Boosting ORR Electrocatalytic Performance of Metal-Free Mesoporous Biomass Carbon by Synergism of Huge Specific Surface Area and Ultrahigh Pyridinic Nitrogen Doping

Abstract

Oxygen reduction reaction (ORR) plays a critical position in direct methanol fuel cells. However, electrocatalytic materials currently utilized in ORR use a rare and expensive metal Pt, so it is vital to develop cathode catalysts with cheap and high ORR activity. Herein, chitosan, a natural material made from chitin, was employed as a complex precursor of carbon source and nitrogen (N) source to synthesize N-doped mesoporous biomass carbon ORR catalysts. Adding different pore agents regulated specific surface area and N type of catalysts. The relationship between the properties of the catalysts and their ORR electrocatalytic performance was investigated. It was luckily found that the addition of ferric nitrate as a pore-forming agent created a huge specific surface area of the N-doped mesoporous biomass carbon (1190 m 2 /g) significantly. More importantly, the synthesized catalyst was doped by whole pyridinic-N at high content (11.58 at %) and inhibited the two-electron reaction efficiently, promoted the four-electron reaction, and accelerated the ORR reaction rate. Furthermore, it provided significant catalytic activity with robust methanol tolerance, and notable cycle stability, indicating the practical applicability of the huge surface area, ultrahigh pyridinic-N-doped mesoporous biomass carbon catalyst.

Sustainable Synthesis of Bright Green Fluorescent Nitrogen‐Doped Carbon Quantum Dots from Alkali Lignin

“…Recently, non‐metal carbon‐based electrocatalysts have attracted great attention because of their excellent stability, low cost, and good methanol tolerance compared with Pt‐based catalysts . In particular, N‐doped CQDs have been widely used in the oxygen reduction reaction (ORR) as the catalyst or cocatalyst .…”

“…Recently,n on-metal carbon-based electrocatalysts have attracted great attentionb ecause of their excellent stability,l ow cost, and good methanolt olerance compared with Pt-based catalysts. [2,57] In particular, N-doped CQDs have been widely used in the oxygen reduction reaction (ORR) as the catalysto r cocatalyst. [58] The electrocatalytic activity of the prepared CQDs was evaluated by cyclic voltammetry (CV) by using ac onventional three-electrode system andl inear sweep voltammetry (LSV) using ar otating disk electrode (RDE).…”

Amino-1H-tetrazole-regulated high-density nitrogen-doped hollow carbon nanospheres for long-life Zn–air batteries

“…22 Zhang, Kwak, Yan, and co-workers also veried the important role played by pyridinic N in the catalysis of ORR. [23][24][25][26] However, Haque and co-workers concluded from experimental results and computational simulation that the total content of N has no inuence on ORR, whereas graphitic N (or quaternary N) was observed to be effective in the ORR via four-electron transfer pathways. 22 Colavita et al, Zhao et al, and Huang et al determined that the synergistic effect between Gr N and Pr N improves the activity and selection of ORR by facilitating the dissociative adsorption of O 2 molecules along with the desorption of intermediates.…”

PEO‐b‐PS Block Copolymer Templated Mesoporous Carbons: A Comparative Study of Nitrogen and Sulfur Doping in the Oxygen Reduction Reaction to Hydrogen Peroxide

“…The two most relevant aspects which determine the ORR activity and selectivity in a carbon material are the nature and content of heteroatom functional groups and the material architecture in terms of surface area and porous structure. Nitrogen or sulfur‐doped carbons can be prepared by thermal, chemical and physical treatments [47–52] of a carbon material or by pyrolysis of suitable precursors or additives containing nitrogen [38, 53] or sulfur [54] such as ionic liquids, [44, 55, 56] polymers, [57–60] and biomasses [61–64] . It is worth mentioning that all these procedures are poorly selective versus the type of functional group that can be pinned into the carbon material.…”

“…Nitrogen or sulfur-dopedc arbons can be prepared by thermal, chemicala nd physical treatments [47][48][49][50][51][52] of ac arbon material or by pyrolysis of suitable precursors or additives containing nitrogen [38,53] or sulfur [54] such as ionic liquids, [44,55,56] polymers, [57][58][59][60] andb iomasses. [61][62][63][64] It is worth mentioning that all these procedures are poorly selective versus the type of functional group that can be pinned into the carbon material. Actually,t his represents the major shortfall of doped carbon and that is why there is still al ot of interest and room for the development and investigation of these materials.…”