Search Results (68)

In this work, the synthesis and structural characterization of the smallest possible member of the family of bis-functionalized {MnMo₆O₂₄} Anderson–Evans polyoxometalates (POMs) is reported. The synthesis of the title compound TBA₃{[HC(CH₂O)₃]₂MnMo₆O₁₈} (1) was accomplished by using trimethylolmethane as the capping unit (TBA: tetra(n-butyl)ammonium, n-B_u4N⁺). The molecular structure of the organic–inorganic POM gave rise to yet undisclosed ¹H-NMR features, which are discussed thoroughly. Single-crystal X-ray diffraction (XRD) analysis revealed a highly regular 3D packing of the polyoxoanions within a matrix of TBA cations. The hybrid POM is of particular interest regarding potential applications in photocatalysis (i.e., hydrogen evolution) and energy storage. Thus, the electrochemical and thermal properties of 1 are also analyzed. Full article

The rapid recombination of photoinduced charge carriers in semiconductors remains a significant challenge for their practical application in photocatalysis. This study presents the design of a step-scheme (S-scheme) heterojunction composed of carbon nitride (g-C₃N₄) and nickel-based metal–organic framework (Ni-MOF) to achieve enhanced charge separation. The establishment of an S-scheme charge transfer configuration at the interface of the Ni-MOF/g-C₃N₄ heterostructure plays a pivotal role in enabling efficient charge carrier separation, and hence, high CO₂ photoreduction efficiency with a CO evolution rate of 1014.6 µmol g⁻¹ h⁻¹ and selectivity of 95% under simulated solar illumination. CO evolution represents an approximately 3.7-fold enhancement compared to pristine Ni-MOF. Density functional theory (DFT) calculations, supported by in situ irradiated X-ray photoelectron spectroscopy (XPS) and electron paramagnetic resonance (EPR) experimental results, confirmed the establishment of a well-defined and strongly bonded interface, which improves the charge transfer and separation following the S-scheme mechanism. This study sheds light on MOF-based S-scheme heterojunctions as fruitful and selective alternatives for practical CO₂ photoreduction. Full article

The strategic design of donor–acceptor (D-A) conjugated porous polymers has emerged as a pivotal methodology for advancing efficient photocatalytic hydrogen evolution. However, conventional D-A polymeric architectures face inherent limitations: excessively strong acceptor units may lower the LUMO energy level, compromising proton (H⁺) reduction capability, while weak D-A interactions result in inadequate light-harvesting capacity and insufficient photogenerated electrons, ultimately diminishing photocatalytic activity. To address these challenges, we developed a new D1-A-D2 conjugated porous polymer (CPP) system. The strategic incorporation of a secondary donor benzothiophene (DBBTh) unit enabled precise bandgap engineering in D₁-A-D₂ CPPs. Experimental results demonstrate that DBBTh integration significantly enhances both light absorption efficiency and proton reduction ability. Under visible-light irradiation (λ > 420 nm), the Py-BKh1 photocatalyst achieved a hydrogen evolution rate (HER) of 10.2 mmol h⁻¹ g⁻¹ with an apparent quantum yield (AQY) of 9.5% at 500 nm. This work provides a groundbreaking paradigm for designing high-performance organic photocatalysts. 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

The exploration of visible light-responsive, efficient, and durable photocatalysts is of great concern for removing organic dyes and antibiotics from wastewater. This work involved the preparation of a CoCN0.02 photocatalyst by simple thermal polymerization. The synthesized catalysts were mainly used for the photocatalytic degradation of tetracycline (TC) pollutants. The photocatalytic efficiency of one of the catalysts reached 97% in 30 min, which was much higher than that of pure g-C₃N₄ (CN). The consistency between the results of kinetic simulations and characterization supported the strong role of Co intercalation sites in photocatalysis. Additionally, using the active species capture experiments, the predominant active species were determined to be •OH, •O₂⁻, and h⁺, thereby allowing us to explore the electron transportation and redox reactions during the process of photocatalysis. This investigation establishes a basis for exploring the evolution of active species in the context of antibiotic pollutants. Full article

This work aims to explore the influence of crystal phase engineering on the photocatalytic hydrogen evolution activity of Ru/C₃N₄ systems. By precisely tuning the combination of Ru precursors and reducing solvents, we successfully synthesized Ru co-catalysts with distinct crystal phases (hcp and fcc) and integrated them with C₃N₄. The photocatalytic hydrogen evolution experiments demonstrated that hcp-Ru/C₃N₄ achieved a significantly higher hydrogen evolution rate (24.23 μmol h⁻¹) compared to fcc-Ru/C₃N₄ (7.44 μmol h⁻¹), with activity reaching approximately 42% of Pt/C₃N₄ under the same conditions. Photocurrent and electrochemical impedance spectroscopy analyses revealed that hcp-Ru/C₃N₄ exhibited superior charge separation and transfer efficiency. Moreover, Gibbs free energy calculations indicated that the hydrogen adsorption energy of hcp-Ru (ΔG_H* = −0.14 eV) was closer to optimal compared to fcc-Ru (−0.32 eV), enhancing the hydrogen generation process. These findings highlight that crystal-phase engineering plays a critical role in tuning the electronic structure and catalytic properties of Ru-based systems, offering insights for the design of highly efficient noble metal catalysts for photocatalysis. Full article

The utilization of covalent triazine frameworks (CTFs) as photocatalysts has witnessed rapid advancements in the field of photocatalysis. However, the presence of residual components in certain CTFs materials is widely ignored as regards their influence on photocatalytic performance. In this study, we find that trifluorosulfonic acid (TfOH) molecules stably exist in the amino-functionalized CTF-NH₂ framework, which enhance the affinity for water. The experimental results indicate that the residual TfOH elevates the VB position of CTF-NH₂, facilitating the oxidization of both water and sacrificial agents. Moreover, the present of TfOH accelerates the separation and transfer of photogenerated charge carriers to the Pt cocatalyst. Consequently, CTF-NH₂-F containing residual TfOH molecules demonstrates a significant enhancement in the photocatalytic hydrogen evolution, achieving about 250 µmol over a duration of 3 h of illumination, which represents a 2.5-fold increase compared to that observed for CTF-NH₂. This research underscores the substantial impact that residues exert on photocatalytic performance. Full article

Photocatalytic hydrogen evolution using inexhaustible clean solar energy is considered as a promising strategy. In order to build an efficient photocatalytic hydrogen production system to satisfy the demands of practical applications, it is of great significance to design photocatalysts that offer high activity, low cost, and high stability. Herein, a series of cheap CdS/Ni(OH)₂ composite photocatalysts were designed and synthesized using the hydrothermal method. The introduction of a Ni(OH)₂ cocatalyst multiplied the reactive active site of cadmium sulfide and promoted the transfer of photoinduced electrons in a semiconductor. Therefore, CdS/Ni(OH)₂ composites demonstrate significantly better photocatalytic performance, and the hydrogen production rate of an optimal CdS/5%Ni(OH)₂ composite is 6.9 times higher than that of blank CdS. Furthermore, the stability test also showed that CdS/Ni(OH)₂ had good stability. This study aims to serve as a rewarding reference for the development of high-performance composite photocatalysts. Full article

Converting solar energy into fuels/chemicals through photochemical approaches holds significant promise for addressing global energy demands. Currently, semiconductor photocatalysis combined with redox techniques has been intensively researched in pollutant degradation and secondary energy generation owing to its dual advantages of oxidizability and reducibility; however, challenges remain, particularly with improving conversion efficiency. Since graphene’s initial introduction in 2004, three-dimensional (3D) graphene-based photocatalysts have garnered considerable attention due to their exceptional properties, such as their large specific surface area, abundant pore structure, diverse surface chemistry, adjustable band gap, and high electrical conductivity. Herein, this review provides an in-depth analysis of the commonly used photocatalysts based on 3D graphene, outlining their construction strategies and recent applications in photocatalytic degradation of organic pollutants, H₂ evolution, and CO₂ reduction. Additionally, the paper explores the multifaceted roles that 3D graphene plays in enhancing photocatalytic performance. By offering a comprehensive overview, we hope to highlight the potential of 3D graphene as an environmentally beneficial material and to inspire the development of more efficient, versatile graphene-based aerogel photocatalysts for future applications. Full article

CdS quantum dots (CdS QDs) are regarded as a promising photocatalyst due to their remarkable response to visible light and suitable placement of conduction bands and valence bands. However, the problem of photocorrosion severely restricts their application. Herein, the CdS QDs-Co₉S₈ hollow nanotube composite photocatalyst has been successfully prepared by loading Co₉S₈ nanotubes onto CdS QDs through an electrostatic self-assembly method. The experimental results show that the introduction of Co₉S₈ cocatalyst can form a stable structure with CdS QDs, and can effectively avoid the photocorrosion of CdS QDs. Compared with blank CdS QDs, the CdS QDs-Co₉S₈ composite exhibits obviously better photocatalytic hydrogen evolution performance. In particular, CdS QDs loaded with 30% Co₉S₈ (CdS QDs-30%Co₉S₈) demonstrate the best photocatalytic performance, and the H₂ production rate reaches 9642.7 μmol·g⁻¹·h⁻¹, which is 60.3 times that of the blank CdS QDs. A series of characterizations confirm that the growth of CdS QDs on Co₉S₈ nanotubes effectively facilitates the separation and migration of photogenerated carriers, thereby improving the photocatalytic hydrogen production properties of the composite. We expect that this work will facilitate the rational design of CdS-based photocatalysts, thereby enabling the development of more low-cost, high-efficiency and high-stability composites for photocatalysis. Full article

Conjugated polymers have attracted significant attention in the field of photocatalysis due to their exceptional properties, including versatile optimization, cost-effectiveness, and structure stability. Herein, two conjugated porous polymers, PhIN-CPP and ThIN-CPP, based on triazines, were meticulously designed and successfully synthesized using benzene and thiophene as building blocks. Based on UV diffuse reflection spectra, the photonic band gaps of PhIN-CPP and ThIN-CPP were calculated as 2.05 eV and 1.79 eV. The PhIN-CPP exhibited a high hydrogen evolution rate (HER) of 5359.92 μmol·g⁻¹·h⁻¹, which is 10 times higher than that of Thin-CPP (538.49 μmol·g⁻¹·h⁻¹). The remarkable disparity in the photocatalytic performance can be primarily ascribed to alterations in the band structure of the polymers, which includes its more stable benzene units, fluffier structure, larger specific surface area, most pronounced absorption occurring in the visible region and highly extended conjugation with a high density of electrons. The ΔE_ST values for PhIN-CPP and ThIN-CPP were calculated as 0.79 eV and 0.80 eV, respectively, based on DFT and TD-DFT calculations, which revealed that the incorporation of triazine units in the as-prepared CMPs could enhance the charge transfer via S1 ↔ T1 and was beneficial to the photocatalytic decomposition of H₂O. This study presents a novel concept for developing a hybrid system for preparation of H₂ by photocatalysis with effectiveness, sustainability, and economy. Full article

Photocatalysis is one of the most promising pathways to relieve the environmental contamination caused by the rapid development of modern technology. In this work, we demonstrate a green manufacturing process for the 3D/3D rod-shaped bamboo charcoal/Bi₂WO₆ photocatalyst (210BC-BWO) by controlled carbonization temperature. A series of morphology characterization and properties investigations (XRD, SEM, UV–vis DRS, transient photocurrent response, N₂ absorption-desorption isotherms) indicate a 210BC-BWO photocatalyst with higher charge separation efficiency, larger surface area, and better adsorption capacity. The excellent photocatalytic performance was evaluated by degrading rhodamine B (RhB) (98.5%), tetracycline hydrochloride (TC-HCl) (77.1%), and H₂ evolution (2833 μmol·g⁻¹·h⁻¹) coupled with furfuryl alcohol oxidation (3097 μmol·g⁻¹·h⁻¹) under visible light irradiation. In addition, the possible mechanisms for degradation of organic pollutants, H₂ evolution, and furfuryl alcohol oxidation were schematically investigated, which make it possible to exert photocatalysis by increasing the active radical. This study shows that the combination of bamboo charcoal and bismuth tungstate can be a powerful photocatalyst that rationally combines H₂ evolution coupled with furfuryl alcohol oxidation and degradation of pollutants. Full article

Photocatalysis is considered as an environmentally friendly method for both solar energy conversion and environmental purification of water, wastewater, air, and surfaces. Among various photocatalytic materials, titania is still the most widely investigated and applied, but more efforts must be carried out considering the synthesis of highly efficient photocatalysts for multifarious applications. It is thought that nanoengineering design of titania morphology might be the best solution. Accordingly, here, titania mesocrystals, assembled from crystallographically oriented nanocrystals, have been synthesized by an easy, cheap, and “green” solvothermal method (without the use of surfactants and templates), followed by simple annealing. The obtained materials have been characterized by various methods, including transmission electron microscopy (TEM), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), X-ray powder diffraction (XRD) and diffuse reflectance spectroscopy (DRS). It has been found that the as-obtained photocatalysts exhibit a unique nanorod-like subunit structure with excellent crystalline and surface properties. However, pristine titania is hardly active for a hydrogen evolution reaction, and thus additional modification has been performed by platinum photodeposition (and silver as a reference). Indeed, the modification with only 2 wt% of noble metals results in a significant enhancement in activity, i.e., ca. 75 and 550 times by silver- and platinum-modified samples, respectively, reaching the corresponding reaction rates of 37 μmol h⁻¹ and 276 μmol h⁻¹. Additionally, titania mesocrystals exhibit high oxidation power under simulated solar light irradiation for the degradation of antibiotics within the tetracycline group (tetracycline (TC), ciprofloxacin (CIP), norfloxacin (NOR) and oxytetracycline hydrochloride (OTC)). It has been found that both experimental results and the density functional theory (DFT) calculations confirm the high ability of titania mesocrystals for oxidative decomposition of tetracycline antibiotics. 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

The inherent properties of TiO₂, including a wide band gap and restricted spectral response range, hinder its commercial application and its ability to harness only 2–3% of solar energy. To address these challenges and unlock TiO₂’s full potential in photocatalysis, C₆₀- and CdS-co-modified nano-titanium dioxide has been adopted in this work to reduce the band gap, extend the absorption wavelength, and control photogenerated carrier recombination, thereby enhancing TiO₂’s light-energy-harnessing capabilities and hydrogen evolution capacity. Using the sol-gel method, we successfully synthesized CdS-C₆₀/TiO₂ composite nanomaterials, harnessing the unique strengths of CdS and C₆₀. The results showed a remarkable average yield of 34.025 μmol/h for TiO₂ co-modified with CdS and C₆₀, representing a substantial 17-fold increase compared to pure CdS. Simultaneously, the average hydrogen generation of C₆₀-modified CdS surged to 5.648 μmol/h, a notable two-fold improvement over pure CdS. This work opens up a new avenue for the substantial improvement of both the photocatalytic degradation efficiency and hydrogen evolution capacity, offering promise of a brighter future in photocatalysis research. Full article