Efficient photocatalytic degradation of emerging ciprofloxacin under visible light irradiation using BiOBr/carbon quantum dot/saponite composite.

The use of visible-driven photocatalysts has fascinated attention as a capable and sustainable approach for wastewater remediation. In this work, BiOBr/carbon quantum dot (CQDs)/saponite composites (CQDs/Clay@BiOBr) were fabricated via hydrothermally using two different CQDs/Clay precursors (in-situ synthesis (IS) and physical mixing (PM)). The obtained products were characterized, and the photocatalytic performances of the prepared samples were evaluated in the photocatalytic decomposition of emerging ciprofloxacin (CIP) pharmaceutical waste. The highest CIP mineralization performance was achieved when a combination of BiOBr and CQDs/Clay (IS) with the appropriate proportion because the strong adhesion between CQDs and clay generate a great heterojunction in the composite. The stronger interaction of CQDs and better distribution of CQDs on the surface of clay in the CQDs/Clay (IS) enhanced the interaction of BiOBr and CQDs, and avoided the re-agglomeration of excess of CQDs on surface of BiOBr which reduce the active surface to receive the light and react with CIP. The ultrafast degradation rate of the optimized CQDs/Clay@BiOBr composite was better compared to others. The significant improvement in the CIP degradation efficiency of the CQDs/Clay@BiOBr composite was attributed to the excellent separation and transportation of photogenerated electrons and holes, as confirmed by photoluminescence, photocurrent density, and electrochemical impedance spectroscopy results. Moreover, the photocatalytic degradation mechanism of CIP in the CQDs/Clay@BiOBr composite was proposed based on the electronic states of each material in the composite and on a scavenger test. Thus, the proposed CQDs/Clay@BiOBr composite can be employed as a potential visible-light-driven photocatalyst for the decomposition of organic contaminants in wastewater.

Atomic-level investigation on significance of photoreduced Pt nanoparticles over g-C3 N4 /bimetallic oxide composites.

Designing an effective photocatalyst for solar-to-chemical fuel conversion presents significant challenges. Herein, g-C3 N4 nanotubes/CuCo2 O4 (CN-NT-CCO) composites decorated with platinum nanoparticles (Pt NPs) were successfully synthesized by chemical and photochemical reductions. The size distribution and location of Pt NPs on the surface of CN-NT-CCO composites were directly observed by TEM. Extended X-ray absorption fine structure (EXAFS) spectra of Pt L3-edge for the above composite confirmed establishment of Pt-N bonds at an atomic distance of 2.09 Šin the photoreduced Pt-bearing composite, which was shorter than in chemically reduced Pt-bearing composites. This proved the stronger interaction of photoreduced Pt NPs with the CN-NT-CCO composite than chemical reduced one. The H2 evolution performance of the photoreduced (PR) Pt@CN-NT-CCO (2079 µmol h-1 g-1 ) was greater than that of the chemically reduced (CR) Pt@CN-NT-CCO composite (1481 µmol h-1 g-1 ). The abundance of catalytically active sites and transfer of electrons from CN-NT to the Pt NPs to participate in the hydrogen evolution are the primary reasons for the improved performance. Furthermore, electrochemical investigations and band edge locations validated the presence of a Z-scheme heterojunction at the Pt@CN-NT-CCO interface. This work offers unique perspectives on the structure and interface design at the atomic level to fabricate high-performance heterojunction photocatalysts.

All-alike hollow nanotubes of g-C3N4 converting photons into fuel by splitting water.

In this article, we present a sapiential method for producing highly effective oxygen-containing CN with hierarchical porous hollow nanotubes (HTCN) using thermal polycondensation of oxalic acid-assisted supramolecular aggregates. As a result of the synergistic effect of spatial charge separation and optical absorption ability, HTCN outperforms pristine CN nanosheets (NSCN) in photocatalytic hydrogen production. This research will provide a novel cognitive perspective and understanding for constructing contemporary hydrogen production photocatalysts.

Charge transfer mechanism through S-scheme heterojunction in in-situ synthesized TiO2/Fe-doped hydroxyapatite for improved photodegradation of xanthate.

The heterojunction structure of the photocatalyst composite, which necessitates a robust interface and sufficient contact areas, holds the key to obtaining high charge carrier migration efficiency. Here, a novel composite, TiO2 nanoparticles/Fe-doped hydroxyapatite (TONPs/FH_CS), is fabricated using a two-step synthetic technique, in which FH_CS is synthesized from artificial converter slag enriched with Fe and Ca. The unique nanorod@plate structure of FH_CS enables the uniform immobilization of TONPs onto FH_CS. Thereby, an n-n type heterojunction exhibits a highly intimate Ti-O-Fe heterointerface. Kelvin probe testing demonstrates the formation of an interfacial electric field oriented from FH_CS to TONPs, which serves as the driving force for interfacial electron transfer through the Ti-O-Fe channels. The photoacoustic signals provide information on electron trap levels and densities, indicating the formation of the electron transfer channels. •O2- and •OH species are responsible for being the active species in this system. A photoexcited carrier transfer pathway exhibiting an S-scheme mechanism with high separation efficiency significantly enhances the utilization of charge carriers in each phase. Thus, improved xanthate degradation has been achieved using a heterojunction containing a photocatalyst derived from industrial solid waste. This work demonstrates the significant potential of steel-making byproduct utilization in industrial wastewater treatment.

Nitridation-free preparation of bimetallic oxide-nitride bifunctional electrocatalysts for overall water splitting.

A novel one-pot surfactant-free synthesis is presented for designing bimetallic oxide-nitride electrocatalysts with tunable morphologies using metal salts and nitrogen-rich precursors. This innovative approach eliminates the need for a distinct nitridation process. Bifunctional electrode Co3O4/MoO3/MoxNy achieved a current density of 10 mA cm-2 while maintaining a cell voltage of 1.52 V, outperforming many bimetallic oxide-nitride catalysts in the scientific literature.

Tailoring Interfacial Physicochemical Properties in Cu2O-TiO2@rGO Heterojunction: Insights from EXAFS and Electron Trap Distribution Analysis.

In this study, a solution-based synthesis technique was utilized to produce Cu2O nanoparticles (NPs) on TiO2 nanofibers (TNF), which were then subsequently coated with reduced graphene oxide (rGO) nanosheets. In the absence of any cocatalyst, CTNF@rGO-3% composite displayed an ideal photocatalytic H2 evolution rate of 96 µmol g-1 h-1 under visible light irradiation, this was 10 times higher than that of pure TNF. At 420 nm, the apparent quantum efficiency of this composite reached a maximum of 7.18%. Kelvin probe force microscopy demonstrated the formation of an interfacial electric field that was oriented from CTNF to rGO and served as the driving force for interfacial electron transfer. The successful establishment of an intimate interface between CTNF@rGO facilitated the efficient transfer of charges and suppressed the rate of recombination of photogenerated electron-hole pairs, leading to a substantial enhancement in photocatalytic performance. X-ray photoelectron spectroscopy, photoluminescence spectra, and electrochemical characterization provide further confirmation that formation of a heterojunction between CTNF@rGO leads to an extension in the lifetimes of the photogenerated charge carriers. The experimental evidence suggests that a p-n heterojunction is the mechanism responsible for the significant photocatalytic activity observed in the CTNF@rGO composite during H2 evolution.

Synthesis, characterization, and application of MOF@clay composite as a visible light-driven photocatalyst for Rhodamine B degradation.

Metal Organic Frameworks (MOFs) with natural clay materials is a relatively new research avenue that appears to reduce high production costs and address the instability issues of pure MOFs. A novel MOF and natural clay composites of MOF@Sp_n (n = 1-4) were fabricated by the in situ precipitation of stable MOF, Zr6O4(OH)4 (ABDC)6 (where ABDC = 2-aminobenzene-1,4-dicarboxylic acid), over natural sepiolite (Sp) clay and used as a photocatalysts for elimination of organic dyes in aqueous media. The formation of MOF@Sp_n due to its strong electrostatic interactions between the positively charged MOF and the negatively charged sepiolite. Optimizing the Sp content in the composite strongly influenced the dispersibility, crystallinity of MOFs, resulting in progressively functional hybrid materials with an excellent optoelectronic properties. The composites lessened the shortcomings of the individual components and made them suitable as a visible light-active, highly efficient, standalone photocatalyst material that can degrade RhB.

Recent development on core-shell photo(electro)catalysts for elimination of organic compounds from pharmaceutical wastewater.

Pharmaceutical organics are a vital milestone in contemporary human research since they treat various diseases and improve the quality of human life. However, these organic compounds are considered one of the major environmental hazards after the conception, along with the massive rise in antimicrobial resistance (AMR) in an ecosystem. There are various biological and catalytic technologies existed to eliminate these organics in aqueous system with their limitation. Advanced Oxidation processes (AOPs) are used to decompose these pharmaceutical organic compounds in the wastewater by generating reactive species with high oxidation potential. This review focused various photocatalysts, and photocatalytic oxidation processes, especially core-shell materials for photo (electro)catalytic application in pharmaceutical wastewater decomposition. Moreover, we discussed in details about the design and recent developments of core shell catalysts and comparison for photocatalytic, electrocatalytic and photo electrocatalytic applications in pharmaceutical wastewater treatment. In addition, the mixture of inorganic and organic core-shell materials, and metal-organic framework-based core-shell catalysts discussed in detail for antibiotic degradation.

Recent development of organic-inorganic hybrid photocatalysts for biomass conversion into hydrogen production.

Over the last few years, photocatalysis using solar radiation has been explored extensively to investigate the possibilities of producing fuels. The production and systematic usage of solar fuels can reduce the use of fossil-based fuels, which are currently the primary source for the energy. It is time for us to exploit renewable sources for our energy needs to progress towards a low-carbon society. This can be achieved by utilizing green hydrogen as the future energy source. Solar light-assisted hydrogen evolution through photocatalytic water splitting is one of the most advanced approaches, but it is a non-spontaneous chemical process and restricted by a kinetically demanding oxidation evolution reaction. Sunlight is one of the essential sources for the photoreforming (PR) of biomass waste into solar fuels, or/and lucrative fine chemicals. Hydrogen production through photoreforming of biomass can be considered energy neutral as it requires only low energy to overcome the activation barrier and an alternate method for the water splitting reaction. Towards the perspective of sustainability and zero emission norms, hydrogen production from biomass-derived feedstocks is an affordable and efficient process. Widely used photocatalyst materials, such as metal oxides, sulphides and polymeric semiconductors, still possess challenges in terms of their performance and stability. Recently, a new class of materials has emerged as organic-inorganic hybrid (OIH) photocatalysts, which have the benefits of both components, with peculiar properties and outstanding energy conversion capability. This work examines the most recent progress in the photoreforming of biomass and its derivatives using OIHs as excellent catalysts for hydrogen evolution. The fundamental aspects of the PR mechanism and different methods of hydrogen production from biomass are discussed. Additionally, an interaction between both composite materials at the atomic level has been discussed in detail in the recent literature. Finally, the opportunities and future perspective for the synthesis and development of OIH catalysts are discussed briefly with regards to biomass photo-reforming.

A simple tactic synthesis of hollow porous graphitic carbon nitride with significantly enhanced photocatalytic performance.

Hollow porous graphitic carbon nitride (porous CN) was synthesized via a simple tactic method, and the resulting porous CN showed an effectively modified surface area, crystal structure and enhanced photocatalytic performance. Optical and electrochemical characterization results demonstrated an increase in the charge transfer rate and a decrease in recombination tendency.

Synthesis and characterization of defective UiO-66 for efficient co-immobilization of arsenate and fluoride from single/binary solutions.

Here, we aimed to synthesize UiO-66 architected fumaric acid mediated lanthanum (La-fum), zirconium (Zr-fum), and cerium (Ce-fum) metal-organic frameworks (MOFs) for co-immobilizations of both arsenate and fluoride from both single and binary systems. The crystalline behavior of Zr-fum MOF was the lowest compared to the other two forms, due to the fact that it required a modulator support as the nucleus growth nature of zirconium moiety is different. The Langmuir maximum adsorption densities of arsenate (fluoride) were 2.689 (4.240), 1.666 (2.255), and 2.174 (4.155) mmol/g for La-fum, Zr-fum, and Ce-fum, respectively and these adsorption densities were found to have record-high values compared with the existing materials in the literature. The arsenate and fluoride adsorption on the MOF materials were confirmed by XPS, PXRD and FTIR studies. The arsenate adsorption mechanism on La-fum and Ce-fum through monodentate complexation confirmed using the distinguished K-edge shell distance in EXAFS studies. The arsenate and fluoride-sorbed materials were recycled using 0.01 M HNO3 and were further utilized for six consecutive cycles for both arsenate and fluoride adsorption indicated the feasibility of the materials. This kind of facile and easy solvothermal synthesized MOFs could pave a way towards the removal of toxins in a practical wastewater as these have superior adsorption properties, stability and reusability.

Mechanism analysis of selenium (VI) immobilization using alkaline-earth metal oxides and ferrous salt.

The immobilization of selenate (SeO42-) using metal oxides (CaO and MgO) and ferrous salt as the immobilization reagents were examined by the leaching test and solid-phase analysis via XRD, XAFS, TGA, and XPS. The results indicated that nearly all of SeO42- was reduced to SeO32- in the CaO-based reaction within 7 days. Then, the generated SeO32- was mainly sorbed onto the iron-based minerals (Fe2O3 and FeOOH) through the formation of both bidentate mononuclear edge-sharing (1E) and monodentate mononuclear corner-sharing (1V) inner-sphere surface complexes, suggested by PHREEQC simulation and EXAFS analysis. Differently, less amount of SeO42- (approximately 45.50%) was reduced to SeO32- for the MgO-based reaction. However, if the curing time increases to a longer time (more than 7 days), the further reduction could occur because there are still Fe(II) species in the matrix. As for the associations of Se in the solid residue, most of the selenium (SeO32- and SeO42-) was preferentially distributed onto the Mg(OH)2 through outer-sphere adsorption. Definitely, this research can provide a deep understanding of the immobilization of selenium using alkaline-earth metal oxide related materials and ferrous substances.

Importance of ZnTiO3 Phase in ZnTi-Mixed Metal Oxide Photocatalysts Derived from Layered Double Hydroxide.

In this study, ZnTi-mixed metal oxides (ZTM), such as ZnTiO3, were synthesized from ZnTi layered double hydroxides by varying the molar ratio of Zn/Ti, calcination temperatures, and synthesis methods (hydrothermal or reflux). The surface electronic characteristics of ZTM were investigated by the energy-resolved distribution of electron traps (ERDTs) using reversed double-beam photoacoustic spectroscopy. The ZTM samples obtained by conducting hydrothermal synthesis at 500 °C showed similar ERDT patterns independent of the molar ratio of Zn/Ti, although ZnTiO3 phase was not observed in the X-ray diffraction pattern, when the Zn/Ti ratio was high. When the ERDT patterns demonstrated a high electron accumulation level near the conduction band bottom in hydrothermal products at 500 °C, a higher photocatalytic phenol degradation efficiency was observed due to the formation of ZnTiO3 phase. This suggested that the product with the high Zn/Ti molar ratio (Zn/Ti = 6) constituted amorphous ZnTiO3.The enhanced photocatalytic performance of ZTM could be attributed to the heterojunction of electrons among ZnO, TiO2, and ZnTiO3, which enabled electron transfer in the composites, prevented charge recombination, and promoted a wider visible light adsorption by ZnTiO3 phase irrespective of its crystallinity.

Fabrication and characterization of ternary sepiolite/g-C3N4/Pd composites for improvement of photocatalytic degradation of ciprofloxacin under visible light irradiation.

The development of high-quality photocatalytic materials for the degradation of organic pollutants under visible light irradiation is a vital field of research. In the present study, a composite of natural sepiolite clay and synthetic graphitic carbon nitride (CN) mixed with dispersed palladium nanoparticles was developed for the efficient photocatalytic degradation of ciprofloxacin (CIP) under visible light irradiation. The sepiolite, CN, and composite materials were characterized by several techniques. The sepiolite/CN composite (SC30%) displayed superior activity than pristine sepiolite and CN, resulted from the generation of new electron trap states in the interfacial contract between sepiolite and CN to suppress the charge recombination of CN. Furthermore, the well-dispersed of 1 wt% Pd-nanoparticles in the SC30% composite collectively enhanced CIP degradation by avoiding the recombination of photogenerated electrons and holes. Additionally, the electron trap states on the surface of all samples were studied using novel reversed double-beam photoacoustic spectroscopy to understand electron transfer in the composites related to the photocatalytic degradation mechanism of CIP. The developed sepiolite/CN/Pd(0) composite can act as a potential catalyst for the degradation of organic pollutants in wastewater under visible light irradiation.

Energy-resolved distribution of electron traps for O/S-doped carbon nitrides by reversed double-beam photoacoustic spectroscopy and the photocatalytic reduction of Cr(vi).

We report for the first time to our knowledge the identification of heteroatom-doped and undoped C3N4 with the energy-resolved distribution of electron traps (ERDT) near the conduction band bottom position (CBB) using reversed double-beam photoacoustic spectroscopy. The ERDT/CBB pattern is used to classify the type of elemental doping in C3N4, related to photocatalytic efficiency.