Synthesis and Structure-Activity Characterization of a Single-Site MoO Catalytic Center Anchored on Reduced Graphene Oxide.

Molecularly derived single-site heterogeneous catalysts can bridge the understanding and performance gaps between conventional homogeneous and heterogeneous catalysis, guiding the rational design of next-generation catalysts. While impressive advances have been made with well-defined oxide supports, the structural complexity of other supports and the nature of the grafted surface species present an intriguing challenge. In this study, single-site Mo(═O) species grafted onto reduced graphene oxide (rGO/MoO) are characterized by XPS, DRIFTS, powder XRD, N physisorption, NH-TPD, aqueous contact angle, active site poisoning assay, Mo EXAFS, model compound single-crystal XRD, DFT, and catalytic performance.

Gallstone-Formation-Inspired Bimetallic Supra-nanostructures for Computed-Tomography-Image-Guided Radiation Therapy.

Inspired by the gallstone formation mechanism, we report a fast one-pot synthesis of high-surface-area bimetallic hierarchical supra-nanostructures. As gallstones are generated from metal cholate complexes, cholate bile acid molecules with Au/Ag metal precursors formed stable nanocomplexes aggregated with metal Au ions and preformed ~2 nm silver halide nanoparticles before reduction. When a reducing agent was added, the metal cholate nanocomplexes quickly formed noble bimetallic hierarchical supra-nanostructures.

Resolution of Electronic and Structural Factors Underlying Oxygen-Evolving Performance in Amorphous Cobalt Oxide Catalysts.

Non-noble-metal, thin-film oxides are widely investigated as promising catalysts for oxygen evolution reactions (OER). Amorphous cobalt oxide films electrochemically formed in the presence of borate (CoBi) and phosphate (CoPi) share a common cobaltate domain building block, but differ significantly in OER performance that derives from different electron-proton charge transport properties. Here, we use a combination of L edge synchrotron X-ray absorption (XAS), resonant X-ray emission (RXES), resonant inelastic X-ray scattering (RIXS), resonant Raman (RR) scattering, and high-energy X-ray pair distribution function (PDF) analyses that identify electronic and structural factors correlated to the charge transport differences for CoPi and CoBi.

Nuclearity effects in supported, single-site Fe(ii) hydrogenation pre-catalysts.

Dimeric and monomeric supported single-site Fe(ii) pre-catalysts on SiO2 have been prepared via organometallic grafting and characterized with advanced spectroscopic techniques. Manipulation of the surface hydroxyl concentration on the support influences monomer/dimer formation. While both pre-catalysts are highly active in liquid-phase hydrogenation, the dimeric pre-catalyst is ∼3× faster than the monomer.

Targeted multimodal nano-reporters for pre-procedural MRI and intra-operative image-guidance.

Multimodal-imaging probes offer a novel approach, which can provide detail diagnostic information for the planning of image-guided therapies in clinical practice. Here we report targeted multimodal Nd-doped upconversion nanoparticle (UCNP) imaging reporters, integrating both magnetic resonance imaging (MRI) and real-time upconversion luminescence imaging (UCL) capabilities within a single platform. Nd-doped UCNPs were synthesized as a core-shell structure showing a bright visible emission upon excitation at the near infrared (minimizing biological overheating and increasing tissue penetration depth) as well as providing strong MRI T2 contrast (high r/r ratio).

Resonance Raman and surface- and tip-enhanced Raman spectroscopy methods to study solid catalysts and heterogeneous catalytic reactions.

Resonance Raman (RR) spectroscopy has several advantages over the normal Raman spectroscopy (RS) widely used for in situ characterization of solid catalysts and catalytic reactions. Compared with RS, RR can provide much higher sensitivity and selectivity in detecting catalytically-significant surface metal oxides. RR can potentially give useful information on the nature of excited states relevant to photocatalysis and on the anharmonic potential of the ground state.

Resonance Raman spectroscopic study of alumina-supported vanadium oxide catalysts with 220 and 287 nm excitation.

We present detailed resonance Raman spectroscopic results excited at 220 and 287 nm for alumina-supported VO(x) catalysts. The anharmonic constant, harmonic wavenumber, anharmonic force constant, bond dissociation energy, and bond length change in the excited state for double bonded VO and single bonded V-O were obtained from fundamental and overtone frequencies. Totally symmetric and nontotally symmetric modes could be discerned and assigned on the basis of the overtone and combination progressions found in the resonance Raman spectra.

A spectroscopic and computational investigation of the vanadomolybdate local structure in the lyonsite phase Mg(2.5)VMoO(8).

The vibrational spectrum of Mg2.5VMoO8 obtained by quantum mechanical simulation is compared with the experimentally observed Raman spectrum. This simulation suggests that the observed band at 1016 cm(-1) is attributed to the Mo=O-Mg stretching from two-coordinate oxygen atoms that are adjacent to Mg2+ cation vacancies.

On the structure of vanadium oxide supported on aluminas: UV and visible raman spectroscopy, UV-visible diffuse reflectance spectroscopy, and temperature-programmed reduction studies.

Vanadia species on aluminas (delta- and gamma-Al2O3) with surface VOx density in the range 0.01-14.2 V/nm2 have been characterized by UV and visible Raman spectroscopy, UV-visible diffuse reflectance spectroscopy (UV-Vis DRS), and temperature-programmed reduction in hydrogen.

Probing the vanadyl and molybdenyl bonds in complex vanadomolybdate structures.

A solid solution was found to exist in the quaternary Li(2)O-MgO-V(2)O(5)-MoO(3) system between the two phases Mg(2.5)VMoO(8) and Li(2)Mg(2)(MoO(4))(3). Both Mg(2.

Structure of Mg2.56V1.12W0.88O8 and vibrational raman spectra of Mg2.5VWO8 and Mg2.5VMoO8.

Mg(2.56)V(1.12)W(0.

Nanocrystalline todorokite-like manganese oxide produced by bacterial catalysis.

We describe the characterization of an unknown and difficult to identify but geochemically and environmentally significant MnOx structure produced by a freshwater bacterium, Leptothrix discophora SP-6, using combined transmission electron microscopy (TEM), extended X-ray absorption fine structure (EXAFS), and UV Raman spectroscopy. The large surface-to-volume ratio of the needle-shaped nanocrystalline MnO2 formed around the bacterial cells coupled to the porous, zeolite-like structure has the potential to catalyze reactions and oxidize and adsorb metals.