A spin promotion effect in catalytic ammonia synthesis.

The need for efficient ammonia synthesis is as urgent as ever. Over the past two decades, many attempts to find new catalysts for ammonia synthesis at mild conditions have been reported and, in particular, many new promoters of the catalytic rate have been introduced beyond the traditional K and Cs oxides. Herein, we provide an overview of recent experimental results for non-traditional promoters and develop a comprehensive model to explain how they work. The model has two components. First, we establish what is the most likely structure of the active sites in the presence of the different promoters. We then show that there are two effects dictating the catalytic activity. One is an electrostatic interaction between the adsorbed promoter and the N-N dissociation transition state. In addition, we identify a new promoter effect for magnetic catalysts giving rise to an anomalously large lowering of the activation energy opening the possibility of finding new ammonia synthesis catalysts.

Enhancement of lithium-mediated ammonia synthesis by addition of oxygen.

Owing to the worrying increase in carbon dioxide concentrations in the atmosphere, there is a need to electrify fossil-fuel­powered chemical processes such as the Haber-Bosch ammonia synthesis. Lithium-mediated electrochemical nitrogen reduction has shown preliminary promise but still lacks sufficient faradaic efficiency and ammonia formation rate to be industrially relevant. Here, we show that oxygen, previously believed to hinder the reaction, actually greatly improves the faradaic efficiency and stability of the lithium-mediated nitrogen reduction when added to the reaction atmosphere in small amounts. With this counterintuitive discovery, we reach record high faradaic efficiencies of up to 78.0 ± 1.3% at 0.6 to 0.8 mole % oxygen in 20 bar of nitrogen. Experimental x-ray analysis and theoretical microkinetic modeling shed light on the underlying mechanism.

Phononic dissipation during "hot" adatom motion: A QM/Me study of O2 dissociation at Pd surfaces.

We augment ab initio molecular dynamics simulations with a quantitative account of phononic dissipation to study the non-equilibrium aftermath of the exothermic oxygen dissociation at low-index (111), (100), and (110) Pd surfaces. Comparing the hyperthermal diffusion arising from a non-instantaneous dissipation of the released chemical energy, we find a striking difference in the resulting "hot" adatom lifetime that is not overall reflected in experimentally recorded product end distances. We rationalize this finding through a detailed mode-specific phonon analysis and identify the dominant dissipation channels as qualitatively different groups of localized surface modes that ultimately lead to intrinsically different rates of dissipation to the Pd bulk. The thus obtained first-principles perspective on non-equilibrium adsorbate-phonon dynamics thereby underscores the sensitive dependence on details of the phononic fine structure, while questioning prevalent assumptions about energy sinks made in commonly used model bath Hamiltonians.

Hot Adatom Diffusion Following Oxygen Dissociation on Pd(100) and Pd(111): A First-Principles Study of the Equilibration Dynamics of Exothermic Surface Reactions.

We augment ab initio molecular dynamics simulations with a quantitative account of phononic dissipation to study the hyperthermal adsorbate dynamics resulting from a noninstantaneous energy dissipation during exothermic surface chemical reactions. Comparing the hot adatom diffusion ensuing O_{2} dissociation over Pd(100) and Pd(111) we find experimentally accessible product end distances to form a rather misleading measure for the lifetime of this hyperthermal state. The lifetime is particularly long at Pd(111) where a random-walk-type diffusion leads only to small net displacements. A detailed phonon analysis rationalizes the slow equilibration through long-lived Rayleigh mode excitations that spatially confine the released energy within a nanoscopic "hot spot" around the impingement region.

Fingerprints of energy dissipation for exothermic surface chemical reactions: O2 on Pd(100).

We present first-principles calculations of the sticking coefficient of O2 at Pd(100) to assess the effect of phononic energy dissipation on this kinetic parameter. For this, we augment dynamical simulations on six-dimensional potential energy surfaces (PESs) representing the molecular degrees of freedom with various effective accounts of surface mobility. In comparison to the prevalent frozen-surface approach, energy dissipation is found to qualitatively affect the calculated sticking curves. At the level of a generalized Langevin oscillator model, we achieve good agreement with experimental data. The agreement is similarly reached for PESs based on two different semi-local density-functional theory functionals. This robustness of the simulated sticking curve does not extend to the underlying adsorption mechanism, which is predominantly directly dissociative for one functional or molecularly trapped for the other. Completely different adsorption mechanisms therewith lead to rather similar sticking curves that agree equally well with the experimental data. This highlights the danger of the prevalent practice to extract corresponding mechanistic details from simple fingerprints of measured sticking data for such exothermic surface reactions.