The reduction of FeO (wüstite) to Fe represents the final and slowest step in the hydrogen-based direct reduction of iron ores for sustainable ironmaking. However, the atomistic-scale mechanisms and kinetics of this process remain poorly understood. Here, we employ ab initio meta-dynamics simulations to investigate reaction pathways and energy barriers for this redox process on FeO(1 0 0) and FeO(1 1 1)_O-terminated surfaces. Differences in surface configurations lead to variations in the number of H₂ molecules required, reaction pathways, and energy barriers. The FeO surface exhibits an autocatalytic effect, facilitating H₂ dissociation and reducing the energy barrier for breaking H₂ molecular bonds. Nevertheless, hydrogen dissociation and adsorption, forming O–H bonds, constitute the primary rate-limiting step. Following this, the Fe-O bond spontaneously breaks in the presence of individual H atoms. Increasing H₂ partial pressure enhances reaction efficiency by raising the density of reactive H₂ molecules, consistent with macroscopic observations. These insights advance the atomistic-scale understanding of hydrogen-based direct reduction, highlighting the influence of pressure and rate-limiting factors.

The hydrogen-based direct reduction of iron ores is a disruptive routine used to mitigate the large amount of CO ₂ emissions produced by the steel industry. The reduction of iron oxides by H ₂ involves a variety of physicochemical phenomena from macroscopic to atomistic scales. Particularly at the atomistic scale, the underlying mechanisms of the interaction of hydrogen and iron oxides is not yet fully understood. In this study, density functional theory (DFT) was employed to investigate the adsorption behavior of hydrogen atoms and H ₂ on different crystal FeO surfaces to gain a fundamental understanding of the associated interfacial adsorption mechanisms. It was found that H ₂ molecules tend to be physically adsorbed on the top site of Fe atoms, while Fe atoms on the FeO surface act as active sites to catalyze H ₂ dissociation. The dissociated H atoms were found to prefer to be chemically bonded with surface O atoms. These results provide a new insight into the catalytic effect of the studied FeO surfaces, by showing that both Fe (catalytic site) and O (binding site) atoms contribute to the interaction between H ₂ and FeO surfaces.

Iron making is the biggest single cause of global warming. The reduction of iron ores with carbon generates about 7% of the global carbon dioxide emissions to produce ≈1.85 billion tons of steel per year. This dramatic scenario fuels efforts to re-invent this sector by using renewable and carbon-free reductants and electricity. Here, the authors show how to make sustainable steel by reducing solid iron oxides with hydrogen released from ammonia. Ammonia is an annually 180 million ton traded chemical energy carrier, with established transcontinental logistics and low liquefaction costs. It can be synthesized with green hydrogen and release hydrogen again through the reduction reaction. This advantage connects it with green iron making, for replacing fossil reductants. the authors show that ammonia-based reduction of iron oxide proceeds through an autocatalytic reaction, is kinetically as effective as hydrogen-based direct reduction, yields the same metallization, and can be industrially realized with existing technologies. The produced iron/iron nitride mixture can be subsequently melted in an electric arc furnace (or co-charged into a converter) to adjust the chemical composition to the target steel grades. A novel approach is thus presented to deploying intermittent renewable energy, mediated by green ammonia, for a disruptive technology transition toward sustainable iron making.

With the aim to find the best simulation routine to accurately predict the ground−state structures and properties of iron oxides (hematite, magnetite, and wustite) using density functional theory (DFT) with Hubbard-U correction, a significant amount of DFT calculations were conducted to investigate the influence of various simulation parameters (energy cutoff, K-point, U value, magnetization setting, smearing value, etc.) and pseudopotentials on the structures and properties of iron oxides. With optimized simulation parameters, the obtained equation of state, lattice constant, bulk moduli, and band gap is much closer to the experimental values compared with previous studies. Due to the strong coupling between the 2p orbital of O and the 3d orbital of Fe, it was found that Hubbard-U correction obviously improved the results for all three kinds of iron oxides including magnetite which has not yet been tested with U correction before, but the U value should be different for different oxides (3 ev, 4 ev, 4 ev for hematite, magnetite, and wustite, respectively). Two kinds of spin magnetism settings for FeO are considered, which should be chosen according to different calculation purposes. The detailed relationship between the parameter settings and the atomic structures and properties were analyzed, and the general principles for future DFT calculation of iron oxides were provided.

Fossil-free ironmaking is indispensable for reducing massive anthropogenic CO ₂ emissions in the steel industry. Hydrogen-based direct reduction (HyDR) is among the most attractive solutions for green ironmaking, with high technology readiness. The underlying mechanisms governing this process are characterized by a complex interaction of several chemical (phase transformations), physical (transport), and mechanical (stresses) phenomena. Their interplay leads to rich microstructures, characterized by a hierarchy of defects ranging across several orders of magnitude in length, including vacancies, dislocations, internal interfaces, and free surfaces in the form of cracks and pores. These defects can all act as reaction, nucleation, and diffusion sites, shaping the overall reduction kinetics. A clear understanding of the roles and interactions of these dynamically-evolving nano-/microstructure features is missing. Gaining better insights into these effects could enable improved access to the microstructure-based design of more efficient HyDR methods, with potentially high impact on the urgently needed decarbonization in the steel industry.

Fundamental understanding of the oxidation behavior of O ₂, H ₂O, and CO ₂ in the process of oxyfuel combustion is of great significance. Extensive MD simulations with reactive force-field (ReaxFF) were performed to compare the gasification behavior under the individual influence of three oxidant molecules on a pristine and a mono-vacant graphene sheet. Distinct differences were observed in almost every aspect including initial kinetics, rate changes, complete/incomplete combustion, gasified regions, and the role of vacancy defects. In the case of O ₂, the nucleation stage is harder while the later stages contained no limiting behavior; The gasification kinetics is highest for H ₂O during initial periods, but the oxidative behavior changes as higher gas consumption levels are reached; CO ₂ has the highest thermodynamic stability and the formation of stable intermediate structures troubles the gasification. Significant out-of-plane activity is observed in the case of H ₂O oxidant. Results suggest that there may be little overlap in the oxidation sites for CO ₂ and H ₂O. In-depth atomic level investigations consistent with the experimental phenomenon will have implications for future design, process optimization, and their commercial application.