Steven D. Conradson

Synthesis-structure-performance correlation for polyaniline-Me-C non-precious metal cathode catalysts for oxygen reduction in fuel cells

In this report, we present the systematic preparation of active and durable non-precious metal catalysts (NPMCs) for the oxygen reduction reaction in polymer electrolyte fuel cells (PEFCs) based on the heat treatment of polyaniline/metal/carbon precursors. Variation of the synthesis steps, heat-treatment temperature, metal loading, and the metal type in the synthesis leads to markedly different catalyst activity, speciation, and morphology. Microscopy studies demonstrate notable differences in the carbon structure as a function of these variables. Balancing the need to increase the catalyst’s degree of graphitization through heat treatment versus the excessive loss of surface area that occurs at higher temperatures is a key to preparing an active catalyst. XPS and XAFS spectra are consistent with the presence of Me–Nx structures in both the Co and Fe versions of the catalyst, which are often proposed to be active sites. The average speciation and coordination environment of nitrogen and metal, however, depends greatly on the choice of Co or Fe. Taken together, the data indicate that better control of the metal-catalyzed transformations of the polymer into new graphitized carbon forms in the heat-treatment step will allow for even further improvement of this class of catalysts.

Speciation of uranyl sorbed at multiple binding sites on montmorillonite

Abstract We have investigated the structures of U (VI) complexes as uranyl moieties sorbed onto a reference montmorillonite, SAz-1, using X-ray absorption fine structure spectroscopy (XAFS). The uranyl-loaded clays were prepared from aqueous solutions of uranyl nitrate in the pH range from 3.0 to 3.5. The U concentrations on the clay ranged from 1.7 to 34.6% of the reported cation exchange capacity (CEC = 1.2 meq/g) of the clay. For all samples, XAFS results indicate that there are two axial oxygen atoms at 1.78–1.80 A, as expected for the uranyl moiety. The average numbers and distances of equatorial oxygen atoms about uranyl sorbed on the clay vary significantly as a function of surface coverage. At high coverage (34.6% CEC), the average number and distance of equatorial oxygen atoms are near those found for the fully hydrated uranyl species in aqueous solution. However, there are fewer equatorial oxygen atoms at a shorter average distance about uranyl sorbed at low coverage (1.7% CEC). At moderate coverage (7.3% CEC), the average number and distance of equatorial oxygen atoms are intermediate between those at higher and lower coverage. These changes suggest that sorbing U is reacting with at least three different sites on the clay as U concentration increases. The existence of multiple surface sites and sorption complexes which are structurally distinct from solution species need to be considered for rigorous modeling of sorption processes.

Organometallic Uranium(V)−Imido Halide Complexes: From Synthesis to Electronic Structure and Bonding

Reaction of (C5Me5)2U(=N-2,4,6-(t)Bu3-C6H2) or (C5Me5)2U(=N-2,6-(i)Pr2-C6H3)(THF) with 5 equiv of CuX(n) (n = 1, X = Cl, Br, I; n = 2, X = F) affords the corresponding uranium(V)-imido halide complexes, (C5Me5)2U(=N-Ar)(X) (where Ar = 2,4,6-(t)Bu3-C6H2 and X = F (3), Cl (4), Br (5), I (6); Ar = 2,6-(i)Pr2-C6H3 and X = F (7), Cl (8), Br (9), I (10)), in good isolated yields of 75-89%. These compounds have been characterized by a combination of single-crystal X-ray diffraction, (1)H NMR spectroscopy, elemental analysis, mass spectrometry, cyclic voltammetry, UV-visible-NIR absorption spectroscopy, and variable-temperature magnetic susceptibility. The uranium L(III)-edge X-ray absorption spectrum of (C5Me5)2U(=N-2,4,6-(t)Bu3-C6H2)(Cl) (4) was analyzed to obtain structural information, and the U=N imido (1.97(1) A), U-Cl (2.60(2) A), and U-C5Me5 (2.84(1) A) distances were consistent with those observed for compounds 3, 5, 6, 8-10, which were all characterized by single-crystal X-ray diffraction studies. All (C5Me5)2U(=N-Ar)(X) complexes exhibit U(V)/U(IV) and U(VI)/U(V) redox couples by voltammetry, with the potential separation between these metal-based couples remaining essentially constant at approximately 1.50 V. The electronic spectra are comprised of pi-->pi* and pi-->nb(5f) transitions involving electrons in the metal-imido bond, and metal-centered f-f bands illustrative of spin-orbit and crystal-field influences on the 5f(1) valence electron configuration. Two distinct sets of bands are attributed to transitions derived from this 5f(1) configuration, and the intensities in these bands increase dramatically over those found in spectra of classical 5f(1) actinide coordination complexes. Temperature-dependent magnetic susceptibilities are reported for all complexes with mu(eff) values ranging from 2.22 to 2.53 mu(B). The onset of quenching of orbital angular momentum by ligand fields is observed to occur at approximately 40 K in all cases. Density functional theory results for the model complexes (C5Me5)2U(=N-C6H5)(F) (11) and (C5Me5)2U(=N-C6H5)(I) (12) show good agreement with experimental structural and electrochemical data and provide a basis for assignment of spectroscopic bands. The bonding analysis describes multiple bonding between the uranium metal center and imido nitrogen which is comprised of one sigma and two pi interactions with variable participation of 5f and 6d orbitals from the uranium center.

Trends in covalency for d- and f-element metallocene dichlorides identified using chlorine K-edge X-ray absorption spectroscopy and time-dependent density functional theory.

We describe the use of Cl K-edge X-ray absorption spectroscopy (XAS) and both ground-state and time-dependent hybrid density functional theory (DFT) to probe the electronic structure and determine the degree of orbital mixing in M-Cl bonds for (C(5)Me(5))(2)MCl(2) (M = Ti, 1; Zr, 2; Hf, 3; Th, 4; U, 5), where we can directly compare a class of structurally similar compounds for d- and f-elements. Pre-edge features in the Cl K-edge XAS data for the group IV transition-metals 1-3 provide direct evidence of covalent M-Cl orbital mixing. The amount of Cl 3p character was experimentally determined to be 25%, 23%, and 22% per M-Cl bond for 1-3, respectively. For actinides, we find a pre-edge shoulder for 4 (Th) and distinct and weak pre-edge features for U, 5. The amount of Cl 3p character was determined to be 9% for 5, and we were unable to make an experimental determination for 4. Using hybrid DFT calculations with relativistic effective core potentials, the electronic structures of 1-5 were calculated and used as a guide to interpret the experimental Cl K-edge XAS data. For transition-metal compounds 1-3, the pre-edge features arise due to transitions from Cl 1s electrons into the 3d-, 4d-, and 5d-orbitals, with assignments provided in the text. For Th, 4, we find that 5f- and 6d-orbitals are nearly degenerate and give rise to a single pre-edge shoulder in the XAS. For U, 5, we find the 5f- and 6d-orbitals fall into two distinct energy groupings, and Cl K-edge XAS data are interpreted in terms of Cl 1s transitions into both 5f- and 6d-orbitals. Time-dependent DFT was used to calculate the energies and intensities of Cl 1s transitions into empty metal-based orbitals containing Cl 3p character and provide simulated Cl K-edge XAS spectra for 1-4. For 5, which has two unpaired 5f electrons, simulated spectra were obtained from transition dipole calculations using ground-state Kohn-Sham orbitals. To the best of our knowledge, this represents the first application of Cl K-edge XAS to actinide systems. Overall, this study allows trends in orbital mixing within a well-characterized structural motif to be identified and compared between transition-metals and actinide elements. These results show that the orbital mixing for the d-block compounds slightly decreases in covalency with increasing principal quantum number, in the order Ti > Zr approximately = Hf, and that uranium displays approximately half the covalent orbital mixing of transition elements.

Determining Relative f and d Orbital Contributions to M–Cl Covalency in MCl62– (M = Ti, Zr, Hf, U) and UOCl5– Using Cl K-Edge X-ray Absorption Spectroscopy and Time-Dependent Density Functional Theory

Chlorine K-edge X-ray absorption spectroscopy (XAS) and ground-state and time-dependent hybrid density functional theory (DFT) were used to probe the electronic structures of O(h)-MCl(6)(2-) (M = Ti, Zr, Hf, U) and C(4v)-UOCl(5)(-), and to determine the relative contributions of valence 3d, 4d, 5d, 6d, and 5f orbitals in M-Cl bonding. Spectral interpretations were guided by time-dependent DFT calculated transition energies and oscillator strengths, which agree well with the experimental XAS spectra. The data provide new spectroscopic evidence for the involvement of both 5f and 6d orbitals in actinide-ligand bonding in UCl(6)(2-). For the MCl(6)(2-), where transitions into d orbitals of t(2g) symmetry are spectroscopically resolved for all four complexes, the experimentally determined Cl 3p character per M-Cl bond increases from 8.3(4)% (TiCl(6)(2-)) to 10.3(5)% (ZrCl(6)(2-)), 12(1)% (HfCl(6)(2-)), and 18(1)% (UCl(6)(2-)). Chlorine K-edge XAS spectra of UOCl(5)(-) provide additional insights into the transition assignments by lowering the symmetry to C(4v), where five pre-edge transitions into both 5f and 6d orbitals are observed. For UCl(6)(2-), the XAS data suggest that orbital mixing associated with the U 5f orbitals is considerably lower than that of the U 6d orbitals. For both UCl(6)(2-) and UOCl(5)(-), the ground-state DFT calculations predict a larger 5f contribution to bonding than is determined experimentally. These findings are discussed in the context of conventional theories of covalent bonding for d- and f-block metal complexes.

Optical spectroscopic studies of the sorption of UO2+2 species on a reference smectite

Abstract The speciation of UO 2+ 2 (uranyl) on a reference smectite (SAz-1 from Cheto, Arizona, USA) has been investigated by electronic emission and Raman vibrational spectroscopies. The spectroscopic studies have been done on uranyl-bearing clays prepared from aqueous solutions of uranyl nitrate in the pH range from ~2.5 to 7 and high initial ionic strength (~0.1–0.3 M). The uranyl loading levels in these samples ranged from ~0.1% to ~53% of the reported cation exchange capacity (~1.2 meq/g). Vibronically resolved emission spectra have been obtained for all samples. These spectra vary significantly in intensity and band-shape as a function of uranyl concentration in the clays and the equilibrium pH of the solutions from which the clays were prepared. For most clay samples the measured emission spectrum is a composite of spectra from multiple uranyl emitters. At the lowest loading levels a uranyl sorption complex with an apparent vibronic spacing of ~750 cm −1 dominates the spectra. At intermediate loading levels an additional uranyl sorption complex also having an apparent vibronic spacing of ~ 750 cm −1 is present at an approximately constant concentration ratio to the species in the most dilute samples. At the highest loading levels, a uranyl sorption complex with a vibronic spacing of ~ 850 cm −1 dominates the spectra. Raman spectra have been obtained for the more concentrated uranyl/clay samples. Two distinct bands (855 cm −1 and 883 cm −1 ) are seen in the spectral region of the totally symmetric uranyl stretch. The 855 cm −1 band correlates with the dominant high-coverage species, while the 883 cm −1 band arises from an additional sorption complex. Comparison of these results with aqueous solution spectral data suggests that monomeric uranyl moieties are responsible for the observed spectral responses in the clay samples, and the multiple spectral components are a result of occupancy by these moieties in several structurally and/or energetically different sites within the clay. It is proposed that the uranyl species responsible for the dominant components in the emission spectra in the low and intermediate coverage clay sample are sorbed to amphoteric edge site(s). The uranyl species responsible for the dominant component in the emission spectrum and the 855 cm −1 Raman band in the high-coverage clays is proposed to be exchanged into the fixed charge site(s). The additional complex identified by the Raman band at 883 cm −1 is also proposed as a sorption complex at fixed-charge sites.

Covalency in Lanthanides. An X-ray Absorption Spectroscopy and Density Functional Theory Study of LnCl6x– (x = 3, 2)

Covalency in Ln-Cl bonds of Oh-LnCl6(x-) (x = 3 for Ln = Ce(III), Nd(III), Sm(III), Eu(III), Gd(III); x = 2 for Ln = Ce(IV)) anions has been investigated, primarily using Cl K-edge X-ray absorption spectroscopy (XAS) and time-dependent density functional theory (TDDFT); however, Ce L3,2-edge and M5,4-edge XAS were also used to characterize CeCl6(x-) (x = 2, 3). The M5,4-edge XAS spectra were modeled using configuration interaction calculations. The results were evaluated as a function of (1) the lanthanide (Ln) metal identity, which was varied across the series from Ce to Gd, and (2) the Ln oxidation state (when practical, i.e., formally Ce(III) and Ce(IV)). Pronounced mixing between the Cl 3p- and Ln 5d-orbitals (t2g* and eg*) was observed. Experimental results indicated that Ln 5d-orbital mixing decreased when moving across the lanthanide series. In contrast, oxidizing Ce(III) to Ce(IV) had little effect on Cl 3p and Ce 5d-orbital mixing. For LnCl6(3-) (formally Ln(III)), the 4f-orbitals participated only marginally in covalent bonding, which was consistent with historical descriptions. Surprisingly, there was a marked increase in Cl 3p- and Ce(IV) 4f-orbital mixing (t1u* + t2u*) in CeCl6(2-). This unexpected 4f- and 5d-orbital participation in covalent bonding is presented in the context of recent studies on both tetravalent transition metal and actinide hexahalides, MCl6(2-) (M = Ti, Zr, Hf, U).

Axial oxygen-centered lattice instabilities and high-temperature superconductivity

Copper K-edge x-ray absorption data indicate that an axial oxygen-centered lattice instability accompanying the 93 K superconducting transition in YBa2Cu3O7 is of a pseudo-(anti)ferroelectric type, in that it appears to involve the softening of a double potential well into a structure in which the difference between the two copper-oxygen distances and the barrier height have both decreased. This softer structure is present only at temperatures within a fluctuation region around the transition. A similar process involving the analogous axial oxygen atom also accompanies the superconducting transition in T1Ba2Ca3Cu4O11, where the superconducting transition temperature Tc is ~120 K. The mean square relative displacement of this oxygen atom in YBa2Cu3O7 is also specifically affected by a reduction in the oxygen content and by the substitution of cobalt for copper, providing further evidence for the sensitivity of the displacement to additional factors that also influence the superconductivity. On the basis of the implied coupling of this ionic motion to the superconductivity, a scenario for high-temperature superconductivity is presented in which both phonon and electronic (charge transfer) channels are synergistically involved.

Ag K-edge EXAFS analysis of DNA-templated fluorescent silver nanoclusters: insight into the structural origins of emission tuning by DNA sequence variations.

DNA-templated silver nanoclusters are promising biological fluorescence probes due to their useful fluorescence properties, including tunability of emission wavelength through DNA template sequence variations. Ag K-edge EXAFS analysis of DNA-templated silver nanoclusters has been used to obtain insight into silver nanocluster bonding, size, and structural correlations to fluorescence. The results indicate the presence of small silver nanoclusters (<30 silver atoms) containing Ag-Ag bonds and Ag-N/O ligations to DNA. The DNA sequence used leads to differences in silver-DNA ligation as well as silver nanocluster size. The results support a model in which cooperative effects of both Ag-DNA ligation and variations in cluster size lead to the tuning of the fluorescence emission of DNA-templated silver nanoclusters.

The incorporation of plutonium and neptunium in zirconolite and perovskite

Abstract The incorporation of Pu and Np in one zirconolite and a number of perovskite formulations has been investigated under oxidising and reducing conditions. The Pu valence in both perovskite and zirconolite was found to vary independently of the crystal chemical design by altering the annealing atmosphere, from Pu 4+ in air to Pu 3+ in 3.5% H 2 /N 2 . For both atmospheres, only tetravalent Np was found in the zirconolite. Tetravalent Np was observed in perovskites fired in air, but trivalent Np was stabilised in suitable perovskite formulations annealed under a reducing atmosphere. A trivalent Np phosphate, NpPO 4 was also prepared under reducing conditions.