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

Differentially-grown cobalt regulators cooperatively involved in the tandem catalysis for high-yield production of second amines

Jinhui Xu1,2, Xiao Wang1,2( ), Ying Wang1,2, Fei Wang1,2, Lingling Zhang1,2, Wenjie Cui1,2, Shuyan Song1,2( ), Hongjie Zhang1,2,3( )
State Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China
School of Applied Chemistry and Engineering, University of Science and Technology of China, Hefei 230026, China
Department of Chemistry, Tsinghua University, Beijing 100084, China
Show Author Information

Graphical Abstract

We demonstrate a new atom landing strategy to the one-pot introduction of Co particle (Cop) and Co cluster (Coc) dual promoters in the Pt/CeO2/CN building units as advanced catalysts for the cascade synthesis of N-benzylaniline. In the applications, the inner Cops play a crucial role of electron donors for Pt particles (Ptps), the outer Cocs are of great significance to optimize the adsorption configuration of imine intermediates. It possesses remarkably increased catalytic performance, achieving 100% nitrobenzene conversion with 94% N-benzylaniline selectivity.

Abstract

One-pot tandem catalysis has been regarded as one of the most atomic economic ways to produce secondary amines, the important platform molecules for chemical synthesis and pharmaceutical manufacture, but it is facing serious issues in overall efficiency. New promotional effects are highly desired for boosting the activity and regulating the selectivity of conventional tandem catalysts. In this work, we report a high-performance tandem catalyst with maximized synergistic effect among each counterpart by preciously manipulating the spatial structure, which involves the active CeO2/Pt component as kernel, the densely-coated N-doped C (NC) layer as selectivity controller, and the differentially-grown Co species as catalytic performance regulators. Through comprehensive investigations, the unique growth mechanism and the promotion effect of Co regulators are clarified. Specifically, the surface-landed Co clusters (Cocs) are crucial to selectivity by altering the adsorption configuration of benzylideneaniline intermediates. Meanwhile, the inner Co particles (Cops) are essential for activity by denoting their electrons to neighboring Ptps. Benefiting from the unique promotion effect, a remarkably-improved catalytic efficiency (100% nitrobenzene conversion with 94% N-benzylaniline selectivity) is achieved at a relatively low temperature of 80 °C, which is much better than that of CeO2/Pt (100% nitrobenzene conversion with 12% N-benzylaniline selectivity) and CeO2/Pt/NC (35% nitrobenzene conversion with 94% benzylideneaniline selectivity).

Keywords

tandem catalysisCeO2hierarchical structureheterogeneous catalystdual-site materials

Electronic Supplementary Material

Download File(s)
12274_2023_6117_MOESM1_ESM.pdf (4.1 MB)

References

[1]

Liu, L.; Li, W. X.; Qi, R.; Zhu, Q. Q.; Li, J.; Fang, Y. Z.; Kong, X. J. Cobalt encapsulated in N-doped graphene sheet for one-pot reductive amination to synthesize secondary amines. Mol. Catal. 2021, 505, 111504.
Crossref Google Scholar
[2]

Schuhmacher, A.; Shiro, T.; Ryan, S. J.; Bode, J. W. Synthesis of secondary and tertiary amides without coupling agents from amines and potassium acyltrifluoroborates (KATs). Chem. Sci. 2020, 11, 7609–7614.
Crossref Google Scholar
[3]

Afanasyev, O. I.; Kuchuk, E.; Usanov, D. L.; Chusov, D. Reductive amination in the synthesis of pharmaceuticals. Chem. Rev. 2019, 119, 11857–11911.
Crossref Google Scholar
[4]

Chen, C.; Fan, R. Y.; Han, M. M.; Zhu, X. G.; Zhang, Y. X.; Zhang, H. M.; Zhao, H. J.; Wang, G. Z. Tunable synthesis of imines and secondary-amines from tandem hydrogenation-coupling of aromatic nitro and aldehyde over NiCo5 bi-metallic catalyst. Appl. Catal. B: Environ. 2021, 280, 119448.
Crossref Google Scholar
[5]

Zhao, H.; Li, B. Y.; Zhao, H. C.; Li, J. F.; Kou, J. F.; Zhu, H. H.; Liu, B.; Li, Z. H.; Sun, X.; Dong, Z. P. Construction of a sandwich-like UiO-66-NH2@Pt@mSiO2 catalyst for one-pot cascade reductive amination of nitrobenzene with benzaldehyde. J. Colloid Interface Sci. 2022, 606, 1524–1533.
Crossref Google Scholar
[6]

Cao, X.; Qin, J. H.; Gou, G. L.; Li, J.; Wu, W.; Luo, S. C.; Luo, Y. T.; Dong, Z. P.; Ma, J. T.; Long, Y. Continuous solvent-free synthesis of imines over uip-γ-Al2O3-CeO2 catalyst in a fixed bed reactor. Appl. Catal. B: Environ. 2020, 272, 118958.
Crossref Google Scholar
[7]

Alshammari, A. S.; Natte, K.; Kalevaru, N. V.; Bagabas, A.; Jagadeesh, R. V. Scalable preparation of stable and reusable silica supported palladium nanoparticles as catalysts for N-alkylation of amines with alcohols. J. Catal. 2020, 382, 141–149.
Crossref Google Scholar
[8]

Han, X. M.; Chen, X.; Zou, Y.; Zhang, S. Electronic state regulation of supported Pt catalysts dictates selectivity of imines/secondary amines from the cascade transformation of nitroarenes and aldehydes. Appl. Catal. B: Environ. 2020, 268, 118451.
Crossref Google Scholar
[9]

Li, M. H.; Chen, S. Y.; Jiang, Q. K.; Chen, Q. L.; Wang, X.; Yan, Y.; Liu, J.; Lv, C. C.; Ding, W. P.; Guo, X. F. Origin of the activity of Co-N-C catalysts for chemoselective hydrogenation of nitroarenes. ACS Catal. 2021, 11, 3026–3039.
Crossref Google Scholar
[10]

Chen, G. R.; Han, J.; Niu, Z. J.; She, P. H.; Li, L.; Guan, B. Y.; Yu, J. H. Regioselective surface assembly of mesoporous carbon on zeolites creating anisotropic wettability for biphasic interface catalysis. J. Am. Chem. Soc. 2023, 145, 9021–9028.
Crossref Google Scholar
[11]

Zhang, Y. R.; Gao, Y. J.; Yao, S. Y.; Li, S. W.; Asakura, H.; Teramura, K.; Wang, H. J.; Ma, D. Sublimation-induced sulfur vacancies in MoS2 catalyst for one-pot synthesis of secondary amines. ACS Catal. 2019, 9, 7967–7975.
Crossref Google Scholar
[12]

Shao, F. J.; Wang, X. J.; Zhao, Z. J.; Wei, Z. Z.; Zhong, X.; Yao, Z. H.; Deng, S. W.; Wang, S. B.; Wang, H.; Li, A. Y. et al. Ru cluster-decorated Cu nanoparticles enhanced selectivity to imine from one-pot cascade transformations. Ind. Eng. Chem. Res. 2022, 61, 3474–3482.
Crossref Google Scholar
[13]

Ge, C. Y.; Sang, X. X.; Yao, W.; Zhang, L.; Wang, D. W. Unsymmetrical indazolyl-pyridinyl-triazole ligand-promoted highly active iridium complexes supported on hydrotalcite and its catalytic application in water. Green Chem. 2018, 20, 1805–1812.
Crossref Google Scholar
[14]

Gunanathan, C.; Milstein, D. Applications of acceptorless dehydrogenation and related transformations in chemical synthesis. Science 2013, 341, 1229712.
Crossref Google Scholar
[15]

Huang, S. T.; Zhao, Z. J.; Wei, Z. Z.; Wang, M. X.; Chen, Y.; Wang, X. S.; Shao, F. J.; Zhong, X.; Li, X. N.; Wang, J. G. Targeted regulation of the selectivity of cascade synthesis towards imines/secondary amines by carbon-coated Co-based catalysts. Green Chem. 2022, 24, 6945–6954.
Crossref Google Scholar
[16]

Chen, C.; Janoszka, N.; Wong, C. K.; Gramse, C.; Weberskirch, R.; Gröschel, A. H. Scalable and recyclable all-organic colloidal cascade catalysts. Angew. Chem., Int. Ed. 2021, 60, 237–241.
Crossref Google Scholar
[17]

Bao, L. Q.; Zhao, C. C.; Li, S. G.; Zhu, Y. Benzalaniline from nitrobenzene and benzaldehyde catalyzed efficiently by an atomically precise palladium nanocluster. Chin. J. Catal. 2019, 40, 1499–1504.
Crossref Google Scholar
[18]

Zhou, P.; Zhang, Z. H.; Jiang, L.; Yu, C. L.; Lv, K. L.; Sun, J.; Wang, S. G. A versatile cobalt catalyst for the reductive amination of carbonyl compounds with nitro compounds by transfer hydrogenation. Appl. Catal. B: Environ. 2017, 210, 522–532.
Crossref Google Scholar
[19]

Nuzhdin, A. L.; Artiukha, E. A.; Bukhtiyarova, G. A.; Derevyannikova, E. A.; Bukhtiyarov, V. I. Synthesis of secondary amines by reductive amination of aldehydes with nitroarenes over supported copper catalysts in a flow reactor. Catal. Commun. 2017, 102, 108–113.
Crossref Google Scholar
[20]

Zhang, Q.; Li, S. S.; Zhu, M. M.; Liu, Y. M.; He, H. Y.; Cao, Y. Direct reductive amination of aldehydes with nitroarenes using bio-renewable formic acid as a hydrogen source. Green Chem. 2016, 18, 2507–2513.
Crossref Google Scholar
[21]

Fertig, R.; Irrgang, T.; Freitag, F.; Zander, J.; Kempe, R. Manganese-catalyzed and base-switchable synthesis of amines or imines via borrowing hydrogen or dehydrogenative condensation. ACS Catal. 2018, 8, 8525–8530.
Crossref Google Scholar
[22]

Long, J. L.; Shen, K.; Li, Y. W. Bifunctional N-Doped Co@C catalysts for base-free transfer hydrogenations of nitriles: Controllable selectivity to primary amines vs imines. ACS Catal. 2017, 7, 275–284.
Crossref Google Scholar
[23]

Li, M. S.; Hao, Y. F.; Cárdenas-Lizana, F.; Keane, M. A. Gold promoted imine production by selective gas phase reductive coupling of nitrobenzene and benzaldehyde. Appl. Catal. A: Gen. 2017, 531, 52–59.
Crossref Google Scholar
[24]

Artiukha, E. A.; Nuzhdin, A. L.; Bukhtiyarova, G. A.; Zaytsev, S. Y.; Plyusnin, P. E.; Shubin, Y. V.; Bukhtiyarov, V. I. One-pot reductive amination of aldehydes with nitroarenes over an Au/Al2O3 catalyst in a continuous flow reactor. Catal. Sci. Technol. 2015, 5, 4741–4745.
Crossref Google Scholar
[25]

Chen, G. X.; Zhao, Y.; Fu, G.; Duchesne, P. N.; Gu, L.; Zheng, Y. P.; Weng, X. F.; Chen, M. S.; Zhang, P.; Pao, C. W. et al. Interfacial effects in iron-nickel hydroxide-platinum nanoparticles enhance catalytic oxidation. Science 2014, 344, 495–499.
Crossref Google Scholar
[26]

Acerbi, N.; Tsang, S. C. E.; Jones, G.; Golunski, S.; Collier, P. Rationalization of interactions in precious metal/ceria catalysts using the d-band center model. Angew. Chem., Int. Ed. 2013, 52, 7737–7741.
Crossref Google Scholar
[27]

Ta, N.; Liu, J. Y.; Chenna, S.; Crozier, P. A.; Li, Y.; Chen, A. L.; Shen, W. J. Stabilized gold nanoparticles on ceria nanorods by strong interfacial anchoring. J. Am. Chem. Soc. 2012, 134, 20585–20588.
Crossref Google Scholar
[28]

Wu, D. D.; Wen, M.; Gu, C.; Wu, Q. S. 2D NiFe/CeO2 basic-site-enhanced catalyst via in-situ topotactic reduction for selectively catalyzing the H2 generation from N2H4·H2O. ACS Appl. Mater. Interfaces 2017, 9, 16103–16108.
Crossref Google Scholar
[29]

Pilger, F.; Testino, A.; Carino, A.; Proff, C.; Kambolis, A.; Cervellino, A.; Ludwig, C. Size control of Pt clusters on CeO2 nanoparticles via an incorporation-segregation mechanism and study of segregation kinetics. ACS Catal. 2016, 6, 3688–3699.
Crossref Google Scholar
[30]

Prins R. Hydrogen spillover. Facts and fiction. Chem. Rev. 2012, 112, 2714–2738.
Crossref Google Scholar
[31]

Im, J.; Shin, H.; Jang, H.; Kim, H.; Choi, M. Maximizing the catalytic function of hydrogen spillover in platinum-encapsulated aluminosilicates with controlled nanostructures. Nat. Commun. 2014, 5, 3370.
Crossref Google Scholar
[32]

Zhang, S.; Chang, C. R.; Huang, Z. Q.; Li, J.; Wu, Z. M.; Ma, Y. Y.; Zhang, Z. Y.; Wang, Y.; Qu, Y. Q. High catalytic activity and chemoselectivity of sub-nanometric Pd clusters on porous nanorods of CeO2 for hydrogenation of nitroarenes. J. Am. Chem. Soc. 2016, 138, 2629–2637.
Crossref Google Scholar
[33]

Li, G.; Abroshan, H.; Chen, Y. X.; Jin, R. C.; Kim, H. J. Experimental and mechanistic understanding of aldehyde hydrogenation using Au25 nanoclusters with Lewis acids: Unique sites for catalytic reactions. J. Am. Chem. Soc. 2015, 137, 14295–14304.
Crossref Google Scholar
[34]

Liu, R.; Mahurin, S. M.; Li, C.; Unocic, R. R.; Idrobo, J. C.; Gao, H. J.; Pennycook, S. J.; Dai, S. Dopamine as a carbon source: The controlled synthesis of hollow carbon spheres and yolk-structured carbon nanocomposites. Angew. Chem., Int. Ed. 2011, 50, 6799–6802.
Crossref Google Scholar
[35]

Long, Y.; Song, S. Y.; Li, J.; Wu, L. L.; Wang, Q. S.; Liu, Y.; Jin, R. C.; Zhang, H. J. Pt/CeO2@MOF core@shell nanoreactor for selective hydrogenation of furfural via the channel screening effect. ACS Catal. 2018, 8, 8506–8512.
Crossref Google Scholar
[36]

Gänzler, A. M.; Casapu, M.; Vernoux, P.; Loridant, S.; Cadete Santos Aires, F. J.; Epicier, T.; Betz, B.; Hoyer, R.; Grunwaldt, J. D. Tuning the structure of platinum particles on ceria in situ for enhancing the catalytic performance of exhaust gas catalysts. Angew. Chem., Int. Ed. 2017, 56, 13078–13082.
Crossref Google Scholar
[37]

Yu, D. J.; Zeng, Y. B.; Qi, Y. X.; Zhou, T. S.; Shi, G. Y. A novel electrochemical sensor for determination of dopamine based on AuNPs@SiO2 core–shell imprinted composite. Biosens. Bioelectron. 2012, 38, 270–277.
Crossref Google Scholar
[38]

Wang, F.; Song, S. Y.; Li, K.; Li, J. Q.; Pan, J.; Yao, S.; Ge, X.; Feng, J.; Wang, X.; Zhang, H. J. A “solid dual-ions-transformation” route to S, N Co-doped carbon nanotubes as highly efficient “metal-free” catalysts for organic reactions. Adv. Mater. 2016, 28, 10679–10683.
Crossref Google Scholar
[39]

Chen, X.; Alouani, M. Effect of metallic surfaces on the electronic structure, magnetism, and transport properties of Co-phthalocyanine molecules. Phys. Rev. B 2010, 82, 094443.
Crossref Google Scholar
[40]

Chen, H. R.; Shen, K.; Mao, Q.; Chen, J. Y.; Li, Y. W. Nanoreactor of MOF-derived yolk-shell Co@C-N: Precisely controllable structure and enhanced catalytic activity. ACS Catal. 2018, 8, 1417–1426.
Crossref Google Scholar
[41]

Wang, X.; Liu, D. P.; Song, S. Y.; Zhang, H. J. Pt@CeO2 multicore@shell self-assembled nanospheres: Clean synthesis, structure optimization, and catalytic applications. J. Am. Chem. Soc. 2013, 135, 15864–15872.
Crossref Google Scholar
[42]

Yang, F.; Wang, X.; Hu, Q. L.; Jiang, D. D.; Lu, Y.; Wang, Y.; Wang, J. H.; Liu, J. H. Carbon nitride initiated photopolymerization into a luminescent elastomer hydrogel. Mater. Chem. Front. 2021, 5, 6491–6501.
Crossref Google Scholar
[43]

Ryu, J.; Ku, S. H.; Lee, H.; Park, C. B. Mussel-inspired polydopamine coating as a universal route to hydroxyapatite crystallization. Adv. Funct. Mater. 2010, 20, 2132–2139.
Crossref Google Scholar
[44]

Paier, J.; Penschke, C.; Sauer, J. Oxygen defects and surface chemistry of ceria: Quantum chemical studies compared to experiment. Chem. Rev. 2013, 113, 3949–3985.
Crossref Google Scholar
[45]

Esch, F.; Fabris, S.; Zhou, L.; Montini, T.; Africh, C.; Fornasiero, P.; Comelli, G.; Rosei, R. Electron localization determines defect formation on ceria substrates. Science 2005, 309, 752–755.
Crossref Google Scholar
[46]

Waite, J. H. Mussel power. Nat. Mater. 2008, 7, 8–9.
Crossref Google Scholar
[47]

She, W.; Wang, J.; Li, X. W.; Li, J. F.; Mao, G. J.; Li, W. Z.; Li, G. M. Highly chemoselective synthesis of imine over Co/Zn bimetallic MOFs derived Co3ZnC-ZnO embed in carbon nanosheet catalyst. J. Catal. 2021, 401, 17–26.
Crossref Google Scholar
[48]

Bera, S. S.; Szostak, M. Cobalt-N-heterocyclic carbene complexes in catalysis. ACS Catal. 2022, 12, 3111–3137.
Crossref Google Scholar
[49]

Mukherjee, A.; Milstein, D. Homogeneous catalysis by cobalt and manganese pincer complexes. ACS Catal. 2018, 8, 11435–11469.
Crossref Google Scholar
[50]

Chen, H. L.; Yang, H.; Omotoso, O.; Ding, L. H.; Briker, Y.; Zheng, Y.; Ring, Z. Contribution of hydrogen spillover to the hydrogenation of naphthalene over diluted Pt/RHO catalysts. Appl. Catal. A: Gen. 2009, 358, 103–109.
Crossref Google Scholar
[51]

Thang, H. V.; Le Minh Pham, T. DFT insights into the electronic structure of Rh single-atom catalysts stabilized on the CeO2 (111) surface. Chem. Phys. Lett. 2022, 803, 139810.
Crossref Google Scholar
[52]

Zhao, L.; Wu, Y. W.; Han, J.; Lu, Q.; Yang, Y. P.; Zhang, L. B. Mechanism of mercury adsorption and oxidation by oxygen over the CeO2 (111) surface: A DFT study. Materials 2018, 11, 485.
Crossref Google Scholar
[53]

Wang, M.; Li, C. M. Excitonic properties of graphene-based materials. Nanoscale 2012, 4, 1044–1050.
Crossref Google Scholar
[54]

Wang, H. L.; Wang, X.; Pan, J.; Zhang, L. L.; Zhao, M.; Xu, J.; Liu, B.; Shi, W. D.; Song, S. Y.; Zhang, H. J. Ball-milling induced debonding of surface atoms from metal bulk for construing high-performance dual-site single-atom catalysts. Angew. Chem., Int. Ed. 2021, 60, 23154–23158.
Crossref Google Scholar
[55]

Shojaie, F. N2 adsorption on the inside and outside the single-walled carbon nanotubes by density functional theory study. Pramana 2018, 90, 4.
Crossref Google Scholar
[56]

Li, Z. J.; Chen, Y. Y.; Lu, X. W.; Li, H. H.; Leng, L. P.; Zhang, T. L.; Horton, J. H. Synthesis of cobalt single atom catalyst by a solid-state transformation strategy for direct C–C cross-coupling of primary and secondary alcohols. Nano Res. 2022, 15, 4023–4031.
Crossref Google Scholar
[57]

Lozano-Blanco, G.; Adamczyk, A. J. Cobalt-catalyzed nitrile hydrogenation: Insights into the reaction mechanism and product selectivity from DFT analysis. Surf. Sci. 2019, 688, 31–44.
Crossref Google Scholar
[58]

Oliva, C.; Van Den Berg, C.; Niemantsverdriet, J. W.; Curulla-Ferré, D. A density functional theory study of HCN hydrogenation to methylamine on Co (111). J. Catal. 2007, 248, 38–45.
Crossref Google Scholar
Nano Research
Volume 17 Issue 4,
April 2024
Pages 2444-2450
DOI: 10.1007/s12274-023-6117-9
Cite this article:
Xu J, Wang X, Wang Y, et al. Differentially-grown cobalt regulators cooperatively involved in the tandem catalysis for high-yield production of second amines. Nano Research, 2024, 17(4): 2444-2450. https://doi.org/10.1007/s12274-023-6117-9
Topics:
NanocatalystsNanoclusters

758

Views

0

Crossref

0

Web of Science

0

Scopus

0

CSCD

Altmetrics
Received: 10 July 2023
Revised: 11 August 2023
Accepted: 20 August 2023
Published: 30 September 2023
© Tsinghua University Press 2023
Return