Understanding hydrazine oxidation electrocatalysis on undoped carbon.

Carbons are ubiquitous electrocatalytic supports for various energy-related transformations, especially in fuel cells. Doped carbons such as Fe-N-C materials are particularly active towards the oxidation of hydrazine, an alternative fuel and hydrogen carrier. However, there is little discussion of the electrocatalytic role of the most abundant component - the carbon matrix - towards the hydrazine oxidation reaction (HzOR). We present a systematic investigation of undoped graphitic carbons towards the HzOR in alkaline electrolyte. Using highly oriented pyrolytic graphite electrodes, as well as graphite powders enriched in either basal planes or edge defects, we demonstrate that edge defects are the most active catalytic sites during hydrazine oxidation electrocatalysis. Theoretical DFT calculations support and explain the mechanism of HzOR on carbon edges, identifying unsaturated graphene armchair defects as the most likely active sites. Finally, these findings explain the 'double peak' voltammetric feature observed on many doped carbons during the HzOR.

Tuning of ORR activity through the stabilization of the adsorbates by hydrogen bonding with substituent groups.

Metallocorroles and metalloporphyrins (M-N-C) are some of the best alternative molecular catalysts for the replacement of the expensive platinum-group metals (PGM) in oxygen reduction reaction (ORR) catalysis in polymer electrolyte membrane (PEM) fuel cells. To date, Co-based corroles have shown the best performance, but still suffer from the poor stability and the toxicity of the Co metal. Mn-N-C are more stable than Co-N-C, and are also less reactive towards peroxide formation. In this work, using first-principles density functional theory calculations, we study the improvement of the Mn-based corrole ORR activity by exploiting hydrogen bonding with substituent groups to modify the adsorption energies of the ORR intermediates and obtain higher onset potential (Vonset) values. We found that by using phenyl acetic acid as a substituent, Vonset increased from 0.54 V for the unsubstituted corrole to ∼0.9 V which is competitive with the Vonset of the Co-based corroles. Our results suggest that hydrogen bonding with substituent groups should be considered in the analysis and design of the reactivity of active sites in non-PGM ORR catalysts.

Temperature and Nuclear Quantum Effects on the Stretching Modes of the Water Hexamer.

The water hexamer has many low-lying isomers, e.g., ring, book, cage, and prism, shifting from two- to three-dimensional structures. We show that this dimensionality change is accompanied by a drop in the quantum nature of the cluster, as manifested in the red shift of the quantal OH stretching modes as compared with their classical counterparts. We obtain this "nuclear quantum effect" (NQE) as the mean deviation between the OH stretch frequencies from velocity autocorrelation Fourier transforms from classical trajectories on a high-level water potential (MB-pol) as compared with scaled harmonic frequencies from high-level quantum chemistry calculations. With a universal scaling factor, the predicted OH frequencies agree with experiment to a mean absolute deviation ≤10 cm-1, which allows unequivocal isomer assignments. By assuming temperature-independent NQEs, we produce the temperature dependence of the cage isomer OH stretch spectrum below 70 K, where it is the dominant structure. All bands widen and blue-shift with increasing temperature, most conspicuously the reddest mode, which thus constitutes a "vibrational thermometer".

Structure, spectroscopy, and dynamics of the phenol-(water)2 cluster at low and high temperatures.

Aqueous solutions are complex due to hydrogen bonding (HBing). While gas-phase clusters could provide clues on the solution behavior, most neutral clusters were studied at cryogenic temperatures. Recent results of Shimamori and Fujii provide the first IR spectrum of warm phenol-(H2O)2 clusters. To understand the temperature (T) effect, we have revisited the structure and spectroscopy of phenol-(H2O)2 at all T. While older quantum chemistry work concluded that the cyclic isomers are the most stable, the inclusion of dispersion interactions reveals that they are nearly isoenergetic with isomers forming π-HBs with the phenyl ring. Whereas the OH-stretch bands were previously assigned to purely local modes, we show that at low T they involve a concerted component. We have calculated the (static) anharmonic IR spectra for all low-lying isomers, showing that at the MP2 level, one can single out one isomer (udu) as accounting for the low-T spectrum to 3 cm-1 accuracy. Yet no isomer can explain the substantial blueshift of the phenyl-OH band at elevated temperatures. We describe the temperature effect using ab initio molecular dynamics with a density functional and basis-set (B3LYP-D3/aug-cc-pVTZ) that provide a realistic description of OH⋯O vs. OH⋯π HBing. From the dipole moment autocorrelation function, we obtain good description for both low- and high-T spectra. Trajectory visualization suggests that the ring structure remains mostly intact even at high T, with intermittent switching between OH⋯O and OH⋯π HBing and lengthening of all 3 HBs. The phenyl-OH blueshift is thus attributed to strengthening of its OH bond. A model for three beads on a ring suggests that this shift is partly offset by the elimination of coupling to the other OH bonds in the ring, whereas for the two water molecules these two effects nearly cancel.

Identification of a Durability Descriptor for Molecular Oxygen Reduction Reaction Catalysts.

The development of durable platinum-group-metal-free oxygen reduction reaction (ORR) catalysts is a key research direction for enabling the wide use of fuel cells. Here, we use a combination of experimental measurements and density functional theory calculations to study the activity and durability of seven iron-based metallophthalocyanine (MPc) ORR catalysts that differ only in the identity of the substituent groups on the MPcs. While the MPcs show similar ORR activity, their durabilities as measured by the current decay half-life differ greatly. We find that the energy difference between the hydrogenated intermediate structure and the final demetalated structure (ΔEdemetalation) of the MPcs is linearly related to the degradation reaction barrier energy. Comparison to the degradation data for the previously studied metallocorrole systems suggested that ΔEdemetalation also serves as a descriptor for the corrole systems and that the high availability of protons at the active site due to the COOH group of the o-corrole decreases the durability.

Temperature Dependence of Intramolecular Vibrational Bands in Small Water Clusters.

Cyclic water clusters are pivotal for understanding atmospheric reactions as well as liquid water, yet the temperature (T) dependence of their dynamics and spectroscopy is poorly studied. The development of highly accurate water potentials, such as MB-pol, partly rectifies this. It remains to account for the quantum nuclear effects (NQE), because quantum nuclear dynamics become increasingly inaccurate at low temperatures. From a practical point of view, we find that NQE can be accounted for simply by subtracting a constant from the frequencies obtained from the velocity autocorrelation functions (VACF) of classical nuclear dynamics, resulting in unprecedented agreement with experiment, mostly within 5 cm-1. We have performed classical simulations of (H2O)n clusters (n = 2-5) from 20 K and up to their melting temperature, calculating both all-atom and partial VACF, thus generating the temperature dependence of the vibrational frequencies (IR and Raman bands). Focusing on the hydrogen-bonded (HBed) OH stretch and HOH bend, we find opposing T dependencies. The HBed OH modes blue shift linearly with T, attributed to ring expansion rather than any specific conformational change. The lowest-frequency Raman concerted mode is predicted to show the largest such shift. In contrast, the HOH bend undergoes a red-shift, with the highest frequency concerted band undergoing the largest red-shift. These results can be explained by a coupled-oscillator model for n hydrogen atoms on a ring, constrained to move either tangentially (stretch) or perpendicularly (bend) to the ring. With increasing temperature and weakening of HBs, the intrinsic force constant increases (stretch) or remains constant (bend), while the nearest-neighbor coupling constant decreases, and this results in the interesting behavior revealed herein. T-dependent Raman studies are required for testing some of these predictions.

Thermally Induced Hydrogen-Bond Rearrangements in Small Water Clusters and the Persistent Water Tetramer.

Small water clusters absorb heat and catalyze pivotal atmospheric reactions. Yet, experiments produced conflicting results on water cluster distribution under atmospheric conditions. Additionally, it is unclear which "phase transitions" such clusters exhibit, at what temperatures, and what are their underlying molecular mechanisms. We find that logarithmically small tails in the radial probability densities of (H2O) n clusters (n = 2 - 6) provide direct testimony for such transitions. Using the best available water potential (MB-pol), an advanced thermostating algorithm (g-BAOAB), and sufficiently long trajectories, we map the "bifurcation", "melting", and (hitherto unexplored) "vaporization" transitions, finding that both melting and vaporization proceed via a "monomer on a ring" conformer, exhibiting huge distance fluctuations at the vaporization temperatures (T v). T v may play a role in determining the atmospheric cluster size distribution such that the dimer and tetramer, with their exceptionally low/high T v values, are under/over-represented in these distributions, as indeed observed in nondestructive mass spectrometric measurements.