Search Results (273)

The photocatalytic reduction of CO₂ in aqueous media offers a sustainable route for solar-to-fuel conversion, yet remains challenged by CO₂’s thermodynamic stability and kinetic inertness, low solubility, and competitive hydrogen evolution. Here, we investigate the interplay between ionic liquids (ILs), photocatalyst supports, and additive composition in directing product selectivity among CO, CH₄, and H₂. Using imidazolium acetate as a benchmark, we demonstrate that ILs not only pre-activate CO₂ but can also undergo decomposition pathways under illumination, notably Kolbe-type reactions leading to methane formation from acetate rather than from CO₂. Comparative studies of Pd-decorated TiO₂ and g-C₃N₄ nanosheets reveal distinct behaviors driven by their interfacial interactions with the imidazolim-based ionic liquid: weak interaction with TiO₂ strongly promotes hydrogen evolution, whereas strong coupling with g-C₃N₄ synergizes with C₁C₄ImOAc to trigger acetate-derived Kolbe reactivity. The systematic evaluation of alternative salts confirms the determinant role of anion basicity and medium-pH-basic anions facilitate CO₂ activation, whereas weakly basic or non-coordinating anions favor water splitting. Overall, these results clarify the dual role of ionic liquids as both CO₂ activators and sacrificial agents, and highlight design principles for improving product selectivity and efficiency in aqueous CO₂ photoreduction systems. Full article

We have developed mold matrices that can be employed to distinguish between enantiomers (D- and L-glucose) and structural isomers (n- and iso-stearic acid) in matrix-assisted laser desorption/ionization mass spectrometry. Utilizing a temperature-responsive polymer, a molecular structure recognition film was created around metal or semiconductor particles, such as silver (Ag) or cadmium telluride (CdTe), forming the core. Molecules that fit the template structure were selectively ionized. To elucidate the properties of the mold matrix, the relationship between molecular recognition rate and peak intensity of analyte ion was investigated by varying polymer film thickness around the core. The relationship between molecular recognition rate and hydrophobicity of the template molecule was also examined. It was found that increasing the amount of polymer forming the molecular recognition film improved the molecular recognition rate. However, the peak intensity of the analyte ion decreased. It was also found that using highly hydrophobic molecules as template molecules resulted in high molecular recognition rates. In addition, a water-splitting photocatalyst was synthesized and utilized to fabricate the mold matrix. It was applicable to both positive and negative ion generation while recognizing the molecular structure of the analyte. Full article

Insufficient harvesting of visible photons, limited adsorption, and fast recombination of photogenerated electron-hole pairs restrict the application of graphitic carbon nitride (g-C₃N₄). Here, we propose a straightforward solid-phase synthesis method for fabricating 2D/2D graphitic carbon nitride/reduced graphene oxide (SCN/GR) hybrid photocatalysts. The synthesis process involves the thermal condensation of three precursors: dicyandiamide (as the g-C₃N₄ source), NH₄Cl (as a pore-forming agent), and graphene oxide (GO, which is in situ reduced to rGO during thermal treatment). The incorporation of reduced graphene oxide (rGO) into the g-C₃N₄ matrix not only narrows the bandgap of the material but also expedites the separation of photogenerated carriers. The photocatalytic activity of the SCN/GR hybrid was systematically evaluated by degrading ciprofloxacin in aqueous solution under different light conditions. The results demonstrated remarkable degradation efficiency: 72% removal within 1 h under full-spectrum light, 81% under UV light, and 52% under visible light. Notably, the introduction of rGO significantly improved the visible light absorption capacity of g-C₃N₄. Additionally, SCN/GR exhibits exceptional cyclic stability, maintaining its structural integrity and photocatalytic properties unchanged across five successive degradation cycles. This study offers a simple yet effective pathway to synthesize 2D/2D composite photocatalysts, which hold significant promise for practical applications in water treatment processes. Full article

In this work, we investigate advanced photocatalyst Bi₃TiNbO₉ as promising piezophotocatalyst in terms of the effect of synthesis methods on the surface chemistry, structure, and catalytic performance in process of contaminant removal. Samples were prepared via solid-state reaction (BTNO-900) and molten salt synthesis (BTNO-800), leading to distinct morphologies and defect distributions. SEM imaging revealed that BTNO-900 consists of agglomerated, irregular particles, while BTNO-800 exhibits well-faceted, plate-like grains. Nitrogen adsorption analysis showed that the molten-synthesized sample possesses a significantly higher specific surface area (5.9 m²/g vs. 1.4 m²/g) and slightly larger average pore diameter (2.8 nm vs. 2.6 nm). High-resolution XPS revealed systematic shifts in binding energies for Bi 4f, Ti 2p, Nb 3d, and O 1s peaks in BTNO-900, accompanied by a higher content of adsorbed oxygen species (57% vs. 7.2%), indicating an increased concentration of oxygen vacancies and surface hydroxylation due to the solid-state synthesis route. Catalytic testing demonstrated that BTNO exhibits enhanced piezocatalytic efficiency of Methylene Blue degradation (~78% for both samples), whereas BTNO-800 shows significantly reduced photocatalytic activity (45.6%) compared to BTNO-900 (84.1%), suggesting recombination effects dominate in the more defective material. Synergism of light and mechanical stress results in piezophotocatalytic degradation for both samples (92.4% and 93.4%, relatively). These findings confirm that synthesis-controlled defect engineering is a key parameter for optimizing the photocatalytic behavior of Bi₃TiNbO₉-based layered oxides and crucial role of its piezocatalytic activity. Full article

Rubber material with high elasticity and viscoelasticity has become the most widely used universal material, and the study of the aging failure mechanism of rubber has been meaningful research in the polymer materials field. Cis-polyisoprene was employed to analyze the mechanism of oxidative degradation under artificial UV irradiation, and the GQDs/g-C₃N₄ photocatalysis with a 2D layered structure prepared by the method of microwave-assisted polymerization enabled to accelerate the degradation procedure. The results showed that the oxidation of cis-polyisoprene occurred during the irradiation for 3 days and the structure of cis-polyisoprene changed. The α-H of the double bond was attacked by oxygen to form hydroperoxide. Then, aldehydes and ketones generated as the addition reaction of double bonds occurred. The content of the hydrogen of C=C reduced, and the oxidative degradation was dominant at the initial aging stage. The crosslinking reaction was dominant at the final aging stage and the average molecular weight decreased from 15.49 × 10⁴ to 8.78 × 10⁴. The GQDs could promote the charge transfer and the photodegradation efficiency and inhibit the electron–hole recombination. The light capture ability of GQDs was improved after compositing with g-C₃N₄. The free radicals ·O₂²⁻ generated after adding GQDs/g-C₃N₄ nanoparticles, and the molecular weight of cis-polyisoprene decreased to 5.79 × 10⁴, with the photocatalytic efficiency increasing by 20%. This work provided academic bases and reference values for the application of photocatalysts in the field of natural rubber degradation and rubber wastewater treatment. Full article

The efficient degradation of antibiotics in pharmaceutical wastewater remains a critical challenge against environmental contaminants. Conventional photocatalysts face potential limitations such as narrow visible-light absorption, rapid carrier recombination, and reliance on precious metal cocatalysts. This review investigates the coordination structure of MXene as a cocatalyst to synergistically enhance photocatalytic antibiotic degradation efficiency and the coordination structure modification mechanisms. MXene’s tunable bandgap (0.92–1.75 eV), exceptional conductivity (100–20,000 S/cm), and abundant surface terminations (-O, -OH, -F) enable the construction of Schottky or Z-scheme heterojunctions with semiconductors (Cu₂O, TiO₂, g-C₃N₄), achieving 50–70% efficiency improvement compared to pristine semiconductors. The “electron sponge” effect of MXene suppresses electron-hole recombination by 3–5 times, while its surface functional groups dynamically optimize pollutant adsorption. Notably, MXene’s localized surface plasmon resonance extends light harvesting from visible (400–800 nm) to near-infrared regions (800–2000 nm), tripling photon utilization efficiency. Theoretical simulations demonstrate that d-orbital electronic configurations and terminal groups cooperatively regulate catalytic active sites at atomic scales. The MXene composites demonstrate remarkable environmental stability, maintaining over 90% degradation efficiency of antibiotic under high salinity (2 M NaCl) and broad pH range (4–10). Future research should prioritize green synthesis protocols and mechanistic investigations of interfacial dynamics in multicomponent wastewater systems to facilitate engineering applications. This work provides fundamental insights into designing MXene-based photocatalysts for sustainable water purification. Full article

Zinc oxide (ZnO), a wide-bandgap semiconductor, has garnered significant interest for photocatalytic applications due to its excellent chemical stability, non-toxicity, and strong oxidative capability. In this study, density functional theory (DFT) calculations were employed to explore the impact of ruthenium (Ru) doping on the structural, electronic, and magnetic properties of wurtzite ZnO. The introduction of Ru leads to bandgap narrowing and the emergence of impurity states, thereby enhancing visible light absorption. Charge density analysis reveals enhanced electron delocalization, while the projected density of states (PDOS) indicates strong hybridization between the Ru 4d orbitals and the ZnO electronic states. The density of states at the Fermi level, N(EF), exhibits a notable dependence on doping concentration and magnetic configuration. For non-magnetic states, N(EF) reaches 11 states/eV and 9.5 states/eV at 12.5% and 25% Ru concentrations, respectively. In ferromagnetic configurations, these values decrease to 0.65 states/eV and 1.955 states/eV, while antiferromagnetic states yield 4.945 states/eV and 0.65 states/eV. These variations highlight Ru’s crucial role in regulating electronic density, thereby affecting electrical conductivity, magnetic properties, and photocatalytic efficiency. The results offer theoretical guidance for designing high-performance Ru-doped ZnO photocatalysts. Full article

Ferroelectric materials have attracted great attention for photocatalytic hydrogen (H₂) evolution due to their internal depolarization fields that promote carrier separation and directional migration. However, conventional inorganic ferroelectrics often suffer from wide band gaps and low conductivity, limiting their solar-to-hydrogen conversion efficiency. Here, we report a two-dimensional (2D) multilayered perovskite ferroelectric, [butylammonium]₂[ethylammonium]₂Pb₃I₁₀ (BAPI), which integrates robust spontaneous polarization (P_s) and excellent semiconductor properties to enable efficient photocatalysis. Under simultaneous light and ultrasonic excitation, BAPI/Pt (1 wt%) achieves a H₂ evolution rate of 1256 μmol g⁻¹ h⁻¹, which is twice that under light alone, due to dynamic polarization modulation that mitigates ionic screening and enhances internal electric fields. Notably, this enhancement vanishes when BAPI transitions to a centrosymmetric, nonpolar phase at 323 K, confirming the critical role of P_s. These findings offer a new pathway toward high-performance ferroelectric photocatalysts for solar hydrogen production. Full article

Reactive oxygen species (ROS) play a central role in photocatalytic processes relevant to environmental remediation and clean energy. This work focused on the computational investigation of ZnO surface reactivity toward H₂O and O₂ adsorption, as a preliminary step in understanding ROS generation pathways. Surface stability and adsorption energies for isolated and co-adsorbed H₂O and O₂ molecules on different ZnO surfaces (both in their pristine form and with oxygen vacancies) were evaluated using DFT calculations at the PBE-D3 level under various surface coverages. The introduction of vacancies on the pristine (001) and (100) surfaces enhanced O₂ binding, particularly in inclined configurations at the defect sites, with the adsorption energies reaching −2.63 eV and −2.04 eV, respectively. However, the (110) surface showed very strong H₂O binding, but weak O₂ adsorption, which only modestly improved with vacancies. Co-adsorption of H₂O and O₂ exhibited synergistic stabilization, especially on the (001) and (100) surfaces, where ROS were formed through proton transfers either between adsorbed H₂O and O₂ or between H₂O and surface oxygen atoms. These findings provide detailed insight into the mechanistic role of surface defects in ROS generation and support the rational design of ZnO-based photocatalysts. Full article

Photocatalysis is a promising strategy for the treatment of dangerous chemical pollutants in the ocean. In this work, a stable copper-based photocatalyst, i.e., {[Cu(BPA)₂]·2I₃}_n (1, BPA = 4,4′-bipyridinium-N-pentanoic acid), exhibited excellent degradation performance in dye pollutant in seawater. According to the structural analysis, this photocatalyst consists of 1-D cationic [Cu(BPA)₂]_n²ⁿ⁺ infinite chain and two I³⁻ polyiodide anions. In the [Cu(BPA)₂]_n²ⁿ⁺ chain, the distorted CuO₄N₂ octahedra are bridged by asymmetric viologen ligand (BPA), which result in a 1-D ladder-shaped chain. Strong C–H···O/I hydrogen bonds contribute to the formation of a 2-D layer along bc-plane, in which I³⁻ anions are stacked among the cationic chains. The strong adsorption from ultraviolet to visible regions together with its high charge separation efficiency implies its usage as excellent visible-light-driven catalysis. Interestingly, good photocatalytic performance for the degradation of Rhodamine B (RhB) in seawater can be observed by using this hybrid as photocatalyst. In detail, 90.6% degradation ratio of RhB can be achieved in 150 min under visible light, which was monitored on a UV–Vis spectrum. This work could pave the way for new ocean pollutant treatments for shipping accidents. Full article

Carbon dots (CDs), a rapidly emerging class of zero-dimensional (0-D) nanomaterials with small particle sizes (<10 nm), have garnered significant scientific interest owing to their exceptional physicochemical properties, non-toxicity, low-cost synthesis, and versatile applications. In recent years, the combination of various inorganic photocatalysts (e.g., metal oxides, metal chalcogenides, metal oxyhalides, MXenes, non-metallic semiconductors) with CDs has gained momentum as a promising strategy to enhance their photocatalytic efficiency. By incorporating CDs, researchers have addressed fundamental challenges in photocatalytic systems, including limited light absorption range, rapid electron–hole recombination rate, low quantum efficiency, etc. The present review is focused on the most recent developments in CDs-based heterostructures for advanced photocatalytic applications, particularly in the field of environmental remediation, providing a comprehensive overview of emerging strategies, synthesis approaches, and the resulting enhancements in photocatalytic water treatment applications. Full article

Addressing global energy and environmental issues calls for the development of effective photocatalysts capable of enabling solar-driven water splitting, a key route toward sustainable hydrogen generation. In this work, we conducted a detailed density functional theory (DFT) study on three bilayer van der Waals (vdW) heterojunctions, Ga₂SSe/GaP, Ga₂SSe/PtSSe, and Ga₂SSe/SnSSe, each explored in four distinct stacking configurations, with Ga₂SSe serving as the base monolayer. We assessed their structural stability, electronic properties, and optical responses to determine their suitability for photocatalytic water splitting. The analysis showed that Ga₂SSe/GaP and Ga₂SSe/SnSSe exhibit type-II band alignment, while Ga₂SSe/PtSSe displays a type-I alignment. Electrostatic potential profiles and Bader charge calculations identified SeGa₂S/SSnSe and SeGa₂S/SeSnS as direct Z-scheme systems, offering efficient charge carrier separation and robust redox potential. For effective water splitting, the band edges must straddle the water redox potentials. Our results indicate that configurations A and B in Ga₂SSe/GaP, along with C and D in Ga₂SSe/SnSSe, fulfill this requirement. These four configurations also exhibit strong absorption in both the visible and ultraviolet spectral ranges. Notably, configurations C and D of Ga₂SSe/SnSSe achieve high solar-to-hydrogen (STH) efficiencies, reaching 38.44% and 21.75%, respectively. Overall, our findings suggest that these direct Z-scheme heterostructures are promising candidates for water splitting photocatalysis. Full article

Photocatalysis offers a cost-effective and eco-friendly approach for environmental remediation, yet traditional powdered photocatalysts suffer from poor recyclability and separation challenges. To address these limitations, we developed a recyclable carbon fiber-supported composite photocatalyst (CC/TiO₂ NRs@MoS₂ NPs) featuring a three-dimensional hierarchical core–shell architecture. This structure comprises a TiO₂ seed layer, vertically aligned TiO₂ nanorod arrays as the core, and a MoS₂ nanoparticle shell, fabricated via sequential deposition. Under simulated solar irradiation, the TiO₂@MoS₂ heterojunction exhibited significantly enhanced uranium adsorption capacity, achieving a remarkable 97.3% photocatalytic removal efficiency within 2 h. At an initial uranium concentration of 200 ppm, the material demonstrated an exceptional extraction capacity of 976.7 mg g⁻¹, outperforming most reported photocatalysts. These findings highlight the potential of this 3D core–shell design for efficient uranium recovery and environmental purification applications. Full article

The controllable loading of a cocatalyst on a semiconductor is the key to further improving the efficiency and stability of visible-light photocatalytic hydrogen production. It is of great practical significance to load a cocatalyst onto a semiconductor spatially separated to realize space charge separation for efficient photocatalytic hydrogen evolution. The inherent anisotropic morphology of one-dimensional nanorods can provide two spatially separated locations at the tip and side surfaces of the nanorods. In this review, we systematically summarize non-centrosymmetric and centrosymmetric cocatalyst-tipped one-dimensional (1D) photocatalysts, including their preparation method, catalytic hydrogen production performance, and catalytic mechanism. This review will bring new vitality to the design, preparation, and application of cocatalyst-tipped one-dimensional nanorods. Full article

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