Impact of channel nanostructures of porous carbon particles on their catalytic performance.

Mesoporous carbon particles have great potential due to their unique structural properties as support materials for catalytic applications. Particle shapes and channel nanostructures of mesoporous carbon particles can determine the reactant/product transport efficiency. However, the role of the channel nanostructure in the catalytic reaction has not been much explored. Herein, we introduce a facile method to fabricate a series of porous carbon particles (PCPs) with controlled channel exposure on the carbon surface and investigate the impact of the channel nanostructure of the PCPs on the catalytic activity. By employing a membrane emulsification method with a controlled solvent evaporation rate, we fabricate block copolymer (BCP) particles with uniform size and regulated degrees of cylindrical channel exposed to the particle surface. Followed by the carbonization of the BCP particles, a low amount (1.3 wt%) of Pt is incorporated into the PCP series to investigate the impact of channel nanostructures on the catalytic oxidation reaction of o-phenylenediamine (OPD). Specifically, PCP featuring highly open channel nanostructures shows a high reaction rate constant of 0.154 mM-1 s-1 for OPD oxidation, showing 5.5 times higher catalytic activity than those of closed channel nanostructures (0.028 mM-1 s-1). This study provides a deeper understanding of the impact of channel nanostructure within mesoporous carbon particles on catalytic activity.

Lens-Shaped Carbon Particles with Perpendicularly-Oriented Channels for High-Performance Proton Exchange Membrane Fuel Cells.

Two-dimensional sheet-like mesoporous carbon particles are promising for maximizing the number of active sites and the mass transport efficiency of proton exchange membrane fuel cells (PEMFCs). Herein, we develop a series of lens-shaped mesoporous carbon (LMC) particles with perpendicularly oriented channels (diameter = 60 nm) and aspect ratios (ARs) varying from 2.1 to 6.2 and apply them for the fabrication of highly efficient PEMFCs. The membrane emulsification affords uniform-sized, lens-shaped block copolymer particles, which are successfully converted into the LMC particles with well-ordered vertical channels through hyper-cross-linking and carbonization steps. Then, an ultralow amount (1 wt %) of platinum (Pt) is loaded into the particles. The LMC particles with higher ARs are packed with a higher density in the cathode and are better aligned on the cathode surface compared to the LMC particles with lower ARs. Thus, the well-ordered channels in the particles facilitate the mass transport of the reactants and products, significantly increasing the PEMFC performance. For example, the LMC particles with the AR of 6.2 show the highest initial single cell performance of 1135 mW cm-2, and the cell exhibits high durability with 1039 mW cm-2 even after 30 000 cycles. This cell performance surpasses that of commercial Pt/C catalysts, even at 1/20 of the Pt loading.

Determination of the Absolute Enantiomeric Excess of the Carbon Nanotube Ensemble by Symmetry Breaking Using the Optical Titration Method.

Symmetry breaking of single-walled carbon nanotubes (SWNTs) has profound effects on their optoelectronic properties that are essential for fundamental study and applications. Here, we show that isomeric SWNTs that exhibit identical photoluminescence (PL) undergo symmetry breaking by flavin mononucleotide (FMN) and exhibit dual PLs and different binding affinities (Ka). Increasing the FMN concentration leads to systematic PL shifts of SWNTs according to structural modality and handedness due to symmetry breaking. Density gradient ultracentrifugation using a FMN-SWNT dispersion displays PL shifts and different densities according to SWNT handedness. Using the optical titration method to determine the PL-based Ka of SWNTs against an achiral surfactant as a titrant, left- and right-handed SWNTs display two-step PL inflection corresponding to respective Ka values with FMN, which leads to the determination of the enantiomeric excess (ee) of the SWNT ensemble that was confirmed by circular dichroism measurement. Decreasing the FMN concentration for the SWNT dispersion leads to enantiomeric selection of SWNTs. The titration-based ee determination of the widely used sodium cholate-based SWNT dispersion was also demonstrated by using FMN as a cosurfactant.

Effect of tight flavin mononucleotide wrapping and its binding affinity on carbon nanotube covalent reactivities.

The controlled functionalization of single-walled carbon nanotubes (SWNTs) is a key to using them in high-end applications. We show that nanotube reactivity after covalent diazonium modification is governed by a chirality-specific surfactant binding affinity to SWNTs. Both metallic and semiconducting SWNTs tightly organized by a helical flavin mononucleotide (FMN) assembly exhibit two hundred times slower reactivity toward 4-methoxy benzenediazonium (4-MBD) than those wrapped by sodium dodecyl sulfate and this reactivity enables chirality- and metallicity-specific behaviours to be probed, as confirmed by absorption, Raman, and photoluminescence (PL) spectroscopy. Each reaction kinetic of the two-step SWNT PL decays originating from electron transfer and the covalent reaction of 4-MBD, respectively, is inversely proportional to the binding affinity (Ka) between FMN and the SWNTs. The observed marginally higher reaction rate of the metallic nanotube compared to the semiconducting one results from the weaker Ka value of the metallic nanotubes with FMN. An enrichment demonstration of a few nanotube chiralities using selective and slow covalent diazonium chemistry demonstrates the importance of the binding affinity between the surfactant and the SWNTs. The study provides a handle on chirality-specific covalent chemistry via surfactant-SWNT binding affinity and impacts on future-sensing schemes.

Binding affinities and thermodynamics of noncovalent functionalization of carbon nanotubes with surfactants.

Binding affinity and thermodynamic understanding between a surfactant and carbon nanotube is essential to develop various carbon nanotube applications. Flavin mononucleotide-wrapped carbon nanotubes showing a large redshift in optical signature were utilized to determine the binding affinity and related thermodynamic parameters of 12 different nanotube chiralities upon exchange with other surfactants. Determined from the midpoint of sigmoidal transition, the equilibrium constant (K), which is inversely proportional to the binding affinity of the initial surfactant-carbon nanotube, provided quantitative binding strengths of surfactants as SDBS > SC ≈ FMN > SDS, irrespective of electronic types of SWNTs. Binding affinity of metallic tubes is weaker than that of semiconducting tubes. The complex K patterns from semiconducting tubes show preference to certain SWNT chiralities and surfactant-specific cooperativity according to nanotube chirality. Controlling temperature was effective to modulate K values by 30% and enables us to probe thermodynamic parameters. Equally signed enthalpy and entropy changes produce Gibbs energy changes with a magnitude of a few kJ/mol. A greater negative Gibbs energy upon exchange of surfactant produces an enhanced nanotube photoluminescence, implying the importance of understanding thermodynamics for designing nanotube separation and supramolecular assembly of surfactant.