Novel hollow microsphere with porous carbon shell embedded with Cu/Co bimetal nanoparticles: Facile large-scale preparation and catalytic hydrogenation performance

doi:10.1016/j.jmst.2021.11.080

Abstract

Abstract:

Non-noble bimetals have attracted extensive attention for their natural aboundance and low cost, but it remains a big challenge to design and synthesize novel supported non-noble bimetal nanocatalyst in a controllable and high-efficient manner. Herein, a novel hollow spherical supported non-noble bimetal nanocatalyst with porous carbon shell as the continuous matrix and Cu/Co bimetal nanoparticles as the dispersion phase is successfully fabricated by a convenient strategy involving spray drying and subsequent heat treatment. The morphology and microstructure depend catalyst activity of the hollow spherical supported catalyst has been studied systematically. It is found that the heating temperature plays a critical role in determining the microstructure and catalytic performance of the products. With an optimal heating temperature of 600 °C, the corresponding product exhibits the highest normalized reaction rate constant (k_n) of 25.4 s^-1 g^-1 for catalytic reduction of 4-notrophenol, which can be attributed to the suitable synergism of the well-defined bimetal structure, combined effect of the two metallic phases and the metal-support interaction. This work provides an additional strategy for the simultaneous formation of both the support and the active loading phase of supported non-noble bimetal nanocatalyst, and may shed some light on the high-efficiency synthesis of other supported heterostructure with various compositions and properties.

Key words: Carbon supported non-noble catalysts, Bimetal nanoparticles, Hollow microspheres, Catalytic hydrogenation

Gaiping Du, Ran Liu, Qianqian Jia, Gang Han, Zhenguo An, Jingjie Zhang. Novel hollow microsphere with porous carbon shell embedded with Cu/Co bimetal nanoparticles: Facile large-scale preparation and catalytic hydrogenation performance[J]. J. Mater. Sci. Technol., 2022, 122: 44-53.

Figures/Tables 15

Fig. 1. Schematic illustration of the synthesis of HCS-Cu/Co-T first forming a hollow spherical structure by spraying drying, following by thermal annealing in inert atmospheres.

Fig. 2. SEM images of the obtained HCS-Cu/Co-600.

Fig. 3. TEM and SAED images of HCS-Cu/Co-600.

Fig. 4. N2 adsorption-desorption isotherms and the corresponding pore diameter distribution curve of the HCS-Cu/Co-600.

Fig. 5. (a) XRD patterns; (b) narrow scan of HCS-Cu/Co-600 and contrast samples.

Fig. 6. Dark-field TEM (DF-TEM) images and EDX mapping images of the HCS-Cu/Co-600 composite catalyst.

Fig. 7. XPS measurements of HCS-Cu/Co-600: (a) survey spectrum, (b) high-resolution Cu 2p and Cu LMM (inset), (c) Co 2p, (d) O 1s.

Fig. 8. TG-DTA curves of the precursor hollow spherical powders heated from 25 to 850 °C with a heating rate of 5 °C/min under nitrogen atmosphere.

Fig. 9. EDX mapping images of HCS-Cu/Co-T, T = (a) 300 °C, (b) 400 °C, (c) 500 °C, (d) 600 °C, (e) 700 °C, (f) 800 °C (the red represents Cu phase, the green represents Co phase).

Fig. 10. (a) XRD patterns; (b) narrow scan of HCS-Cu/Co-T (T = 300 °C, 400 °C, 500 °C, 600 °C, 700 °C, 800 °C), nano Cu, nano Co and nano Cu&Co.

Fig. 11. (a) ID/IG data from Raman spectrum, (b) the electrical conductivity of the HCS-Cu/Co-T (T = 400-800 °C). (b) presents the electrical conductivity of HCS-Cu/Co-T at various HT. With the HT of 300, 400, 500 °C, the electrical conductivity is 4.77 × 10-8, 1.12 × 10-7, 8.90 × 10-7 S/mm, respectively. As the temperature increases to 600 and 700 °C, the electrical conductivity increases quickly to 3.54 × 10-4 and 1.79 × 10-2 S/mm. Subsequently, the conductivity rises rapidly to 0.186 S/mm with the further increase of HT into 800 °C. The electrical conductivity enhances 7 orders of magnitude over HT from 300 °C to 800 °C, indicating the sensitivity of conductive property towards microstructure constructed by heating treatment.

Fig. 12. Experimental plots of (a) At/A0 vs time t, (b) -ln(At/A0) vs time t of 4-NP reduction by NaBH4 over obtained HCS-Cu/Co-T (T = 400-800 °C) catalysts.

Fig. 13. Experimental plots of (a) At/A0 vs time t, (b) -ln(At/A0) vs time t of 4-NP reduction by NaBH4 over catalysts including obtained HCS-Cu/Co-600, Cu+Co+C-600, Cu+C-600, Co+C-600, commercial nano Cu and Co powders. (The legends of the two pictures (a) and (b) are the same.)

Fig. 14. The ka and kn of 4-NP reduction by NaBH4 over catalysts: (a) HCS-Cu/Co-T (T = 400-800 °C), (b) HCS-Cu/Co-600, Cu+Co+C-600, Cu+C-600, Co+C-600, commercial nano Cu and Co powders.

Fig. 15. (a) Reusability test of the HCS-Cu/Co-600 catalyst for the catalytic reduction of 4-NP, (b) the conversion of 4-NP within 60 s by HCS-Cu/Co-600 catalyst in cycle experiment, (c) kn and nNaBH4/n4-NP of reported relative catalysts and catalyst obtained in this work for catalyzing the 4-NP conversion reaction. Refs. [53,54,29,55,44,56].

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