Nitrogen-modified metal-organic framework-based carbon: An effective non-precious electrocatalyst for oxygen reduction reaction

doi:10.1016/j.catcom.2020.106135

Catalysis Communications

Volume 146, November 2020, 106135

https://doi.org/10.1016/j.catcom.2020.106135 Get rights and content

Highlights

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MOF-based catalyst is developed from polypyrrole coated MIL-101.
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It has high surface area with favorable graphite and pyridine nitrogen.
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C-MIL-101@PPy catalyst has good ORR performance.

Abstract

Metal-organic framework (MOF) based composite materials have attracted significant research interest in the electrocatalytic field. In this study, a carbonized polypyrrole coated MOF composite electrocatalyst (C-MIL-101@PPy) is developed, which is a nitrogen-modified MOF-based carbon used as non-precious oxygen reduction reaction (ORR) electrocatalyst. Physical characterizations prove that the C-MIL-101@PPy electrocatalyst has high nitrogen doping (2.53 at.%) and effective graphite and pyridinium nitrogen doping (86.6%). When compared with commercial Pt/C, as-obtained C-MIL-101@PPy electrocatalyst shows good ORR performance (∆E_1/2 = −22 mV) with good stability (87.8%) and methanol tolerance. All results indicate that MOF-based C-MIL-101@PPy electrocatalyst is an effective and promising electrocatalyst for ORR.

Graphcial abstract

Introduction

The state-of-the-art metal-organic framework (MOF), with a regular special morphology, adjustable apertures, and large specific surface area, has drawn wide research interest as a novel class of materials [[1], [2], [3], [4]]. For electrocatalytic applications, the most classic way is using MOF as templates to obtain a series of nanocomposites. Many studies have shown that MOF can be used as template materials to prepare catalysts with many advantages [5,6]. It consists of a hollow and porous structure, which can avoid metal mass loss, and uniform pore size for improving the catalytic performance, while the regular structure is beneficial for the uniform distribution of the metal components and carbon. Currently, there are several reports that MOF can be used as a precursor or as a sacrificial template/precursor for preparation of various functional nanostructures, such as derived alloys, oxides, nitrides, carbides, and carbon materials, exhibiting excellent performance in electrocatalysis [7].

Carbonization of polymer materials, such as melamine resin, polyaniline, and chitosan, can result in a final carbon product with high nitrogen content and other good properties [[8], [9], [10]]. Polypyrrole (PPy) has good environmental stability, high electrical conductivity, and good redox property, making it one of the most promising and ideal polymer nitrogen modifiers to prepare carbon-based electrocatalytic materials. Recently, it has been proven that MOF as a skeleton/template is coated with high nitrogen content polymer materials and that, through the carbonization process, it can obtain good conductivity, stability, and oxygen reduction reaction (ORR) electrocatalytic performance [[11], [12], [13], [14], [15]]. Therefore, designing ways of incorporating active sites into the MOF-structure to make an advanced electrocatalyst would be an effective strategy to get improved catalytic activity toward ORR.

In this work, a MOF of MIL-101 is coated with polypyrrole and then carbonized to obtain a target electrocatalyst of C-MIL-101@PPy, which is a nitrogen-modified MOF-based carbon, to be used as non-precious electrocatalyst for ORR. Subsequently, a series of tests show that as-prepared C-MIL-101@PPy electrocatalyst has a high nitrogen ratio (2.53 at.%). When compared with commercial Pt/C, the C-MIL-101@PPy electrocatalyst has good ORR catalytic activity, methanol tolerance, and stability (87.8%). This C-MIL-101@PPy electrocatalyst would be an effective non-precious electrocatalyst for ORR in the future.

Section snippets

Preparation of MIL-101(Fe)

Firstly, iron nitrate hexahydrate (1.35 g, 5 mmol) and terephthalic acid (0.415 g, 2.5 mmol) were dissolved in N, N-dimethylformamide (DMF, 30 mL). Then, the solution was transferred to a 100 mL hydrothermal reaction vessel and reacted for 12 h at 110 °C. The product was cooled to room temperature and was repeatedly washed with DMF and ethanol. Finally, the solid was dried in an oven at 60 °C for 12 h, which is MIL-101(Fe) (CAS:1189182-67-9).

Preparation of C-MIL-101@PPy electrocatalyst

During the preparation, the C-MIL-101@PPy

Results and discussion

MOF-based composite materials have attracted significant research interest in the electrocatalysis field. However, the direct carbonization of MOF is not ideal in ORR performance due to limited catalysis active sites. Thus, most MOF materials, such as MIL-101, require introducing other components to increase active sites. Consequently, carbonization of polypyrrole-coated MIL-101 is a beneficial strategy for obtaining an effective ORR electrocatalyst. As shown in Fig. 1, C-MIL-101@PPy

Conclusion

In this study, C-MIL-101@PPy electrocatalyst, a nitrogen-modified MOF-based carbon material used as a non-precious ORR electrocatalyst, is developed by carbonization of polypyrrole coated MIL-101 composite. The polypyrrole makes the final C-MIL-101@PPy electrocatalyst having higher nitrogen doping (2.53 at.%) and a more effective nitrogen doping type (86.6%). The results demonstrate that as-prepared C-MIL-101@PPy electrocatalyst has better ORR electrocatalytic activity, stability, and methanol

Declaration of Competing Interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

Acknowledgments

This work is supported by the National Natural Science Foundation of China (21561019), the program of Changjiang Scholars and Innovative Research Team in University (IRT_15R56), and the Foundation of a Hundred Youth Talents Training Program of Lanzhou Jiaotong University and the Instrument Analysis Center of Lanzhou Jiaotong University.

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Short communicationNitrogen-modified metal-organic framework-based carbon: An effective non-precious electrocatalyst for oxygen reduction reaction

Highlights

Abstract

Graphcial abstract

Introduction

Section snippets

Preparation of MIL-101(Fe)

Preparation of C-MIL-101@PPy electrocatalyst

Results and discussion

Conclusion

Declaration of Competing Interest

Acknowledgments

Appl. Catal. B Environ.

Green Energy Environ.

Carbon

Electrochim. Acta

Ceram. Int.

Carbon

Energy

Electrochim. Acta

J. Power Sources

Electrochim. Acta

Nano Energy

Carbon

Lamellar metal organic framework-derived Fe-N-C non-noble electrocatalysts with bimodal porosity for efficient oxygen reduction

ACS Appl. Mater. Interfaces

Short communication
Nitrogen-modified metal-organic framework-based carbon: An effective non-precious electrocatalyst for oxygen reduction reaction