This work aims to reveal the origin of the large onset overpotential and sluggish kinetics of the oxygen reduction reaction (ORR) on Pt, a standing problem that hinders the progress of fuel cell technology. By investigating various possible reaction steps and pathways through detailed DFT calculations on Pt(111) surface covered by rationalized phase structures of oxygenated adsorbates, we show that the ORR overpotential and Tafel kinetics originate from the potential-dependent formation of a site-blocking spectator phase, √3 × √3-structured oxygen adatoms (O*), which coexists with a relatively weak blocking phase, (√3 × √3)­R30°-patterned adsorption network of hydroxyl group (OH*) and water molecule (H2O*) at ORR relevant potentials. The OH*/H2O* phase provides sites for ORR to proceed through a dissociative pathway consisting of four proton/electron transfer (PET) steps. The first step, PET-coupled O2 adsorption, is identified as the activity-determining step. Different from the usual beliefs, we found the O2 and O* do not directly accept proton during the reduction steps; rather, OH* and H2O* act as PET mediators to facilitate the O2 adsorption and dissociation and the O* reduction. These findings unveil the distinctly multiple roles of various oxygenated adsorbates as intermediates, spectators, and PET mediators in ORR. The implications of these findings on designing Pt-based catalysts are discussed. It is concluded that the binding strength of O* impacts the ORR activity of Pt-based surface predominantly by modulating the number of the available active sites, rather than the activation barriers for the rate-determining step.

The electrochemical oxygenation processes of Pt(111) surface are investigated by combining density functional theory (DFT) calculations and Monto Carlo (MC) simulations. DFT calculations are performed to construct force-field parameters for computing the energy of (√3 × √3)R30°-structured OH*-H2O* hydrogen-bonding networks (differently dissociated water bilayer) on the Pt(111) surface, with which MC simulations are conducted to probe the reversible H2O* ↔ OH* conversion in OH*-H2O* networks. The simulated isotherm (relation between electrode potential and OH* coverage) agrees well with that predicted by the experimental cyclic voltammetry (CV) in the potential region of 0.55-0.85 V (vs RHE). It is suggested that the butterfly shape of CV in this region is due to different variation trends of Pt-H2O* distance in low and high OH* coverages. DFT calculation results indicate that the oxidative voltammetry in the potential region from 0.85 V to ca. 1.07 V is associated with the dissociation of OH* to O*, which yields surface structures consisting of OH*-H2O* networks and (√3 × √3)-structured O* clusters. The high stability of the half-dissociated water bilayer (OH*-H2O* hydrogen-bonding network with equal OH* and H2O* coverages) formed in the butterfly region makes OH* dissociation initially very difficult in energetics, but become facile once starts due to the destabilization of OH* by the formed O* nearby. This explains the experimentally observed nucleation and growth behavior of O* phase formation and the high asymmetry of oxidation-reduction voltammetry in this potential region.

The conservative potential, arising from a coarse-grain (CG) mapping scheme for nonbonded atomistic particles, is studied. This is a bottom-up approach from first-principles that maps atomistic particles to fluid element-like subcells whose centers lie on a regular, cubic lattice. Unlike standard CG mapping schemes, the current one uses dynamic labeling which on-the-fly changes the CG labels of the particles. The subcells can also be different sizes and shapes, in principle. Equilibrium atomistic molecular dynamics trajectories for different Lennard-Jones fluids are calculated and converted to CG ones, from which CG probability distribution functions are calculated. Correlation studies show position and mass CG variables are uncoupled in a given subcell, as are different vector components of position. Furthermore, the strongest coupling occurs with neighboring cells in specific directions, and the resulting distribution is well described by a multivariate Gaussian. This implies the CG potential has a generalized quadratic form, whose derivative can be determined analytically. A microscopic rationalization is provided for the signs and relative magnitudes of different correlation coefficients, and in some cases, a connection is made with bulk properties of the fluid. We argue the generalized quadratic form should be robust to changes in the particulars of the CG scheme, as well as the nature of the atomistic intermolecular potential. Only a few potential parameters need to be calculated from the underlying atomistic system. This is significant because it indicates the transferability of this form to other, more complex systems. This transferability will be tested in future work, where mapping schemes with fuzzy boundaries will be considered.

We extend our previous work (Luo, S.; Thachuk, M. J. Phys. Chem. A 2021, 125, 64866497) on determining conservative potentials for lattice-like, coarse-grain (CG) mapping schemes to the case where the boundaries between different spatial regions are not sharply defined but are fuzzy. In other words, the system is divided into interpenetrating “subcells” such that atomistic particles continuously change their memberships as they move through space. This is done by using fuzzy switching functions to define overlapping regions between subcells with fractional particle occupations. In this case, a full mass matrix is required to describe the system, and its off-diagonal elements are nonzero and contribute to the CG potential. As the overlapping region increases in size, we observe the mass distribution transitions from a discrete spectrum, through an intermediate state, and finally to a continuous Gaussian-like function. We interpret this as a quantitative measure for signaling when a continuum-theory description of the system is appropriate. Nonzero correlations among all CG variables are calculated and are found to depend strongly on the degree of overlap. In particular, those for the diagonal mass elements decrease in magnitude, and there exists a specific value of the overlap for which the correlations are zero. Other correlations are strong only when the overlap is quite large, so there is a trade-off between the complexity of the interactions in the system and the degree of fuzziness between the subcells. However, if the number of particles in a subcell is large enough and the overlap is moderate, then the CG potential is found to be well-approximated by a generalized quadratic function. These results demonstrate the transition between atomistic and continuum resolutions in a system and have implications for designing CG schemes with mixed atomistic and continuum character.