Dynamics at polarized carbon dioxide-iron oxyhydroxide interfaces unveil the origin of multicarbon product formation

Surface-sensitive ambient pressure X-ray photoelectron spectroscopy and near-edge X-ray absorption fine structure spectroscopy combined with an electrocatalytic reactivity study, multilength-scale electron microscopy, and theoretical modeling provide insights into the gas-phase selective reduction of carbon dioxide to isopropanol on a nitrogen-doped carbon-supported iron oxyhydroxide electrocatalyst. Dissolved atomic carbon forms at relevant potentials for carbon dioxide reduction from the reduction of carbon monoxide chemisorbed on the surface of the ferrihydrite-like phase. Theoretical modeling reveals that the ferrihydrite structure allows vicinal chemisorbed carbon monoxide in the appropriate geometrical arrangement for coupling. Based on our observations, we suggest a mechanism of three-carbon-atom product formation, which involves the intermediate formation of atomic carbon that undergoes hydrogenation in the presence of hydrogen cations upon cathodic polarization. This mechanism is effective only in the case of thin ferrihydrite-like nanostructures coordinated at the edge planes of the graphitic support, where nitrogen edge sites stabilize these species and lower the overpotential for the reaction. Larger ferrihydrite-like nanoparticles are ineffective for electron transport

The Fermi energy as common parameter to describe charge compensation mechanisms: A path to Fermi level engineering of oxide electroceramics

Chemical substitution, which can be iso- or heterovalent, is the primary strategy to tailor material properties. There are various ways how a material can react to substitution. Isovalent substitution changes the density of states while heterovalent substitution, i.e. doping, can induce electronic compensation, ionic compensation, valence changes of cations or anions, or result in the segregation or neutralization of the dopant. While all these can, in principle, occur simultaneously, it is often desirable to select a certain mechanism in order to determine material properties. Being able to predict and control the individual compensation mechanism should therefore be a key target of materials science. This contribution outlines the perspective that this could be achieved by taking the Fermi energy as a common descriptor for the different compensation mechanisms. This generalization becomes possible since the formation enthalpies of the defects involved in the various compensation mechanisms do all depend on the Fermi energy. In order to control material properties, it is then necessary to adjust the formation enthalpies and charge transition levels of the involved defects. Understanding how these depend on material composition will open up a new path for the design of materials by Fermi level engineering

Assessing Catalytic Rates of Bimetallic Nanoparticles with Active Site Specificity - A Case Study using NO Decomposition

Bimetallic alloys have emerged as an important class of catalytic materials, spanning a wide range of shapes, sizes, and compositions. The combinatorics across this wide materials space makes predicting catalytic turnovers of individual active sites challenging. Herein, we introduce the stability of active sites as a descriptor for site-resolved reaction rates. The site stability unifies structural and compositional variations in a single descriptor. We compute this descriptor using coordination-based models trained with DFT calculations. Our approach enables instantaneous predictions of catalytic turnovers for nanostructures up to 12 nm in size. Using NO decomposition as probe reaction, we identify sites on Au-Pt nanoparticles that, because of local structure and composition, yield one-to-two orders of magnitude increase in rate compared to sites on monometallic Pt. By prescribing specific sizes, morphologies, and compositions of optimal catalytic nanoparticles, our method guides experiments towards designing bimetallic catalysts with optimal turnovers

The Work Function of TiO2

Polycrystalline anatase thin films, (001)- and (101)-oriented anatase TiO 2 single crystals and (001)- and (110)-oriented rutile TiO 2 single crystals with various surface treatments were studied by photoelectron spectroscopy to obtain their surface potentials. Regardless of orientations and polymorph, a huge variation of the Fermi level and work function was achieved by varying the surface condition. The most strongly oxidized surfaces are obtained after oxygen plasma treatment with a Fermi level ∼2.6 eV above the valence band maximum and ionization potentials of up to 9.5 eV (work function 7.9 eV). All other treated anatase surfaces exhibit an ionization potential independent of surface condition of 7.96 ± 0.15 eV. The Fermi level positions and the work functions vary by up to 1 eV. The ionization potential of rutile is ∼0.56 eV lower than that of anatase in good agreement with recent band alignment studies

The Work Function of TiO₂

Polycrystalline anatase thin films, (001)- and (101)-oriented anatase TiO₂ single crystals and (001)- and (110)-oriented rutile TiO₂ single crystals with various surface treatments were studied by photoelectron spectroscopy to obtain their surface potentials. Regardless of orientations and polymorph, a huge variation of the Fermi level and work function was achieved by varying the surface condition. The most strongly oxidized surfaces are obtained after oxygen plasma treatment with a Fermi level ∼2.6 eV above the valence band maximum and ionization potentials of up to 9.5 eV (work function 7.9 eV). All other treated anatase surfaces exhibit an ionization potential independent of surface condition of 7.96±0.15 eV. The Fermi level positions and the work functions vary by up to 1 eV. The ionization potential of rutile is ∼0.56 eV lower than that of anatase in good agreement with recent band alignment studies

Designing multifunctional CoOx layers for efficient and stable electrochemical energy conversion

Disordered and porous metal oxides are promising as earth-abundant and cost-effective alternatives to noble-metal electrocatalysts. Herein, we leverage non-saturated oxidation in plasma-enhanced atomic layer deposition to tune structural, mechanical, and optical properties of biphasic CoOx thin films, thereby tailoring their catalytic activities and chemical stabilities. To optimize the resulting film properties, we systematically vary the oxygen plasma power and exposure time in the deposition process. We find that short exposure times and low plasma powers incompletely oxidize the cobaltocene precursor to Co(OH)2 and result in the incorporation of carbon impurities. These Co(OH)2 films are highly porous and catalytically active, but their electrochemical stability is impacted by poor adhesion to the substrate. In contrast, long exposure times and high plasma powers completely oxidize the precursor to form Co3O4, reduce the carbon impurity incorporation, and improve the film crystallinity. While the resulting Co3O4 films are highly stable under electrochemical conditions, they are characterized by low oxygen evolution reaction activities. To overcome these competing properties, we applied the established relation between deposition parameters and functional film properties to design bilayer films exhibiting simultaneously improved electrochemical performance and chemical stability. The resulting biphasic films combine a highly active Co(OH)2 surface with a stable Co3O4 interface layer. In addition, these coatings exhibit minimal light absorption, thus rendering them well suited as protective catalytic layers on semiconductor light absorbers for application in photoelectrochemical devices

Zirconium Oxynitride Thin Films for Photoelectrochemical Water Splitting.

Transition metal oxynitrides are a promising class of functional materials for photoelectrochemical (PEC) applications. Although these compounds are most commonly synthesized via ammonolysis of oxide precursors, such synthetic routes often lead to poorly controlled oxygen-to-nitrogen anion ratios, and the harsh nitridation conditions are incompatible with many substrates, including transparent conductive oxides. Here, we report direct reactive sputter deposition of a family of zirconium oxynitride thin films and the comprehensive characterization of their tunable structural, optical, and functional PEC properties. Systematic increases of the oxygen content in the reactive sputter gas mixture enable access to different crystalline structures within the zirconium oxynitride family. Increasing oxygen contents lead to a transition from metallic to semiconducting to insulating phases. In particular, crystalline Zr2ON2-like films have band gaps in the UV-visible range and are n-type semiconductors. These properties, together with a valence band maximum position located favorably relative to the water oxidation potential, make them viable photoanode candidates. Using chopped linear sweep voltammetry, we indeed confirm that our Zr2ON2 films are PEC-active for the oxygen evolution reaction in alkaline electrolytes. We further show that high-vacuum annealing boosts their PEC performance characteristics. Although the observed photocurrents are low compared to state-of-the-art photoanodes, these dense and planar thin films can offer a valuable platform for studying oxynitride photoelectrodes, as well as for future nanostructuring, band gap engineering, and defect engineering efforts