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Nanoscale zerovalent iron (nZVI) is considered as a highly efficient material for sequestrating arsenite, but the origin of its high efficacy as well as the chemical transformations of arsenite during reaction is not well understood. Here, we report an in situ X-ray absorption spectroscopy (XAS) study to investigate the complex mechanism of nZVI reaction with arsenite under anaerobic conditions at the time scale from seconds to days. The time-resolved XAS analysis revealed a gradual oxidation of AsIII to AsV in the course of minutes to hours in both the solid and liquid phase for the high (above 0.5 g/L) nZVI dose system. When the reaction time increased up to 60 days, AsV became the dominant species. The quick-scanning extended X-ray absorption fine structure (QEAXFS) was introduced to discover the transient intermediate at the highly reactive stage, and a small red-shift in As K-edge absorption edge was observed. The QEAXFS combined with density functional theory (DFT) calculation suggested that the red-shift is likely due to the electron donation in a Fe-O-As complex and possible active sites of As sequestrations include Fe(OH)4 and 4-Fe cluster. This is the first time that the transient reaction intermediate was identified in the As-nZVI sequestration system at the fast-reacting early stage. This study also demonstrated usefulness of in situ monitoring techniques in environmental water research.

TiO2 has long been recognized as a stable and reusable photocatalyst for water splitting and pollution control. However, it is an inefficient anode material in the absence of photoactivation due to its low electron conductivity. To overcome this limitation, a series of conductive TiO2 nanotube array electrodes have been developed. Even though nanotube arrays are effective for electrochemical oxidation initially, deactivation is often observed within a few hours. To overcome the problem of deactivation, we have synthesized cobalt-doped Black-TiO2 nanotube array (Co-Black NTA) electrodes that are stable for more than 200 h of continuous operation in a NaClO4 electrolyte at 10 mA cm-2. Using X-ray photoelectron spectroscopy, X-ray absorption spectroscopy, electron paramagnetic resonance spectroscopy, and DFT simulations, we are able to show that bulk oxygen vacancies (Ov) are the primary source of the enhanced conductivity of Co-Black. Cobalt doping both creates and stabilizes surficial oxygen vacancies, Ov, and thus prevents surface passivation. The Co-Black electrodes outperform dimensionally stable IrO2 anodes (DSA) in the electrolytic oxidation of organic-rich wastewater. Increasing the loading of Co leads to the formation of a CoO x film on top of Co-Black electrode. The CoO x /Co-Black composite electrode was found to have a lower OER overpotential (352 mV) in comparison to a DSA IrO2 (434 mV) electrode and a stability that is greater than 200 h in a 1.0 M KOH electrolyte at a current density of 10 mA cm-2.

NaNO2/MgO/titania spheres prepared via aerosol-assisted self-assembly (AASA) were used as sorbents for CO2 adsorption at moderate temperature. The titania framework as support would allow MgO to disperse well, thereby increasing the contact between MgO and NaNO2 to enhance carbonation. In this study, the effect of Mg/Ti molar ratio and NaNO2 addition amount on CO2 adsorption was investigated. Results showed that the sorbent prepared by AASA with Mg/Ti molar ratio of 2 following the introduction of 30 wt% NaNO2 presented ∼1 μm particle size with rough sphere surface morphology and mesoporous properties, where the surface area and pore volume were 72 m2/g and 0.18 cm3/g, respectively. With NaNO2 addition, the kinetics and capacity of CO2 adsorption significant increased. In the cyclic adsorption/desorption experiment, the superior stability over the NaNO2/MgO/titania spheres was mainly ascribed to the confined space suppressed the degree of the sintering effect. These results indicated the potential application of the nanochannel-restricted sorbent for rapid, high-capacity, and stable CO2 capture at moderate temperatures. [ABSTRACT FROM AUTHOR]

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Through the addition of a solid-state precursor, a large-scale, transparent, and free-standing film of 1-D rutile/anatase TiO2 nanorod arrays can be fabricated by dynamically changing the acidity and concentrations of titanium and chloride ions, and creating anatase growth-friendly conditions. [ABSTRACT FROM AUTHOR]

We investigated the ammonium removal abilities of natural and synthetic zeolites with distinct Si/Al ratios and various surface areas to study how adsorption and ion exchange processes in zeolites perform under different ammonium concentrations and different temperatures. Five zeolites—natural mordenite, chabazite, erionite, clinoptilolite, and synthetic merlinoite—were immersed in 20, 50, and 100 mg/kg ammonium solutions. The results demonstrate that zeolites under high ammonium concentrations (100 mg/kg) possess higher physical adsorption capacity (0.398–0.468 meq/g), whereas those under lower ammonium concentrations (20 mg/kg) possess greater ion exchange properties (64–99%). The ion exchange ability of zeolites is extremely dependent on the cation content of the zeolites, and the cation content is affected by the Si/Al ratio. The surface area of zeolites also has a partial influence on its physical adsorption ability. When the surface area is less than 100 m2/g, the adsorption ability of zeolite increases obviously with surface area; however, adsorption ability is saturated as the surface area becomes larger than this critical value of 100 m2/g. When we placed the zeolites in 50 mg/kg ammonium concentration at different temperatures (5–50 °C), we found that the zeolites exhibited the highest ammonium removal ability at 30 °C and the potassium release was enhanced at 30–40 °C. [ABSTRACT FROM AUTHOR]

NaNO 2 /MgO/titania spheres prepared via aerosol-assisted self-assembly (AASA) were used as sorbents for CO 2 adsorption at moderate temperature. The titania framework as support would allow MgO to disperse well, thereby increasing the contact between MgO and NaNO 2 to enhance carbonation. In this study, the effect of Mg/Ti molar ratio and NaNO 2 addition amount on CO 2 adsorption was investigated. Results showed that the sorbent prepared by AASA with Mg/Ti molar ratio of 2 following the introduction of 30 wt% NaNO 2 presented ∼1 μm particle size with rough sphere surface morphology and mesoporous properties, where the surface area and pore volume were 72 m 2 /g and 0.18 cm 3 /g, respectively. With NaNO 2 addition, the kinetics and capacity of CO 2 adsorption significant increased. In the cyclic adsorption/desorption experiment, the superior stability over the NaNO 2 /MgO/titania spheres was mainly ascribed to the confined space suppressed the degree of the sintering effect. These results indicated the potential application of the nanochannel-restricted sorbent for rapid, high-capacity, and stable CO 2 capture at moderate temperatures.

Although the low-temperature reaction mechanism of catalytic CO oxidation reaction remains unclear, the active sites of copper play a crucial role in this mechanism. One-step aerosol-assisted self-assembly (AASA) process has been developed for the synthesis of mesoporous Cu-doped TiO 2 microspheres (CuTMS) to incorporate copper into the TiO 2 lattice. This strategy highly enhanced the dispersion of copper from 41.10 to 83.65%. Long-term stability of the as-synthesized CuTMS materials for catalytic CO oxidation reaction was monitored using real-time mass spectrum. Isolated CuO and Cu-O-Ti were formed as determined by X-ray photoelectron spectroscopy (XPS). The formation of the Cu-O-Ti bonds in the crystal lattice changes the electron densities of Ti(IV) and O, causing a subsequent change in Ti(III)/Ti(IV) and O non /O Total ratio. 20CuTMS contained the highest lattice distortion (0.44) in which the O non /O Total ratio is lowest (0.18). This finding may be attributed to the absolute formation of the Cu-O-Ti bonds in the crystal lattice. However, the decrease of Ti(III)/Ti(IV) ratio to about 0.35 of 25CuTMS was caused by the CuO cluster formation on the surface. N 2 O titration-assisted H 2 temperature-programmed reduction and in-situ Fourier transform infrared spectroscopy revealed the properties of copper and effects of active sites., (Copyright © 2020 Elsevier B.V. All rights reserved.)

TiO 2 has long been recognized as a stable and reusable photocatalyst for water splitting and pollution control. However, it is an inefficient anode material in the absence of photoactivation due to its low electron conductivity. To overcome this limitation, a series of conductive TiO 2 nanotube array electrodes have been developed. Even though nanotube arrays are effective for electrochemical oxidation initially, deactivation is often observed within a few hours. To overcome the problem of deactivation, we have synthesized cobalt-doped Black-TiO 2 nanotube array (Co-Black NTA) electrodes that are stable for more than 200 h of continuous operation in a NaClO 4 electrolyte at 10 mA cm -2 . Using X-ray photoelectron spectroscopy, X-ray absorption spectroscopy, electron paramagnetic resonance spectroscopy, and DFT simulations, we are able to show that bulk oxygen vacancies (O v ) are the primary source of the enhanced conductivity of Co-Black. Cobalt doping both creates and stabilizes surficial oxygen vacancies, O v , and thus prevents surface passivation. The Co-Black electrodes outperform dimensionally stable IrO 2 anodes (DSA) in the electrolytic oxidation of organic-rich wastewater. Increasing the loading of Co leads to the formation of a CoO x film on top of Co-Black electrode. The CoO x /Co-Black composite electrode was found to have a lower OER overpotential (352 mV) in comparison to a DSA IrO 2 (434 mV) electrode and a stability that is greater than 200 h in a 1.0 M KOH electrolyte at a current density of 10 mA cm -2 ., Competing Interests: The authors declare no competing financial interest.

Nanotubular TiO2 has attracted considerable attention owing to its unique functional properties, including high surface area and vectorial charge transport along the nanotube, making it a good photocatalytic material. Anodic TiO2-nanotube (TiNT) arrays on a Ti foil substrate were prepared by electrochemical anodic oxidation and SEM/HRTEM/XRD analyses have suggested that the walls of TiO2 tubes are formed from stacked [101] planes (anatase). Both HRTEM and XRD indicate an interplanar spacing of d101 = 0.36 nm in the wall structure. Despite the large amount of work done on nanotube synthesis, a thorough investigation of the electronic and atomic structures of free-standing TiNT arrays has not yet been carried out. X-ray absorption spectroscopy (XAS), resonant inelastic X-ray scattering (RIXS) and scanning photoelectron microscopy (SPEM) are employed herein to examine the electronic and atomic structures at the top and bottom of TiNT arrays. These analyses demonstrate the presence of mixed valence states of the Ti ions (Ti(3+) and Ti(4+)) and a structural distortion at the bottom cap region of the TiNT. Additionally, the results obtained herein suggest the formation of a defective anatase phase at the bottom cap barrier layer between the Ti foil substrate and TiNT during the growth of electrochemically anodized nanotubes.