RESUMEN
Estrone is an emerging contaminant found in waters and soils all over the world. Conventional water treatment methods are not suitable for estrone removal due to its nonpolarity and low bioavailability. Heterogeneous photocatalysis is a promising approach; however, pristine semiconductors need optimization for efficient estrone photodegradation. Herein, we compared Zn-Cr LDH/GCN heterostructures obtained by three different synthesis methods. The influence of the GCN content in the heterostructure on photoactivity was also tested. The morphology, structure, and electronic properties of the materials were analyzed and compared. The photocatalytic kinetic tests were conducted with 1 ppm of estrone in both UV and visible light, separately. The HLDH-G50 material, obtained by the hydrothermal route and containing 50 wt % of GCN exhibited the highest photocatalytic efficiency. After 1 h, 99.5% of the estrone was degraded in visible light. In UV light, the pollutant concentration was below the detection limit after 0.5 h. The superior effectiveness was caused by numerous factors such as high homogeneity of the formed heterostructure, lower band gap energy of hydrothermal LDH, and increased photocurrent. These characteristics led to prolonged lifetimes of charge carriers, a wider light absorption range, and uniformity of the material for predictable performance. This study highlights the importance of a proper heterostructure engineering strategy for acquiring highly effective photocatalysts designed for water purification. In particular, this work provides innovative insight into comparing different synthesis methods and their influence on materials' properties.
RESUMEN
The field of photocatalysis has been evolving since 1972 since Honda and Fujishima's initial push for using light as an energy source to accomplish redox reactions. Since then, many photocatalysts have been studied, semiconductors or otherwise. A new photocatalytic application to convert N2 gas to ammonia (N2 fixation or nitrogen reduction reaction; NRR) has emerged. Many researchers have steered their research in this direction due to developments in the ease of ammonia detection through UV-Vis spectroscopy. This concept will specifically discuss Bi2 WO6 -based materials, techniques to enhance their photocatalytic activity (CO2 reduction, H2 production, pollutant removal, etc.), and their current application in photocatalytic NRR. Initially, a brief introduction of Bi2 WO6 along with its VB and CB potentials will be compared to various redox potentials. A final topic of interest would be a brief description of photocatalytic nitrogen fixation with additional consideration to Bi2 WO6 -based materials in N2 fixation. A major problem with photocatalytic NRR is the false ammonia quantification in Bi-based materials, which will be discussed in detail and also ways to minimize them.
RESUMEN
Photocatalytic N2 fixation is a complex reaction, thereby prompting researchers to design and analyze highly efficient materials. Herein, one-pot hydrothermal Bi2WO6-BiOCl (BW-BiOCl) heterojunctions were synthesized by varying the molar ratio of tungsten: chlorine precursor. Major morphological transformations in BiOCl were observed wherein it turned from thick sheets â¼230 nm in pure BiOCl to â¼30 nm in BW-BiOCl. This was accompanied by extensive growth of {001} facets verified from X-ray diffraction (XRD) and field-emission scanning electron microscopy (FESEM) analyses. A p-n heterojunction was formed between Bi2WO6 and BiOCl evidenced via photoluminescence (PL), time-resolved photoluminescence (TRPL), photocurrent response, and electrochemical impedance spectroscopy (EIS) analyses. The formation of heterojunction between Bi2WO6 and BiOCl led to the reduction of the work function in the BW-BiOCl 0.25 hybrid confirmed via ultraviolet photoelectron spectroscopy (UPS) analysis. BW-BiOCl 0.25 could produce ammonia up to 345.1 µmol·L-1·h-1 owing to the formation of a robust heterojunction with an S-scheme carrier transport mechanism. Recycle tests resulted in no loss in N2 reduction activities with post-catalytic analysis, showcasing the high stability of the synthesized heterojunction. Novel performance was owed to its excellent chemisorption of N2 gas on the heterojunction surface verified by N2-temperature programmed desorption (TPD). BW-BiOCl 0.25 also displayed a superior rate constant of 3.03 × 10-2 min-1 for 90 min CIP degradation time, higher than pristine BiOCl and Bi2WO6. Post-photocatalytic Fourier transform infrared (FTIR) spectroscopy of BW-BiOCl 0.25 revealed the presence of C-H stretching peaks in the range of 2850-2960 cm-1 due to adsorbed CIP and methanol species in CIP degradation and N2 fixation, respectively. This also confirmed the enhanced adsorption of reacting species onto the heterojunction surface.