 23, 3421-3428.
Crossref Google Scholar
[3]
Jiao, L.; Wan, G.; Zhang, R.; Zhou, H.; Yu, S. H.; Jiang, H. L. From metal-organic frameworks to single-atom Fe implanted N-doped porous carbons: Efficient oxygen reduction in both alkaline and acidic media. Angew. Chem., Int. Ed. 2018, 57, 8525-8529.
Crossref Google Scholar
[4]
Wang, X. Q.; Chen, Z.; Zhao, X. Y.; Yao, T.; Chen, W. X.; You, R.; Zhao, C. M.; Wu, G.; Wang, J.; Huang, W. X. et al. Regulation of coordination number over single Co sites: Triggering the efficient electroreduction of CO2. Angew. Chem., Int. Ed. 2018, 57, 1944-1948.
Crossref Google Scholar
[5]
Li, X. G.; Bi, W. T.; Chen, M. L.; Sun, Y. X.; Ju, H. X.; Yan, W. S.; Zhu, J. F.; Wu, X. J.; Chu, W. S.; Wu, C. Z. et al. Exclusive Ni-N4 sites realize near-unity CO selectivity for electrochemical CO2 reduction. J. Am. Chem. Soc. 2017, 139, 14889-14892.
Crossref Google Scholar
[6]
Yang, Q. H.; Yang, C. C.; Lin, C. H.; Jiang, H. L. Metal-organic-framework-derived hollow N-doped porous carbon with ultrahigh concentrations of single Zn atoms for efficient carbon dioxide conversion. Angew. Chem., Int. Ed. 2019, 58, 3511-3515.
Crossref Google Scholar
[7]
Han, L. L.; Liu, X. J.; Chen, J. P.; Lin, R. Q.; Liu, H. X.; Lü, F.; Bak, S.; Liang, Z. X.; Zhao, S. Z.; Stavitski, E. et al. Atomically dispersed molybdenum catalysts for efficient ambient nitrogen fixation. Angew. Chem., Int. Ed. 2019, 58, 2321-2325.
Crossref Google Scholar
[8]
Chen, W. X.; Pei, J. J.; He, C. T.; Wan, J. W.; Ren, H. L.; Zhu, Y. Q.; Wang, Y.; Dong, J. C.; Tian, S. B.; Cheong, W. C. et al. Rational design of single molybdenum atoms anchored on N-doped carbon for effective hydrogen evolution reaction. Angew. Chem., Int. Ed. 2017, 56, 16086-16090.
Crossref Google Scholar
[9]
Qiu, H. J.; Ito, Y.; Cong, W. T.; Tan, Y. W.; Liu, P.; Hirata, A.; Fujita, T.; Tang, Z.; Chen, M. W. Nanoporous graphene with single-atom nickel dopants: An efficient and stable catalyst for electrochemical hydrogen production. Angew. Chem., Int. Ed. 2015, 54, 14031-14035.
Crossref Google Scholar
[10]
Fei, H. L.; Dong, J. C.; Feng, Y. X.; Allen, C. S.; Wan, C. Z.; Volosskiy, B.; Li, M. F.; Zhao, Z. P.; Wang, Y. L.; Sun, H. T. et al. General synthesis and definitive structural identification of MN4C4 single-atom catalysts with tunable electrocatalytic activities. Nat. Catal. 2018, 1, 63-72.
Crossref Google Scholar
[11]
Fei, H. L.; Dong, J. C.; Arellano-Jiménez, M. J.; Ye, G. L.; Dong Kim, N.; Samuel, E. L. G.; Peng, Z. W.; Zhu, Z.; Qin, F.; Bao, J. M. et al. Atomic cobalt on nitrogen-doped graphene for hydrogen generation. Nat. Commun. 2015, 6, 8668.
Google Scholar
[12]
Zhang, L. Z.; Jia, Y.; Gao, G. P.; Yan, X. C.; Chen, N.; Chen, J.; Soo, M. T.; Wood, B.; Yang, D. J.; Du, A. J. et al. Graphene defects trap atomic Ni species for hydrogen and oxygen evolution reactions. Chem 2018, 4, 285-297.
Google Scholar
[13]
Sun, T. T.; Zhao, S.; Chen, W. X.; Zhai, D.; Dong, J. C.; Wang, Y.; Zhang, S. L.; Han, A. J.; Gu, L.; Yu, R. et al. Single-atomic cobalt sites embedded in hierarchically ordered porous nitrogen-doped carbon as a superior bifunctional electrocatalyst. Proc. Natl. Acad. Sci. USA 2018, 115, 12692-12697.
Google Scholar
[14]
Guan, J. Q.; Duan, Z. Y.; Zhang, F. X.; Kelly, S. D.; Si, R.; Dupuis, M.; Huang, Q. G.; Chen, J. Q.; Tang, C. H.; Li, C. Water oxidation on a mononuclear manganese heterogeneous catalyst. Nat. Catal. 2018, 1, 870-877.
Google Scholar
[15]
Ji, S. F.; Chen, Y. J.; Zhang, Z. D.; Cheong, W. C.; Liu, Z. R.; Wang, D. S.; Li, Y. D. Single-atomic-site cobalt stabilized on nitrogen and phosphorus co-doped carbon for selective oxidation of primary alcohols. Nanoscale Horiz. 2019, 4, 902-906.
Google Scholar
[16]
Lv, L. B.; Yang, S. Z.; Ke, W. Y.; Wang, H. H.; Zhang, B.; Zhang, P. F.; Li, X. H.; Chisholm, M. F.; Chen, J. S. Mono-atomic Fe centers in nitrogen/carbon monolayers for liquid-phase selective oxidation reaction. ChemCatChem 2018, 10, 3539-3545.
Google Scholar
[17]
Su, H.; Gao, P.; Wang, M. Y.; Zhai, G. Y.; Zhang, J. J.; Zhao, T. J.; Su, J.; Antonietti, M.; Li, X. H.; Chen, J. S. Grouping effect of single Ni-N4 sites in Nitrogen-doped carbon boosts hydrogen transfer coupling of alcohols and amines. Angew. Chem., Int. Ed. 2018, 57, 15194-15198.
Google Scholar
[18]
Han, Y. H.; Wang, Z. Y.; Xu, R. R.; Zhang, W.; Chen, W. X.; Zheng, L. R.; Zhang, J.; Luo, J.; Wu, K. L.; Zhu, Y. Q. et al. Ordered porous nitrogen-doped carbon matrix with atomically dispersed cobalt sites as an efficient catalyst for dehydrogenation and transfer hydrogenation of N-heterocycles. Angew. Chem., Int. Ed. 2018, 57, 11262-11266.
Google Scholar
[19]
Wang, S. H.; Shang, L.; Li, L. L.; Yu, Y. J.; Chi, C. W.; Wang, K.; Zhang, J.; Shi, R.; Shen, H. Y.; Waterhouse, G. I. N. et al. Metal-organic-framework-derived mesoporous carbon nanospheres containing porphyrin-like metal centers for conformal phototherapy. Adv. Mater. 2016, 28, 8379-8387.
Google Scholar
[20]
Liu, Y. X.; Wang, H. H.; Zhao, T. J.; Zhang, B.; Su, H.; Xue, Z. H.; Li, X. H.; Chen, J. S. Schottky barrier induced coupled interface of electron-rich N-doped carbon and electron-deficient Cu: In-built Lewis acid-base pairs for highly efficient CO2 fixation. J. Am. Chem. Soc. 2019, 141, 38-41.
Google Scholar
[21]
Su, H.; Zhang, K. X.; Zhang, B.; Wang, H. H.; Yu, Q. Y.; Li, X. H.; Antonietti, M.; Chen, J. S. Activating cobalt nanoparticles via the Mott-Schottky effect in nitrogen-rich carbon shells for base-free aerobic oxidation of alcohols to esters. J. Am. Chem. Soc. 2017, 139, 811-818.
Google Scholar
[22]
Li, X. H.; Antonietti, M. Polycondensation of boron- and nitrogen-codoped holey graphene monoliths from molecules: Carbocatalysts for selective oxidation. Angew. Chem., Int. Ed. 2013, 52, 4572-4576.
Google Scholar
[23]
Zhang, K. X.; Su, H.; Wang, H. H.; Zhang, J. J.; Zhao, S. Y.; Lei, W. W.; Wei, X.; Li, X. H.; Chen, J. S. Atomic-scale Mott-Schottky heterojunctions of boron nitride monolayer and graphene as metal-free photocatalysts for artificial photosynthesis. Adv. Sci. 2018, 5, 1800062.
Google Scholar
[24]
Berteotti, A.; Vacondio, F.; Lodola, A.; Bassi, M.; Silva, C.; Mor, M.; Cavalli, A. Predicting the reactivity of nitrile-carrying compounds with cysteine: A combined computational and experimental study. ACS Med. Chem. Lett. 2014, 5, 501-505.
Google Scholar
[25]
Burow, M.; Markert, J.; Gershenzon, J.; Wittstock, U. Comparative biochemical characterization of nitrile-forming proteins from plants and insects that alter myrosinase-catalysed hydrolysis of glucosinolates. FEBS J. 2006, 273, 2432-2446.
Google Scholar
[26]
Fleming, F. F.; Yao, L. H.; Ravikumar, P. C.; Funk, L.; Shook, B. C. Nitrile-containing pharmaceuticals: Efficacious roles of the nitrile pharmacophore. J. Med. Chem. 2010, 53, 7902-7917.
Google Scholar
[27]
Fang, Z. X.; Chen, Y.; Wang, B. R.; Jiao, S. H; Pang, G. S. Heterostructure Ag@WO3-x composites with high selectivity for breaking azo-bond. Chem. Res. Chin. Univ. 2018, 34, 517-522.
Google Scholar
[28]
Dutta, I.; Yadav, S.; Sarbajna, A.; De, S.; Hölscher, M.; Leitner, W.; Bera, J. K. Double dehydrogenation of primary amines to nitriles by a ruthenium complex featuring pyrazole functionality. J. Am. Chem. Soc. 2018, 140, 8662-8666.
Google Scholar
[29]
Oishi, T.; Yamaguchi, K.; Mizuno, N. Catalytic oxidative synthesis of nitriles directly from primary alcohols and ammonia. Angew. Chem., Int. Ed. 2009, 48, 6286-6288.
Google Scholar
[30]
Martin, A.; Narayana Kalevaru, V.; Lücke, B. Defined vanadium phosphorus oxides and their use as highly effective catalysts in ammoxidation of methyl aromatics. Catal. Today. 2003, 78, 311-317.
Google Scholar
[31]
Kim, J.; Chang, S. A new combined source of “CN” from N,N-dimethylformamide and ammonia in the palladium-catalyzed cyanation of aryl C-H bonds. J. Am. Chem. Soc. 2010, 132, 10272-10274.
Google Scholar
[32]
Tseng, K. N. T.; Rizzi, A. M.; Szymczak, N. K. Oxidant-free conversion of primary amines to nitriles. J. Am. Chem. Soc. 2013, 135, 16352-16355.
Google Scholar
[33]
Hammond, C.; Schümperli, M. T.; Hermans, I. Insights into the oxidative dehydrogenation of amines with nanoparticulate iridium oxide. Chem.—Eur. J. 2013, 19, 13193-13198.
Google Scholar
[34]
Tseng, K.-N. T.; Szymczak, N. K. Dehydrogenative oxidation of primary amines to nitriles. Synlett. 2014, 25, 2385-2389.
Google Scholar
[35]
Preger, Y.; Root, T. W.; Stahl, S. S. Platinum-based heterogeneous catalysts for nitrile synthesis via aerobic oxidative coupling of alcohols and ammonia. ACS Omega 2018, 3, 6091-6096.
Google Scholar
[36]
Wang, Y. Z.; Furukawa, S.; Yan, N. Identification of an active NiCu catalyst for nitrile synthesis from alcohol. ACS Catal. 2019, 9, 6681-6691.
Google Scholar
[37]
Molla, R. A.; Ghosh, K.; Tuhina, K.; Islam, S. M. An aerobic oxidative synthesis of aryl nitriles and primary aryl amides from benzylic alcohols catalyzed by a polymer supported Cu(II) complex. New J. Chem. 2015, 39, 921-930.
Google Scholar
[38]
Dornan, L. M.; Cao, Q.; Flanagan, J. C. A.; Crawford, J. J.; Cook, M. J.; Muldoon, M. J. Copper/TEMPO catalysed synthesis of nitriles from aldehydes or alcohols using aqueous ammonia and with air as the oxidant. Chem. Commun. 2013, 49, 6030-6032.
Google Scholar
Nano Research
Volume 13 Issue 8,
August 2020
Pages 2079-2084
DOI: 10.1007/s12274-020-2810-0
Cite this article:
Wang H-H, Lv L-B, Zhang S-N, et al. Synergy of Fe-N4 and non-coordinated boron atoms for highly selective oxidation of amine into nitrile. Nano Research, 2020, 13(8): 2079-2084. https://doi.org/10.1007/s12274-020-2810-0
Topics:
BoronCatalyst activityCatalyst selectivity CyanidesElectron density measurement

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Received: 25 February 2020
Revised: 21 March 2020
Accepted: 12 April 2020
Published: 05 August 2020
© Tsinghua University Press and Springer-Verlag GmbH Germany, part of Springer Nature 2020
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