Anisotropy of Pt nanoparticles on carbon- and oxide-support and their structural response to electrochemical oxidation probed by in situ techniques.

Identifying the structural response of nanoparticle-support ensembles to the reaction conditions is essential to determine their structure in the catalytically active state as well as to unravel the possible degradation pathways. In this work, we investigate the (electronic) structure of carbon- and oxide-supported Pt nanoparticles during electrochemical oxidation by in situ X-ray diffraction, absorption spectroscopy as well as the Pt dissolution rate by in situ mass spectrometry. We prepared ellipsoidal Pt nanoparticles by impregnation of the carbon and titanium-based oxide support as well as spherical Pt nanoparticles on an indium-based oxide support by a surfactant-assisted synthesis route. During electrochemical oxidation, we show that the oxide-supported Pt nanoparticles resist (bulk) oxide formation and Pt dissolution. The lattice of smaller Pt nanoparticles exhibits a size-induced lattice contraction in the as-prepared state with respect to bulk Pt but it expands reversibly during electrochemical oxidation. This expansion is suppressed for the Pt nanoparticles with a bulk-like relaxed lattice. We could correlate the formation of d-band vacancies in the metallic Pt with Pt lattice expansion. PtOx formation is strongest for platelet-like nanoparticles and we explain this with a higher fraction of exposed Pt(100) facets. Of all investigated nanoparticle-support ensembles, the structural response of RuO2/TiO2-supported Pt nanoparticles is the most promising with respect to their morphological and structural integrity under electrochemical reaction conditions.

Dissolution of Platinum Single Crystals in Acidic Medium.

Platinum single crystal basal planes consisting of Pt(111), Pt(100), Pt(110) and reference polycrystalline platinum Pt(poly) were subjected to various potentiodynamic and potentiostatic electrochemical treatments in 0.1 M HClO4 . Using the scanning flow cell coupled to an inductively coupled plasma mass spectrometer (SFC-ICP-MS) the transient dissolution was detected on-line. Clear trends in dissolution onset potentials and quantities emerged which can be related to the differences in the crystal plane surface structure energies and coordination. Pt(111) is observed to have a higher dissolution onset potential while the generalized trend in dissolution rates and quantities was found to be Pt(110)>P(100)≈Pt(poly)>Pt(111).

The Carbocation Rearrangement Mechanism, Clarified.

The role of protonated cyclopropane (PCP(+)) structures in carbocation rearrangement is a decades-old topic that continues to confound. Here, quantum-chemical computations (PBE molecular dynamics, PBE and CCSD optimizations, CCSD(T) energies) are used to resolve the issue. PCP(+) intermediates are neither edge-protonated nor corner-protonated (normally) but possess "closed" structures mesomeric between these two. An updated mechanism for hexyl ion rearrangement is presented and shown to resolve past mysteries from isotope-labeling experiments. A new table of elementary-step barrier heights is provided. The mechanism and barrier heights should be useful in understanding and predicting product distributions in organic reactions, including petroleum modification.

Challenges in predicting ΔrxnG in solution: the mechanism of ether-catalyzed hydroboration of alkenes.

Ab initio (coupled-cluster and density-functional) calculations of Gibbs reaction energies in solution, with new entropy-of-solvation damping terms, were performed for the ether-catalyzed hydroboration of alkenes. The goal was to test the accuracy of continuum-solvation models for reactions of neutral species in nonaqueous solvents, and the hope was to achieve an accuracy sufficient to address the mechanism in the "Pasto case": B2H6 + alkene in THF solvent. Brown's SN2/SN1 "dissociative" mechanism, of SN2 formation of borane-ether adducts followed by SN1 alkene attack, was at odds with Pasto's original SN2/SN2 hypothesis, and while Brown could prove his mechanism for a variety of cases, he could not perform the experimental test with THF adducts in THF solvent, where the higher THF concentrations might favor an SN2 second step. Two diboranes were tested: B2H6, used by Pasto, and (9BBN)2 (9BBN = 9-borabicyclo[3.3.1]nonane, C8H15B), used by Brown. The new entropy terms resulted in improved accuracy vs traditional techniques (∼2 kcal mol(-1)), but this accuracy was not sufficient to resolve the mechanism in the Pasto case.

Particle Size Effect on Platinum Dissolution: Practical Considerations for Fuel Cells.

The high costs of polymer membrane electrolyte fuel cells (PEMFCs) remain a roadblock for a competitive market with combustion engine vehicles. The PEMFC costs can be reduced by decreasing the size of Pt nanoparticles in the catalyst layer, thereby increasing the Pt dispersion and utilization. Furthermore, high-power performance loss due to O2 transport resistance is alleviated by decreasing the particle size and increasing dispersion. However, firm conclusions on how Pt particle size impacts durability remain elusive due to synthetic difficulties in exclusively varying single parameters (e.g., particle size and loading). Therefore, here the particle size of Pt nanoparticles was varied from 2.0 to 2.8 and 3.7 nm while keeping the loading constant (30 wt %) on a Vulcan support using the two-step surfactant-free toolbox method. By studying the electrochemical dissolution in situ using online inductively coupled plasma mass spectrometry (online ICP-MS), mass-specific dissolution trends are revealed and are attributed to particle-size-dependent changes in electrochemically active surface area. Such degradation trends are critical for the start/stop of PEMFCs and currently require the implementation of potential control systems in consumer vehicles. Additionally, shifts in the onset of anodic dissolution and also oxidation to more negative potentials with decreasing particle size were observed. These results indicate a similar mechanism of anodic dissolution related to place-exchange when moving from extended polycrystalline Pt to nanoparticle scales. The negative shifts in the onset as the particle size decreases highlight a practical limitation for PEMFCs during load/idle conditions: without further material improvements, which inhibit Pt dissolution, reduction in costs and improvement in high-power performance via increased Pt utilization and dispersion will not be possible by decreasing particle sizes further.

Effect of Ionic Liquid Modification on the ORR Performance and Degradation Mechanism of Trimetallic PtNiMo/C Catalysts.

Ionic liquids (ILs) modification, following the concept of "solid catalyst with ionic liquid layer (SCILL)", has been demonstrated to be an effective approach to improving both activity and stability of Pt-based catalysts for the oxygen reduction reaction. In this work, the SCILL concept has been applied to a trimetallic PtNiMo/C system, which has been documented recently to be significantly advantageous over the benchmark PtNi-based catalysts for oxygen reduction. To achieve this, two hydrophobic ILs ([BMIM][NTF2] and [MTBD][BETI]) were used to modify PtNiMo/C with four IL-loading amounts between 7 and 38 wt %. We found that the Pt mass activity (@0.9 V) could be improved by up to 50% with [BMIM][NTF2] and even 70% when [MTBD][BETI] is used. Exceeding a specific IL loading amount, however, leads to a mass transport related activity drop. Moreover, it is also disclosed that both ILs can effectively suppress the formation of nonreactive oxygenated species, while at the same time imposing little effect on the electrochemical active surface area. For a deeper understanding of the degradation mechanism of pristine and IL modified PtNiMo/C, we applied identical location transmission electron microscopy and in situ scanning flow cell coupled to inductively coupled plasma mass spectrometry techniques. It is disclosed that the presence of ILs has selectively accelerated the dissolution of Mo and eventually results in a more severe degradation of PtNiMo/C. This shows that future research needs to identify ILs that prevent the Mo dissolution to leverage the potential of the IL modification of PtNiMo catalysts.

Tuning the Electrocatalytic Performance of Ionic Liquid Modified Pt Catalysts for the Oxygen Reduction Reaction via Cationic Chain Engineering.

Modifying Pt catalysts using hydrophobic ionic liquids (ILs) has been demonstrated to be a facile approach for boosting the performance of Pt catalysts for the oxygen reduction reaction (ORR). This work aims to deepen the understanding and initiate a rational molecular tuning of ILs for improved activity and stability. To this end, Pt/C catalysts were modified using a variety of 1-methyl-3-alkylimidazolium bis(trifluoromethanesulfonyl)imide ([C n C1im][NTf2], n = 2-10) ILs with varying alkyl chain lengths in imidazolium cations, and the electrocatalytic properties (e.g., electrochemically active surface area, catalytic activity, and stability) of the resultant catalysts were systematically investigated. We found that ILs with long cationic chains (C6, C10) efficiently suppressed the formation of nonreactive oxygenated species on Pt; however, at the same time they blocked active Pt sites and led to a lower electrochemically active surface area. It is also disclosed that the catalytic activity strongly correlates with the alkyl chain length of cations, and a distinct dependence of intrinsic activity on the alkyl chain length was identified, with the maximum activity obtained on Pt/C-[C4C1im][NTf2]. The optimum arises from the counterbalance between more efficient suppression of oxygenated species formation on Pt surfaces and more severe passivation of Pt surfaces with elongation of the alkyl chain length in imidazolium cations. Moreover, the presence of an IL can also improve the electrochemical stability of Pt catalysts by suppressing the Pt dissolution, as revealed by combined identical-location transmission electron microscopy (TEM) and in situ inductively coupled plasma mass spectrometry (ICP-MS) analyses.