The fabrication of nanocomposites of a metal–organic framework with two-dimensional materials for photocatalytic water splitting and environmental remediation has been the focus of the scientific community for many years now.
The development of heterojunctions is the current focus of the scientific community as these materials are visible light active and the staggered positioning of their band edges combats electron-hole recombination which is the downside of most photocatalysts. In this work, a two- step hydrothermal synthesis protocol was utilized to fabricate a novel observable-light active material, composed of platelet-like BiVO 4 and a titanium-based metal organic framework (MOF) called MIL-125(Ti). The tuning of specific morphologies, such as platelet-like in BiVO 4 , provides the exposure of most reactive facets which are more reactive towards photooxidation of organics in water, thus increasing their efficiency. The as-synthesized heterojunction was characterized by Transmission electron microscopy (TEM), scanning transmission microscopy (SEM), X-Ray diffraction (XRD), Raman spectroscopy, ultraviolet-visible diffuse reflectance spectra (UV-Vis DRS), X-Ray photoelectron spectroscopy (XPS) and photoluminescence (PL) spectra. The formation of the heterojunction lead to a positive shift of the 3-2 Bi:Ti valence band (VB) (1.78 eV) when compared to 1.27 eV VB position of BiVO 4 . The PL and photoelectrochemical measurements revealed that the heterojunction photocatalyst designated 3-2 Bi-Ti demonstrated inhibited recombination rate (platelet-like BiVO 4 > 3-2 Bi:Ti (PM) > MIL-125 > 1–1 Bi:Ti > 2–3 Bi:Ti > 3-2 Bi:Ti) and highly efficient interfacial charge shuttle between platelet-like BiVO 4 and MIL-125(Ti) through the formed n - n junction.
Metal–organic frameworks (MOFs) are promising materials for the removal and photodegradation of pesticides in water. Characteristics such as large surface area, crystalline structure and catalytic properties give MOFs an advantage over other traditional adsorbents. The application of MOFs in environmental remediation is hindered by their ability to only absorb in the UV region. Therefore, combining them with an excellent charge carrier 2D material such as black phosphorus (BP) provides an attractive composite for visible-light-driven degradation of pesticides. In the study, a nanocomposite of black phosphorus and MIL-125(Ti), defined as BpMIL, was prepared using a two-stage hydrothermal and sonication route. The as-prepared composite was characterized using transmission electron microscopy (TEM), scanning electron microscopy (SEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), electrochemical impedance spectroscopy (EIS) and photoluminescence (PL) spectroscopy. These techniques revealed that the circular and sheet-like morphology of the nanocomposites had minimum charge recombination, allowing them to be effective photocatalysts. Furthermore, the photocatalysts exhibited extended productive utilization of the solar spectrum with inhibited recombination rate and could be applied in visible-light-driven water treatment. The photodegradation of diazinon in water was studied using a series of BpMIL (4%, 6% and 12% by mass) nanocomposites as a photocatalyst. The optimal composite was determined to be 4%BpMIL. The degradation parameters were optimized and these included photocatalyst dosage, initial diazinon concentration and pH of the solution. The optimal conditions for the removal and degradation of diazinon were: neutral pH, [diazinon] = 20 mg/L, photocatalyst dosage = 0.5 g/L, achieving 96% removal of the pesticide after 30 min with 4%BpMIL, while MIL-125(Ti) showed 40% removal. The improved photodegradation efficiency of the 4%BpMIL composite was attributed to Ti3+-Ti4+ intervalence electron transfer and the synergistic effect between MIL-125(Ti) and BP. The photodegradation followed pseudo-first-order kinetics with a rate constant of 1.6 × 10−2 min−1.
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