Current trends in structural development and modification strategies for metal-organic frameworks (MOFs) towards photocatalytic H2 production: A review

Photocatalytic H₂ generation using semiconductor photocatalysts is considered as a cost-effective and eco-friendly technology for solar to energy conversion; however, the present photocatalysts have been recognized to depict low efficiency. Currently, porous coordination polymers known as metal-organic frameworks (MOFs) constituting flexible and modifiable porous structure and having excess active sites are considered to be appropriate for photocatalytic H₂ production. This review highlights current progress in structural development of MOF materials along with modification strategies for enhanced photoactivity. Initially, the review discusses the photocatalytic H₂ production mechanism with the concepts of thermodynamics and mass transfer with particular focus on MOFs. Elaboration of the structural categories of MOFs into Type I, Type II, Type III and classification of MOFs for H₂ generation into transition metal based, post-transition metal based, noble-metal based and hetero-metal based has been systematically discussed. The review also critically deliberate various modification approaches of band engineering, improvement of charge separation, efficient irradiation utilization and overall efficiency of MOFs including metal modification, heterojunction formation, Z-scheme formation, by introducing electron mediator, and dye based composites. Also, the MOF synthesized derivatives for photocatalytic H₂ generation are elaborated. Finally, future perspectives of MOFs for H₂ generation and approaches for efficiency improvement have been suggested.     

Electrospun Zn-doped Ga2O3 nanofibers and their application in photodegrading rhodamine B dye

Ultrawide band gap semiconductor materials have attracted considerable attention in recent years owing to their great potential in the photocatalytic field. In this study, Zn-doped Ga₂O₃ nanofibers with various concentrations were synthesized via electrospinning; they exhibited a superior photocatalytic degradation performance of rhodamine B dye compared to that of undoped Ga₂O₃ nanofibers. The Zn dopant replaced Ga sites via replacement doping, which could increase the concentration of oxygen vacancies and lead to enhanced photocatalytic properties. When the Zn concentration increased, a Ga₂O₃/ZnGa₂O₄ hybrid structure formed, which could further enhance the photocatalytic performance. The separation of photogenerated carriers due to Zn doping and heterojunctions were the primary causes of the enhanced photocatalytic performance. This study provides experimental data for the fabrication of high-performance photocatalysts based on Ga₂O₃ nanomaterials.     

Magnetic field-enhanced photocatalytic nitrogen fixation over defect-rich ferroelectric Bi2WO6

Photocatalytic N₂ fixation is a promising and sustainable manufacturing process of ammonia (NH₃); however, the NH₃ production rate by this method is very low, thus severely restricting further application of this sustainable technology. Therefore, developing an efficient photocatalyst for N₂ fixation under mild conditions is urgently required. Herein, ferroelectric Bi₂WO₆ materials with different surface oxygen defects were prepared, and the concentration of corresponding defects was controlled by adjusting the thermal reduction time. The abundant oxygen defects in Bi₂WO₆ can provide more reactive sites to promote the effective adsorption of N₂, and the photogenerated charge carrier can be efficiently separated benefiting from the internal electric field. These would weaken the N₂ triple bond and reduce the activation energy barrier for the conversion of N₂ to NH₃ under mild conditions. In the absence of sacrificial agents and cocatalysts, the optimized Bi₂WO₆ with oxygen defects shows an indigenous NH₃ yield of 132.175 μmol·g^-1·L^-1·h^-1, which is more than two times higher than that of the original Bi₂WO₆. Surprisingly, the Bi₂WO₆ with oxygen defects produced more than eight times NH₃ (471.13 μmol·g^-1·L^-1·h^-1) than that of the original Bi₂WO₆ when assisted by an external magnetic field, thus providing a new perspective for further enhancing the N₂ fixation performance.     

Increasing the photocatalytic and fungicide activities of Ag3PO4 microcrystals under visible-light irradiation

The present study reports for the first time the performance of silver phosphate (Ag₃PO₄) microcrystals as photocatalyst (degradation of Rodamine B-RhB) and antifungal agent (against Candida albicans–C. albicans) under visible-light irradiation (455 nm). Ag₃PO₄ microcrystals were synthesized by a simple co-precipitation (CP) method at room temperature. The structural and electronic properties of the as-synthetized Ag₃PO₄ have been investigated before and after 4 cycles of RhB degradation under visible light using X-ray diffraction (XRD), micro-Raman spectroscopy, UV–Vis spectrophotometer and field emission scanning electron microscopy (FE-SEM) images. The antifungal activity was analyzed in planktonic cells and 48h-biofilm of C. albicans by colony forming units (CFU) counting, confocal laser and FE-SE microscopies. Statistical analysis was carried out using SPSS software. Morphological and structural modifications of Ag₃PO₄ were observed upon recycling. After 4 recycles, the material maintained its photodegradation property; an eightfold increase in the efficiency of Ag₃PO₄ was observed in planktonic cells and a two fold increase in biofilm when irradiated under visible light. Thus, higher antifungal effectiveness against C. albicans was obtained when associated with visible-light irradiation.     

State of the art advancement in rational design of g-C3N4 photocatalyst for efficient solar fuel transformation,environmental decontamination and future perspectives

Recently, the graphite based heterogeneous photocatalysts has attained tremendous research attention in various environmental applications. Among them, the graphitic carbon nitride (g-C₃N₄) is categorized as a unique solar active particle with its outstanding intrinsic properties i.e., adequate band configuration, excellent light absorptivity and thermo-physical durability, which make it highly useful and reliable for revenue transformation and ecological concerns. Considering the intrinsic potential of g-C₃N₄ in photocatalysis, so far, no report has been done in literature for its extraordinary configuration, morphological characteristics and perspective tuning for said applications. To overcome this research gap, our primary emphasis of this review regarding photocatalysis is to provide layout as well as the advancement of visible-light-fueled materials as highly stabilized and extremely effective ones for pragmatic implementation. Thus, this existing comprehensive assessment conducts a systematic survey over visible light driven non-metal novel g-C₃N₄. The major advancement of this evaluation is the fabrication of well-designed nanosized g-C₃N₄ photocatalysts with unique configurable frameworks and compositions. Furthermore, alternative techniques in order to customize the analogue band configuration and noticeable cultivation such as metal (cation), nonmetal (anion) doping, worthy metal activating, and alloy initiation with certain semiconductors are discussed in detail. In addition to this, g-C₃N₄ photocatalytic functionalities towards photocatalytic hydrogen evolution, CO₂ photoreduction, biological metal ions deterioration as well as bacterial sanitization are also presented and discussed in detail. Therefore, we believe that such a pivotal compact assessment can provide a roadmap in several perspectives on the currently underway obstacles in the innovation of effective g-C₃N₄ catalytic design processes. Moreover, this critical assessment will ultimately serve as a useful supplement in the research area of g-C₃N₄ nanosized photocatalysts and for the researchers working on its key aspects in diverse range of natural, chemistry, engineering and environmental applications.     

One step method of structure engineering porous graphitic carbon nitride for efficient visible-light photocatalytic reduction of Cr(Ⅵ)

Porous g-C3N4 nanosheets (PCN) were prepared by the nickel-assisted one-step thermal polymerization method.Hydrogen (H2) which was produced by the reaction between nickel (Ni) foam and ammonia (NH3) defined the structure and properties of PCN.During the formation of PCN,the participation of H2 not only enhanced the spacing between layers but also boosted the specific surface area that more active sites were exposed.Additionally,H2 promoted pores formation in the nanosheets,which was beneficial to the transfer of photons through lamellar structure and improved the absorption efficiency of visible light.Remarkably,the obtained PCN possessed better Cr(Ⅵ) photocatalytic reduction efficiency than pure g-C3N4.The reaction rate constant (k) of PCN (0.013 min-1) was approximately twice that of bare g-C3N4 (0.007 min-1).Furthermore,the effects of original pH and concentration of Cr(Ⅵ)-containing solution on removal efficiency of Cr(Ⅵ) were explored.A possible photocatalytic mechanism was proposed based on the experiments of radical scavengers and photoelectrochemical characterizations.     

CuxNi1-xO nanostructures and their nanocomposites with reduced graphene oxide: Synthesis,characterization, and photocatalytic applications

NiO nanostructure was synthesized using a simple co-precipitation method and was embedded on reduced graphene oxide surface via ultrasonication. Structural investigations were made through X-ray diffraction (XRD) and functional groups were confirmed by Fourier transform infrared spectroscopy (FTIR). XRD analysis revealed the grain size reduction with doping. Fourier transform infrared spectroscopy confirmed the presence of metal-oxygen bond in pristine and doped NiO nanostructure as well as the presence of carbon containing groups. Scanning electron microscopy (SEM) indicated that the particle size decreased when NiO nanostructure was doped with copper. BET surface area was found to increase almost up to 43 m²/g for Cu doped NiO nanostructure/rGO composite. Current-voltage measurements were performed using two probe method. UV–Visible spectroscopic profiles showed the blue and red shift for Cu doped NiO nanostructure and Cu doped NiO Nanostructure/rGO composite respectively. Rate constant for Cu doped NiO nanostructure/rGO composite found to increase 4.4 times than pristine NiO nanostructure.     

Enhanced photodegradation of Rhodamine B under visible light by N-K2Ti4O9/MIL-101 composite

N-K₂Ti₄O₉/MIL-101 composites were successfully synthesized by a facile hydrothermal method, and were characterized by powder X-ray diffraction, UV–vis diffuse reflectance spectroscopy, the valence band X-ray photoelectron spectroscopy, field emission transmission electron microscopy, photoluminescence emission spectra, N₂ adsorption–desorption and thermogravimetric analysis. Photocatalytic activities of N-K₂Ti₄O₉, MIL-101 and the composites were investigated by the degradation of Rhodamine B (RhB) under visible light irradiation. The results show that the composites exhibit higher photocatalytic activity as compared with the pure materials. The synergistically enhanced photocatalytic activity of the composites is due to big adsorption capacity of MIL-101 and high separation efficiency of photogenerated electron-hole pairs through interfaces between N-K₂Ti₄O₉ and MIL-101.     

Enhanced photocatalytic activity of nonstoichiometric crystalline TaO2F and Ta2O5 with carbon coating

Pure and carbon-coated tantalum-based oxides photocatalysts were synthesized via the mesocrystalline precursor transformation method by annealing pure and polydopamine-coated (NH₄)₂Ta₂O₃F₆ mesocrystals in Ar. The oxygen-poor atmosphere thermal annealing process assisted the formation of nonstoichiometric TaO₂F mesocrystals with more F and Ta₂O₅ nanorods with oxygen vacancies and the associated lower valence state Ta ions (Ta⁴⁺). Furthermore, the carbon coating, decomposed from coated polydopamine, helped to control their particle size within 100 nm by isolating the connection of (NH₄)₂Ta₂O₃F₆ subunits. Hence, as-synthesized products, particularly carbon-coated Ta₂O₅ nanosheets, owning large surface area (67.6 m² g^?1), fine particle size (<100 nm), excellent electronic conductivity, decreased bandgap energy, enhanced and extended absorption in the visible range, exhibited preferable photocatalytic activity in the photodegradation of methylene blue, reaching a 76.54 % and 41.71 % removal under ultraviolet and visible light illumination, suggesting a promising candidate for wide-range responsive photocatalytic applications.     

Dye removal by polymer derived ceramic nanobeads

Emulsion processed polymer derived ceramic (PDC) nanobeads are used for Methylene Blue dye removal from aqueous solutions. The PDC nanobeads, produced at 600 °C and 1200 °C pyrolysis, are subsequently coated with titania (anatase). Titania-coated nanobeads show less than 35%, i.e., limited dye adsorption capability in dark. Instead, enhanced total removal efficiency (∼97%) is obtained when the initial adsorption is succeeded by photodegradation under UV. Direct reusability tests show that even after the third cycle, very high regeneration efficiencies being above 92% are observed for titania-coated nanobeads.