Understanding how the local environment of a “single-atom” catalyst affects stability and reactivity remains a challenge. We present an in-depth study of copper1, silver1, gold1, nickel1, palladium1, platinum1, rhodium1, and iridium1 species on Fe3O4(001), a model support in which all metals occupy the same twofold-coordinated adsorption site upon deposition at room temperature. Surface science techniques revealed that CO adsorption strength at single metal sites differs from the respective metal surfaces and supported clusters. Charge transfer into the support modifies the d-states of the metal atom and the strength of the metal–CO bond. These effects could strengthen the bond (as for Ag1–CO) or weaken it (as for Ni1–CO), but CO-induced structural distortions reduce adsorption energies from those expected on the basis of electronic structure alone. The extent of the relaxations depends on the local geometry and could be predicted by analogy to coordination chemistry.

The α-Fe2O3(11̅02) surface (also known as the hematite r-cut or (012) surface) was studied using low-energy electron diffraction (LEED), X-ray photoelectron spectroscopy (XPS), ultraviolet photoelectron spectroscopy (UPS), scanning tunneling microscopy (STM), noncontact atomic force microscopy (nc-AFM), and ab initio density functional theory (DFT)+U calculations. Two surface structures are stable under ultrahigh vacuum (UHV) conditions; a stoichiometric (1 × 1) surface can be prepared by annealing at 450 °C in ≈10–6 mbar O2, and a reduced (2 × 1) reconstruction is formed by UHV annealing at 540 °C. The (1 × 1) surface is close to an ideal bulk termination, and the undercoordinated surface Fe atoms reduce the surface bandgap by ≈0.2 eV with respect to the bulk. The work function is measured to be 5.7 ± 0.2 eV, and the VBM is located 1.5 ± 0.1 eV below EF. The images obtained from the (2 × 1) reconstruction cannot be reconciled with previously proposed models, and a new “alternating trench” structure is proposed based on an ordered removal of lattice oxygen atoms. DFT+U calculations show that this surface is favored in reducing conditions and that 4-fold-coordinated Fe2+ cations at the surface introduce gap states approximately 1 eV below EF. The work function on the (2 × 1) termination is 5.4 ± 0.2 eV.

Determining the structure of water adsorbed on solid surfaces is a notoriously difficult task and pushes the limits of experimental and theoretical techniques. Here, we follow the evolution of water agglomerates on FeO(001); a complex mineral surface relevant in both modern technology and the natural environment. Strong OH-HO bonds drive the formation of partially dissociated water dimers at low coverage, but a surface reconstruction restricts the density of such species to one per unit cell. The dimers act as an anchor for further water molecules as the coverage increases, leading first to partially dissociated water trimers, and then to a ring-like, hydrogen-bonded network that covers the entire surface. Unraveling this complexity requires the concerted application of several state-of-the-art methods. Quantitative temperature-programmed desorption (TPD) reveals the coverage of stable structures, monochromatic X-ray photoelectron spectroscopy (XPS) shows the extent of partial dissociation, and noncontact atomic force microscopy (AFM) using a CO-functionalized tip provides a direct view of the agglomerate structure. Together, these data provide a stringent test of the minimum-energy configurations determined via a van der Waals density functional theory (DFT)-based genetic search.

The adsorption of CO 2 on the Fe 3 O 4 (001)-( √ 2 × √ 2)R45 • surface was studied experimentally using temperature programmed desorption (TPD), photoelectron spectroscopies (UPS and XPS), and scanning tunneling microscopy. CO 2 binds most strongly at defects related to Fe 2+ , including antiphase domain boundaries in the surface reconstruction and above incorporated Fe interstitials. At higher coverages, CO 2 adsorbs at fivefold-coordinated Fe 3+ sites with a binding energy of 0.4 eV. Above a coverage of 4 molecules per (• unit cell, further adsorption results in a compression of the first monolayer up to a density approaching that of a CO 2 ice layer. Surprisingly, desorption of the second monolayer occurs at a lower temperature (≈84 K) than CO 2 multilayers (≈88 K), suggestive of a metastable phase or diffusion-limited island growth. The paper also discusses design considerations for a vacuum system optimized to study the surface chemistry of metal oxide single crystals, including the calibration and characterisation of a molecular beam source for quantitative TPD mea-

Single‐atom catalysts (SACs) bridge homo‐ and heterogeneous catalysis because the active site is a metal atom coordinated to surface ligands. The local binding environment of the atom should thus strongly influence how reactants adsorb. Now, atomically resolved scanning‐probe microscopy, X‐ray photoelectron spectroscopy, temperature‐programmed desorption, and DFT are used to study how CO binds at different Ir1 sites on a precisely defined Fe3O4(001) support. The two‐ and five‐fold‐coordinated Ir adatoms bind CO more strongly than metallic Ir, and adopt structures consistent with square‐planar IrI and octahedral IrIII complexes, respectively. Ir incorporates into the subsurface already at 450 K, becoming inactive for adsorption. Above 900 K, the Ir adatoms agglomerate to form nanoparticles encapsulated by iron oxide. These results demonstrate the link between SAC systems and coordination complexes, and that incorporation into the support is an important deactivation mechanism.

Benchmarking DFT calculations against precise normal incidence X-ray standing wave measurements.

The Rh1/Fe3O4(001) “single-atom” catalyst evolves differently upon exposure to O2 and CO, which results in distinct mechanisms of CO2 production.

The oxygen evolution reaction (OER) is thought to occur via a four-step mechanism with *O, *OH, and *OOH as adsorbed intermediates. Linear scaling of the *OH and **OOH adsorption energies is proposed to limit the oxides' efficiency as OER catalysts, but the use of simple descriptors to screen candidate materials neglects potentially important water−water interactions. Here, we use a combination of temperature-programmed desorption (TPD), Xray photoemission spectroscopy (XPS), noncontact atomic force microscopy (nc-AFM), and density functional theory (DFT)-based computations to show that highly stable HO−H 2 O dimer species form at the (11̅ 02) facet of hematite; a promising anode material for photoelectrochemical water splitting. The UHVbased results are complemented by measurements following exposure to liquid water and are consistent with prior X-ray scattering results. The presence of strongly bound water agglomerates is generally not taken into account in OER reaction schemes but may play a role in determining the required OER overpotential on metal oxides.