Atomic-scale studies of catalysis
by spinel oxides

@article{Kraushofer2023,

title = {Oxygen-Terminated (1 × 1) Reconstruction of Reduced Magnetite Fe_{3}O_{4}(111)},

author = {Florian Kraushofer and Matthias Meier and Zdeněk Jakub and Johanna Hütner and Jan Balajka and Jan Hulva and Michael Schmid and Cesare Franchini and Ulrike Diebold and Gareth S. Parkinson},

doi = {10.1021/acs.jpclett.3c00281},

year  = {2023},

date = {2023-03-28},

urldate = {2023-03-28},

volume = {14},

number = {13},

pages = {3258--3265},

publisher = {American Chemical Society (ACS)},

abstract = {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 Feoct2 termination under reducing conditions. All three structures change the coordination of iron in the kagome Feoct1 layer to be tetrahedral. With atomically resolved microscopy techniques, we show that the termination that coexists with the Fetet1 termination consists of tetrahedral iron capped by 3-fold coordinated oxygen atoms. This structure explains the inert nature of the reduced patches.},

keywords = {P02, P04, P07},

pubstate = {published},

tppubtype = {article}

}

@article{Wang2022,

title = {Surface chemistry on a polarizable surface: Coupling of CO with KTaO _{3}(001)},

author = {Zhichang Wang and Michele Reticcioli and Zdenek Jakub and Igor Sokolović and Matthias Meier and Lynn A Boatner and Michael Schmid and Gareth S. Parkinson and Ulrike Diebold and Cesare Franchini and Martin Setvin},

url = {https://www.science.org/doi/10.1126/sciadv.abq1433},

doi = {10.1126/sciadv.abq1433},

year  = {2022},

date = {2022-08-19},

urldate = {2022-08-19},

journal = {Science Advances},

volume = {8},

issue = {33},

publisher = {American Association for the Advancement of Science (AAAS)},

abstract = {Polarizable materials attract attention in catalysis because they have a free parameter for tuning chemical reactivity. Their surfaces entangle the dielectric polarization with surface polarity, excess charge, and orbital hybridization. How this affects individual adsorbed molecules is shown for the incipient ferroelectric perovskite KTaO_{3}. This intrinsically polar material cleaves along (001) into KO- and TaO_{2}-terminated surface domains. At TaO_{2} terraces, the polarity-compensating excess electrons form a two-dimensional electron gas and can also localize by coupling to ferroelectric distortions. TaO_{2} terraces host two distinct types of CO molecules, adsorbed at equivalent lattice sites but charged differently as seen in atomic force microscopy/scanning tunneling microscopy. Temperature-programmed desorption shows substantially stronger binding of the charged CO; in density functional theory calculations, the excess charge favors a bipolaronic configuration coupled to the CO. These results pinpoint how adsorption states couple to ferroelectric polarization.},

keywords = {P02, P04, P07},

pubstate = {published},

tppubtype = {article}

}

@article{Sombut2022,

title = {Role of Polarons in Single-Atom Catalysts: Case Study of Me_{1}[Au_{1},Pt_{1} and Rh_{1}] on TiO_{2}(110)},

author = {Panukorn Sombut and Lena Puntscher and Marlene Atzmüller and Zdenek Jakub and Michele Reticcioli and Matthias Meier and Gareth S. Parkinson and Cesare Franchini},

doi = {10.1007/s11244-022-01651-0},

year  = {2022},

date = {2022-07-25},

journal = {Topics in Catalysis},

volume = {65},

pages = {1620--1630},

abstract = {The local environment of metal-oxide supported single-atom catalysts plays a decisive role in the surface reactivity and related catalytic properties. The study of such systems is complicated by the presence of point defects on the surface, which are often associated with the localization of excess charge in the form of polarons. This can affect the stability, the electronic configuration, and the local geometry of the adsorbed adatoms. In this work, through the use of density functional theory and surface-sensitive experiments, we study the adsorption of Rh_{1}, Pt_{1}, and Au_{1} metals on the reduced TiO_{2}(110) surface, a prototypical polaronic material. A systematic analysis of the adsorption configurations and oxidation states of the adsorbed metals reveals different types of couplings between adsorbates and polarons. As confirmed by scanning tunneling microscopy measurements, the favored Pt_{1} and Au_{1} adsorption at oxygen vacancy sites is associated with a strong electronic charge transfer from polaronic states to adatom orbitals, which results in a reduction of the adsorbed metal. In contrast, the Rh_{1} adatoms interact weakly with the excess charge, which leaves the polarons largely unaffected. Our results show that an accurate understanding of the properties of single-atom catalysts on oxide surfaces requires a careful account of the interplay between adatoms, vacancy sites, and polarons.},

keywords = {P04, P07},

pubstate = {published},

tppubtype = {article}

}

@article{SCIADV2022,

title = {CO oxidation by Pt_{2}/Fe_{3}O_{4}: Metastable dimer and support configurations facilitate lattice oxygen extraction},

author = {Matthias Meier and Jan Hulva and Zdenek Jakub and Florian Kraushofer and Mislav Bobić and Roland Bliem and Martin Setvin and Michael Schmid and Ulrike Diebold and Cesare Franchini and Gareth S. Parkinson},

url = {https://www.science.org/doi/10.1126/sciadv.abn4580},

doi = {10.1126/sciadv.abn4580},

year  = {2022},

date = {2022-04-01},

urldate = {2022-04-01},

journal = {ScienceAdvances},

volume = {8},

issue = {13},

pages = {eabn4580},

abstract = {Heterogeneous catalysts based on subnanometer metal clusters often exhibit strongly size-dependent properties, and the addition or removal of a single atom can make all the difference. Identifying the most active species and deciphering the reaction mechanism is extremely difficult, however, because it is often not clear how the catalyst evolves in operando. Here, we use a combination of atomically resolved scanning probe microscopies, spectroscopic techniques, and density functional theory (DFT)–based calculations to study CO oxidation by a model Pt/Fe_{3}O_{4}(001) “single-atom” catalyst. We demonstrate that (PtCO)_{2} dimers, formed dynamically through the agglomeration of mobile Pt-carbonyl species, catalyze a reaction involving the oxide support to form CO_{2}. Pt_{2} dimers produce one CO_{2} molecule before falling apart into two adatoms, releasing the second CO. Olattice extraction only becomes facile when both the Pt-dimer and the Fe_{3}O_{4} support can access metastable configurations, suggesting that substantial, concerted rearrangements of both cluster and support must be considered for reactions occurring at elevated temperature.},

keywords = {P02, P04, P07},

pubstate = {published},

tppubtype = {article}

}

@article{Mirabella2021,

title = {Ni-modified Fe_{3}O_{4}(001) surface as a simple model system for understanding the oxygen evolution reaction},

author = {Francesca Mirabella and Matthias Müllner and Thomas Touzalin and Michele Riva and Zdenek Jakub and Florian Kraushofer and Michael Schmid and Marc T M Koper and Gareth S. Parkinson and Ulrike Diebold},

doi = {10.1016/j.electacta.2021.138638},

year  = {2021},

date = {2021-09-01},

urldate = {2021-09-01},

journal = {Electrochimica Acta},

volume = {389},

pages = {138638},

publisher = {Elsevier BV},

abstract = {Electrochemical water splitting is an environmentally friendly technology to store renewable energy in the form of chemical fuels. Among the earth-abundant first-row transition metal-based catalysts, mixed Ni-Fe oxides have shown promising performance for effective and low-cost catalysis of the oxygen evolution reaction (OER) in alkaline media, but the synergistic roles of Fe and Ni cations in the OER mechanism remain unclear. In this work, we report how addition of Ni changes the reactivity of a model iron oxide catalyst, based on Ni deposited on and incorporated in a magnetite Fe_{3}O_{4}(001) single crystal, using a combination of surface science techniques in ultra-high vacuum such as low energy electron diffraction (LEED), x-ray photoelectron spectroscopy (XPS), low-energy ion scattering (LEIS), and scanning tunneling microscopy (STM), as well as atomic force microscopy (AFM) in air, and electrochemical methods such as cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) in alkaline media. A significant improvement in the OER activity is observed when the top surface presents an iron fraction among the cations in the range of 20-40%, which is in good agreement with what has been observed for powder catalysts. Furthermore, a decrease in the OER overpotential is observed following surface aging in electrolyte for three days. At higher Ni load, AFM shows the growth of a new phase attributed to an (oxy)-hydroxide phase which, according to CV measurements, does not seem to correlate with the surface activity towards OER. EIS suggests that the OER precursor species observed on the clean and Ni-modified surfaces are similar and Fe-centered, but form at lower overpotentials when the surface Fe:Ni ratio is optimized. We propose that the well-defined Fe_{3}O_{4}(001) surface can serve as a model system for understanding the OER mechanism and establishing the structure-reactivity relation on mixed Fe-Ni oxides.},

keywords = {P02, P04, pre-TACO},

pubstate = {published},

tppubtype = {article}

}

@article{Hulva2021,

title = {Unraveling CO adsorption on model single-atom catalysts},

author = {Jan Hulva and Matthias Meier and Roland Bliem and Zdenek Jakub and Florian Kraushofer and Michael Schmid and Ulrike Diebold and Cesare Franchini and Gareth S. Parkinson},

doi = {10.1126/science.abe5757},

year  = {2021},

date = {2021-01-22},

urldate = {2021-01-22},

journal = {Science},

volume = {371},

number = {6527},

pages = {375--379},

publisher = {American Association for the Advancement of Science (AAAS)},

abstract = {Understanding how the local environment of a “single-atom” catalyst affects stability and reactivity remains a challenge. We present an in-depth study of copper_{1}, silver_{1}, gold_{1}, nickel_{1}, palladium_{1}, platinum_{1}, rhodium_{1}, and iridium_{1} species on Fe_{3}O_{4}(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 Ag_{1}–CO) or weaken it (as for Ni_{1}–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.},

keywords = {P02, P04, P07, pre-TACO},

pubstate = {published},

tppubtype = {article}

}

@article{Timmermann2020,

title = {IrO_{2} Surface Complexions Identified through Machine Learning and Surface Investigations},

author = {Jakob Timmermann and Florian Kraushofer and Nikolaus Resch and Peigang Li and Yu Wang and Zhiqiang Mao and Michele Riva and Yonghyuk Lee and Carsten Staacke and Michael Schmid and Christoph Scheurer and Gareth S. Parkinson and Ulrike Diebold and Karsten Reuter},

doi = {10.1103/physrevlett.125.206101},

year  = {2020},

date = {2020-11-10},

urldate = {2020-11-10},

journal = {Physical Review Letters},

volume = {125},

number = {20},

pages = {206101},

publisher = {American Physical Society (APS)},

abstract = {A Gaussian approximation potential was trained using density-functional theory data to enable a global geometry optimization of low-index rutile IrO_{2} facets through simulated annealing. Ab initio thermodynamics identifies (101) and (111) (1×1) terminations competitive with (110) in reducing environments. Experiments on single crystals find that (101) facets dominate and exhibit the theoretically predicted (1×1) periodicity and x-ray photoelectron spectroscopy core-level shifts. The obtained structures are analogous to the complexions discussed in the context of ceramic battery materials.},

keywords = {P02, P04, pre-TACO},

pubstate = {published},

tppubtype = {article}

}

@article{Grumelli2020,

title = {Electrochemical Stability of the Reconstructed Fe_{3}O_{4}(001) Surface},

author = {Doris Grumelli and Tim Wiegmann and Sara Barja and Finn Reikowski and Fouad Maroun and Philippe Allongue and Jan Balajka and Gareth S. Parkinson and Ulrike Diebold and Klaus Kern and Olaf M Magnussen},

doi = {10.1002/anie.202008785},

year  = {2020},

date = {2020-07-29},

urldate = {2020-07-29},

journal = {Angewandte Chemie - International Edition},

volume = {59},

number = {49},

pages = {21904--21908},

publisher = {Wiley},

abstract = {Establishing the atomic-scale structure of metal-oxide surfaces during electrochemical reactions is a key step to modeling this important class of electrocatalysts. Here, we demonstrate that the characteristic (√2×√2)R45° surface reconstruction formed on (001)-oriented magnetite single crystals is maintained after immersion in 0.1 M NaOH at 0.20 V vs. Ag/AgCl and we investigate its dependence on the electrode potential. We follow the evolution of the surface using in situ and operando surface X-ray diffraction from the onset of hydrogen evolution, to potentials deep in the oxygen evolution reaction (OER) regime. The reconstruction remains stable for hours between −0.20 and 0.60 V and, surprisingly, is still present at anodic current densities of up to 10 mA cm^{−2} and strongly affects the OER kinetics. We attribute this to a stabilization of the Fe_{3}O_{4} bulk by the reconstructed surface. At more negative potentials, a gradual and largely irreversible lifting of the reconstruction is observed due to the onset of oxide reduction.},

keywords = {P02, P04, pre-TACO},

pubstate = {published},

tppubtype = {article}

}

@article{Jakub2019,

title = {Local Structure and Coordination Define Adsorption in a Model Ir_{1}/Fe_{3}O_{4} Single-Atom Catalyst},

author = {Zdenek Jakub and Jan Hulva and Matthias Meier and Roland Bliem and Florian Kraushofer and Martin Setvin and Michael Schmid and Ulrike Diebold and Cesare Franchini and Gareth S. Parkinson},

doi = {10.1002/anie.201907536},

year  = {2019},

date = {2019-07-24},

urldate = {2019-07-24},

journal = {Angewandte Chemie - International Edition},

volume = {58},

number = {39},

pages = {13961--13968},

publisher = {Wiley},

abstract = {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 Ir_{1} sites on a precisely defined Fe_{3}O_{4}(001) support. The two- and five-fold-coordinated Ir adatoms bind CO more strongly than metallic Ir, and adopt structures consistent with square-planar Ir^{I} and octahedral Ir^{III} 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.},

keywords = {P02, P04, P07, pre-TACO},

pubstate = {published},

tppubtype = {article}

}