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New organic dyes comprising carbazole, iminodibenzyl, or phenothiazine moieties, respectively, as the electron donors, and cyanoacetic acid or acrylic acid moieties as the electron acceptors/anchoring groups were synthesized and characterized. The influence of heteroatoms on carbazole, iminodibenzyl and phenothiazine donors, and cyano-substitution on the acid acceptor is evidenced by spectral, electrochemical, photovoltaic experiments, and density functional theory calculations. The phenothiazine dyes show solar-energy-to-electricity conversion efficiency (η) of 3.46–5.53%, whereas carbazole and iminodibenzyl dyes show η of 2.43% and 3.49%, respectively.

Speciation of copper in the fly ash solidification process has been studied by X-ray based spectroscopies inthe present work. Fourier transformed EXAFS (extended X-ray absorption fine structural) spectra of the solidified fly ashes showed that the bond distance of Cu-O (first shell) was 1.96 A with a coordination number (CN) of about 3.0. However, in the second shell of copper atoms, the bond distance of Cu-(O)-Cu was decreased by 0.12-0.22 A during solidification, which might cause the stabilization of the CuO species in the solidified fly ash matrix. By the least-squares fits of the XANES (X-ray absorption near edge structural) spectra, fractions of the main copper species in the solidified fly ashes such as CuCl2 (0.08-0.11), Cu2O (0.07-0.09), Cu(OH)2 (0.31-0.33), and CuO (0.49-0.52) were observed. Combined EXAFS and XANES observations suggested that chemical reactions such as hydroxylation of CuCl2 and oxidation of Cu2O and/or metallic Cu might involve in the solidification process, which also led to a significant reduction of the leachability of copper from the solidified fly ashes.

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Experimentally, CCl4 was effectively mineralized by CuO to yield stable inorganic species of CO2 and CuCl2 (CCl4 + 2CuO --> 2CuCl2 + CO2). High CCl4 conversions (63-83%) were found in the mineralization process performed at 513-603 K for 10-30 min. Using X-ray-absorption near edge structure (XANES) and X-ray photoelectron spectroscopies, we found that most CuCl2 was encapsulated in the CCl4-mineralized product solid (mineralization at 513 K for 30 min). At higher mineralization temperatures (563-603 K), CuCl2 was found to be predominant on the surfaces of the mineralization product. Speciation of copper in the mineralization product solid was also studied by extended X-ray absorption fine structure (EXAFS) spectroscopy. Bond distances of Cu-O and Cu-Cl in the CCl4-mineralized product solid were 1.93-1.94 and 2.10-2.12 , respectively, which were greater than those of normal CuO and CuCl2 by 0.03-0.07 A. The increase of the bond distances for Cu-O and Cu-Cl might be due to Cl insertion and concomitant structural perturbation of unreacted CuO in the mineralization process. Forthe second shell around copper atom, bond distances of Cu-(O)-Cu also increased by 0.03-0.05 A, and the coordination numbers of Cu-O and Cu-(O)-Cu decreased, as expected, in the mineralization process. In addition, stoichiometrically excess oxygen atoms were found on the solid surfaces, and they might play an important role in the mineralization of CCl4, leading to the formation of CO2 and Cl. Chloride atoms might be further captured by CuO, yielding CuCl2 in the mineralization process. This work exemplifies the utilization of X-ray spectroscopies (XANES, EXAFS, and XPS) to reveal the speciation and possible reaction pathway in a very complex mineralization process in detail.

Microwaves were applied to reduce the activation energy of chlorobenzene in aqueous solution and enhance its removal using nanoscale zero-valent iron (Fe 0 ) or zero-valent copper (Cu 0 ) particles as dielectric media. When Fe 0 and Cu 0 particles absorb microwave energy, the electrical potential difference causes the metal electrons to rotate faster, thus producing more heat. The microwave-irradiated metal particles reduced the chlorobenzene activation energy by 6.1 kJ/mol (13.3 kJ/mol versus 19.4 kJ/mol) for Fe 0 and 5.4 kJ/mol (15.8 kJ/mol versus 21.4 kJ/ mol) for Cu 0 and enhanced the chlorobenzene removal 4.1 times (82.8% versus 20.4%) for Fe 0 and 3.7 times (72.1% versus 19.5%) for Cu 0 . The Fe 0 has a higher standard reduction potential than Cu 0 ; it is capable of removing more chlorobenzene than Cu 0 (82.8% versus 72.1%). Using the microwave-induced nano-scale iron or copper particle is effective in treating toxic organic substances, as demonstrated in this study. Water Environ. Res., 82, 642 (2010).