Catalytic Activity and Electrochemical Stability of Ru1-xMxO2 (M = Zr, Nb, Ta): Computational and Experimental Study of the Oxygen Evolution Reaction.

We use computations and experiments to determine the effect of substituting zirconium, niobium, and tantalum within rutile RuO2 on the structure, oxygen evolution reaction (OER) mechanism and activity, and electrochemical stability. Calculated electronic structures altered by Zr, Nb, and Ta show surface regions of electron density depletion and accumulation, along with anisotropic lattice parameter shifts dependent on the substitution site, substituent, and concentration. Consistent with theory, X-ray photoelectron spectroscopy experiments show shifts in binding energies of O-2s, O-2p, and Ru-4d peaks due to the substituents. Experimentally, the substituted materials showed the presence of two phases with a majority phase that contains the metal substituent within the rutile phase and a second, smaller-percentage RuO2 phase. Our experimental analysis of OER activity shows Zr, Nb, and Ta substituents at 12.5 atom % induce lower activity relative to RuO2, which agrees with computing the average of all sites; however, Zr and Ta substitution at specific sites yields higher theoretical OER activity than RuO2, with Zr substitution suggesting an alternative OER mechanism. Metal dissolution predictions show the involvement of cooperative interactions among multiple surface sites and the electrolyte. Zr substitution at specific sites increases activation barriers for Ru dissolution, however, with Zr surface dissolution rates comparable to those of Ru. Experimental OER stability analysis shows lower Ru dissolution from synthesized RuO2 and Zr-substituted RuO2 compared to commercial RuO2 and comparable amounts of Zr and Ru dissolved from Zr-substituted RuO2, aligned with our calculations.

Role of inorganic layers on polysulfide decomposition at sodium-metal anode surfaces for room temperature Na/S batteries.

Sodium metal is a promising anode material for room-temperature sodium sulfur batteries. Due to its high reactivity, typical liquid electrolytes (e.g. carbonate-based solvents and a Na salt) can undergo reduction to form a solid electrolyte interphase (SEI) layer, with inorganic components such as Na2CO3, Na2O, and NaOH, covering the anode surface along with other SEI organic products. One of the challenges is to understand the effect of the SEI film on the decomposition of soluble sodium polysulfide molecules (e.g., Na2S8) upon shuttling from the cathode to anode during battery cycling. Here, we use ab initio molecular dynamics (AIMD) simulations to study the role of an inorganic SEI used as a model passivation layer in polysulfide decomposition. Compared to other film chemistries, it is found that the Na2CO3 film can suppress decomposition with the slowest reduction rate and the smallest amount of charge transfer towards Na2S8. The Na2CO3 film can maintain its structural properties during the simulations. In contrast, Na2O and NaOH allow some decomposed polysulfide fragments to be inserted into the SEI layer. Moreover, the decomposition of Na2S8 on both Na2O and NaOH SEI layers is more reactive with more charge transfer to Na2S8 when compared to that of Na2CO3. Thus, the ability of the SEI to suppress polysulfide decomposition is in the order: Na2CO3 > NaOH ∼ Na2O. Analyses of the density of states reveal that the Na2S8 molecule receives electrons from the Na metal directly in the presence of n-type semiconductor films of Na2CO3 and NaOH, while the charge migration behavior is different in a p-type semiconductor Na2O with the SEI film donating its electrons to the polysulfide solely. Thus, this work adds new insights into charge transfer behavior of inorganic thin film SEIs that could be present at the initial stages of SEI formation.

A structure and activity relationship for single-walled carbon nanotube growth confirmed by in situ observations and modeling.

The structure and phase transformation of a cobalt (Co) catalyst, during single walled carbon nanotube (SWCNT) growth, is elucidated for inactive, active and deactivated nanoparticles by in situ imaging using an environmental transmission electron microscope. During nanotube growth, the structure was analyzed using Miller indices to determine the types of planes that favor anchoring or liftoff of nanotubes from the Co catalyst. Density functional theory was further applied to model the catalyst interactions to compare the work of adhesion of the catalyst's faceted planes to understand the interactions of different Miller planes with the graphene structure. Through in-depth studies of multiple distinct Co nanoparticles, we established a dominant nanoparticle phase for SWCNT growth. In addition, we identified the preferred lattice planes and a threshold for work of adhesion to allow the anchoring and liftoff of SWCNTs.

Mechanisms of alumina growth via atomic layer deposition on nickel oxide and metallic nickel surfaces.

We aim at elucidating the mechanism of the trimethyl aluminum (TMA) decomposition on oxidized nickel (NiO) and metallic nickel (Ni) facets in the absence of a source of hydroxyl groups. This TMA decomposition mechanism constitutes the earliest stage of growth of Al2O3 coatings with the atomic layer decomposition (ALD) method, which stabilizes nickel catalysts in energy-intensive processes such as the dry reforming of methane. Our first-principles calculations suggest thermodynamic favorability for the TMA decomposition on metallic nickel compared to oxidized nickel. Moreover, the decomposition of TMA on metallic nickel showed almost no differences in terms of energy barriers between flat and stepped surfaces. Regarding the impact of the CH3 radicals formed after TMA decomposition, we calculated stronger adsorption on metallic nickel facets than on oxidized nickel, and these adsorption energies are comparable to the adsorption energies calculated in earlier works on Al2O3 ALD growth on palladium surfaces. These results lead us to believe in the growth of porous Al2O3 coatings triggered by CH3 contamination rather than due to preferential TMA decomposition on stepped and/or defective facets. The CH3 radicals are likely to be thermally stable at temperatures used during Al2O3 ALD processes, partially passivating the surface towards further TMA decomposition.