Skip to main content

Zinc cobalt bimetallic nanoparticles embedded in porous nitrogen-doped carbon frameworks for the reduction of nitro compounds

  • Xuejuan Xu (a1), Hui Li (a1), Hongtao Xie (a1), Yuhua Ma (a1), Tingxiang Chen (a1) and Jide Wang (a1)...

The development of highly efficient and stable inexpensive catalysts for the reduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP) by NaBH4 in an aqueous solution by utilizing metal-organic frameworks (MOFs) as precursor and template remains a hot topic. Herein, a simple self-template strategy was developed to synthesize a porous nitrogen-doped carbon frameworks embedded with zinc and cobalt nanoparticles (Zn0.3Co2.7@NC) catalyst by thermal annealing of the bimetallic zinc-cobalt zeolitic imidazolate framework (Zn0.3Co2.7-ZIF) as an effective precursor and template. The resulting Zn0.3Co2.7@NC catalysts show an excellent catalytic activity for the reduction of 4-NP and the reduction reaction was completed only in 5 min with nearly 100% conversion. The apparent rate constant for the reaction of 4-NP reduction was estimated to be 0.683 min−1. Moreover, the catalyst was extended to reduce other nitro compounds and exhibited excellent catalytic activity. When compared to other related catalysts in the literature, the catalytic activity of catalyst is superior. Therefore, the resulting Zn0.3Co2.7@NC is expected to get more extensive application in the field of catalysis.

Corresponding author
a) Address all correspondence to these authors. e-mail:
Hide All

Contributing Editor: Edson Roberto Leite

Hide All
1. Raula, M., Rashid, M.H., Lai, S., Roy, M., and Mandal, T.K.: Solvent-adoptable polymer Ni/NiCo alloy nanochains: Highly active and versatile catalysts for various organic reactions in both aqueous and nonaqueous media. ACS Appl. Mater. Interfaces 4, 878 (2012).
2. Torres Galvis, H.M., Bitter, J.H., Khare, C.B., Ruitenbeek, M., Dugulan, A.I., and de Jong, K.P.: Supported iron nanoparticles as catalysts for sustainable production of lower olefins. Science 335, 835 (2012).
3. van Speybroeck, V., Gani, R., and Meier, R.J.: The calculation of thermodynamic properties of molecules. Chem. Soc. Rev. 39, 1764 (2010).
4. Lin, Y., Qiao, Y., Wang, Y., Yan, Y., and Huang, J.: Self-assembled laminated nanoribbon-directed synthesis of noble metallic nanoparticle-decorated silica nanotubes and their catalytic applications. J. Mater. Chem. 22, 18314 (2012).
5. Yan, N., Zhao, Z., Li, Y., Wang, F., Zhong, H., and Chen, Q.: Synthesis of novel two-phase Co@SiO2 nanorattles with high catalytic activity. Inorg. Chem. 53, 9073 (2014).
6. Zhao, M., Deng, K., He, L., Liu, Y., Li, G., Zhao, H., and Tang, Z.: Core–shell palladium nanoparticle@metal-organic frameworks as multifunctional catalysts for cascade reactions. J. Am. Chem. Soc. 136, 1738 (2014).
7. Chughtai, A.H., Ahmad, N., Younus, H.A., Laypkov, A., and Verpoort, F.: Metal-organic frameworks: Versatile heterogeneous catalysts for efficient catalytic organic transformations. Chem. Soc. Rev. 44, 6804 (2015).
8. Stock, N. and Biswas, S.: Synthesis of metal-organic frameworks (MOFs): Routes to various MOF topologies, morphologies, and composites. Chem. Rev. 112, 933 (2012).
9. Aijaz, A., Fujiwara, N., and Xu, Q.: From metal-organic framework to nitrogen-decorated nanoporous carbons: High CO2 uptake and efficient catalytic oxygen reduction. J. Am. Chem. Soc. 136, 6790 (2014).
10. Bak, W., Kim, H.S., Chun, H., and Yoo, W.C.: Facile synthesis of metal/metal oxide nanoparticles inside a nanoporous carbon matrix (M/MO@C) through the morphology-preserved transformation of metal-organic framework. Chem. Commun. 51, 7238 (2015).
11. Chen, Y-Z., Wang, C., Wu, Z-Y., Xiong, Y., Xu, Q., Yu, S-H., and Jiang, H-L.: From bimetallic metal-organic framework to porous carbon: High surface area and multicomponent active dopants for excellent electrocatalysis. Adv. Mater. 27, 5010 (2015).
12. Bai, C., Yao, X., and Li, Y.: Easy access to amides through aldehydic C–H bond functionalization catalyzed by heterogeneous Co-based catalysts. ACS Catal. 5, 884 (2015).
13. Kim, M., Nam, D-H., Park, H-Y., Kwon, C., Eom, K., Yoo, S., Jang, J., Kim, H-J., Cho, E., and Kwon, H.: Cobalt-carbon nanofibers as an efficient support-free catalyst for oxygen reduction reaction with a systematic study of active site formation. J. Mater. Chem. A 3, 14284 (2015).
14. Zhong, W., Liu, H., Bai, C., Liao, S., and Li, Y.: Base-free oxidation of alcohols to esters at room temperature and atmospheric conditions using nanoscale Co-based catalysts. ACS Catal. 5, 1850 (2015).
15. Bai, S., Shen, X., Zhu, G., Li, M., Xi, H. and Chen, K.: In situ growth of Ni(x)Co(100-x) nanoparticles on reduced graphene oxide nanosheets and their magnetic and catalytic properties. Appl. Mater. and Interfaces 4, 23782386 (2012).
16. Hu, L., Zhang, R., Wei, L., Zhang, F., and Chen, Q.: Synthesis of FeCo nanocrystals encapsulated in nitrogen-doped graphene layers for use as highly efficient catalysts for reduction reactions. Nanoscale 7, 450454 (2014).
17. Su, P., Xiao, H., Zhao, J., Yao, Y., Shao, Z., Li, C., and Yang, Q.: Nitrogen-doped carbon nanotubes derived from Zn–Fe–ZIF nanospheres and their application as efficient oxygen reduction electrocatalysts with in situ generated iron species. Chem. Sci. 4, 2941 (2013).
18. Aguirre-Díaz, L.M., Gándara, F., Iglesias, M., Snejko, N., Gutiérrez-puebla, E., and Monge, M.Á.: Tunable catalytic activity of solid solution metal-organic frameworks in one-pot multicomponent reactions. J. Am. Chem. Soc. 137, 6132 (2015).
19. Hou, Y-L., Sun, R.W-Y., Zhou, X-P., Wang, J-H., and Li, D.: A copper(i)/copper(ii)-salen coordination polymer as a bimetallic catalyst for three-component Strecker reactions and degradation of organic dyes. Chem. Commun. 50, 2295 (2014).
20. Long, J., Shen, K., Chen, L., and Li, Y.: Multimetal-MOF-derived transition metal alloy NPs embedded in an N-doped carbon matrix: Highly active catalysts for hydrogenation reactions. J. Mater. Chem. A 4, 10254 (2016).
21. Naeem, S., Ribes, A., White, A.J.P., Haque, M.N., Holt, K.B., and Wilton-Ely, J.D.E.T.: Multimetallic complexes and functionalized nanoparticles based on oxygen- and nitrogen-donor combinations. Inorg. Chem. 52, 4700 (2013).
22. Liao, Y., Zhang, D., Wang, Q., Wen, T., Jia, L., Zhong, Z., Bai, F., Tang, L., Que, W., and Zhang, H.: Open-top TiO2 nanotube arrays with enhanced photovoltaic and photochemical performances via a micromechanical cleavage approach. J. Mater. Chem. A 3, 14279 (2015).
23. Shi, Z-Q., Jiao, L-X., Sun, J., Chen, Z-B., Chen, Y-Z., Zhu, X-H., Zhou, J-H., Zhou, X-C., Li, X-Z., and Li, R.: Cobalt nanoparticles in hollow mesoporous spheres as a highly efficient and rapid magnetically separable catalyst for selective epoxidation of styrene with molecular oxygen. RSC Adv. 4, 47 (2014).
24. Liu, Y., Liu, B., Liu, Y., Wang, Q., Hu, W., Jing, P., Liu, L., Yu, S., and Zhang, J.: Improvement of catalytic performance of preferential oxidation of CO in H2-rich gases on three-dimensionally ordered macro- and meso-porous Pt–Au/CeO2 catalysts. Appl. Catal., B 142–143, 615 (2013).
25. Rong, F., Zhao, J., Su, P., Yao, Y., Li, M., Yang, Q., and Li, C.: Zinc-cobalt oxides as efficient water oxidation catalysts: The promotion effect of ZnO. J. Mater. Chem. A 3, 40104017 (2015).
26. Huang, Z-F., Song, J., Li, K., Tahir, M., Wang, Y-T., Pan, L., Wang, L., Zhang, X., and Zou, J-J.: Hollow cobalt-based bimetallic sulfide polyhedra for efficient all-pH-value electrochemical and photocatalytic hydrogen evolution. J. Am. Chem. Soc. 138, 1359 (2016).
27. Li, X., Zeng, C., Jiang, J., and Ai, L.: Magnetic cobalt nanoparticles embedded in hierarchically porous nitrogen-doped carbon frameworks for highly efficient and well-recyclable catalysis. J. Mater. Chem. A 4, 74767482 (2016).
28. Rakap, M. and Özkar, S.: Intrazeolite cobalt(0) nanoclusters as low-cost and reusable catalyst for hydrogen generation from the hydrolysis of sodium borohydride. Appl. Catal., B 91, 21 (2009).
29. Rakap, M. and Özkar, S.: Hydroxyapatite-supported cobalt(0) nanoclusters as efficient and cost-effective catalyst for hydrogen generation from the hydrolysis of both sodium borohydride and ammonia-borane. Catal. Today 183, 17 (2012).
30. Li, X., Gao, X., Ai, L., and Jiang, J.: Mechanistic insight into the interaction and adsorption of Cr(VI) with zeolitic imidazolate framework-67 microcrystals from aqueous solution. Chem. Eng. J. 274, 238246 (2015).
31. Wu, R., Qian, X., Zhou, K., Wei, J., Lou, J., and Ajayan, P.M.: Porous spinel Zn x Co3−x O4 hollow polyhedra templated for high-rate lithium-ion batteries. ACS Nano 8, 6297 (2014).
32. Peng, S., Li, L., Tan, H., Cai, R., Shi, W., Li, C., Mhaisalkar, S.G., Srinivasan, M., Ramakrishna, S., and Yan, Q.: MS2 (M = Co and Ni) hollow spheres with tunable interiors for high-performance supercapacitors and photovoltaics. Adv. Funct. Mater. 24, 2155 (2014).
33. Xiao, Y., Liu, S., Li, F., Zhang, A., Zhao, J., Fang, S., and Jia, D.: 3D hierarchical Co3O4 twin-spheres with an urchin-like structure: Large-scale synthesis, multistep-splitting growth, and electrochemical pseudocapacitors. Adv. Funct. Mater. 22, 4052 (2012).
34. Kong, A., Mao, C., Lin, Q., Wei, X., Bu, X., and Feng, P.: From cage-in-cage MOF to N-doped and Co-nanoparticle-embedded carbon for oxygen reduction reaction. Dalton Trans. 44, 6748 (2015).
35. Wei, J., Hu, Y., Wu, Z., Liang, Y., Leong, S., Kong, B., Zhang, X., Zhao, D., Simon, G.P., and Wang, H.: A graphene-directed assembly route to hierarchically porous Co–N x /C catalysts for high-performance oxygen reduction. J. Mater. Chem. A 3, 16867 (2015).
36. Zhang, Z., Hao, J., Yang, W., and Tang, J.: Defect-rich CoP/nitrogen-doped carbon composites derived from a metal-organic framework: High-performance electrocatalysts for the hydrogen evolution reaction. ChemCatChem 7, 1920 (2015).
37. , Y., Wang, Y., Li, H., Lin, Y., Jiang, Z., Xie, Z., Kuang, Q., and Zheng, L.: Mof-derived porous Co/C nanocomposites with excellent electromagnetic wave absorption properties. ACS Appl. Mater. Interfaces 7, 13604 (2015).
38. Torad, N.L., Hu, M., Ishihara, S., Sukegawa, H., Belik, A.A., Imura, M., Ariga, K., Sakka, Y., and Yamauchi, Y.: Direct synthesis of MOF-derived nanoporous carbon with magnetic Co nanoparticles toward efficient water treatment. Small 10, 2096 (2014).
39. Khemasiri, N., Chananonnawathorn, C., Klamchuen, A., Jessadaluk, S., Pankiew, A., Vuttivong, S., Eiamchai, P., Horprathum, M., Pornthreeraphat, S., Kasamechonchung, P., Tantisantisom, K., Boonkoom, T., Songsiririthigul, P., Nakajima, H., and Nukeaw, J.: Crucial role of reactive pulse-gas on a sputtered Zn3N2 thin film formation. RSC Adv. 6, 94905 (2016).
40. Jiang, N., Georgiev, D.G., Jayatissa, A.H., Collins, R.W., Chen, J., and McCullen, E.: Zinc nitride films prepared by reactive RF magnetron sputtering of zinc in nitrogen containing atmosphere. J. Phys. D: Appl. Phys. 45, 135101 (2012).
41. Kong, X-K., Sun, Z-Y., Chen, M., Chen, C-L., and Chen, Q-W.: Metal-free catalytic reduction of 4-nitrophenol to 4-aminophenol by N-doped graphene. Energy Environ. Sci. 6, 3260 (2013).
42. Yang, Y., Zhang, W., Ma, X., Zhao, H., and Zhang, X.: Facile construction of mesoporous N-Doped carbons as highly efficient 4-nitrophenol reduction catalysts. ChemCatChem 7, 3454 (2015).
43. Ma, L., Shen, X., Zhu, G., Ji, Z., and Zhou, H.: CoP nanoparticles deposited on reduced graphene oxide sheets as an active electrocatalyst for the hydrogen evolution reaction. Carbon 77, 255265 (2015).
44. Wu, K-L., Wei, X-W., Zhou, X-M., Wu, D-H., Liu, X-W., Ye, Y., and Wang, Q.: NiCo2 alloys: Controllable synthesis, magnetic properties, and catalytic applications in reduction of 4-nitrophenol. J. Phys. Chem. C 115, 1626816274 (2011).
45. Yang, Y., Zhang, Y., Sun, C.J., Li, X., Zhang, W., Ma, X., Ren, Y., and Zhang, X.: Heterobimetallic metal-organic framework as a precursor to prepare a nickel/nanoporous carbon composite catalyst for 4-nitrophenol reduction. ChemCatChem 6, 30843090 (2014).
46. Bai, S., Shen, X., Zhu, G., Li, M., Xi, H., and Chen, K.: In situ growth of Ni x Co100−x nanoparticles on reduced graphene oxide nanosheets and their magnetic and catalytic properties. ACS Appl. Mater. Interfaces 4, 23782386 (2012).
47. Wang, X., Liu, D., Song, S., and Zhang, H.: Heterobimetallic metal-organic framework as a precursor to prepare a nickel/nanoporous carbon composite catalyst for 4-nitrophenol reduction. J. Am. Chem. Soc. 135, 1586415872 (2013).
48. Li, J., Liu, C.Y., and Liu, Y.: Au/graphene hydrogel: Synthesis, characterization and its use for catalytic reduction of 4-nitrophenol. J. Mater. Chem. 22, 84268430 (2012).
49. Ai, L., Yue, H., and Jiang, J.: Environmentally friendly light-driven synthesis of Ag nanoparticles in situ grown on magnetically separable biohydrogels as highly active and recyclable catalysts for 4-nitrophenol reduction. J. Mater. Chem. 22, 2344723453 (2012).
50. Tang, S.C., Vongehr, S., and Meng, X.K.: Environmentally friendly light-driven synthesis of Ag nanoparticles in situ grown on magnetically separable biohydrogels as highly active and recyclable catalysts for 4-nitrophenol reduction. J. Phys. Chem. C 114, 977982 (2010).
Recommend this journal

Email your librarian or administrator to recommend adding this journal to your organisation's collection.

Journal of Materials Research
  • ISSN: 0884-2914
  • EISSN: 2044-5326
  • URL: /core/journals/journal-of-materials-research
Please enter your name
Please enter a valid email address
Who would you like to send this to? *


Type Description Title
Supplementary materials

Xu supplementary material
Xu supplementary material

 Word (4.6 MB)
4.6 MB


Full text views

Total number of HTML views: 0
Total number of PDF views: 0 *
Loading metrics...

Abstract views

Total abstract views: 0 *
Loading metrics...

* Views captured on Cambridge Core between <date>. This data will be updated every 24 hours.

Usage data cannot currently be displayed