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Nitrogen doping in carbon materials can modify the employed carbon material’s electronic and structural properties, which helps in creating a stronger metal-support interaction. In this study, the role of nitrogen doping in improving the durability of Pt catalysts supported on a three-dimensional vertically aligned carbon nanofiber (VACNF) array towards oxygen reduction reaction (ORR) was explored. The nitrogen moieties present in the N-VACNF enhanced the metal-support interaction and contributed to a reduction in the Pt particle size from 3.1 nm to 2.3 nm. The Pt/N-VACNF catalyst showed better durability when compared to Pt/VACNF and Pt/C catalysts with similar Pt loading. DFT calculations validated the increase in the durability of the Pt NPs with an increase in pyridinic N and corroborated the molecular ORR pathway for Pt/N-VACNF. Moreover, the Pt/N-VACNF catalyst was found to have excellent tolerance towards methanol crossover. 

This study reports the preparation of a set of hybrid materials consisting of molybdenum disulfide (MoS 2 ) nanopatches on reduced graphene oxide (rGO) nanosheets by microwave specific heating of graphene oxide and molecular molybdenum precursors followed by thermal annealing in 3% H 2 and 97% Ar. The microwave process converts graphene oxide to ordered rGO nanosheets that are sandwiched between uniform thin layers of amorphous molybdenum trisulfide (MoS 3 ). The subsequent thermal annealing converts the intermediate layers into MoS 2 nanopatches with two-dimensional layered structures whose defect density is tunable by controlling the annealing temperature at 250, 325 and 600 °C, respectively. All three MoS 2 /rGO samples and the MoS 3 /rGO intermediate after the microwave step show a high Li-ion intercalation capacity in the initial 10 cycles (over 519 mA h g MoSx −1 , ∼3.1 Li + ions per MoS 2 ) which is attributed to the small MoS 2 nanopatches in the MoS 2 /rGO hybrids while the effect of further S-rich defects is insignificant. In contrast, the Zn-ion storage properties strongly depend on the defects in the MoS 2 nanopatches. The highly defective MoS 2 /rGO hybrid prepared by annealing at 250 °C shows the highest initial Zn-ion storage capacity (∼300 mA h g MoSx −1 ) and close to 100% coulombic efficiency, which is dominated by pseudocapacitive surface reactions at the edges or defects in the MoS 2 nanopatches. The fast fading in the initial cycles can be mitigated by applying higher charge/discharge currents or extended cycles. This study validates that defect engineering is critical for improving Zn-ion storage. 

Vertically aligned carbon nanofibers (VACNFs) are promising supports for oxygen reduction reaction (ORR) electrocatalysts in fuel cells. Although experimentally these catalytic systems have shown great potential, there is lack of molecular understanding of the catalytic sites and reaction mechanisms. This work investigated the origin of the ORR reactivities of the platinum catalysts on multi‐edged VACNFs (Pt/VACNF) using a multiscale modeling approach combining Density Functional Theory (DFT) and classical Molecular Dynamics (MD) simulations. Based on the ReaxFF potential, all nanoscale Pt particles (Pt₅₅, P₁₀₀, and Pt₁₄₇) are stabilized by the open edges located axially along the VACNF walls. The calculated first‐shell coordination numbers,, of surface Pt atoms are 6.63, 7.27, and 7.85, respectively, suggesting that the percentage of low coordination sites increases as the particle size decreases. The adsorption energies of OOH, O, and OH on Pt₅₅were systematically probed using DFT calculations. These adsorption energies retain a linear correlation against the generalized coordination numbers (). For Pt nanoparticles supported on VACNF, we found that the OOH and OH bind stronger than on Pt (111) by 0.14 and 0.17 eV, respectively, which can hinder the ORR activity with lower limiting potential than Pt (111). Our theoretical prediction is in good agreement with the linear sweeping voltammetry that revealed a left shift of the half‐wave potential.

 

Nitrogen‐doped graphitic carbon materials have been widely used as a catalyst support in the methanol oxidation reaction (MOR). In this study, we report the role of three‐dimensionally architectured in‐situ N‐doped vertically aligned carbon nanofibers (VACNF) as a catalyst support for MOR in acidic and alkaline media. The abundant graphitic edge sites at the sidewall of N‐doped VACNF strongly anchor the deposited platinum group metal (PGM) catalysts and induce a partial electron transfer between the PGM catalysts and support. Density Functional Theory (DFT) calculations reveal that the strong metal‐support interaction substantially increases the adsorption energy of OH, particularly near the N‐doping sites, which helps to compete and remove the adsorbed intermediate species generated during MOR. The PGM catalysts on N‐doped VACNF support exhibits CO stripping at lower potentials comparing to the commercial Vulcan carbon support and presents an enhanced electrocatalytic performance and better durability for MOR.