CO2 photoreduction with water vapor has been studied on three TiO2 nanocrystal polymorphs (anatase, rutile, and brookite) that were engineered with defect-free and oxygen-deficient surfaces, respectively. It was demonstrated that helium pretreatment of the as-prepared TiO2 at a moderate temperature resulted in the creation of surface oxygen vacancies (VO) and Ti3+ sites on anatase and brookite but not on rutile. The production of CO and CH4 from CO2 photoreduction was remarkably enhanced on defective anatase and brookite TiO2 (up to 10-fold enhancement) as compared to the defect-free surfaces. Defective brookite was photocatalytically more active than anatase and rutile, probably because of a lower formation energy of VO on brookite. The results from in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) analyses suggested that (1) defect-free TiO2 was not active for CO2 photoreduction since no CO2 – is generated, and (2) CO2 photoreduction to CO possibly underwent different reaction pathways on oxygen-deficient anatase and brookite via different intermediates (e.g., CO2 – on anatase; CO2 – and HCOOH on brookite). The combined DRIFTS and photoactivity studies reported in this paper have provided new insights to the role of surface defects in CO2 photoreduction on TiO2 nanocrystals, and revealed significant information on the much less studied but promising brookite phase.

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BACKGROUND: Firefighting foam-contaminated ground water, which contains high levels of perfluoroalkyl substances (PFAS), is frequently found around airports. In 2018 it was detected that employees at a municipal airport in northern Sweden had been exposed to high levels of short-chain PFAS along with legacy PFAS (i.e., PFOA, PFHxS, and PFOS) through drinking water. OBJECTIVES: In this study, we aimed to describe the PFAS profile in drinking water and biological samples (paired serum and urine) and to estimate serum half-lives of the short-chain PFAS together with legacy PFAS. METHODS: Within 2 weeks after provision of clean water, blood sampling was performed in all 26 airport employees. Seventeen of them were then followed up monthly for 5 months. PFHxA, PFHpA, PFBS, PFPeS, and PFHpS together with legacy PFAS in water and biological samples were quantified using LC/MS/MS. Half-lives were estimated by assuming one compartment, first-order elimination kinetics. RESULTS: The proportions of PFHxA, PFHpA, and PFBS were higher in drinking water than in serum. The opposite was found for PFHxS and PFOS. The legacy PFAS accounted for about 50% of total PFAS in drinking water and 90% in serum. Urinary PFAS levels were very low compared with serum. PFBS showed the shortest half-life {average 44 d [95% confidence interval (CI): 37, 55 d]}, followed by PFHpA [62 d (95% CI: 51, 80 d)]. PFPeS and PFHpS showed average half-lives as 0.63 and 1.46 y, respectively. Branched PFOS isomers had average half-lives ranging from 1.05 to 1.26 y for different isomers. PFOA, PFHxS, and linear PFOS isomers showed average half-lives of 1.77, 2.87, and 2.93 y, respectively. DISCUSSION: A general pattern of increasing half-lives with increasing chain length was observed. Branched PFOS isomers had shorter half-lives than linear PFOS isomers.

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α-Fe(2)O(3) nanoparticle-loaded carbon nanofiber composites were fabricated via electrospinning FeCl(3)·6H(2)O salt-polyacrylonitrile precursors in N,N-dimethylformamide solvent and the subsequent carbonization in inert gas. Scanning electron microscopy, transmission electron microscopy, energy dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, X-ray diffraction, and elemental analysis were used to study the morphology and composition of α-Fe(2)O(3)-carbon nanofiber composites. It was indicated that α-Fe(2)O(3) nanoparticles with an average size of about 20 nm have a homogeneous dispersion along the carbon nanofiber surface. The resultant α-Fe(2)O(3)-carbon nanofiber composites were used directly as the anode material in rechargeable lithium half cells, and their electrochemical performance was evaluated. The results indicated that these α-Fe(2)O(3)-carbon nanofiber composites have high reversible capacity, good capacity retention, and acceptable rate capability when used as anode materials for rechargeable lithium-ion batteries.

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SiO2/V2O5/TiO2 catalysts were synthesized for removing elemental mercury (Hg0) from simulated coal-combustion flue gas. Experiments were carried out in fixed-bed reactors using both pellet and powder catalysts. In contrast to the SiO2-TiO2 composites developed in previous studies, the V2O5 based catalysts do not need ultraviolet light activation and have higher Hg0 oxidation efficiencies. For Hg0 removal by SiO2-V2O5 catalysts, the optimal V2O5 loading was found between 5 and 8%, which may correspond to a maximum coverage of polymeric vanadates on the catalyst surface. Hg0 oxidation follows an Eley-Rideal mechanism where HCI, NO, and NO2 are first adsorbed on the V2O5 active sites and then react with gas-phase Hg0. HCI, NO, and NO2 promote Hg oxidation, while SO2 has an insignificant effect and water vapor inhibits Hgo oxidation. The SiO2-TiO2-V2O5 catalysts exhibit greater Hg0 oxidation efficiencies than SiO2-V2O5, may be because the V-O-Ti bonds are more active than the V-O-Si bonds. This superior oxidation capability is advantageous to power plants equipped with wet-scrubbers where oxidized Hg can be easily captured. The findings in this work revealed the importance of optimizing the composition and microstructures of SCR (selective catalytic reduction) catalysts for Hg0 oxidation in coal-combustion flue gas.