Probing the correlation between Pt-support interaction and oxygen reduction reaction activity in mesoporous carbon materials modified with Pt-N active sites

Brandiele, Riccardo; Durante, Christian; Zerbetto, Mirco; Vicentini, Nicola; Kosmala, Tomasz; Badocco, Denis; Pastore, Paolo; Rizzi, Gian Andrea; Isse, Abdirisak Ahmed; Gennaro, Armando

doi:10.1016/j.electacta.2018.04.182

Cited by 47 publications

(49 citation statements)

References 48 publications

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“…This result suggests a cooperative effect among S defects and that the metal–support interaction is more effective when the support contains a high number of sulfur defects, as observed from the XPS analysis. In all cases, the interaction energy can be considered high, based on the coarse scale that we used in our previous work . We recall that, based on the average Pt−C bond energy, we considered the interaction as high, medium, or low if Δ E

_{Pt_{4}}

<−280 kJ mol −1 , between −280 and −200 kJ mol −1 , or >−200 kJ mol −1 , respectively.…”

Section: Resultsmentioning

confidence: 99%

“…With most of the surfaces (with the exceptions of near‐over and far‐over configurations), the cluster loses its tetrahedral geometry with the atoms adopting a configuration that resembles a Pt 3 +Pt arrangement, obtained by pulling one of the Pt atoms closest to the graphitic surface approximately 1 Å far away from the Pt cluster. Such a rearrangement was not observed on nitrogen defects reported in a previous paper, with the only exception being the N‐pyrrolic defect, which was observed to give very high interaction energies. Another similarity between N‐pyrrolic and thiophenic defects is the fact that the N‐pyrrolic defect is characterized by a five‐atom ring surrounded by two CH 2 groups.…”

Section: Resultsmentioning

confidence: 99%

“…The effects that seem to mostly influence the adsorption energy are: i) the “deformation” of the cluster into a Pt 3 +Pt arrangement; ii) the number of Pt−C bonds; iii) the possible interaction of Pt atoms with hetero surface atoms (which can be led by the partial charges on the Pt atoms); and iv) the top, bridge, or hollow position of the Pt atoms closest to the surface (with the bridge as the most favorable). Table S1 in the Supporting Information reports a list of these events, with an associated (rough) energy contribution optimized in the previous works . With respect to the past simulations with Pt 4 clusters, we needed to refine the parameter that we called “cluster deformation”, changing it into the new label Pt 3 Pt, with a lower associated energy penalty of 250 kJ mol −1 , which was estimated as the energy to break one Pt−Pt bond of the Pt 4 cluster .…”

Section: Resultsmentioning

confidence: 99%

“…Table S1 in the Supporting Information reports a list of these events, with an associated (rough) energy contribution optimized in the previous works . With respect to the past simulations with Pt 4 clusters, we needed to refine the parameter that we called “cluster deformation”, changing it into the new label Pt 3 Pt, with a lower associated energy penalty of 250 kJ mol −1 , which was estimated as the energy to break one Pt−Pt bond of the Pt 4 cluster . The estimation of the energy with this empirical model is provided in Table S2 in the Supporting Information.…”

Section: Resultsmentioning

confidence: 99%

“…It has been extensively demonstrated that nitrogen‐doped carbon exerts a strong interaction with the supported Pt NPs, improving their electronic properties and catalytic activity . Also, sulfur affords a clear metal–support interaction between Pt NPs and the carbon support –.…”

Section: Introductionmentioning

confidence: 99%

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Mesoporous Carbon with Different Density of Thiophenic‐Like Functional Groups and Their Effect on Oxygen Reduction

et al. 2019

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The metal–support interactions between sulfur‐doped carbon supports (SMCs) and Pt nanoparticles (NPs) were investigated, aiming at verifying how sulfur functional groups can improve the electrocatalytic performance of Pt NPs towards the oxygen reduction reaction (ORR). SMCs were synthetized, tailoring the density of sulfur functional groups, and Pt NPs were deposited by thermal reduction of Pt(acac)2. The extent of the metal–support interaction was proved by X‐ray photoelectron spectroscopy (XPS) analysis, which revealed a strong electronic interaction, proportional to the density of sulfur defects, whereas XRD spectra provided evidence of higher strain in Pt NPs loaded on SMC. DFT simulations confirmed that the metal–support interaction was strongest in the presence of a high density of sulfur defects. The combination of microstrain and electronic effects resulted in a high catalytic activity of supported Pt NPs towards ORR, with linear correlations of the half‐wave potential E1/2 or the kinetic current jk with the sulfur content in the support. Furthermore, a mass activity value (550 A g−1) well above the United States Department of Energy target of 440 A g−1 at 0.9 V (vs. reversible hydrogen electrode, RHE), was determined.

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_{Pt_{4}}

<−280 kJ mol −1 , between −280 and −200 kJ mol −1 , or >−200 kJ mol −1 , respectively.…”

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Mesoporous Carbon with Different Density of Thiophenic‐Like Functional Groups and Their Effect on Oxygen Reduction

et al. 2019

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Metal Porphyrins as Single Site Catalyst Models Explored by Electrochemical Scanning Tunneling Microscopy: A New Perspective in Electrocatalysis

Facchin

Durante

2022

Advanced Sustainable Systems

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M–N–C materials featuring M–Nx single site catalysts, where for example M = Co, Mg, or Fe coordinating x atoms of nitrogen, have been intensely investigated as promising candidates to replace Pt group metals in a variety of electrocatalytic reactions, for example in the O2 reduction reactions (ORR). However, despite the recent emerging of atomic resolution techniques, there is still a lack of understanding of the precise configuration of the M–Nx single site. For example, metal porphyrins are known to act as catalysts for O2 and they are indeed good model systems for mimicking M–N4 sites. In particular, it would be of interest to gain more information on the precise dynamic of the catalytic process at atomic scale, especially in an electrochemical environment, i.e., at electrode/electrolyte interphase. An approach that is becoming more and more consolidated is to combine the information coming from electrochemistry and scanning tunneling microscopy techniques in electrochemical scanning tunneling microscopy (EC‐STM) and the result is that a precise dynamic of the catalytic site at atomic scale can be investigated. This review aims to emphasize the main results and advances of EC‐STM in investigating small molecule electrocatalysis and specifically O2 reduction at metal porphyrins M–N4 model system.

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Nitrogen‐Doped Mesoporous Carbon Electrodes Prepared from Templating Propylamine‐Functionalized Silica

et al. 2020

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In this paper, nitrogen doped carbon materials with mesopores 4–8 nm‐wide and a high surface area of ca.1100 m2 g−1 were synthesized according to an innovative hard template method. Sucrose was used as carbon source and propylamine functionalized silica acted as both nitrogen source and templating agent. The novel doped carbons were compared with mesoporous carbons featuring similar texture properties (pore size and surface area) but obtained by the pyrolysis of sucrose or 1,10‐phenantholine and employing non‐functionalized silica as a templating agent. The interest of this investigation is to understand how doping occurs when a functionalized silica is employed, and whether the nitrogen doping remains a surface property or it is extended also to the bulk of the material, influencing the morphological and the electrical properties of the resulting carbon. X‐ray photoemission spectroscopy, elemental analysis, and EDX confirmed the doping action of the functionalized silica and the electrochemical characterization allowed to compare the different performances as supercapacitor materials.

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Probing the correlation between Pt-support interaction and oxygen reduction reaction activity in mesoporous carbon materials modified with Pt-N active sites

Cited by 47 publications

References 48 publications

Mesoporous Carbon with Different Density of Thiophenic‐Like Functional Groups and Their Effect on Oxygen Reduction

Mesoporous Carbon with Different Density of Thiophenic‐Like Functional Groups and Their Effect on Oxygen Reduction

Metal Porphyrins as Single Site Catalyst Models Explored by Electrochemical Scanning Tunneling Microscopy: A New Perspective in Electrocatalysis

Nitrogen‐Doped Mesoporous Carbon Electrodes Prepared from Templating Propylamine‐Functionalized Silica

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