A novel nitrogen-containing electrocatalyst for oxygen reduction reaction from blood protein pyrolysis

doi:10.1016/j.jpowsour.2013.07.037

Journal of Power Sources

Volume 245, 1 January 2014, Pages 841-845

https://doi.org/10.1016/j.jpowsour.2013.07.037 Get rights and content

Highlights

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A novel N-containing electrocatalyst for ORR was fabricated by using pyrolysis of blood protein.
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Addition of carbon support into carbonization process may produce better catalytic activity.
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High-temperature pyrolysis process can transfer the pyridinic-N to pyrrolic-N significantly.
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The content of pyrrolic-N group plays an important role in improvement of the ORR catalytic activity.

Abstract

We report a new strategy to design carbon-based electrocatalysts containing nitrogen through the co-pyrolysis of blood protein and carbon black support. The results show that the nitrogen in electrocatalysts is primarily in the form of pyridinic- and pyrrolic-type nitrogen species. High-temperature pyrolysis processes can transfer a significant amount of pyridinic-N to pyrrolic-N. The electrocatalyst containing a higher amount of the pyrrolic-N configuration exhibits better electrocatalytic activity towards oxygen reduction reaction in terms of onset potential, half-wave potential, and limited current density. It is suggested that the pyrrolic-N configuration may be the electrocatalytically active site and may be responsible for the enhanced ORR performance in alkaline media. The carbon black support also plays an important role in the pyrolysis process, improving the ORR catalytic activity.

Introduction

The oxygen reduction reaction (ORR) at the cathode plays a key role in metal–air batteries [1] and fuel cells [2]. Carbon-supported platinum particles are the most effective catalyst for the ORR [3], but sluggish oxygen reduction, high cost, and low abundance limit the commercialization of these technologies. Many research efforts have been done on the reduction of Pt loading and exploration of novel non-precious catalysts to reduce fuel cell cost. It is interesting that heat-treated carbon materials have received enormous attention as non-precious electrode materials for ORR, especially for N-doped carbon nanotubes and N-doped graphene [4], [5], [6], [7]. Additional N-containing materials were fabricated by several bioproteins, such as collagen [8] and hemoglobin [9], [10]. Quite recently, several groups have reported the preparation and oxygen reduction electrocatalytic behavior of N-containing electrocatalysts using hemin biomaterial as an effective precursor or N-enriched amino acids as nitrogen sources [11], [12], [13], [14], [15]. These works mainly focus on the use of natural porphyrinatoiron complexes contained inside hemin or the selection of nitrogen sources to form the catalytic sites.

Many heat-treated materials have reasonably good electrocatalytic activity towards ORR, but their stability is still far below the requirements for the practical application of new energy. The exhibited catalytic properties may be substantially attributed to the presence of C–N active sites in the carbon structure [4], [16], [17], [18], [19]. However, the detailed C–N bonding configuration responsible for the ORR catalytic activity of N-containing carbons remains elusive. Additionally, to create N-containing electrocatalysts, in addition to the requirement of complex procedures and expensive equipment, the precursors also need to be handled carefully because of their toxic and corrosive nature [5]. Therefore, the development of a simple and effective method for fabricating electrocatalysts to replace the commercial Pt-based catalysts has remained a challenge.

Blood protein (BP) from animals can be obtained from the meat industry, and it includes an abundance of hemoprotein and various amino acids. These substances can successfully produce active electrocatalysts for ORR in acidic and alkaline environments. BP material could be a potential precursor for preparing highly active electrocatalysts for ORR, as supported by our previous reports [20]. To overcome the current obstacles, in this work, we develop a new approach to synthesize a novel N-containing electrocatalyst (BP350C1000) BP material with high ORR catalytic activity and stability through the use of high-temperature pyrolysis. Our results indicate that BP350C1000 with higher percentage of pyrrolic-N improves ORR activity substantially, suggesting that pyrrolic-N plays an active role in ORR electrocatalysis.

Section snippets

Materials

Porcine BP was supplied by the Food Testing Center of Chongqing Bureau of Quality and Technology Supervision, China. Carbon black (Vulcan XC-72R) was purchased from Cabot^® and pretreated in a solution containing 10% HNO₃ and 30% H₂O₂ at 80 °C for 12 h.

Catalyst preparation

First, 0.5 g of BP was decomposed in flowing N₂ at 350 °C for 5 h. The yielded pyropolymer as a precursor was mixed with the pretreated carbon black support (mass ratio of 1:1) by ball milling. The obtained substance was further treated in flowing

Catalyst characterization

In Fig. 1(a), the XRD patterns of three N-containing electrocatalysts show similar phase compositions. The only other peaks observed are two amorphous-carbon peaks, centered at 2θ values of ≈24° and ≈44°, which are ascribed to the graphitic planes (002) and (101), respectively [20]. The broad peak at 24° reveals the domination of the disordered carbon phase in electrocatalysts, while the weak broad peak at 44° suggests the existence of graphitic layers with smaller sizes and lower

Conclusions

Herein, we report a facile method to design an ORR electrocatalyst from the pyrolysis of the BP350 pyropolymer combined with a carbon support. The nitrogen exists mainly in the pyridinic- and pyrrolic-N configurations in all carbonized materials. It is interesting that the high-temperature pyrolysis process changes a significant amount of the pyridinic-N to the pyrrolic-N configuration. BP350C1000 contains a higher percentage of the pyrrolic-N configuration, which is promising for four-electron

Acknowledgments

This work was supported by the Natural Science Fund of China (Project No. 21273292) and the Fundamental Research Funds for the Central Universities (Project No. CDJXS12220002). We also thank Wenjing Yang and Lin Chen for helpful discussions.

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Short communicationA novel nitrogen-containing electrocatalyst for oxygen reduction reaction from blood protein pyrolysis

Highlights

Abstract

Introduction

Section snippets

Materials

Catalyst preparation

Catalyst characterization

Conclusions

Acknowledgments

Appl. Energy

Appl. Catal. B: Environ.

Electrochem. Commun.

Electrochem. Commun.

Electrochem. Commun.

Int. J. Hydrogen Energy

Electrochem. Commun.

J. Power Sources

J. Power Sources

Carbon

Int. J. Electrochem. Sci.

New Carbon Mater.

J. Power Sources

Microporous Mesoporous Mater.

J. Power Sources

Short communication
A novel nitrogen-containing electrocatalyst for oxygen reduction reaction from blood protein pyrolysis