Solvothermal Synthesis of Nitrogen-Containing Graphene for Electrochemical Oxygen Reduction in Acid Media

Lyth, Stephen Matthew; Nabae, Yuta; Islam, Nazrul; Hayakawa, Teruaki; Kuroki, Shigeki; Kakimoto, Masa Aki; Miyata, Seizo

doi:10.1380/ejssnt.2012.29

Cited by 23 publications

(21 citation statements)

References 40 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Non‐PGM electrocatalysts are often variations on N‐coordinated Fe or Co in a carbon matrix (i.e., Fe/N/C, Co/N/C), or simply metal‐free N‐doped carbon . N‐doped carbon nanotube powders, nanotube arrays, graphene, nanocages, and carbon nitrides have been studied in recent years for reactions including: (i) the ORR, (ii) photocatalytic water splitting, and (iii) photocatalytic CO 2 reduction. In (iii), the primary products include CO, methanol, and ethanol, but at low quantum yield .…”

Section: Introductionmentioning

confidence: 99%

“…In (iii), the primary products include CO, methanol, and ethanol, but at low quantum yield . We have previously demonstrated that carbon nitride (g‐C 3 N 4 ) exhibits ORR activity, especially when synthesized on a conductive support with large surface area . High temperature treatment played a critical role in the catalytic activity, with optimal activity achieved after pyrolysis at 1000 °C .…”

Section: Introductionmentioning

confidence: 99%

“…Non-PGMe lectrocatalysts are often variations on N-coordinated Fe or Co in ac arbon matrix (i.e.,F e/N/C, Co/N/ C), or simply metal-free N-doped carbon. [10,11] N-doped carbon nanotubep owders, [12] nanotube arrays, [13] graphene, [14,15] nanocages, [16] and carbon nitrides [17][18][19][20][21][22] have been studied in recent years for reactions including:( i) the ORR, [17][18][19][20][21][22] (ii)photocatalytic water splitting, [23,24] and (iii)photocatalytic CO 2 reduction.I n (iii), the primary productsi nclude CO, methanol, and ethanol, but at low quantum yield. [25,26] We have previously demonstrated that carbon nitride (g-C 3 N 4 )e xhibits ORR activity,e specially when synthesized on ac onductive support with large surface area.…”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

A Nitrogen‐Doped Carbon Catalyst for Electrochemical CO₂ Conversion to CO with High Selectivity and Current Density

et al. 2016

View full text Add to dashboard Cite

We report characterization of a non-precious metal-free catalyst for the electrochemical reduction of CO to CO; namely, a pyrolyzed carbon nitride and multiwall carbon nanotube composite. This catalyst exhibits a high selectivity for production of CO over H (approximately 98 % CO and 2 % H ), as well as high activity in an electrochemical flow cell. The CO partial current density at intermediate cathode potentials (V=-1.46 V vs. Ag/AgCl) is up to 3.5× higher than state-of-the-art Ag nanoparticle-based catalysts, and the maximum current density is 90 mA cm . The mass activity and energy efficiency (up to 48 %) were also higher than the Ag nanoparticle reference. Moving away from precious metal catalysts without sacrificing activity or selectivity may significantly enhance the prospects of electrochemical CO reduction as an approach to reduce atmospheric CO emissions or as a method for load-leveling in relation to the use of intermittent renewable energy sources.

show abstract

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

A Nitrogen‐Doped Carbon Catalyst for Electrochemical CO₂ Conversion to CO with High Selectivity and Current Density

et al. 2016

View full text Add to dashboard Cite

show abstract

“…Recently, solvothermal chemistry has been employed for synthesizing graphene, which has made it possible to produce large quantities with varying quality. [8][9][10] Polymer electrolyte membrane fuel cells (PEFCs) are clean and environmentally friendly power sources for stationary, portable, and vehicular applications. They display rapid response times, high power densities and are extremely energy efficient.…”

mentioning

confidence: 99%

Defective Graphene Foam: A Platinum Catalyst Support for PEMFCs

Liu

Daio

Sasaki

et al. 2014

J. Electrochem. Soc.

Self Cite

View full text Add to dashboard Cite

Gram-scale synthesis of defective graphene foam from low-cost precursors is reported as a catalyst support material for platinum in fuel cell cathodes. The material was produced by combustion of sodium ethoxide, followed by washing and heat-treatment in various gases. The BET surface area is higher than 1500 m 2 /g. The defects in the material result in excellent distribution of platinum nanoparticles on the surface. The electrochemical performance is compared with platinum-decorated carbon black and commercially obtainable graphene using cyclic voltammetry, linear sweep voltammetry, and membrane electrode assemblies. Pt-decorated graphene foam has larger electrochemical surface area (101 m 2 /g) and higher mass activity (176 A/g Pt ). However, durability and fuel cell power density still require improvements. This graphene foam is a potentially useful catalyst support, especially for use in polymer electrolyte membrane fuel cells.

show abstract

“…To avoid the presence of transition metals, our group began synthesis of nitrogen-doped graphene foam via thermal decomposition of sodium alkoxides and subsequent heat-treatment. 30,31 Due to the high surface area and unique structure of these electrocatalysts, the ORR currents achieved were much higher than those previously obtained. Due to the purity of the precursors, and the synthesis in Teflon vessels, such samples are proven to be free of metal contamination.…”

mentioning

confidence: 76%

Metal-Free Nitrogen-Doped Carbon Foam Electrocatalysts for the Oxygen Reduction Reaction in Acid Solution

Liu

Yu²,

Daio

et al. 2016

J. Electrochem. Soc.

View full text Add to dashboard Cite

Metal-free, nitrogen-doped carbon foam is utilized as a model non-precious electrocatalyst system to investigate the role of nitrogen in the oxygen reduction reaction (ORR) in the absence of iron contamination. This graphene-like foam displays relatively high activity for the ORR in acid, despite being proven free from transition-metal impurities. The onset potential is 0.85 V RHE , the mass activity is 2.8 A/g at 0.6 V RHE , and the current density is −4.0 mA/cm 2 . The maximum electron transfer number is calculated to be 3.6, revealing that a 4-electron pathway is possible in nitrogen-doped carbon, even in the absence of transition-metal coordination sites. The excellent electrochemical activity is attributed to the large surface area (700 m 2 /g), improved conductivity after graphitization, and the relatively high proportion of tertiary (graphite-like) nitrogen. Non-platinum group metal (non-PGM) electrocatalysts for the oxygen reduction reaction (ORR) are desired in order to reduce the cost and improve the durability of proton exchange membrane fuel cells (PEMFCs). Transition metal-based electrocatalysts have long been suggested as alternative electrocatalysts. Starting in the 1970's, early attempts were made to utilize transition metal-containing macrocyclic complexes as biomimetric ORR electrocatalysts, taking inspiration from their usefulness in nature.1 However, soon it was discovered that heat-treatment of these macrocycles resulted in better activity and durability, 2 leading to debate over the precise chemical composition of the active site. Later still, it was realized that the macrocyclic complex was not necessary at all, but that seemingly arbitrary mixtures of Fe (or Co), nitrogen and carbon could lead to very active electrocatalysts. 3Since then, a vast amount of research output has been produced from a number of groups across the world. [4][5][6][7][8] In recent years, such electrocatalysts have become a mainstream research topic, with the DOE setting specific targets for a non-PGM cathode in a H 2 /air PEMFC; namely a volumetric activity of 300 A/cm 3 measured at 800 mV iR-free by 2017. 9 These targets have been all but met, 10 and non-PGM electrocatalysts are now commercially available.The issue of the nature of the active site has never gone away, and is still frequently debated.11 Complicating the issue is the fact that the ORR can proceed via either a 4-or 2-electron pathway to produce water or hydrogen peroxide (which can then further decompose to water), respectively. The 4-electron pathway is most desired in fuel cells, but the 2-electron pathway is significantly present in most non-precious electrocatalysts. The consensus in recent years has drifted toward the active site being comprised of pyridinic nitrogen atoms near a defect or edge, coordinated with a transition metal atom, with strong evidence of this provided by Mossbauer spectroscopy. 12 The clustering of nitrogen atoms in this manner has been observed in graphene in high resolution scanning tunneling microscopy (STM) measuremen...

show abstract

Solvothermal Synthesis of Nitrogen-Containing Graphene for Electrochemical Oxygen Reduction in Acid Media

Cited by 23 publications

References 40 publications

A Nitrogen‐Doped Carbon Catalyst for Electrochemical CO₂ Conversion to CO with High Selectivity and Current Density

A Nitrogen‐Doped Carbon Catalyst for Electrochemical CO₂ Conversion to CO with High Selectivity and Current Density

Defective Graphene Foam: A Platinum Catalyst Support for PEMFCs

Metal-Free Nitrogen-Doped Carbon Foam Electrocatalysts for the Oxygen Reduction Reaction in Acid Solution

Contact Info

Product

Resources

About

Solvothermal Synthesis of Nitrogen-Containing Graphene for Electrochemical Oxygen Reduction in Acid Media

Cited by 23 publications

References 40 publications

A Nitrogen‐Doped Carbon Catalyst for Electrochemical CO2 Conversion to CO with High Selectivity and Current Density

A Nitrogen‐Doped Carbon Catalyst for Electrochemical CO2 Conversion to CO with High Selectivity and Current Density

Defective Graphene Foam: A Platinum Catalyst Support for PEMFCs

Metal-Free Nitrogen-Doped Carbon Foam Electrocatalysts for the Oxygen Reduction Reaction in Acid Solution

Contact Info

Product

Resources

About

A Nitrogen‐Doped Carbon Catalyst for Electrochemical CO₂ Conversion to CO with High Selectivity and Current Density

A Nitrogen‐Doped Carbon Catalyst for Electrochemical CO₂ Conversion to CO with High Selectivity and Current Density