Search Results (47)

This study employs density functional theory (DFT) to investigate the electronic and optical properties of molybdenum (Mo) and chalcogen (S, Se, Te) co-doped anatase TiO₂. Two co-doping configurations were examined: Model 1, where the dopants are adjacent, and Model 2, where the dopants are farther apart. The incorporation of Mo into anatase TiO₂ resulted in a significant bandgap reduction, lowering it from 3.22 eV (pure TiO₂) to range of 2.52–0.68 eV, depending on the specific doping model. The introduction of Mo-4d states below the conduction band led to a shift in the Fermi level from the top of the valence band to the bottom of the conduction band, confirming the n-type doping characteristics of Mo in TiO₂. Chalcogen doping introduced isolated electronic states from Te-5p, S-3p, and Se-4p located above the valence band maximum, further reducing the bandgap. Among the examined configurations, Mo–S co-doping in Model 1 exhibited most optimal structural stability structure with the fewer impurity states, enhancing photocatalytic efficiency by reducing charge recombination. With the exception of Mo–Te co-doping, all co-doped systems demonstrated strong oxidation power under visible light, making Mo-S and Mo-Se co-doped TiO₂ promising candidates for oxidation-driven photocatalysis. However, their limited reduction ability suggests they may be less suitable for water-splitting applications. The study also revealed that dopant positioning significantly influences charge transfer and optoelectronic properties. Model 1 favored localized electron density and weaker magnetization, while Model 2 exhibited delocalized charge density and stronger magnetization. These findings underscore the critical role of dopant arrangement in optimizing TiO₂-based photocatalysts for solar energy applications. Full article

Graphitic carbon nitride (g-C₃N₄) is emerging as one of the most promising non-metallic semiconductors for the degradation of pollutants in water by photocatalytic processes. Its exceptional reduction–oxidation (redox) potentials and adequate band gap of approximately 2.7 eV give it the ability to absorb in the visible light range. However, the characteristic sensitivity to light absorption is limited, leading to rapid recombination of electron–hole pairs. Therefore, different strategies have been explored to optimize this charge separation, among which the formation of heterostructures based on g-C₃N₄ is highlighted. This review addresses recent advances in photocatalysis mediated by g-C₃N₄ heterostructures, considering the synthesis methods enabling the optimization of the morphology and active interface of these materials. Next, the mechanisms of charge transfer are discussed in detail, with special emphasis on type II, type S, and type Z classifications and their influence on the efficiency of photodegradation. Subsequently, the progress in the application of these photocatalysts for the degradation of water pollutants, such as toxic organic dyes, pharmaceutical pollutants, pesticides, and per- and polyfluoroalkyl substances (PFAS), are analyzed, highlighting both experimental advances and remaining challenges. Finally, future perspectives oriented towards the optimization of heterostructures, the efficiency of synthesis methods, and the practical application of these in photocatalytic processes for environmental remediation. Full article

Photocatalytic hydrogen (H₂) production offers a promising solution to energy shortages and environmental challenges by converting solar energy into chemical energy. Hydrogen, as a versatile energy carrier, can be generated through photocatalysis under sunlight or via electrolysis powered by solar or wind energy. However, the advancement of photocatalysis is hindered by the limited availability of effective visible light-responsive semiconductors and the challenges of charge separation and transport. To address these issues, researchers are focusing on the development of novel nanostructured semiconductors and composite materials that can enhance photocatalytic performance. In this paper, we provide an overview of the advanced photocatalytic materials prepared so far that can be activated by sunlight, and their efficiency in H₂ production. One of the key strategies in this research area concerns improving the separation and transfer of electron–hole pairs generated by light, which can significantly boost H₂ production. Advanced hybrid materials, such as organic–inorganic hybrid composites consisting of a combination of polymers with metal oxide photocatalysts, and the creation of heterojunctions, are seen as effective methods to improve charge separation and interfacial interactions. The development of Schottky heterojunctions, Z-type heterojunctions, p–n heterojunctions from nanostructures, and the incorporation of nonmetallic atoms have proven to reduce photocorrosion and enhance photocatalytic efficiency. Despite these advancements, designing efficient semiconductor-based heterojunctions at the atomic scale remains a significant challenge for the realization of large-scale photocatalytic H₂ production. In this review, state-of-the-art advancements in photocatalytic hydrogen production are presented and discussed in detail, with a focus on photocatalytic nanostructures, heterojunctions and hybrid composites. Full article

The development of photothermal-assisted photocatalytic systems with broad-spectrum solar utilization and high charge separation efficiency remains a critical challenge for antibiotic degradation. Herein, we report novel black g-C₃N₄ (BCN) materials synthesized via a one-step thermal copolymerization strategy using C/N precursors and tetrachlorofluorescein. After the introduction of tetrachlorofluorescein, the color of the sample changes, which gives BCN enhanced light absorption and a significant photothermal effect for poorly heating-assisted photocatalysis. The synergistic coupling of photothermal and photocatalytic processes enabled the optimal BCN-U sample to achieve exceptional degradation efficiency (89% within 120 min) for a typical antibiotic (e.g., tetracycline) under an LED lamp as the visible light source, outperforming conventional yellow g-C₃N₄ (YCN-U) by a factor of 1.37. Mechanistic studies revealed that the photothermal effect facilitates carrier separation via thermal-driven electron excitation while accelerating reactive oxygen species (•OH and •O₂⁻) generation. The synergistic interplay between photocatalysis and photothermal effects, which improved mass transfer, ensures robust stability, which provides new insights into designing dual-functional carbon nitride-based materials for sustainable environmental remediation. Full article

Photocatalytic H₂ production is one of the most promising approaches for sustainable energy. The literature presents a plethora of carefully designed systems aimed at harnessing solar energy and converting it into chemical energy. However, the main drawback of the reported photocatalysts is their stability. Thus, the development of a cost-effective and stable photocatalyst, suitable for real-world applications remains a challenge. An ideal photocatalyst for H₂ production must possess appropriate band-edge energy positions, an effective sacrificial agent, and a suitable cocatalyst. Among the various photocatalysts studied, TiO₂ stands out due to its stability, abundance, and non-toxicity. However, its efficiency in the visible spectrum is limited by its wide bandgap. Metal doping is an effective strategy to enhance electron–hole separation and improve light absorption efficiency, thereby boosting H₂ synthesis. Common metal cocatalysts used as TiO₂ dopants include platinum (Pt), gold (Au), copper (Cu), nickel (Ni), cobalt (Co), ruthenium (Ru), iron (Fe), and silver (Ag), as well as bimetallic combinations such as Ni-Fe, Ni-Cu, Nb-Ta, and Ni-Pt. In all cases, doped TiO₂ exhibits higher H₂ production performance compared to undoped TiO₂, as metals provide additional reaction sites and enhance charge separation. The use of bimetallic dopants further optimizes the hydrogen evolution reaction. Additionally, porphyrins, with their strong visible light absorption and efficient electron transfer properties, have demonstrated potential in TiO₂ photocatalysis. Their incorporation expands the photocatalyst’s light absorption range into the visible spectrum, enhancing H₂ production efficiency. This review paper explores the principles and advancements in metal- and porphyrin-doped TiO₂ photocatalysts, highlighting their potential for sustainable hydrogen production. Full article

Photocatalysis is a key strategy for the development of sustainable solar-driven chemical processes. In this work, we report the synthesis and characterization of a novel organometallo–ionosilica material derived from the self-condensation of an alcoxysilane functionalized Ir(III) complex. In acetonitrile suspension, the material retains the photophysical properties of its precursor in solution in the same solvent, together with a significant absorption in the visible between 400 and 500 nm. As a heterogeneous photocatalyst, the material showed high efficiency in the reductive dehalogenation of 2-bromoacetophenone under blue light irradiation, achieving high yields of conversion of about 90%, and excellent recyclability in seven catalytic cycles, retaining more than 70% of the catalytic efficiency. All these properties of the self-condensed material highlight its potential as an efficient and sustainable heterogeneous photocatalyst for applications in organic synthesis and solar-driven redox processes. Full article

Vacancy defect graphitic carbon nitride (g-C₃N₄) and conjugated polyimide (PI) polymer photocatalysts have become increasingly recognized as metal-free photocatalysts featuring an appropriate bandgap. The narrow absorption spectrum of visible light and the rapid recombination rate of the photoexcited charge carriers in PI polymers and g-C₃N₄ impede its photocatalytic performance. The presence of oxygen vacancies (OVs) in PI polymer photocatalysts, as well as nitrogen vacancies (NVs) and carbon vacancies (CVs) in g-C₃N₄, can significantly enhance the migration of photogenerated electrons. Adding vacancies to improve the electronic structure and band gap width can greatly enhance the photocatalytic efficiency of PI polymers and g-C₃N₄. Defect engineering is important for increasing the photocatalytic ability of PI-polymer and g-C₃N₄. There remains a notable absence of thorough review papers covering the synthesis, characterization, and applications of vacancy-rich PI-polymer and g-C₃N₄ in photocatalysis. This review paper examines the roles of OVs in PI-polymer, NVs, and CVs in g-C₃N₄ and thoroughly summarizes the preparation approaches employed before and after, as well as during polymerization. This review scrutinizes spectroscopic characterization techniques, such as EPR, XPS, PAS, XRD, FTIR, and NMR, for vacancy defect analysis. We also reviewed the role of vacancies, which include light absorption, photogenerated charge carrier separation, and transfer dynamics. This review could serve as a comprehensive understanding, a vacancy-engineered design framework, and a practical guide for synthesizing and characterizing. Full article

Bismuth-based photocatalytic materials have been widely used in the field of photocatalysis in recent years due to their unique layered structure. However, single bismuth-based photocatalytic materials are greatly limited in their photocatalytic performance due to their poor response to visible light and easy recombination of photogenerated charges. At present, constructing semiconductor heterojunctions is an effective modification method that improves quantum efficiency by promoting the separation of photogenerated electrons and holes. In this study, the successful preparation of an In₂O₃/Bi₂WO₆ (In₂O₃/BWO) II-type semiconductor heterojunction composite material was achieved. XRD characterization was performed to conduct a phase analysis of the samples, SEM and TEM characterization for a morphology analysis of the samples, and DRS and XPS testing for optical property and elemental valence state analyses of the samples. In the II-type semiconductor junction system, photogenerated electrons (e⁻) on the In₂O₃ conduction band (CB) migrate to the BWO CB, while holes (h⁺) on the BWO valence band (VB) transfer to the In₂O₃ VB, promoting the separation of photoinduced charges, raising the quantum efficiency. When the molar ratio of In₂O₃/BWO is 2:6, the photocatalytic degradation degree of rhodamine B (RhB) is 59.4% (44.0% for BWO) after 60 min illumination, showing the best photocatalytic activity. After four cycles, the degradation degree of the sample was 54.3%, which is 91.4% of that of the first photocatalytic degradation experiment, indicating that the sample has good reusability. The XRD results of 2:6 In₂O₃/BWO before and after the cyclic experiments show that the positions and intensities of its diffraction peaks did not change significantly, indicating excellent structural stability. The active species experiment results imply that h⁺ is the primary species. Additionally, this study proposes a mechanism for the separation, migration, and photocatalysis of photoinduced charges in II-type semiconductor junctions. Full article

The conversion of nitrogen (N₂) and water (H₂O) into NH₃ by photocatalysis under ambient conditions has been considered an environmentally friendly strategy. However, developing effective catalysts for N₂ fixation is still challenging. Herein, we report a bimetallic JH Fe, Co/TiO₂ derived from NH₂-MIL-125(Ti) by the fast Joule heating (FJH) method for visible–light–driven catalytic N₂ fixation. It was found that the photocatalytic N₂ reduction efficiency of bimetallic FC@TiO₂-JH was improved, enabling an NH₃ yield rate of 110.14 µmol g⁻¹ h⁻¹ without any sacrificial agents. Furthermore, the rate was higher than those of Fe@TiO₂-JH and Co@TiO₂-JH, suggesting that the synergistic effect between Fe and Co broke the electronic equilibrium and increased the center of its d-band, enhancing electronic feedback to the antibonding π* orbitals of N₂ while weakening the bonding energy of N≡N. Meanwhile, the rate was about 2.75 times higher than that of FC@TiO₂-TF, which was calcined in a tube furnace. It is assumed that FJH might lead to the formation of lattice defects, leading to localized charge deficiency, enhanced carrier separation, and transport. Thus, doping of Fe and Co synergistically interacted with the defects produced from FJH, facilitating the photocatalytic reduction process. As detected, it had a greater ability to separate hole–electron pairs and transferred electrons to adsorbed N₂ at faster rates. Our work demonstrates a prospective strategy for designing bimetallic catalysts derived from NH₂-MIL-125(Ti) for N₂ fixation. Full article

Two-dimensional (2D) materials have emerged as a frontier in materials science, offering unique properties due to their atomically thin nature. Among these materials, bismuthene stands out due to its exceptional optical, electronic, and catalytic characteristics. Bismuthene exhibits high charge carrier mobility, stability, and a tunable bandgap (0.3–1.0 eV), making it highly suitable for applications in transistors, spintronics, biomedicine, and photocatalysis. This work explores the so far reported synthesis methods for obtaining 2D bismuthene, including bottom-up approaches like chemical vapor deposition and molecular beam epitaxy, and top-down methods such as liquid-phase exfoliation and mechanical exfoliation. Recent advancements in understanding 2D bismuthene structural phases, electronic properties modulated by spin-orbit coupling, and its potential applications in next-generation photocatalysts are also reviewed. As is retrieved by our literature review, 2D bismuthene shows great promise for addressing significant environmental challenges. For instance, in CO₂ reduction, integrating bismuthene into 2D/2D heterostructures enhances electron transfer efficiency, thereby improving selectivity toward valuable products, such as CH₄ and formic acid. In organic pollutant degradation, bismuth subcarbonate (Bi₂O₂CO₃) nanosheets, obtained from 2D bismuthene, have demonstrated high photocatalytic degradation of antibiotics under visible light irradiation, due to their increased surface area and efficient generation of reactive species. Moreover, bismuthene-based materials exhibit potential in the photocatalytic water-splitting process for hydrogen production, overcoming issues associated with UV-light dependence and sacrificial agent usage. This review underscores the versatile applications of 2D bismuthene in advancing photocatalytic technologies, offering insights into future research directions and potential industrial applications. Full article

Photocatalysis based on titanium dioxide (TiO₂) has become a promising method to remediate industrial and municipal effluents in an environmentally friendly manner. However, the efficiency of TiO₂ is hampered by problems such as rapid electron–hole recombination and limited solar spectrum absorption. Furthermore, the sensitization of TiO₂ through heterojunctions with other materials has gained attention. Vanadium, specifically in the form of ammonium vanadate ((NH₄)₂V₃O₈), has shown promise as a photocatalyst due to its ability to effectively absorb visible light. However, its use in photocatalysis remains limited. Herein, we present a novel synthesis method to produce lamellar (NH₄)₂V₃O₈ as a sensitizer in a supramolecular hybrid photocatalyst of TiO₂–stearic acid (SA), contributing to a deeper understanding of its structural and magnetic characteristics, expanding the range of visible light absorption, and improving the efficiency of photogenerated electron–hole separation. Materials, such as TiO₂–SA and (NH₄)₂V₃O₈, were synthesized and characterized. EPR studies of (NH₄)₂V₃O₈ demonstrated their orientation-dependent magnetic properties and, from measurements of the angular variation of g-values, suggest that the VO₂⁺ complexes are in axially distorted octahedral sites. The photocatalytic results indicate that the 2D/2D heterojunction layered TiO₂/vanadate at a ratio (1:0.050) removed 100% of the methylene blue, used as a model contaminant in this study. The study of the degradation mechanism of methylene blue emphasizes the role of reactive species such as hydroxyl radicals (^•OH) and superoxide ions (O₂^•−). These species are crucial for breaking down contaminant molecules, leading to their degradation. The band alignment between ammonium vanadate ((NH₄)₂V₃O₈) and TiO₂–SA, shows effective separation and charge transfer processes at their interface. Furthermore, the study confirms the chemical stability and recyclability of the TiO₂–SA/(NH₄)₂V₃O₈ photocatalyst, demonstrated that it could be used for multiple photocatalytic cycles without a significant loss of activity. This stability, combined with its ability to degrade organic pollutants under solar irradiation, means that the TiO₂–SA/(NH₄)₂V₃O₈ photocatalyst is a promising candidate for practical environmental remediation applications. Full article

Noble metal nanomaterials with a localized surface plasmon resonance effect exhibit outstanding advantages in areas such as photothermal therapy and photocatalysis. As a unique plasmonic metal nanostructure, gold nanobipyramids have been attracting much interest due to their strong specific local electric field intensity, large optical cross sections, and high refractive index sensitivity. In this study, we propose a novel three-component hetero-nanostructure composed of rough gold nanobipyramids (R-Au NBPs), Pt, and CdS. Initially, purified gold nanobipyramids are regrown to form R-Au NBPs that have a certain degree of roughness. These R-Au NBP substrates with a rough surface provide more hotspots and strengthen the intensity of localized electric fields. Subsequently, Pt and CdS nanoparticles are selectively deposited onto the surface of R-Au NBPs. Pt nanoparticles can provide more active sites. Each component of this hetero-nanostructure directly contacts others, creating multiple electron transfer channels. This novel design allows for tunable localized plasmon resonance wavelengths ranging from the visible to near-infrared regions. These factors contribute to the final superior photothermal conversion performance of the R-Au/Pt-CdS nanohybrids. Under the irradiation of near-infrared light (1064 nm), the photothermal conversion efficiency of R-Au/Pt-CdS reached 38.88%, which is 4.49, 1.5, and 1.22 times higher than that of Au NBPs, R-Au NBPs, and R-Au NBPs/Pt, respectively. Full article

Wide bandgap semiconductor-based photocatalysts are usually limited by their low solar energy conversion efficiency due to their limited absorption solar wavelength, their rapid surface recombination of the photogenerated electron–hole pairs, and their low charge-carrier mobility. Here, we report a novel stepwise solution synthesis for achieving a new photocatalytic core–shell consisting of a titanate nanowire/reduced graphene oxide shell (or titanate/rGO) 1D-nanocomposite. The new core–shell nanocomposite maximized the specific surface area, largely reduced the charge transfer resistance and reaction energy barrier, and significantly improved the absorption of visible light. The core–shell nanocomposites’ large on/off current ratio and rapid photo-responses boosted the photocurrent by 30.0%, the photocatalysis rate by 50.0%, and the specific surface area by 16.4% when compared with the results for the pure titanate nanowire core. Our numerical simulations support the effective charge separation on the new core–shell nanostructure, which can help further advance the novel photocatalysis. Full article

In recent years, oxygen vacancy (V_O) engineering has become a research hotspot in the field of photocatalysis. Herein, an efficient GQDs/BiOCl-V_O heterojunction photocatalyst was fabricated by loading graphene quantum dots (GQDs) onto BiOCl nanosheets containing oxygen vacancies. ESR and XPS characterizations confirmed the formation of oxygen vacancy. Combining experimental analysis and DFT calculations, it was found that oxygen vacancy promoted the chemical adsorption of O₂, while GQDs accelerated electron transfer. Benefiting from the synergistic effect of oxygen vacancy, GQDs, and dye sensitization, the as-prepared GQDs/BiOCl-V_O sample exhibited improved efficiency for RhB degradation under visible-light irradiation. A 2 wt% GQDs/BiOCl-V_O composite effectively degraded 98% of RhB within 20 min. The main active species were proven to be hole (h⁺) and superoxide radical (·O₂⁻) via ESR analysis and radical trapping experiments. This study provided new insights into the effective removal of organic pollutants from water by combining defect engineering and quantum dot doping techniques in heterojunction catalysts. Full article

Construction of a homojunction is an effective strategy for effective charge transfer to suppress charge carrier recombination in augmented photocatalysis. The present work reveals the synthesis of homojunction formation through the reinforcement of Cd nanostructures into a solid lattice of zinc vanadate (Zn₃V₂O₈, ZnV) using the hydrothermal method. The formation of a homojunction between cadmium vanadate (CdV, Cd₃V₂O₈) and ZnV was confirmed by various spectroscopic and electron microscopic techniques such as Fourier-transform infrared (FTIR), X-ray diffraction (XRD), scanning electron microscopy (SEM) associated with energy-dispersive X-ray (EDX) mapping, transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and ultraviolet–visible spectrophotometry (UV–Vis). The synthesized material was explored for photocatalytic hydrogen (PC H₂) production using the water splitting process under visible-light illumination. The spectroscopic and experimental results revealed that the formation of a CdV/ZnV homojunction significantly improved the transport of photogenerated charge carriers (electron–hole pairs) and thus resulted in enhanced H₂ production efficiency (366.34 μmol g⁻¹ h⁻¹) as compared to pristine ZnV (229.09 μmol g⁻¹ h⁻¹) and CdV (274.91 μmol g⁻¹ h⁻¹) using methanol as a sacrificial reagent (SR) with water under visible-light illumination. The synergistic effect of Cd on ZnV NPs resulted in band gap reduction and broadened visible light absorption which was attributed to enhanced H₂ production. The current study explains how a homojunction affects various features of important factors behind photocatalytic activity, which supports significant insights into the advancement of materials in the future. Full article