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This study aims to elucidate the role of hydrogen desorption profiles obtained through temperature programmed desorption (TPD) analysis of carbon materials for revealing their carbon edge sites. Accordingly, the H 2 desorption profiles of several carbon materials, such as activated carbon, carbon black, reduced graphene oxide (rGO), phenol resin carbon, graphite, high-temperature treated carbon, and carbon nanotubes (CNTs), were investigated. The kinetic analysis of the profiles revealed that H 2 desorption is a second-order reaction initiated by the association of edge hydrogen. Furthermore, the relationship between the total number of edge hydrogens in a sample and the peak temperature of H 2 desorption represents the spatial distribution of edge hydrogens in the carbon structure. Additionally, most of the activated carbons, carbon blacks, and rGOs exhibited a uniform distribution of edge hydrogen throughout their carbon structures. In contrast, the edge hydrogen in graphite, high-temperature treated carbon, and CNTs were heterogeneously distributed throughout their structures. [Display omitted] [ABSTRACT FROM AUTHOR]

A deuterium-labeled temperature-programmed desorption (TPD) technique was developed to accurately characterize functional groups on the surface of carbon-based materials. After the protic hydrogen of the functional groups on activated carbons was substituted by deuterium, TPD analysis revealed the desorption of deuterium compounds (D 2 O, DHO, D 2 , DH). The functional groups were estimated from the predicted desorption mechanisms of these deuterium compounds, which can be distinguished according to the functional groups and their surrounding chemical structures. Thus, this technique provides information on not only the type of functional groups but also the extensive chemical structure around them. The phenolic group, ether, and edge hydrogen formed on the activated carbons were separately quantified, and the functional groups were further classified into 12 types by the nearby chemical structures. Comparison with IR spectra indicated that the deuterium-labeled TPD gave qualitatively reasonable results. This technique is useful for obtaining a deeper understanding of the surface chemical structure of carbon-based materials. Image 1 [ABSTRACT FROM AUTHOR]

In polymer electrolyte fuel cells, the oxygen reduction reaction (ORR) rate increases at high temperatures. Therefore, ORR catalysts must be designed for use at high temperatures and require evaluation. To address the problem of decreased dissolved oxygen concentrations in conventional channel flow double electrode (CFDE) systems, this study develops a CFDE system capable of electrochemical measurement at 120 °C that can evaluate the ORR activity of Pt-supported carbon (Pt/C) and carbon-based non-precious metal catalysts (NPMC). The ORR activity increased with an increasing reaction temperature, regardless of the catalyst, and the current density ratios at 120 °C and room temperature were estimated to be 2.4 and 5.4 for Pt/C and NPMC, respectively. This indicates that the NPMC ORR activity increased significantly with the increasing reaction temperature. This increased activation energy, which is approximately 2.3 times greater than that of Pt/C at the overpotential of 0.38 V, contributes to a significant increase in the ORR activity at higher temperatures. [Display omitted] • An improved channel flow double electrode system is developed. • Kinetic analysis of ORR up to 120 °C was performed by using the system. • The activation energy of NPMC is higher than Pt/C catalyst. • ORR activity of NPMC increased significantly with the increasing reaction temperature. [ABSTRACT FROM AUTHOR]

The warped graphene layer (WGL) has garnered attention as a potential alternative to Pt for oxygen reduction reaction (ORR) catalysts and as a platform for enhancing the activity of Pt or molecular catalysts through interactions. We propose an in-situ nano-templating method for the preparation and mass production of WGLs and demonstrate its efficiency. The in-situ nano-templating method facilitates the synthesis of materials with three-dimensional curvature by concurrently generating nanoparticles and carbonizing. The synthesized WGLs exhibited high ORR activity in acidic conditions. Although the ORR activity was not correlated with the surface area, it was strongly correlated with the curvature radius of the WGLs. This activity was considered to arise owing to the optimization of oxygen adsorption ΔG 0 with the decrease in the curvature radius of the WGLs; furthermore, the physicochemical characteristics of WGL possesses continuity of carbon layers and exhibit a Fermi level higher than the O 2 /H 2 O reduction potential. This report elucidates experimentally that WGLs contribute to ORR activity, suggesting the importance of incorporating WGLs in the development of non-precious metal catalysts. [Display omitted] [ABSTRACT FROM AUTHOR]

The control of the electronic states of carbon-based materials is of great importance for the widespread use of carbon materials as electronic devices and catalysts. This article reports a novel method of controlling the electronic states of carbon-based materials by establishing covalent bonds between inorganic support materials and carbon thin films. Carbon thin films of 1 nm thickness were grown on inorganic substrates (Al 2 O 3 , AlN, and ZrO 2) using chemical vapor deposition. Covalent bond formation was confirmed between the substrates and the carbon films. The investigations of field effect transistor characteristics and work function revealed the different relationships between the Dirac points and Fermi levels of carbon films depending on the type of substrate. The Fermi level of the films grown on Al 2 O 3 or ZrO 2 was found to be lower than the Dirac point energy level, with the ZrO 2 sample exhibiting the lowest Fermi level. In contrast, the Fermi level of the film grown on AlN was located at a higher energy than the Dirac point. The Fermi level of the carbon film depends on the inorganic substrate, and the change in the Fermi level can be explained by the nature of the covalent bonds between the substrate and the film. Controlling the energy levels of the valence electrons of carbon thin film depending on the composition of the substrate on which the carbon thin film is grown. [Display omitted] [ABSTRACT FROM AUTHOR]

Onion-like carbon (OLC) is known to form as an intermediate structure when nanodiamond (ND) is heat treated at 1100–1500 °C. In this letter, we report on the electrochemical activity of its oxygen reduction reaction (ORR) when prepared at temperatures from 1000 to 2000 °C. The ORR activity is found to exhibit excellent correlation with the degree of defects, with OLC prepared at 1400 °C found to have the highest activity. This is attributed to the formation of curved graphitic layers containing edges during ND-OLC transformation, which function as active sites for the adsorption and subsequent reduction of oxygen. [ABSTRACT FROM AUTHOR]

Trace amounts of edge sites in natural graphite, synthetic graphite and high-temperature treated coke are quantitatively analyzed from the numbers of hydrogen atoms and oxygen-containing functional groups at carbon edge sites. For the analysis of hydrogen content, a new analytical technique is developed. The oxygen-containing functional groups are analyzed with a highly sensitive temperature-programmed desorption (TPD) technique. These techniques allow us to estimate the trace amounts of edge sites in the range of 1–10 × 10 −4 at.% with extremely high accuracy and reveal that the concentration and the type of edges sites differ depending on the type and the particle size of these graphitized carbons. Moreover, the average sizes of graphene sheets in these carbons are estimated from the total number of edge sites. The graphene sheet size thus obtained is compared with the crystallite sizes, L a , and the average particle size, and such comparison provides deep insight into the understanding of carbon molecular structure in the graphitized carbons. [ABSTRACT FROM AUTHOR]

The use of carbon cathode catalysts in polymer electrolyte fuel cells instead of the current platinum catalysts is attracting increasing attention. We claim that two factors are important for enhancing the activity of carbon cathode catalysts in the oxygen reduction reaction (ORR): the formation of a nanoshell structure and co-doping with boron and nitrogen. Herein, we investigate the preparation and characterization of active ORR carbon catalysts that combine the above factors. Boron and nitrogen (BN)-doped nanoshell-containing carbon (BN-NSCC) was prepared by carbonizing a mixture of poly(furfuryl alcohol), cobalt phthalocyanine, melamine, and a trifluoroborane–methanol complex at 1000 °C. Transmission electron microscopy and X-ray photoelectron spectroscopy revealed the formation of nanoshell structures with distorted graphitic layers and the introduction of boron and nitrogen atoms, respectively. The ORR activity was evaluated in oxygen-saturated 0.5 mol dm −3 H 2 SO 4 using Koutecky–Levich analysis. The BN-NSCC showed an eight to ten times higher ORR activity than undoped NSCC, with an increased number of electrons participating in the reaction. Tafel analysis revealed a change in the rate-determining step caused by BN-doping. Thus, the combination of a nanoshell structure and co-doping with boron and nitrogen was found to improve the ORR activity of carbon catalysts. [ABSTRACT FROM AUTHOR]

This study reports the synergistic improvement of the oxygen reduction reaction (ORR) activity of a carbon catalyst prepared from a phenol–formaldehyde resin by simultaneous incorporation of Cu and Fe phthalocyanines. This carbon catalyst exhibited higher ORR activities than those prepared with either Cu or Fe phthalocyanines, with an approx. 28-fold maximum ORR current enhancement observed when Cu/Fe = 75:25 was incorporated into the carbon precursor. Surface and structural characterizations of these catalysts suggested that the incorporated Cu played a role in suppressing the catalytic activity of Fe, forming the reported nanoshell structure, and in keeping more nitrogen atoms attached to carbons. The incorporation of Cu in the carbon catalyst provided a doping effect for nitrogen into the carbon structure and inhibited catalytic graphitization caused by Fe species. These effects resulted in a distinctive carbon structure in the nanoshell. These multiple effects of Cu incorporation were considered key factors in the enhancement of ORR activity caused by Fe and Cu incorporation. [ABSTRACT FROM AUTHOR]

The activity of non-precious metal catalysts (NPMCs) has now reached a stage at which they can be considered as possible alternatives to Pt for some proton exchange membrane fuel cell (PEMFC) applications. However, despite significant efforts over the past 50 years on catalyst development, only limited studies have been performed on NPMC-based cathode catalyst layer (CCL) designs. In this work, an extensive ionomer study is performed to investigate the impact of ionomer equivalent weight on performance, which has uncovered two crucial findings. Firstly, it is demonstrated that beyond a critical CCL conductance, no further improvement in performance is observed. The procedure used to determine this critical conductance can be used by other researchers in this field to aid in their design of high performing NPMC-based CCLs. Secondly, it is shown that the stability of NPMC-based CCLs can be improved through the use of low equivalent weight ionomers. This represents a completely unexplored pathway for further stability improvements, and also provides new insights into the possible degradation mechanisms occurring in NPMC-based CCLs. These findings have broad implications on all future NPMC-based CCL designs. [ABSTRACT FROM AUTHOR]

Carbon catalysts for the oxygen reduction reaction (ORR) were prepared from mixtures of humic acid and cobalt compounds. To examine the effects of cobalt and nitrogen on the ORR, cobalt phthalocyanine (CoPc), cobalt chloride (CoCl 2 ) and phthalocyanine (H 2 Pc) were mixed with the humic acid and carbonized at 800 °C. The carbons were washed with hydrochloric acid to remove metals on the surface of the carbons. The carbon prepared by mixing HA, CoCl 2 and H 2 Pc (HA–CoCl 2 –H 2 Pc) had the highest ORR activity, while the carbons, HA–CoPc and HA–H 2 Pc, had lower ORR activities. HA–CoCl 2 had moderate activity. The results imply that both of cobalt and nitrogen are important to obtain ORR catalysts with higher activities. A uniform distribution of Co atoms in the precursor is also important to obtain carbon alloy catalysts with higher ORR activities. TANSO 2015 (No. 267), 94–100. [ABSTRACT FROM AUTHOR]

Hard carbons emerge as one of the most promising candidate for an anode of Na-ion batteries. This research focuses on the carbon monolith derived from resorcinol-formaldehyde (RF) gels as a model hard carbon electrode. A series of binder-free monolithic carbon electrodes heat-treated at varied temperatures allow the comparative investigation of the correlation between carbon nanotexture and electrochemical Na + -ion storage. The increase in carbonization temperature exerts a favorable influence on electrode performance, especially in the range between 1600 °C and 2500 °C. The comparison between Li + - and Na + -storage behaviors in the carbon electrodes discloses that the Na + -trapping in nanovoids is negligible when the carbonization temperature is higher than 1600 °C. On the other hand, the high-temperature sintering at 2500–3000 °C enlarges the resistance for Na + -insertion into interlayer spacing as well as Na + -filling into nanovoids. In addition, the study on the effect of pore size clearly demonstrates that not the BET surface area but the surface area related to meso- and macropores is a predominant factor for the initial irreversible capacity. The outcomes of this work are expected to become a benchmark for other hard carbon electrodes prepared from various precursors. [ABSTRACT FROM AUTHOR]

A major hurdle to the widespread commercialization of proton exchange membrane fuel cells (PEMFCs) is the high loading of noble metal (Pt/Pt-alloy) catalyst at the cathode, which is necessary to facilitate the inherently sluggish oxygen reduction reaction (ORR). To eliminate the use of Pt/Pt-alloy catalysts at the cathode of PEMFCs and thus significantly reduce the cost, extensive research on non-precious metal catalysts (NPMCs) has been carried out over the past decade. Major advances in improving the ORR activity of NPMCs, particularly Fe- and Co-based NPMCs, have elevated these materials to a level at which they can start to be considered as potential alternatives to Pt/Pt-alloy catalysts. Unfortunately, the stability (performance loss following galvanostatic experiments) of these materials is currently unacceptably low and the durability (performance loss following voltage cycling) remains uncertain. The three primary mechanisms of instability are: (a) Leaching of the metal site, (b) Oxidative attack by H 2 O 2 , and (c) Protonation followed by possible anion adsorption of the active site. While (a) has largely been solved, further work is required to understand and prevent losses from (b) and/or (c). Thus, this review is focused on historical progress in (and possible future strategies for) improving the stability/durability of NPMCs. [ABSTRACT FROM AUTHOR]

By using non-graphitizable and graphitizable carbons prepared from poly(furfulyl alcohol) and poly(vinyl chloride), respectively, an attempt is made to determine the number of carbon edge sites by analyzing their hydrogen content and the amounts of surface oxygen complexes and localized spins. It is found that, at the present preparation conditions, the number of hydrogen-terminated edges is much higher than the number of surface oxygen complexes regardless of the type of carbon and the heat-treatment temperature, but the contribution of the localized spins derived from σ free radicals in closed spaces and/or triplet carbene/carbyne species may become comparable to the hydrogen content when the heat-treatment temperature is higher. Moreover, the average sizes of graphene layers in these carbons are estimated from the total number of edge sites. This analysis suggests that the actual size in the poly(furfulyl alcohol)-derived carbons is much larger than the size detected with transmission electron microscopy. This large difference is discussed in relation to a real structure of graphene layers in non-graphitizable carbons. [ABSTRACT FROM AUTHOR]

A catalyst support can improve the catalytic activity of metal catalysts, and this phenomenon is well known as the support effect. The effective use of this support effect is considered important for improving catalytic activity. However, the factors affecting this phenomenon are complex. It is, therefore, important to understand the interaction between the support and metal catalyst as well as the surface characteristics of the support for elucidating this phenomenon. Carbon is a useful support material because of its high chemical and thermal stability and electroconductivity. Moreover, its surface properties can be controlled by doping the carbon structure with heteroatoms. In this study, the catalytic activity of metal particles supported on heteroatom-doped carbon materials was evaluated to investigate the support effect of the doped carbon. The catalytic activity of carbon-supported Ni particles in benzene hydrogenation was improved by introducing N and B into the carbon support. In particular, Ni supported on N-doped carbon showed a two-fold improvement in activity compared to that supported on undoped carbon. A compensation effect was confirmed for the catalytic activity of Ni particles. The results suggest that the introduction of heteroatoms into the carbon support changed the adsorption energy of the reactant on Ni, thereby improving the Ni catalytic activity. [Display omitted] • A catalyst support can improve the catalytic activity of metal catalysts. • Ni on B- and N-doped carbons has better activity than Ni on undoped carbon. • Heteroatoms on carbon change the energy of reactant adsorption onto Ni. • A compensation effect was confirmed for the activity of Ni on doped carbon. [ABSTRACT FROM AUTHOR]