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In this study, iron oxalate dihydrate (FOD-ore) was produced from iron ore by the process using oxalic acid to extract iron, followed by photo-reduction. Several techniques, such as X-ray powder diffraction (XRD), Raman, scanning electron microscopy with energy dispersive X-Ray analysis (SEM-EDX), ultraviolet–visible diffuse reflectance spectroscopy (UV-DRS), photoluminescence spectroscopy (PL), and X-ray photoelectron spectroscopy (XPS), were used to determine the physicochemical properties of the FOD-ore sample. To compare the photocatalytic activity of FOD-ore, commercial hematite (Fe2O3) was used as a precursor to creating iron oxalate (FOD). The FOD-ore was applied to the photocatalytic degradation of rhodamine B (RhB), a model organic pollutant in wastewater. Using the produced FOD-ore, we were able to degrade more than 85% of RhB within 90 min at a rate approximately 1.4 times higher than that with FOD. FOD-ore demonstrated greater light absorption than FOD, resulting in improved RhB degradation performance. Moreover, the enhanced separation and transport of photogenerated electron-hole pairs can be attributed to the increased photocatalytic RhB degradation rate of FOD-ore, confirmed by photoluminescence results. Therefore, FOD-ore can be utilized as a potential photocatalyst in the degradation process for other organic pollutants under light irradiation.

Pd nanoparticles (PdNPs) were successfully deposited on the surface of Fe(III)-modified hydroxyapatite (HAp), which was subsequently used as a photocatalyst for simultaneous photocatalytic H2 evolution and xylose conversion. The structural phase and morphology of the pristine HAp, FeHAp, and Pd@FeHAp were examined using XRD, SEM, and TEM instruments. At 20 °C, Pd@FeHAp provided a greater xylose conversion than pristine HAp and FeHAp, about 2.15 times and 1.41 times, respectively. In addition, lactic acid and formic acid production was increased by using Pd@FeHAp. The optimal condition was further investigated using Pd@FeHAp, which demonstrated around 70% xylose conversion within 60 min at 30 °C. Moreover, only Pd@FeHAp produced H2 under light irradiation. To clarify the impact of Fe(III) doping in FeHAp and heterojunction between PdNPs and FeHAp in the composite relative to pure Hap, the optical and physicochemical properties of Pd@FeHAp samples were analyzed, which revealed the extraordinary ability of the material to separate and transport photogenerated electron-hole pairs, as demonstrated by a substantial reduction in photoluminescence intensity when compared to Hp and FeHAp. In addition, a decrease in electron trap density in the Pd@FeHAp composite using reversed double-beam photoacoustic spectroscopy was attributed to the higher photocatalytic activity rate. Furthermore, the development of new electronic levels by the addition of Fe(III) to the structure of HAp in FeHAp may improve the ability to absorb light by lessening the energy band gap. The photocatalytic performance of the Pd@FeHAp composite was improved by lowering charge recombination and narrowing the energy band gap. As a result, a newly developed Pd@FeHAp composite might be employed as a photocatalyst to generate both alternative H2 energy and high-value chemicals.

Cu-HyS-urea and Cu-HyS-NaOH, which are hydrotalcite-like copper hydroxyl salts, were prepared by two different methods, urea hydrolysis and precipitation, respectively. Both synthesis methods provided the successful formation of a copper hydroxyl salt, Cu2(OH)3NO3. From XRD and UV-DRS results, the product from the urea hydrolysis methods (Cu-HyS-urea) displayed higher crystallinity, small bandgap energy (Eg), and high light absorption ability because of some intercalated carbonate anions. For the Cr(VI) removal test, the Cu-HyS-NaOH showed superior adsorption of Cr(VI) than Cu-HyS-urea due to a higher specific surface area, confirmed by BET analysis. However, the Cu-HyS-urea presented higher photocatalytic Cr(VI) reduction under light irradiation than Cu-HyS-NaOH, owing to narrow Eg, less recombination, and a high transfer of the photogenerated charge carriers, proven by the results from photoluminescence, photocurrent density, and electrochemical impedance spectroscopy. Thus, this work provides a new function of the hydrotalcite-like copper hydroxyl salts (Cu-HyS-urea and Cu-HyS-NaOH) that can be utilized not only for adsorption of Cr(VI) but also as photocatalysts for Cr(VI) reduction under light irradiation.

In this work, g-C3N4/TiO2 composites were fabricated through a hydrothermal method for the efficient photocatalytic degradation of imidacloprid (IMI) pesticide. The composites were fabricated at varying loading of sonochemically exfoliated g-C3N4 (denoted as CNS). Complementary characterization results indicate that the heterojunction between the CNS and TiO2 formed. Among the composites, the 0.5CNS/TiO2 material gave the highest photocatalytic activity (93% IMI removal efficiency) under UV-Vis light irradiation, which was 2.2 times over the pristine g-C3N4. The high photocatalytic activity of the g-C3N4/TiO2 composites could be ascribed to the band gap energy reduction and suppression of photo-induced charge carrier recombination on both TiO2 and CNS surfaces. In addition, it was found that the active species involved in the photodegradation process are OH• and holes, and a possible mechanism was proposed. The g-C3N4/TiO2 photocatalysts exhibited stable photocatalytic performance after regeneration, which shows that g-C3N4/TiO2 is a promising material for the photodegradation of imidacloprid pesticide in wastewater.

Metal-doped graphitic carbon nitride (MCN) materials have shown great promise as effective photocatalysts for the conversion of acetic acid to carbon dioxide under UV–visible irradiation and are superior to pristine carbon nitride (g-C3N4, CN). In this study, the effects of metal dopants on the physicochemical properties of metal-doped CN samples (Fe-, Cu-, Zn-, FeCu-, FeZn-, and CuZn-doped CN) and their catalytic activity in the photooxidation of acetic acid were investigated and discussed for their correlation, especially on their surface and bulk structures. The materials in the order of highest to lowest photocatalytic activity are FeZn_CN, FeCu_CN, Fe_CN, and Cu_CN (rates of CO2 evolution higher than for CN), followed by Zn_CN, CuZn_CN, and CN (rates of CO2 evolution lower than CN). Although Fe doping resulted in the extension of the light absorption range, incorporation of metals did not significantly alter the crystalline phase, morphology, and specific surface area of the CN materials. However, the extension of light absorption into the visible region on Fe doping did not provide a suitable explanation for the increase in photocatalytic efficiency. To further understand this issue, the materials were analyzed using two complementary techniques, reversed double-beam photoacoustic spectroscopy (RDB-PAS) and electron spin resonance spectroscopy (ESR). The FeZn_CN, with the highest electron trap density between 2.95 and 3.00 eV, afforded the highest rate of CO2 evolution from acetic acid photodecomposition. All Fe-incorporated CN materials and Cu-CN reported herein can be categorized as high activity catalysts according to the rates of CO2 evolution obtained, higher than 0.15 μmol/min−1, or >1.5 times higher than that of pristine CN. Results from this research are suggestive of a correlation between the rate of CO2 evolution via photocatalytic oxidation of acetic acid with the threshold number of free unpaired electrons in CN-based materials and high electron trap density (between 2.95 and 3.00 eV).

Methylene blue (MB) is a dye widely used as an optical redox indicator in analytical chemistry, whose color change is also affected by pH. It was irreversibly adsorbed on polymeric carbon nitride (g-C3N4) prepared either from urea or from melamine cyanurate. Electron spin resonance (ESR) showed an increase in radicals or unpaired electrons in the MB-g-C3N4 system in comparison to pure g-C3N4. Upon treatment with potassium hydroxide, an abrupt color change from blue to purple occurred, together with a decrease in the ESR signal. Exposure to air caused a shift to the initial blue color, and, as suggested by UV-Vis spectroscopy data, the system returned to its original state, before the treatment with alkali. This behavior suggests the suitability of the MB-g-C3N4 system as a promising reusable sensor for the detection of exposure to air (and/or to carbon dioxide) of products stored under vacuum or in a controlled atmosphere. Thus, visual indicators based on this material may find applications as cost-effective leakage indicators for the modified atmosphere package (MAPs) industry, in particular to assess food safety or for electronic packaging.

An n-type organic carbon nitride semiconductor, C2N, was synthesized by the pyrolysis of uric acid, and its properties were investigated by scanning electron and transmission electron microscopies, X-ray powder diffraction, and vibrational, UV-visible and X-ray photoelectron spectroscopies. This novel material, composed of crystalline flakes, featured a broad absorption centered at 700 nm, possibly due to charge transfer, and a 2.49 eV band gap. Its catalytic performance was assessed for the treatment of effluents with the diazo dye Congo red, comparing it with that of boron carbon nitrogen oxide, BCNO. Both wide band gap semiconductors exhibited decolorizing activity in the dark, although the mechanisms were different and were not photocatalytic: BCNO was more effective towards the adsorption-coordination due to the presence of B-O, while C2N was effective towards the adsorption and the advancement of the oxidation reaction. Their kinetic constants (0.19 and 0.02 min−1 for BCNO and C2N, respectively) were comparable to those of intermetallic compounds studied for azo dyes degradation in dark conditions. In view of the high color removal efficiency (97% after 20 min) and good reusability of BCNO, this study suggests a potential application of this catalyst for wastewater treatment, alone or in combination with C2N.

Functional nanomaterials find numerous applications in electrochemical biosensors and lab-on-a-chip devices, such as the glucose sensors used by diabetic patients. In this work, polymeric carbon nitride (g-C3N4) −which mimicks peroxidases behavior− was used, in combination with 3,3′,5,5′-tetramethylbenzidine (TMB) −a redox indicator−, to detect glucose in a quantitative way. The utilization of two non-noble metal co-catalysts, Fe(III) and Cu(II), embedded in the polymer structure by adsorption (Cu(II)–Fe(III)-g-C3N4), considerably increased the sensitivity towards glucose as compared to that of pristine g-C3N4. TMB and glucose oxidase (GOx) were also adsorbed on the catalyst, resulting in a solid-state composite that changed its color from yellow to green when exposed to a solution containing glucose. The UV–Vis monitoring of the intensity of the band at 675 nm, associated with oxidized TMB, showed that the response of the Cu(II)–Fe(III)-g-C3N4 system was faster than that of the one based on pristine g-C3N4. This behavior was further confirmed by electron spin resonance (ESR) spectroscopy. Moreover, ESR experiments conducted with 5,5-dimethyl-1-pyrroline N-oxide (DMPO) evidenced that the Cu(II)–Fe(III)-g-C3N4 catalyst was able to produce about twice as many radicals as pristine g-C3N4. The proposed composite material may hold promise as a solid substrate for glucose sensing, given that concentration levels in the low ppb range can be detected by UV–Vis diffuse reflectance spectroscopy and concentrations above 100 ppm (μM) can be easily detected by the naked eye.