arXiv subjects

Zdeněk Jakub

Publications and source records attributed to Zdeněk Jakub.

5 recordsLinked to original sources

arXiv2026

Structural flexibility dictates reactivity of single-atom catalysts

Unravelling the origins of single-atom catalyst reactivity is a central challenge in heterogeneous catalysis research. A key question is whether the activity arises solely from atomic isolation or from distinct structural and electronic configurations of the single atoms. Here, we use precisely defined Fe-N$_3$ and Fe-N$_4$ model catalyst sites synthesized on an inert support to quantify the effect of coordination geometry on chemical reactivity. Both the Fe-N$_3$ and Fe-N$_4$ models have the same electronic configuration (high-spin Fe$^{2+}$ with S=2), and even their d-orbital occupancies and positions with respect to Fermi level are almost identical. Despite this electronic similarity, the adsorption energy of CO differs by more than 0.6 eV between the Fe-N$_3$ and Fe-N$_4$ sites, as indicated by density functional theory computations and confirmed by atomically-resolved scanning tunneling microscopy experiments. We trace this reactivity difference to the structural flexibility of the Fe-N$_3$ sites, which allows strengthening of the Fe 3d$_{xz/yz}$-CO 2$π$* back-bonding by lifting the Fe atom from the -N$_3$ plane. These results demonstrate that coordination geometry plays a crucial role in defining the reactivity of single-atom catalysts, and that such effects cannot be predicted by analysis of the sites' electronic structures alone.

cond-mat.mtrl-sci↗

arXiv2023

Oxygen-Terminated (1x1) Reconstruction of Reduced Magnetite Fe$_3$O$_4$(111)

The (111) facet of magnetite (Fe$_3$O$_4$) has been studied extensively by experimental and theoretical methods, but controversy remains regarding the structure of its low-energy surface terminations. Using density functional theory (DFT) computations, we demonstrate three reconstructions that are more favorable than the accepted Fe$_{\rm oct2}$ termination in reducing conditions. All three structures change the coordination of iron in the kagome Fe$_{\rm oct1}$ layer to tetrahedral. With atomically-resolved microscopy techniques, we show that the termination that coexists with the Fe$_{\rm tet1}$ termination consists of tetrahedral iron capped by three-fold coordinated oxygen atoms. This structure explains the inert nature of the reduced patches.

cond-mat.mtrl-sci↗

arXiv2022

Single Rh adatoms stabilized on α-Fe2O3(1-102) by co-adsorbed water

Oxide-supported single-atom catalysts are commonly modelled as a metal atom substituting surface cation sites in a low-index surface. Adatoms with dangling bonds will inevitably coordinate molecules from the gas phase, and adsorbates such as water can affect both stability and catalytic activity. Here, we use scanning tunneling microscopy (STM), noncontact atomic force microscopy (ncAFM), and x-ray photoelectron spectroscopy (XPS) to show that high densities of single Rh adatoms are stabilized on alpha-Fe2O3(1-102) in the presence of 2x10^(-8) mbar of water at room temperature, in marked contrast to the rapid sintering observed under UHV conditions. Annealing to 50 °C in UHV desorbs all water from the substrate leaving only the OH groups coordinated to Rh, and high-resolution ncAFM images provide a direct view into the internal structure. We provide direct evidence of the importance of OH ligands in the stability of single atoms, and argue that their presence should be assumed when modelling SAC systems.

cond-mat.mtrl-sci↗

arXiv2019

Self-limited Growth of an Oxyhydroxide Phase at the Fe3O4(001) Surface in Liquid and Ambient Pressure Water

Atomic-scale investigations of metal oxide surfaces exposed to aqueous environments are vital to understand degradation phenomena (e.g. dissolution and corrosion) as well as the performance of these materials in applications. Here, we utilize a new experimental setup for the UHV-compatible dosing of liquids to explore the stability of the Fe3O4(001)-c(2x2) surface following exposure to liquid and ambient pressure water. X-ray photoelectron spectroscopy (XPS) and low energy electron diffraction (LEED) data show that extensive hydroxylation causes the surface to revert to a bulk-like (1x1) termination. However, scanning tunnelling microscopy (STM) images reveal a more complex situation, with the slow growth of an oxyhydroxide phase, which ultimately saturates at approximately 40% coverage. We conclude that the new material contains OH groups from dissociated water coordinated to Fe cations extracted from subsurface layers, and that the surface passivates once the surface oxygen lattice is saturated with H because no further dissociation can take place. The resemblance of the STM images to those acquired in previous electrochemical STM (EC-STM) studies lead us to believe a similar structure exists at the solid-electrolyte interface during immersion at pH 7.

physics.chem-ph↗

arXiv2018

Adsorption of CO on the Fe3O4(001) Surface

The interaction of CO with the Fe3O4(001)-(rt2xrt2)R45° surface was studied using temperature programmed desorption (TPD), scanning tunneling microscopy (STM) and x-ray photoelectron spectroscopy (XPS), the latter both under ultrahigh vacuum (UHV) conditions and in CO pressures up to 1 mbar. In general, the CO-Fe3O4 interaction is found to be weak. The strongest adsorption occurs at surface defects, leading to small TPD peaks at 115 K, 130 K and 190 K. Desorption from the regular surface occurs in two distinct regimes. For coverages up to 2 CO molecules per (rt2xrt2)R45° unit cell, the desorption maximum shows a large shift with increasing coverage, from initially 105 K to 70 K. For coverages between 2 and 4 molecules per (rt2xrt2)R45° unit cell, a much sharper desorption feature emerges at 50 K. Thermodynamic analysis of the TPD data suggests a phase transition from a dilute 2D gas into an ordered overlayer with CO molecules bound to surface Fe3+ sites. XPS data acquired at 45 K in UHV are consistent with physisorption. Some carbon-containing species are observed in the near-ambient-pressure XPS experiments at room temperature, but are attributed to contamination and/or reaction with CO with water from the residual gas. No evidence was found for surface reduction or carburization by CO molecules.

cond-mat.mtrl-sci↗