Nb2O5, LiNbO3, and (Na, K)NbO3 Thin Films from High-Concentration Aqueous Nb-Polyoxometalates.

Synthesizing functional materials from water contributes to a sustainable energy future. On the atomic level, water drives complex metal hydrolysis/condensation/speciation, acid-base, ion pairing, and solvation reactions that ultimately direct material assembly pathways. Here, we demonstrate the importance of Nb-polyoxometalate (Nb-POM) speciation in enabling deposition of Nb2O5, LiNbO3, and (Na, K)NbO3 (KNN) from high-concentration solutions, up to 2.5 M Nb for Nb2O5 and ∼1 M Nb for LiNbO3 and KNN. Deposition of KNN from 1 M Nb concentration represents a potentially important advancment in lead-free piezoelectrics, an application that requires thick films. Solution characterization via small-angle X-ray scattering and Raman spectroscopy described the speciation for all precursor solutions as the [HxNb24O72](x-24) POM, as did total pair distribution function analyses of X-ray scattering of amorphous gels prior to conversion to oxides. The tendency of the Nb24-POM to form extended networks without crystallization leads to conformal and well-adhered films. The films were characterized by X-ray diffraction, atomic force microscopy, scanning electron microscopy, ellipsometry, and X-ray photoelectron spectroscopy. As a strategy to convert aqueous deposition solutions from {Nb10}-POMs to {Nb24}-POMs, we devised a general procedure to produce doped Nb2O5 thin films including Ca, Ag, and Cu doping.

Contribution of the Sub-Surface to Electrocatalytic Activity in Atomically Precise La0.7 Sr0.3 MnO3 Heterostructures.

Electrocatalytic reactions are known to take place at the catalyst/electrolyte interface. Whereas recent studies of size-dependent activity in nanoparticles and thickness-dependent activity of thin films imply that the sub-surface layers of a catalyst can contribute to the catalytic activity as well, most of these studies consider actual modification of the surfaces. In this study, the role of catalytically active sub-surface layers was investigated by employing atomic-scale thickness control of the La0.7 Sr0.3 MnO3 (LSMO) films and heterostructures, without altering the catalyst/electrolyte interface. The activity toward the oxygen evolution reaction (OER) shows a non-monotonic thickness dependence in the LSMO films and a continuous screening effect in LSMO/SrRuO3 heterostructures. The observation leads to the definition of an "electrochemically-relevant depth" on the order of 10 unit cells. This study on the electrocatalytic activity of epitaxial heterostructures provides new insight in designing efficient electrocatalytic nanomaterials and core-shell architectures.

Surface chemistry of 2-propanol and O2 mixtures on SnO2(110) studied with ambient-pressure x-ray photoelectron spectroscopy.

Tin dioxide (SnO2) has various applications due to its unique surface and electronic properties. These properties are strongly influenced by Sn oxidation states and associated defect chemistries. Recently, the oxidation of volatile organic compounds (VOCs) into less harmful molecules has been demonstrated using SnO2 catalysts. A common VOC, 2-propanol (isopropyl alcohol, IPA), has been used as a model compound to better understand SnO2 reaction kinetics. We have used ambient-pressure x-ray photoelectron spectroscopy (AP-XPS) to characterize the surface chemistry of IPA and O2 mixtures on stoichiometric, unreconstructed SnO2(110)-(1 × 1) surfaces. AP-XPS experiments were performed for IPA pressures ≤3 mbar, various IPA/O2 ratios, and several reaction temperatures. These measurements allowed us to determine the chemical states of adsorbed species on SnO2(110)-(1 × 1) under numerous experimental conditions. We found that both the IPA/O2 ratio and sample temperature strongly influence reaction chemistries. AP-XPS valence-band spectra indicate that the surface was partially reduced from Sn4+ to Sn2+ during reactions with IPA. In situ mass spectrometry and gas-phase AP-XPS results indicate that the main reaction product was acetone under these conditions. For O2 and IPA mixtures, the reaction kinetics substantially increased and the surface remained solely Sn4+. We believe that O2 replenished surface oxygen vacancies and that SnO2 bridging and in-plane oxygen are likely the active oxygen species. Moreover, addition of O2 to the reaction results in a reduction in formation of acetone and an increase in formation of CO2 and H2O. Based on these studies, we have developed a reaction model that describes the catalytic oxidation of IPA on stoichiometric SnO2(110)-(1 × 1) surfaces.

Enhanced Visible-Light-Driven Hydrogen Production through MOF/MOF Heterojunctions.

A strategy for enhancing the photocatalytic performance of MOF-based systems (MOF: metal-organic framework) is developed through the construction of MOF/MOF heterojunctions. The combination of MIL-167 with MIL-125-NH2 leads to the formation of MIL-167/MIL-125-NH2 heterojunctions with improved optoelectronic properties and efficient charge separation. MIL-167/MIL-125-NH2 outperforms its single components MIL-167 and MIL-125-NH2, in terms of photocatalytic H2 production (455 versus 0.8 and 51.2 µmol h-1 g-1, respectively), under visible-light irradiation, without the use of any cocatalysts. This is attributed to the appropriate band alignment of these MOFs, the enhanced visible-light absorption, and long charge separation within MIL-167/MIL-125-NH2. Our findings contribute to the discovery of novel MOF-based photocatalytic systems that can harvest solar energy and exhibit high catalytic activities in the absence of cocatalysts.

Efficient Mercury Capture Using Functionalized Porous Organic Polymer.

The primary challenge in materials design and synthesis is achieving the balance between performance and economy for real-world application. This issue is addressed by creating a thiol functionalized porous organic polymer (POP) using simple free radical polymerization techniques to prepare a cost-effective material with a high density of chelating sites designed for mercury capture and therefore environmental remediation. The resulting POP is able to remove aqueous and airborne mercury with uptake capacities of 1216 and 630 mg g-1 , respectively. The material demonstrates rapid kinetics, capable of dropping the mercury concentration from 5 ppm to 1 ppb, lower than the US Environmental Protection Agency's drinking water limit (2 ppb), within 10 min. Furthermore, the material has the added benefits of recyclability, stability in a broad pH range, and selectivity for toxic metals. These results are attributed to the material's physical properties, which include hierarchical porosity, a high density of chelating sites, and the material's robustness, which improve the thiol availability to bind with mercury as determined by X-ray photoelectron spectroscopy and X-ray absorption fine structure studies. The work provides promising results for POPs as an economical material for multiple environmental remediation applications.

Advanced Photoemission Spectroscopy Investigations Correlated with DFT Calculations on the Self-Assembly of 2D Metal Organic Frameworks Nano Thin Films.

Metal-organic frameworks (MOFs) deposited from solution have the potential to form 2-dimensional supramolecular thin films suitable for molecular electronic applications. However, the main challenges lie in achieving selective attachment to the substrate surface, and the integration of organic conductive ligands into the MOF structure to achieve conductivity. The presented results demonstrate that photoemission spectroscopy combined with preparation in a system-attached glovebox can be used to characterize the electronic structure of such systems. The presented results demonstrate that porphyrin-based 2D MOF structures can be produced and that they exhibit similar electronic structure to that of corresponding conventional porphyrin thin films. Porphyrin MOF multilayer thin films were grown on Au substrates prefunctionalized with 4-mercaptopyridine (MP) via incubation in a glovebox, which was connected to an ultrahigh vacuum system outfitted with photoelectron spectroscopy. The thin film growth process was carried out in several sequential steps. In between individual steps the surface was characterized by photoemission spectroscopy to determine the valence bands and evaluate the growth mode of the film. A comprehensive evaluation of X-ray photoemission spectroscopy (XPS), ultraviolet photoelectron spectroscopy (UPS), and inverse photoemission spectroscopy (IPES) data was performed and correlated with density functional theory (DFT) calculations of the density of states (DOS) of the films involved to yield the molecular-level insights into the growth and the electronic properties of MOF-based 2D thin films.