Atomic-scale studies of catalysis
by spinel oxides

@article{Tangpakonsab_2024a,

title = {Mechanistic Insights into CO and H_{2} Oxidation on Cu/CeO_{2} Single Atom Catalysts: A Computational Investigation},

author = {Parinya Tangpakonsab and Alexander Genest and Gareth S. Parkinson and Günther Rupprechter},

url = {https://chemrxiv.org/engage/chemrxiv/article-details/673325d25a82cea2fadefd76},

year  = {2024},

date = {2024-11-14},

urldate = {2024-11-14},

journal = {ChemRxiv},

abstract = {Single atom catalysts (SACs) have attracted significant interest due to their unique properties and potential for enhancing catalytic performance in various chemical reactions. In this study, we atomistically explore adsorption properties and catalytic performance of single Cu atoms anchored at low-index CeO_{2} surfaces, focusing on the oxidation of CO and H_{2}. Utilizing density functional theory (DFT) calculations, we report that Cu adatoms bind favorably on different CeO_{2} surfaces, following a stability order of (100)>(110)>(111). The charge transfer from a single adsorbed Cu atom to Ce leads to the reduction of Ce^{4+} to Ce^{3+} and the oxidation of Cu^{0} to Cu^{+}. This strengthens molecular bonds at Cu sites, particularly for CO due to the less populated d-band, while H_{2} shows a by ~1 eV weaker adsorption. CO oxidation is energetically more favorable than H_{2} oxidation on the Cu/CeO_{2}(111) surface. The rate-controlling steps for the Mars-van Krevelen oxidation involve the formation of a bent CO_{2}^{-} intermediate for CO and H_{2}O for H_{2}. The lattice oxygen atom at the interface plays a key role for both oxidation processes. Our findings highlight the potential of single atom catalyst, Cu/CeO_{2}, for CO adsorption and oxidation in heterogeneous catalysis.},

keywords = {P04, P08},

pubstate = {published},

tppubtype = {article}

}

@article{Redondo2024,

title = {Real-space investigation of polarons in hematite Fe_{2}O_{3}},

author = {Jesus Redondo and Michele Reticcioli and Vit Gabriel and Dominik Wrana and Florian Ellinger and Michele Riva and Giada Franceschi and Erik Rheinfrank and Igor Sokolovic and Zdenek Jakub and Florian Kraushofer and Aji Alexander and Laerte L. Patera and Jascha Repp and Michael Schmid and Ulrike Diebold and Gareth S. Parkinson and Cesare Franchini and Pavel Kocan and Martin Setvin},

url = {https://arxiv.org/abs/2303.17945

https://www.science.org/doi/10.1126/sciadv.adp7833},

year  = {2024},

date = {2024-11-01},

urldate = {2024-09-27},

journal = {Science Advances},

volume = {10},

issue = {44},

pages = {eadp7833},

abstract = {In polarizable materials, electronic charge carriers interact with the surrounding ions, leading to quasiparticle behaviour. The resulting polarons play a central role in many materials properties including electrical transport, optical properties, surface reactivity and magnetoresistance, and polaron properties are typically investigated indirectly through such macroscopic characteristics. Here, noncontact atomic force microscopy (nc-AFM) is used to directly image polarons in Fe_{2}O_{3} at the single quasiparticle limit. A combination of Kelvin probe force microscopy (KPFM) and kinetic Monte Carlo (KMC) simulations shows that Ti doping dramatically enhances the mobility of electron polarons, and density functional theory (DFT) calculations indicate that a metallic transition state is responsible for the enhancement. In contrast, hole polarons are significantly less mobile and their hopping is hampered further by the introduction of trapping centres.},

keywords = {P02, P04, P07},

pubstate = {published},

tppubtype = {article}

}

@article{Romano_2024b,

title = {Structure of the water/magnetite interface from sum frequency generation experiments and neural network based molecular dynamics simulations},

author = {Salvatore Romano and Harsharan Kaur and Moritz Zelenka and Pablo Montero De Hijes and Moritz Eder and Gareth S. Parkinson and Ellen H. G. Backus and Christoph Dellago},

url = {https://arxiv.org/abs/2410.12717},

year  = {2024},

date = {2024-10-16},

urldate = {2024-10-16},

journal = {arXiv},

abstract = {Magnetite, a naturally abundant mineral, frequently interacts with water in both natural settings and various technical applications, making the study of its surface chemistry highly relevant. In this work, we investigate the hydrogen bonding dynamics and the presence of hydroxyl species at the magnetite-water interface using a combination of neural network potential-based molecular dynamics simulations and sum frequency generation vibrational spectroscopy. Our simulations, which involved large water systems, allowed us to identify distinct interfacial species, such as dissociated hydrogen and hydroxide ions formed by water dissociation. Notably, water molecules near the interface exhibited a preference for dipole orientation towards the surface, with bulk-like water behavior only re-emerging beyond 60 Å from the surface. The vibrational spectroscopy results aligned well with the simulations, confirming the presence of a hydrogen bond network in the surface ad-layers. The analysis revealed that surface-adsorbed hydroxyl groups orient their hydrogen atoms towards the water bulk. In contrast, hydrogen-bonded water molecules align with their hydrogen atoms pointing towards the magnetite surface.},

keywords = {P04, P11, P12},

pubstate = {published},

tppubtype = {article}

}

@article{Ryan_2024a,

title = {Quantitative Measurement of Cooperative Binding in Partially Dissociated Water Dimers at the Hematite “R-Cut” Surface},

author = {Paul T. P. Ryan and Panukorn Sombut and Ali Rafsanjani-Abbasi and Chunlei Wang and Fulden Eratam and Francesco Goto and Ulrike Diebold and Matthias Meier and David A. Duncan and Gareth S. Parkinson},

url = {https://arxiv.org/abs/2406.18264

https://pubs.acs.org/doi/10.1021/acs.jpcc.4c04537},

year  = {2024},

date = {2024-09-30},

urldate = {2024-09-30},

journal = {The Journal of Physical Chemistry C},

volume = {128},

issue = {40},

pages = {16977–16985},

abstract = {Water–solid interfaces pervade the natural environment and modern technology. On some surfaces, water–water interactions induce the formation of partially dissociated interfacial layers; understanding why is important to model processes in catalysis or mineralogy. The complexity of the partially dissociated structures often makes it difficult to probe them quantitatively. Here, we utilize normal incidence X-ray standing waves (NIXSW) to study the structure of partially dissociated water dimers (H_{2}O–OH) at the α-Fe_{2}O_{3}(012) surface (also called the (11̅02) or “R-cut” surface): a system simple enough to be tractable yet complex enough to capture the essential physics. We find the H_{2}O and terminal OH groups to be the same height above the surface within experimental error (1.45 ± 0.04 and 1.47 ± 0.02 Å, respectively), in line with DFT-based calculations that predict comparable Fe–O bond lengths for both water and OH species. This result is understood in the context of cooperative binding, where the formation of the H-bond between adsorbed H_{2}O and OH induces the H_{2}O to bind more strongly and the OH to bind more weakly compared to when these species are isolated on the surface. The surface OH formed by the liberated proton is found to be in plane with a bulk truncated (012) surface (−0.01 ± 0.02 Å). DFT calculations based on various functionals correctly model the cooperative effect but overestimate the water–surface interaction.},

keywords = {P02, P04, P07},

pubstate = {published},

tppubtype = {article}

}

@article{Pittenauer_2024a,

title = {On the dependence of the catalytic activity of nickel-ferrite nanoparticles in the oxidative dehydrogenation of 2-propanol on the crystallite size},

author = {Michael Pittenauer and Raffael Rameshan and Florian Schrenk and Chunlei Wang and Moritz Eder and Gareth S. Parkinson and Christoph Rameshan and Karin Föttinger},

url = {https://chemrxiv.org/engage/chemrxiv/article-details/670d0de851558a15ef07c30d},

year  = {2024},

date = {2024-09-18},

urldate = {2024-09-18},

journal = {ChemRxiv},

abstract = {Nickel ferrite spinel nanoparticles of different crystallite sizes were prepared in a glycine assisted sol-gel autocombustion reaction and characterised by powder x-ray diffraction, attenuated total reflection infrared spectroscopy, near ambient pressure x-ray photoelectron spectroscopy, nitrogen physisorption, hydrogen and carbon monoxide temperature programmed reduction and oxygen and carbon dioxide temperature programmed desorption. A different distribution of Ni^{2+} cations in the tetrahedrally and octahedrally coordinated sites of the spinel lattice and an increased reducibility of the smaller crystallite size sample were identified as the main impacts of different crystallite size. Their catalytic activity in the oxidative dehydrogenation of 2-propanol was investigated by temperature programmed reaction studies using different ratios of 2-propanol:O_{2} as well as of possible parallel and consecutive reactions at atmospheric pressure and maximum 400 °C. Operando-DRIFTS-MS studies at different 2-propanol:O_{2} ratios were carried out under continuous-flow conditions at atmospheric pressure as well. Thereby, the increased reducibility of the small crystallite size sample could be linked to an unselective activity for dehydrogenation yielding acetone and hydrogen, partial oxidation of 2-propanol and acetone, and total combustion leading to a complex network of reactions going on, being further pushed by an excess of oxygen. Ex-situ x-ray diffraction measurements were performed following the temperature programmed reaction experiments. The large crystallite size sample was found to be generally less active, but more selective towards non-oxidative dehydrogenation. Ex-situ x-ray diffraction measurements performed following the temperature programmed reaction experiments confirmed the increased reducibility of the smaller crystallite size sample. In the operando IR studies, 2-propoxide, adsorbed acetone, carbonates and acetates were identified as species occurring in the reaction. },

keywords = {P04, P10},

pubstate = {published},

tppubtype = {article}

}

@article{Rafsanjani_2024a,

title = {Digging Its Own Site: Linear Coordination Stabilizes a Pt_{1}/Fe_{2}O_{3} Single-Atom Catalyst},

author = {Ali Rafsanjani-Abbasi and Florian Buchner and Faith J. Lewis and Lena Puntscher and Florian Kraushofer and Panukorn Sombut and Moritz Eder and Jiří Pavelec and Erik Rheinfrank and Giada Franceschi and Viktor Birschitzky and Michele Riva and Cesare Franchini and Michael Schmid and Ulrike Diebold and Matthias Meier and Georg K. H. Madsen and Gareth S. Parkinson},

url = {https://doi.org/10.1021/acsnano.4c08781},

year  = {2024},

date = {2024-09-18},

urldate = {2024-09-18},

journal = {ACS Nano},

volume = {18},

issue = {39},

pages = {26920–26927},

abstract = {Determining the local coordination of the active site is a prerequisite for the reliable modeling of single-atom catalysts (SACs). Obtaining such information is difficult on powder-based systems and much emphasis is placed on density functional theory computations based on idealized low-index surfaces of the support. In this work, we investigate how Pt atoms bind to the (11̅02) facet of α-Fe_{2}O_{3}; a common support material in SACs. Using a combination of scanning tunneling microscopy, X-ray photoelectron spectroscopy, and an extensive computational evolutionary search, we find that Pt atoms significantly reconfigure the support lattice to facilitate a pseudolinear coordination to surface oxygen atoms. Despite breaking three surface Fe–O bonds, this geometry is favored by 0.84 eV over the best configuration involving an unperturbed support. We suggest that the linear O–Pt–O configuration is common in reactive Pt-based SAC systems because it balances thermal stability with the ability to adsorb reactants from the gas phase. Moreover, we conclude that extensive structural searches are necessary to determine realistic active site geometries in single-atom catalysis.},

keywords = {P02, P04, P07, P09},

pubstate = {published},

tppubtype = {article}

}

@article{Wang_2024b,

title = {A Multitechnique Study of C_{2}H_{4} Adsorption on a Model Single-Atom Rh_{1} Catalyst},

author = {Chunlei Wang and Panukorn Sombut and Lena Puntscher and Manuel Ulreich and Jiri Pavelec and David Rath and Jan Balajka and Matthias Meier and Michael Schmid and Ulrike Diebold and Cesare Franchini and Gareth S. Parkinson},

url = {https://doi.org/10.1021/acs.jpcc.4c03588},

year  = {2024},

date = {2024-09-05},

journal = {The Journal of Physical Chemistry C},

volume = {128},

issue = {37},

pages = {15404–15411},

abstract = {Single-atom catalysts are potentially ideal model systems to investigate structure–function relationships in catalysis if the active sites can be uniquely determined. In this work, we study the interaction of C_{2}H_{4} with a model Rh/Fe_{3}O_{4}(001) catalyst that features 2-, 5-, and 6-fold coordinated Rh adatoms, as well as Rh clusters. Using multiple surface-sensitive techniques in combination with calculations of density functional theory (DFT), we follow the thermal evolution of the system and disentangle the behavior of the different species. C_{2}H_{4} adsorption is strongest at the 2-fold coordinated Rh_{1} with a DFT-determined adsorption energy of −2.26 eV. However, desorption occurs at lower temperatures than expected because the Rh migrates into substitutional sites within the support, where the molecule is more weakly bound. The adsorption energy at the 5-fold coordinated Rh sites is predicated to be −1.49 eV, but the superposition of this signal with that from small Rh clusters and additional heterogeneity leads to a broad C_{2}H_{4} desorption shoulder in TPD above room temperature.},

keywords = {P02, P04, P07},

pubstate = {published},

tppubtype = {article}

}

@article{Rath2024,

title = {Infrared Reflection Absorption Spectroscopy Setup with Incidence Angle Selection for Surfaces of Non-Metals},

author = {David Rath and Vojtěch Mikerásek and Chunlei Wang and Moritz Eder and Michael Schmid and Ulrike Diebold and Gareth S. Parkinson and Jiří Pavelec},

url = {https://arxiv.org/abs/2403.19263},

doi = {https://doi.org/10.1063/5.0210860},

year  = {2024},

date = {2024-06-07},

urldate = {2024-06-07},

journal = {Review of Scientific Instruments},

volume = {95},

issue = {6},

pages = {065106},

publisher = {arXiv},

abstract = {Infrared Reflection Absorption Spectroscopy (IRAS) on dielectric single crystals is challenging because the optimal incidence angles for light-adsorbate interaction coincide with regions of low IR reflectivity. Here, we introduce an optimized IRAS setup that maximizes the signal-to-noise ratio for non-metals. This is achieved by maximizing light throughput, and by selecting optimal incidence angles that directly impact the peak heights in the spectra. The setup uses a commercial FTIR spectrometer and is usable in ultra-high vacuum (UHV). Specifically, the design features sample illumination and collection mirrors with a high numerical aperture inside the UHV system, and an adjustable aperture to select the incidence angle range on the sample. This is important for p-polarized measurements on dielectrics, because the peaks in the spectra reverse direction at the Brewster angle (band inversion). The system components are connected precisely via a single flange, ensuring long-term stability. We studied the signal-to-noise (SNR) variation in p-polarized IRAS spectra for one monolayer of CO on TiO_{2}(110) as a function of incidence angle range, where a maximum signal-to-noise ratio of 70 was achieved at 4 cm^{-1} resolution in five minutes measurement time. The capabilities for s-polarization are demonstrated by measuring one monolayer D_{2}O adsorbed on a TiO_{2}(110) surface, where a SNR of 65 was achieved at a delta_R/R0 peak height of 1.4x10-4 in twenty minutes.},

keywords = {P02, P04},

pubstate = {published},

tppubtype = {article}

}

@article{Wang2024,

title = {CO‐Induced Dimer Decay Responsible for Gem‐Dicarbonyl Formation on a Model Single‐Atom Catalyst},

author = {Chunlei Wang and Panukorn Sombut and Lena Puntscher and Zdenek Jakub and Matthias Meier and Jiri Pavelec and Roland Bliem and Michael Schmid and Ulrike Diebold and Cesare Franchini and Gareth S. Parkinson},

doi = {10.1002/anie.202317347},

issn = {1521-3773},

year  = {2024},

date = {2024-01-31},

journal = {Angewandte Chemie - International Edition},

number = {e202317347},

publisher = {Wiley},

abstract = {The ability to coordinate multiple reactants at the same active site is important for the wide-spread applicability of single-atom catalysis. Model catalysts are ideal to investigate the link between active site geometry and reactant binding, because the structure of single-crystal surfaces can be precisely determined, the adsorbates imaged by scanning tunneling microscopy (STM), and direct comparisons made to density functional theory. In this study, we follow the evolution of Rh_{1} adatoms and minority Rh_{2} dimers on Fe_{3}O_{4}(001) during exposure to CO using time-lapse STM at room temperature. CO adsorption at Rh_{1} sites results exclusively in stable Rh_{1}CO monocarbonyls, because the Rh atom adapts its coordination to create a stable pseudo-square planar environment. Rh_{1}(CO)_{2} gem-dicarbonyl species are also observed, but these form exclusively through the breakup of Rh_{2} dimers via an unstable Rh_{2}(CO)_{3} intermediate. Overall, our results illustrate how minority species invisible to area-averaging spectra can play an important role in catalytic systems, and show that the decomposition of dimers or small clusters can be an avenue to produce reactive, metastable configurations in single-atom catalysis.},

keywords = {P02, P04, P07},

pubstate = {published},

tppubtype = {article}

}

@article{Gamba2023,

title = {Formation and stability of Fe-rich terminations of the Fe_{3}O_{4}(001) surface},

author = {Oscar Gamba and Moritz Eder and Matthias Poglitsch and Jiri Pavelec and Panukorn Sombut and Matthias Meier and Ulrike Diebold and Michael Schmid and Gareth S. Parkinson},

doi = {10.1088/2053-1591/ad0ac5},

year  = {2023},

date = {2023-11-22},

urldate = {2023-11-22},

journal = {Materials Research Express},

volume = {10},

number = {116517},

issue = {44},

publisher = {IOP Publishing},

abstract = {Understanding how the structure of iron oxide surfaces varies with their environment is essential for rationalizing their role in (geo-)chemistry and optimizing their application in modern technologies. In this paper, we create Fe-rich terminations of Fe_{3}O_{4}(001) by depositing iron directly onto the 'subsurface cation vacancy'-reconstructed surface, which is the most stable surface under ultrahigh vacuum conditions. Scanning tunneling microscopy and x-ray photoelectron spectroscopy data reveal that the excess iron is initially accommodated as two-fold coordinated adatoms and later incorporates into the subsurface cation vacancies. As the coverage increases, small patches of the octahedral pair termination (also known as the 'Fe dimer' termination) nucleate, eventually covering the entire surface after the deposition of 2 iron atoms per (√2×√2)R45° unit cell. This conclusion effectively rules out some existing models for the termination and provides support for the model proposed by Rustad \textit{et al.} (Surface Science 432, L583-L588, 1999), highlighting the need for further theoretical work to complete the Fe_{3}O_{4}(001) surface phase diagram. The octahedral pair termination is found to be unstable above 523 K and upon exposure to molecular O2 because the excess iron atoms agglomerate to form small FeO_{x} clusters.},

keywords = {P02, P04},

pubstate = {published},

tppubtype = {article}

}