To provide guidelines to accelerate the Haber–Bosch (HB) process for synthesis of ammonia from hydrogen and nitrogen, we used Quantum Mechanics (QM) to determine the reaction mechanism and free energy reaction barriers under experimental reaction conditions (400 °C and 20 atm) for all 10 important surface reactions on the Fe(211) reconstructed (Fe(211)R) surface. These conditions were then used in full kMC modeling for 30 minutes to attain steady state. We find that the stable surface under Haber–Bosch conditions is the missing row 2 × 1 reconstructed surface (211)R and that the Turn Over Frequency (TOF) is 18.7 s⁻¹ per 2 × 2 surface site for 1.5 Torr NH₃ pressure, but changes to 3.5 s⁻¹ for 1 atm, values close (within 6%) to the ones on Fe(111). The experimental ratio between (211) and (111) rates at low (undisclosed) NH₃ pressure was reported to be 0.75. The excellent agreement with experiment on two very different surfaces and reaction mechanisms is a testament of the accuracy of QM modeling. In addition, our kinetic analysis indicates that Fe(211)R is more active than Fe(111) at high pressure, close to HB industrial conditions, and that (211)R is more abundant than (111) via a steady-state Wulff construction under HB conditions. Thus, at variance with common thinking, we advocate the Fe(211)R surface as the catalytically active phase of pure iron ammonia synthesis catalyst under HB industrial conditions.

To discover more efficient industrial catalysts for ammonia synthesis via the Haber-Bosch (HB) process, we employed quantum-mechanics (QM)-based hierarchical high throughput catalyst screening (HHTCS) to test a wide group of elements (34) as candidates to dope the Fe(111) catalyst subsurface. The QM free-energy reaction network of HB over Fe(111) yields ten barriers as potentially rate-determining, of which we select four as prototypical, arrange them hierarchically, and define a corresponding set of screening criteria, which we then use to screen candidate catalysts. This leads to two promising candidates (Co and Ni), from which we selected the most promising (Ni) for a complete QM and kinetic study. The kinetic Monte Carlo (kMC) simulations predict a 16-fold increase in HB turn over frequency (TOF) for the Ni-doped catalyst compared to the pure Fe(111) surface under realistic conditions. The 16-fold increase in HB turn over frequency (TOF) is a significant improvement and may trigger future experimental studies to validate our prediction. This TOF improvement could lead to similar reaction rates as with pure Fe but at areaction temperature decreased by 100 degrees from 773 to 673 K and a total reactant pressure decreased by 6 times from 201 atm to 34 atm. We interpret the reasons underlying this improvement using Valence Bond and kinetic analyses. We suggest this Ni-doped Fe(111) catalyst as a candidate to reduce the world energy consumption for the HB process while satisfying future needs for energy and environment.

Boron carbide is super-strong and has many important engineering applications such as body armor and cutting tools. However, the extended applications of boron carbide have been limited by its low fracture toughness arising from anomalous brittle failure when subjected to hypervelocity impact or under high pressure. This abnormal brittle failure is directly related to the formation of a tiny amorphous shear band of 2–3 nm in width and several hundred nm in length. In this Perspective, we discuss mitigating the amorphous shear bands in boron carbide from various strategies including microalloying, grain boundary engineering, stoichiometry control, and the addition of a second phase. Combined with recent theoretical and experimental studies, we discuss strategies that can be applied in synthesizing and producing boron carbide-based materials with improved ductility by suppressing the formation of the amorphous shear band.

The coordination chemistry of various fission and decay products, such as actinides and lanthanides, are crucial to the commercial deployment of molten salt reactors as they can affect the thermophysical properties. Here, we examined the structure, coordination environment, and physical properties such as the density and the vibrational density of states for three lanthanide species, namely Ce, Eu, and Sm in the LiCl–KCl eutectic system using a combination of quantum mechanics simulations and spectroscopic experiments. Quantum mechanics molecular dynamics (QM-MD) modelling was employed to determine the physical properties of each system resulting in accurate local coordination of each species. Then, the vibrational density of states (DOS) was determined using a two-phase thermodynamic modelling which was then compared to the experimentally obtained Raman spectra of the species in molten LiCl–KCl having the eutectic composition. We find that Ce³⁺, Eu³⁺ and Sm³⁺ all adopt octahedral local coordination environments in the eutectic salt composition in good agreement with experimental results. Ce³⁺ is found to fluctuate between an octahedral six-coordinated and a seven-coordinated structure due to the increased local proximity of Cl in the eutectic salt, resulting in a lower fluidicity/diffusivity than the other trivalent lanthanides studied. The thermophysical properties of the eutectic composition with trivalent lanthanides were not significantly different from the pure eutectic salt composition, but several changes were noted.