This research investigated the mechanism of perchlorate (ClO(4)(-)) formation from chlorate (ClO(3)(-)) on boron-doped diamond (BDD) film anodes by use of a rotating disk electrode reactor. Rates of ClO(4)(-) formation were determined as functions of the electrode potential (2.29-2.70 V/standard hydrogen electrode, SHE) and temperature (10-40 °C). At all applied potentials and a ClO(3)(-) concentration of 1 mM, ClO(4)(-) production rates were zeroth-order with respect to ClO(4)(-) concentration. Experimental and density functional theory (DFT) results indicate that ClO(3)(-) oxidation proceeds via a combination of direct electron transfer and hydroxyl radical oxidation with a measured apparent activation energy of 6.9 ± 1.8 kJ·mol(-1) at a potential of 2.60 V/SHE. DFT simulations indicate that the ClO(4)(-) formation mechanism involves direct oxidation of ClO(3)(-) at the BDD surface to form ClO(3)(•), which becomes activationless at potentials > 0.76 V/SHE. Perchloric acid is then formed via the activationless homogeneous reaction between ClO(3)(•) and OH(•) in the diffuse layer next to the BDD surface. DFT simulations also indicate that the reduction of ClO(3)(•) can occur at radical sites on the BDD surface to form ClO(3)(-) and ClO(2), which limits the overall rate of ClO(4)(-) formation.

Vanadium oxide gels derived from aqueous solutions of V2O5 and H2O2 have been investigated using in situ 51V NMR and laser Raman spectroscopic techniques. On the basis of this characterization, a pathway for peroxovanadate decomposition has been proposed, including the presence of two peroxovanadate dimers. New Raman bands and assignments for these species are reported. Gelation was observed to begin both during and after the peroxovanadate decomposition, depending on the initial molar ratios of H2O2/V and the total concentration of vanadium. Experimental 51V NMR evidence suggested that the VO2 + species was directly involved in the formation of the gel.

Vanadium oxide gels derived from the reaction of H2O2 and V2O5 have been investigated using 51V MAS NMR, TGA, XRD, SEM, and laser Raman spectroscopy. Based primarily on the 51V MAS NMR and TGA results, the coordinations of five distinct vanadia sites have been detailed, which possibly include a previously unreported dimer. The relative concentration of these sites changed as dehydration progressed, and a model of this process has been proposed based on the numerical analysis of the NMR MAS spectra. In addition, the coordination of the most tightly bound water has been postulated. Depending on sample treatment, it was possible to synthesize both layered and nonlayered materials. The laser Raman spectra revealed differences between layered and nonlayered materials. These differences have been attributed to the interaction of coordinated water molecules, which were trapped between layers and held firmly in place, thus restricting or altering certain Raman-active vibrations.

Boron-doped diamond (BDD) film electrodes were use to electrochemically destroy N-nitrosodimethylamine (NDMA) in reverse osmosis (RO) concentrates. Batch experiments were conducted ito investigate the effects of dissolved organic carbon (DOC), chloride (Cl(-)), bicarbonate (HCO(3-) and hardness on rates of NDMA destruction via both oxidation and reduction. Experimental results showed that NDMA oxidation rates were not affected by DOC, Cl(-), or HCO(3-) at concentrations present in RO concentrates. However, hydroxyl radical scavenging at 100 mM concentrations of HCO(3-) and Cl(-) shifted the reaction mechanism of NDMA oxidation from hydroxyl radical mediated to direct electron transfer oxidation. In the 100 mM Cl(-) electrolyte experimental evidence suggests that the in situ production of ClO(3)(.)also contributes to NDMA oxidation. Density functional theory calculations support a reaction mechanism between ClO(3)(.) and NDMA, with an activation barrier of 7.2 kJ/mol. Flow-through experiments with RO concentrate yielded surface area normalized first-order rate constants for NDMA (40.6 +/- 3.7 L/m(2) h) and DOC (as C) (38.3 +/- 2.2 L/m(2) h) removal that were mass transfer limited at a 2 mA/cm(2) current density. This research shows that electrochemical oxidation using BDD electrodes has an advantage over other advanced oxidation processes, as organics were readily oxidized in the presence of high HCO(3-) concentrations.

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The environments for oxygen sites in crystalline V(2)O(5) and in layered vanadia gels produced via sol-gel synthesis have been investigated using (17)O MAS and 3QMAS NMR. For crystalline V(2)O(5), three structural oxygen sites were observed: V=O (vanadyl), V(2)O (doubly coordinated), and V(3)O (triply coordinated). Line-shape parameters for these sites were determined from numerical simulations of the MAS spectra. For the vanadia gels at various stages of dehydration, assignments have been proposed for numerous vanadyl, doubly coordinated, and triply coordinated oxygen sites. In addition, by correlating the (17)O MAS and 3QMAS NMR, (51)V MAS NMR, and thermogravimetric analysis data, the coordination of water sites has been established. On the basis of these results, the gel structure and its evolution at various stages of hydration have been detailed. Upon rehydration of the layered gel, we observed a preferred site for initial water readsorption. The oxygen atoms of these readsorbed water molecules readily exchanged into all types of oxygen sites even at room temperature.

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VPO catalyst transformations were investigated using in situ laser Raman spectroscopy. During reduction−oxidation step changes, (VO)2P2O7 was readily converted to αII-, δ-VOPO4, and ultimately to β-VOPO4 in O2/N2; these V5+ phases were eliminated in n-butane/N2. A wet N2 feed (5−10% H2O in N2) transformed (VO)2P2O7 and αI-, αII-, β-, δ-, γ-VOPO4 to V2O5 at temperatures above 400 °C. The presence of water vapor facilitated the loss of oxygen atoms involved in V−O−P bonding, and separated vanadium oxide and phosphorus oxide species were formed. The isolated vanadium oxide species could be transformed to V2O5; phosphorus species likely diffused from the catalyst lattice in the form of acid phosphates.