Visible light-driven CO2 photoreduction by a Re(I) complex immobilized onto CuO/Nb2O5 heterojunctions.

The immobilization of Re(I) complexes onto metal oxide surfaces presents an elegant strategy to enhance their stability and reusability toward photocatalytic CO2 reduction. In this study, the photocatalytic performance of fac-[ClRe(CO)3(dcbH2)], where dcbH2 = 4,4'-dicarboxylic acid-2,2'-bipyridine, anchored onto the surface of 1%m/m CuO/Nb2O5 was investigated. Following adsorption, the turnover number for CO production (TONCO) in DMF/TEOA increased significantly, from ten in solution to 370 under visible light irradiation, surpassing the TONCO observed for the complex onto pristine Nb2O5 or CuO surfaces. The CuO/Nb2O5 heterostructure allows for efficient electron injection by the Re(I) center, promoting efficient charge separation. At same time CuO clusters introduce a new absorption band above 550 nm that contributes for the photoreduction of the reaction intermediates, leading to a more efficient CO evolution and minimization of side reactions.

CO2-plasma surface treatment of graphite sheet electrodes for detection of chloramphenicol, ciprofloxacin and sulphanilamide.

Graphite sheet (GS) electrodes are flexible and versatile substrates for sensing electrochemical; however, their use has been limited to incorporate (bio)chemical modifiers. Herein, we demonstrated that a cold (low temperature) CO2 plasma treatment of GS electrodes provides a substantial improvement of the electrochemical activity of these electrodes due to the increased structural defects on the GS surface as revealed by Raman spectroscopy (ID/IG ratio), and scanning electron microscopy images. XPS analyses confirmed the formation of oxygenated functional groups at the GS surface after the plasma treatment that are intrinsically related to the substantial increase in the electron transfer coefficient (K0 values increased from 1.46 × 10-6 to 2.09 × 10-3 cm s-1) and with reduction of the resistance to charge transfer (from 129.8 to 0.251 kΩ). The improved electrochemical activity of CO2-GS electrodes was checked for the detection of emerging contaminant species, such as chloramphenicol (CHL), ciprofloxacin (CIP) and sulphanilamide (SUL) antibiotics, at around + 0.15, + 1.10 and + 0.85 V (versus Ag/AgCl), respectively, by square wave voltammetry. Limit of detection values in the submicromolar range were achieved for CHL (0.08 µmol L-1), CIP (0.01 µmol L-1) and SFL (0.11 µmol L-1), which enabled the sensor to be successfully applied to natural waters and urine samples (recovery values from 85 to 119%). The CO2-GS electrode is highly stable and inexpensive ($0.09 each sensor) and can be easily inserted in portable 3D printed cells for environmental on-site analyses.

Unveiling the efficiency of microwave-assisted hydrothermal treatment for the preparation of SrTiO3 mesocrystals.

Material processing has become essential for the proper control, tuning and consequent application of the properties of micro/nanoparticles. In this case, we report herein the capability of the microwave-assisted hydrothermal (MAH) method to prepare the SrTiO3 compound, as a case study of inorganic compounds. Analyses conducted by X-ray diffraction, X-ray photoelectron and X-ray absorption spectroscopies confirmed that the MAH route enables the formation of pristine SrTiO3. The results indicated that the combination of thermal and non-thermal effects during the MAH treatment provides ideal conditions for an efficient and rapid synthesis of pristine SrTiO3 mesocrystals. Scanning electron microscopy images revealed a cube-like morphology (of ca. 1 µm) formed via a self-assembly process, influenced by the MAH time. Additionally, photoluminescence measurements revealed a broad blue emission related to intrinsic defects, which decreased with the MAH synthesis time.

Insights into the photocatalytic performance of Bi2O2CO3/BiVO4 heterostructures prepared by one-step hydrothermal method.

This paper describes the synthesis of Bi2O2CO3/BiVO4 heterostructures through a one-step method based on the difference in solubility between two semiconductors that possess a metal in common. The as-synthesized Bi2O2CO3/BiVO4 heterostructures were characterized by X-ray diffraction (XRD), thermogravimetric analysis (TGA), Raman spectroscopy, ultraviolet-visible diffuse reflectance spectroscopy (UV-vis DRS), scanning electron microscopy (SEM), transmission electron microscopy (TEM), N2 physisorption, X-ray photoelectron spectroscopy (XPS) and time resolved photoluminescence spectroscopy (TRPL). The role of the heterojunction formed was evaluated by methylene blue (MB) dye and amiloride photodegradation. The formation of the heterostructure was observed indirectly by the great increase in the thermal stability of the Bi2O2CO3 phase when compared to its pure phase. The amount of heterojunctions formed between the Bi2O2CO3 and BiVO4 was tuned by vanadium precursor concentration. The proposed strategy was efficient for obtaining Bi2O2CO3/BiVO4 heterostructures with enhanced photocatalytic performance when compared to their isolated phases, MB and amiloride photodegradation occurred mainly by the action of ˙OH radicals, i.e. by an indirect mechanism. Based on TRPL spectroscopy and VB-XPS results, an enhancement of photoactivity related to an increase in the spatial separation of photo-generated electron/hole pairs was observed due to the formation of a type-II heterostructure.

An Understanding of the Photocatalytic Properties and Pollutant Degradation Mechanism of SrTiO3 Nanoparticles.

Strontium titanate nanoparticles have attracted much attention due to their physical and chemical properties, especially as photocatalysts under ultraviolet irradiation. In this paper, we analyze the effect of heating rate during the crystallization process of SrTiO3 nanoparticles in the degradation of organic pollutants. The relationship between structural, morphological and photocatalytic properties of the SrTiO3 nanoparticles was investigated using different techniques. Transmission electron microscopy and N2 adsorption results show that particle size and surface properties are tuned by the heating rate of the SrTiO3 crystallization process. The SrTiO3 nanoparticles showed good photoactivity for the degradation of methylene blue, rhodamine B and methyl orange dyes, driven by a nonselective process. The SrTiO3 sample with the largest particle size exhibited higher photoactivity per unit area, independent of the molecule to be degraded. The results pointed out that the photodegradation of methylene blue dye catalyzed by SrTiO3 is caused by the action of valence band holes (direct pathway), and the indirect mechanism has a negligible effect, i.e. degradation by O2 (-•) and (•) OH radicals attack.