Photocatalytic Degradation Mechanism Research Articles

Tailored Polymeric Carbon Nitride Coupled with Bi2O3 for Constructing Z‐Scheme Heterojunction with Enhanced Photocatalytic Activity

AbstractThe great demand for visible‐light‐induced catalysts with high photocatalytic performance has stimulated extensive interest in constructing g‐C3N4‐based Z‐Scheme heterojunctions. In this research work, the g‐C3N4/Bi2O3 Z‐Scheme heterojunction by precipitation‐hydrothermal method was constructed, and characterized by various techniques. The g‐C3N4/Bi2O3‐1 composite exhibited a transient photocurrent response approximately 7 and 5 times higher than that of bare g‐C3N4 and Bi2O3, respectively, and showed higher visible photocatalytic activity with 99.8 % degradation of methylene blue (MB) within 75 min. Meanwhile, the pH effect on the photocatalytic degradation of MB was investigated. Radicals trapping experiments showed that •OH free radical played a predominant role for the degradation of MB, EPR analysis confirmed the presence of superoxide radicals, which combined with the band structure of the composites, confirmed the Z‐Scheme of the heterojunction. A possible mechanism for photocatalytic degradation of MB dyes in g‐C3N4/Bi2O3‐1 composites was also proposed. This study provided a new avenue for the development of novel g‐C3N4‐based Z‐Scheme heterojunction materials with prospective applications in the fields of energy and environment.

Outstanding photocatalytic activity of a mechano-thermally synthesized Z-scheme BiFeO3- Fe2O3 heterostructure

In this study, α-Bi2O3 and α-Fe2O3 powder mixtures experienced a novel mechano-thermal procedure, which includes high-energy ball milling followed by heat treatment, resulting in the successful synthesis of a BiFeO3-Fe2O3 nanocomposite. Simultaneous thermal analysis (STA) and X-ray diffraction (XRD) showed that the formation and characteristics of BiFeO3-Fe2O3 nanocomposite are greatly influenced by the milling process, heat-treatment temperature, and the α-Bi2O3:α-Fe2O3 molar ratio. X-ray photoelectron spectroscopy (XPS) spectra confirmed the presence of Bi, Fe, and O, indicating the formation of the BiFeO3 phase. Field emission scanning electron microscopy (FESEM) analysis showed the development of plate-like microstructures in the BiFeO3 phase with an average thickness of 88 nm. Diffuse reflectance spectroscopy (DRS) indicated that the 20 h-milled nanocomposite with a molar ratio of α-Bi2O3:α-Fe2O3 (1:3) exhibited the lowest band gap of 2.38 eV after heat treatment at 750 °C. The reduction in photoluminescence (PL) peaks and increase in photocurrent in the above sample suggested a decrease in charge carrier recombination rate, leading to high photocatalytic activity of 85 and 42% for methylene blue (MB) and methyl orange (MO) degradation, respectively. The effect of various pH levels on the photocatalytic activity of both dyes was examined, with MO degrading by 94% in an acidic environment after 300 min of visible light exposure, while MB experienced similar degradation in an alkaline setting. The kinetics and mechanism of photocatalytic degradation were extensively studied using the Langmuir-Hinshelwood (L-H) model, revealing the significant role of hydroxyl radicals in photodegradation. A Z-scheme mechanism for charge transfer in the nanocomposite was postulated, drawing upon radical scavenging and Mott-Schottky experiments. The prepared photocatalyst showed excellent stability and reusability following a cyclic experiment.

Revealing the Enhanced Visible-light-driven Photocatalytic Activity of In2S3/CeO2 Heterojunction: Bandgap Structure Analysis and Active Radicals Determination

Background: The widespread presence of persistent organic pollutants, such as dyes in effluent from printing and textile industries, poses a significant threat to aquatic life and human health. Photocatalytic degradation is widely recognized as a promising technology to address this pollution crisis. The efficiency of photocatalysis is intricately tied to both the active radicals and the band structure of the catalyst. These factors play a crucial role in governing the photodegradation of dye molecules. Methods: In2S3/CeO2 heterojunctions were synthesized using an in-situ precipitation method and subsequently analyzed through SEM, XRD, and XPS techniques. Notably, the bandgap structure of the heterojunctions was examined through UV-Vis DRS. The photocatalytic performance of the synthesized samples was assessed by studying the degradation of methyl orange. To further validate the photocatalytic process, EPR spectroscopy was employed to confirm the presence of radicals generated within the heterojunction. Results: The heterojunction displayed a characteristic type-II structure, enhancing light absorption and facilitating the separation of photoinduced carriers. Among the In2S3/CeO2 composites, the one with a 15 wt% CeO2 content exhibited the highest photocatalytic activity, achieving an 88% degradation of methyl orange after 90 min of exposure to visible light irradiation. Additionally, •O2 − is identified as the primary active species responsible for degradation. Conclusion: UV-Vis DRS illustrated the improved transfer and separation of photogenerated electrons attributed to the optimized band structure of the heterojunction. EPR spectroscopy yielded valuable information on active radicals, thereby proposing the photocatalytic degradation mechanism.

Use of Natural Zeolite Clinoptilolite in the Preparation of Photocatalysts and Its Role in Photocatalytic Activity

The use of natural zeolite clinoptilolite in preparing photocatalysts and its function in photocatalysis are discussed in this review. The importance of advanced oxidation processes (AOPs) and the potential of heterogeneous photocatalysis in removing environmental pollutants are emphasized. The review focuses on the synergistic effects of clinoptilolite with semiconductors (TiO2, ZnO, CuO, SnO2, and NiO) to prepare stable and active photocatalysts, highlighting recent advancements in this field. It explores clinoptilolite’s structural characteristics, highlighting its microporous nature, adaptable framework, and improved textural properties due to acid and alkali treatments. Particle size, crystal phase, and calcination temperature are three key synthesis parameters that affect photocatalytic activity and are highlighted in the discussion of these parameters and their methods. A discussion is held regarding the processes and mechanisms of photocatalytic degradation of different organic compounds under varying irradiation conditions, including UV, visible, and ambient sunlight. Clinoptilolite is vital in improving supported semiconductor oxides’ photocatalytic efficiencies, which aid in pollutant degradation and environmental remediation.

Tm3+/Yb3+:NaGdF4 nanoparticles decorated g-C3N4/BiOBr0.75I0.25 multicomponent heterostructure: Structural, optical properties and UV–Visible-NIR responsive photocatalytic degradation of Rhodamine B and reduction of Cr(VI)

A wide solar spectral range responsive multicomponent heterostructure photocatalyst NGT/g-C3N4/BiOBr0.75I0.25 was successfully synthesized and used for the UV–visible-NIR photodegradation of the dye Rhodamine B and photoreduction of highly toxic hexavalent chromium ions. Our study shows that the heterostructure overcomes the drawbacks of limited visible-light absorption and fast charge recombination of g-C3N4. Herein, the incorporation of BiOBr0.75I0.25 extends the absorption in the visible region and endorses the separation rate of photogenerated charge carriers. Additionally, the upconversion nanoparticles NaGdF4: Tm/Yb (NGT) with its higher infrared light absorption capacity and characteristic emission spectral overlapping with absorption range of g-C3N4/BiOBr0.75I0.25 nanocomposite, further facilitates the photocatalytic activity of the NGT/g-C3N4/BiOBr0.75I0.25 heterostructured nanocomposite. Extensive structural, morphological, and compositional analysis was done using XRD, TEM, SEM, FE-SEM, XPS, and FTIR measurements. The PL emission, time-resolved decay, and electrochemical impedance spectroscopy were used to probe the separation rate of photogenerated electron-hole pairs and efficient energy transfer in NGT/g-C3N4/BiOBr0.75I0.25 heterostructured nanocomposite. The possible photocatalytic degradation mechanism was comprehensively proposed through a combination of UV–Vis absorption, Mott Schottky, and scavenger test analysis. The photodegradation efficiency of the heterojunction was 98 %, which is much higher than the bare g-C3N4 (74 %). Moreover, the heterostructure exhibited excellent long-term reusability, maintaining the photodegradation efficiency of 97.02 % even after four consecutive degradation cycles, establishing it as a preferable material for photocatalytic dye degradation. Additionally, NGT/g-C3N4/BiOBr0.75I0.25 heterostructured nanocomposite also demonstated better performance for the photoreduction of Cr(VI) to Cr(III), achieving photocatalytic efficiency of 98.86 % under acidic condition.

Nitrogen-doped carbon quantum dot as electron acceptor anchored on graphitic carbon nitride nanosheet for improving rhodamine B degradation

Carbon quantum dots (CQDs) hold significant promise for wastewater treatment because of their remarkable attributes, including robust stability, outstanding biocompatibility, minimal toxicity, superior water dispersibility, cost-effective production, and exceptional photo-stability.In this study, CQDs were synthesized using microplasma and tested for the degradation of rhodamine B (RhB) (5 mg/L) under different conditions, with a Solar simulator and UVA illumination. Specifically, graphitic carbon nitride nanosheets (NCN) in conjugation with carbon quantum dots (NCN@CQD) were prepared with different amounts of CQD. The synthesized CQD, NCN, and NCN@CQD underwent characterization using various compositional and structural analytical techniques. The results show that nitrogen species were effectively incorporated into the CQDs framework and CQDs are anchored on NCN forming NCN@CQD successfully. Subsequently, all samples were then investigated in degrading Rhodamin B, RhB, to assess the photocatalytic activity. The results reveal that the presence of CQDs substantially improved the photocatalytic efficiency of NCN. Specifically, the CQDs anchored on NCN exhibited a substantial enhancement in the photoactivity for RhB decomposition under a solar light simulator, surpassing that of pure NCN. The amount of CQD in the NCN@CQD sample exerted a strong influence on the photocatalytic activity. All NCN@CQD samples exhibited remarkable enhancements in both adsorption and photocatalytic performance compared to pure CQD and NCN samples. In an optimization study, a best NCN@CQ photocatalyst was identified, showing a 40 % enhancement of photocatalytic efficiency compared to the use of NCN alone. A visible light photocatalytic activity of 91 % can be attained within 150 min, exhibiting a reaction rate constant of 0.0135 min−1 toward RhB decomposition, which was double as for the individual NCN (0.0067 min−1). The boosted photocatalytic activity resulting from the synergistic effect between NCNs and CQDs can be attributed to the efficient function of CQD as an electron acceptor. The proposed mechanism of photocatalytic degradation of RhB is illustrated in detail.

The Synthesis of Ag/TiO2 via the DC Magnetron Sputtering Method and Its Application in the Photocatalytic Degradation of Methyl Orange in Na2SO4 Solution

TiO2 and TiO2 films modified with Ag (Ag/TiO2) were prepared via the DC magnetron sputtering method and the degree of modification was controlled via the sputtering power and time of Ag. The microstructures and properties of these films were characterized using field emission scanning electron microscopy, X-ray diffractometry, ultraviolet–visible diffuse reflectance spectrometry, atomic force microscopy, and X-ray photoelectron spectroscopy (XPS). The results show that the prepared films have an anatase structure. Compared with pure TiO2, Ag deposition can improve the utilization of light. The three-dimensional images of Ag/TiO2 clearly show that with the increase in Ag sputtering power and sputtering time, Ag particles on the surface of the film gradually increase, and the structure of the film is relatively dense. The photocatalytic effect of Ag/TiO2 films is the best when the Ag sputtering power is 5 W and the sputtering time is 50 s. Under high-pressure mercury lamp irradiation, the photocatalytic degradation rate of methyl orange (MO) in pure MO solution with Ag/TiO2-5 W-50 s can reach 100% within 55 min, whereas that in MO-Na2SO4 mixed solution can reach 99.55% within 65 min. The results suggest that the presence of Na2SO4 in MO solution can inhibit the degradation of MO using Ag/TiO2, the result of XPS suggests that Na2SO4 accelerates the oxidation of Ag, which may lead to an increase in the recombination rate of photogenerated electron–hole pairs and a decrease in the degradation rate. During the process of recycling photocatalysts, the degradation rate of MO was apparently reduced. A possible reason is that the Ag particles have been oxidized and products of photocatalytic degradation are on the surface of the photocatalyst. The photocatalytic degradation mechanism was studied.

A novel dual S-scheme heterojunction photocatalyst KBCN/t-BiVO4/m-BiVO4 induced by phase-transformed bismuth vanadate for highly efficient degradation of ciprofloxacin in full-spectrum: Degradation pathway, DFT calculation and mechanism insight

A novel KBr-g-C3N4/t-BiVO4/m-BiVO4 (15KBCN/mtBVO-P, P means PVP) heterojunction photocatalyst is synthesized using a hydrothermal method with the assistance of surfactant polyvinylpyrrolidone (PVP). Field emission scanning electron microscope (FESEM), transmission electron microscope (TEM), and X-ray powder diffraction (XRD) confirm the formation of the heterostructure and changes in the crystal structure. Under sunlight illumination, 15KBCN/mtBVO-P exhibits the strongest photocatalytic degradation performance for ciprofloxacin (CIP), reaching 95.3 % within 240 min, the apparent kinetic constant is approximately 3.4, 2.4, and 3.3 times higher than CN, t-BVO, and m-BVO. The outstanding CIP degradation rate is observed under simulated solar and visible light, with over 93.0 % and 85.8 % in 60 min and 120 min. The enhanced photocatalytic performance is attributed to the in-situ generation of the mixed-phase BiVO4 by precise crystal phase regulation. Furthermore, the charge transport and photocatalytic degradation mechanism of 15KBCN/mtBVO-P is revealed. Degradation pathways and ecotoxicity of CIP and its degradation products were elucidated through LC-MS/MS technology, DFT calculations, and QSAR models. This study presents a pioneering perspective on the fabrication and development of g-C3N4-based dual S-scheme heterojunction photocatalysts for practical application.

Photocatalytic treatment of organic dyes using metal oxides and nanocomposites: A quantitative study

Abstract This comprehensive and quantitative research offers a thorough analysis of how metal oxides and nanocomposites are used in the photocatalytic treatment of organic dyes. It explores the challenges and opportunities of employing photocatalytic conversion technologies, discussing the optimal conditions for efficient degradation. The mechanisms of photocatalytic degradation are elucidated, highlighting the steps involved in transforming organic dyes into harmless by-products. Additionally, the article examines the factors that enhance the overall efficiency of photocatalytic conversion and compares its cost-effectiveness to other treatment methods. Various photocatalysts, with a focus on metal oxides and nanocomposites, are analyzed in terms of their advantages and limitations in degrading organic dyes. This article serves as a valuable resource for researchers and practitioners seeking sustainable and economical wastewater treatment solutions through efficient and eco-friendly photocatalytic approaches.

Preparation, characterization and photocatalytic studies of defect pyrochlore, KMn0·33Te1·67O6 and its composite with g-C3N4

Skeletal materials belonging to the defect pyrochlore family have been the subject of considerable interest due to their remarkable properties. In this work, a highly efficient, stable and visible light active composite photocatalytic system consisting of defect pyrochlore of composition KMn0·33Te1·67O6 (KMnTeO) and g-C3N4 (g-CN) has been successfully prepared by simple physical mixing of pre-prepared KMnTeO and g-CN components synthesized in solid state and thermal treatment of low-cost melamine, respectively. Structural, morphological and optical properties of as-prepared catalysts were deduced from powder X-ray Diffraction (XRD), Fourier Transform Infrared (FT-IR), Raman, Field Emission Scanning Electron Microscopy-Energy Dispersive X-ray Spectroscopy (FESEM-EDX), Transmission Electron Microscopy-High Resolution Transmission Electron Microscopy (TEM-HRTEM), Ultraviolet–Visible Diffuse Reflectance Spectroscopy (UV–Vis DRS), X-ray Photoelectron Spectroscopy (XPS) and Photoluminescence (PL) measurements. The lattice parameter “a” of parent KMnTeO was obtained from Rietveld refinement of its powder XRD pattern. The FT-IR and Raman spectra of KMnTeO gave characteristic bands belonging to the defect pyrochlore structure. The photocatalytic activities of KMnTeO and composite KMnTeO-g-CN were evaluated by the degradation of methylene blue (MB). Scavenger experiments were carried out to identify the reactive species responsible for the degradation of MB. Furthermore, the reusability and stability of the photocatalysts were explored. The probable photocatalytic mechanism for MB degradation over the composite KMnTeO-g-CN was surmised according to the scavenger experiments. The work provides a new approach for the development of novel defect pyrochlore based composite photocatalysts to treat industrial wastewater containing organic pollutants.

Direct Z-scheme charge transfer Bi2O3/UiO-66-NH2 heterojunctions for boosted photocatalytic degradation of tetracycline hydrochloride in different water systems

The development of hybrid heterostructure photocatalysts with enhanced visible light absorption capacity holds significant importance in environmental remediation. However, the challenge persists in exploiting strong visible-light responsive photocatalysts with both high efficiency and stability. Herein, we successfully synthesized a hybrid Z-scheme heterojunction of Bi2O3 and UiO-66-NH2 (Bi2O3/UiO-66-NH2) through a simple hydrothermal route. The visible light photocatalytic performance of Z-scheme Bi2O3/UiO-66-NH2 heterojunction is systematically evaluated for persistent antibiotic tetracycline hydrochloride (TC-HCl) both in the clean and real water matrix. All heterojunction catalysts exhibit superior photodegradation capabilities compared to pristine Bi2O3 and UiO-66-NH2. The optimal ratio of the two components heterojunction (BUN-150), in particular, demonstrates the highest removal efficiencies for TC-HCl (95 %) within a 90-min timeframe. This remarkable photocatalytic performance is credited to the Z-scheme charge transfer occurring at the interface of Bi2O3 and UiO-66-NH2 in Bi2O3/UiO-66-NH2 heterojunction. The active species experiments and electron paramagnetic resonance analyses are conducted to identify the active reactive species during the TC-HCl degradation (·OH, h+, and ·O2−), and a precise photocatalytic degradation mechanism is explained. Additionally, the photodegradation intermediates of TC-HCl are detected using the HPLC-MS analysis to explain the degradation pathways of TC-HCl. This research paves the way for the development of novel Z-scheme Bi2O3-based heterojunction catalysts for outstanding photocatalytic applications.

Efficient photodegradation of antibiotics by g-C3N4 and 3D flower-like Bi2WO6 perovskite structure: Insights into the preparation, evaluation, and potential mechanism

Antibiotics are emerging organic pollutants that have attracted huge attention owing to their abundant use and associated ecological threats. The aim of this study is to develop and use photocatalysts to degrade antibiotics, including tetracycline (TC), ciprofloxacin (CIP), and amoxicillin (AMOX). Therefore, a novel Z-scheme heterojunction composite of g-C3N4 (gCN) and 3D flower-like Bi2WO6 (BW) perovskite structure was designed and developed, namely Bi2WO6/g-C3N4 (BW/gCN), which can degrade low-concentration of antibiotics in aquatic environments under visible light. According to the Density Functional Theory (DFT) calculation and the characterization results of X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FITR), Scanning electron microscopy - energy spectroscopy (SEM-EDS) and X-ray photoelectron spectroscopy (XPS), this heterojunction was formed in the recombination process. Furthermore, the results of 15 wt%-BW/gCN photocatalytic experiments showed that the photodegradation rates (Rp) of TC, CIP, and AMOX were 92.4%, 90.1% and 82.3%, respectively, with good stability in three-cycle photocatalytic experiments. Finally, the quenching experiment of free radicals showed that the holes (h+) and superoxide radicals (·O2−) play a more important role than the hydroxyl radicals (·OH) in photocatalysis. In addition, a possible antibiotic degradation pathway was hypothesized on the basis of High performance liquid chromatography (HPLC) analysis. In general, we have developed an effective catalyst for photocatalytic degradation of antibiotic pollutants and analyzed its photocatalytic degradation mechanism, which provides new ideas for follow-up research and expands its application in the field of antibiotic composite pollution prevention and control.

Hydrothermal preparation of magnetic recyclable In-doped MoO3/SrFe12O19 ternary nanocomposites with enhanced visible-light-driven photocatalytic performance

SrFe12O19 as a novel magnetic matrix has drawn increasing attention in photocatalysis. In the current study, a novel magnetically recoverable In-MoO3/SrFe12O19 ternary composite photocatalyst was fabricated with the hydrothermal method, and the photocatalytic activity was evaluated by degrading rhodamine B (RhB) solution through simulated solar irradiation. The results demonstrated that the outstanding degradation rate of RhB (96.5%) could be achieved within 70 min when the mass ratio of both doped In and SrFe12O19 in the ternary composite photocatalyst was 5% (5-IMS-5). The enhancement of the photocatalytic degradation performance was mainly related to the self-sensitization of RhB, the magnetic field effect of SrFe12O19, and the introduction of impurity energy levels by In doping. More importantly, the degradation rate of RhB by 5-IMS-5 was still up to 90.8% after 4 times of recycling, verifying that the prepared ternary composite sample has good recyclability and stability. This study proves a novel ternary composite photocatalyst that can be used for organic wastewater treatment, and its photocatalytic degradation mechanism provides great reference significance for the synthesis of other SrFe12O19-based magnetic semiconductor photocatalysts.

S-scheme Bi/Bi2WO6/TiO2 nanofiber photocatalyst for efficient degradation of sulfamethoxazole

Improving the efficiency of photogenerated carrier separation by designing heterojunction photocatalysts remains an important challenge. In this study, TiO2 nanofibers were prepared by electrospinning, Bi/Bi2WO6/TiO2 heterojunctions were constructed by hydrothermal method, and verified by characterization techniques. The heterojunction had good photodegradation activity to sulfamethoxazole (SMX) under ultraviolet and visible light irradiation (96.4 % within 60 min). The enhanced photodegradation activity of Bi/Bi2WO6/TiO2 nanocomposites can be attributed to the synergistic effect of S-Scheme mechanism and Bi metal plasma action. In addition, Bi metals can generate a large number of electron-hole pairs under the action of surface plasmon resonance (SPR). In addition, the influence factors such as pH, SMX concentration and catalyst loading were studied. According to the detected intermediates, the photocatalytic degradation pathway of SMX was studied. The results of free radical capture experiment and ESR show that ·O2– and h+ free radicals play an important role in the decomposition of SMX. The cyclic experiments show that Bi/Bi2WO6/TiO2 nanocomposites have excellent stability and reuse characteristics. Finally, the mechanism of photocatalytic degradation of SMX was described. This study provides a promising perspective for the preparation and development of S-Scheme heterojunction photocatalysts based on Bi2WO6.

Ti-MOG derived TiO2 facet heterojunction rich in C/Ti3+/Ov for adsorption-photocatalytic removal of pharmaceutical pollutants from water

Developing efficient, stable, and broad-spectrum responsive photocatalysts is an effective way to degrade pharmaceutical pollutants in water. In this work, using concentrated hydrochloric acid (HCl) as a modulator, titanium metal–organic gel (Ti-MOG) was prepared and used as a template for calcination in air to obtain anatase TiO2 facet heterojunction rich in C/Ti3+/oxygen vacancy (Ov) (MOG-TiO2), which has a hierarchical porous structure, large specific surface area, and highly dispersed active site. Compared to P25, P25 + C and MIL-125(Ti) derived TiO2 (MOF-TiO2), MOG-TiO2 exhibited obviously enhanced adsorption-photocatalytic performance for tetracycline (TC) and low concentrations ethenzamide (ETH) under broad-spectrum light irradiation. The photocatalytic degradation efficiency of ETH by MOG-TiO2 reached 92.8, 100 and 98.7 % within 240, 60 and 6 min under Vis, UV and VUV light illumination, respectively, which were much higher than those of P25 (62.7, 33.2 and 73.0 %), P25 + C (61.7, 31.2 and 72.5 %) and MOF-TiO2 (79.2, 86.8 and 88.7 %). Furthermore, concentrated HCl promoted the formation of Ti3+/Ov in MOG-TiO2, which was conducive to the improvement of its photocatalytic performance. MOG-TiO2 also displayed great adsorption-photocatalytic stability and reusability. Moreover, the biotoxicity of TC toward E. coli DH5a obviously decreased after photocatalytic degradation. Based on the TiO2 facet heterojunction rich in C/Ti3+/Ov and the generation of hole, hydroxyl radicals, and superoxide radicals, the possible photocatalytic degradation mechanism of MOG-TiO2 was proposed. Overall, this work provides insights into constructing a novel hierarchical porous carbon-doped facet heterojunction photocatalyst for efficient pharmaceutical contaminants removal.

Construction of coordination polymer [Ni(ppda) (tib) (H2O)]·H2O and photocatalytic degradation of indigo carmine

Semiconductor coordination polymers have garnered significant attention as photocatalysts for wastewater treatment owing to their adaptable structure, expansive specific surface area, and outstanding selectivity, stability, and sensitivity. In this study, coordination polymer [Ni(ppda) (tib) (H2O)]·H2O was synthesized utilizing flexible phenyldiacetic acid (H2ppda) and rigid 1,3,5-tris(1-imidazolyl)benzene (tib). Crystal structure analysis revealed that the three-linked tib ligands and the central Ni(II) ion create a wavy 2D surface. Additionally, cis-ppda2- ligands form a 1D wave chain alongside central Ni(II), which traverse through a 2D layer. Adjacent layers are interlaced via ppda2−, resulting in a complex 3D supramolecular structure. The fundamental framework of [Ni(ppda) (tib) (H2O)]·H2O exhibits stability up to 316 °C and remains stable over 5 cycles, with a band gap energy of 2.9 eV, rendering it a viable candidate for catalytic applications. In aqueous systems, [Ni(ppda) (tib) (H2O)]·H2O demonstrates efficient photocatalytic degradation of Indigo Carmine (IC), achieving a degradation rate of 98.5% and a reaction rate of 0.027 min−1, showcasing commendable selectivity and semiconductor properties. The primary photocatalytic degradation mechanism involves the synergistic formation of ·OH and ·O2- active species through the interaction between [Ni(ppda) (tib) (H2O)]·H2O and H2O2, facilitating the oxidative degradation of dye molecules.

Synthesis of Ag2ZnGeO4/g-C3N4 binary heterostructure: A Z-scheme heterojunction photocatalyst for enhanced tetracycline degradation under visible light

Accumulation of tetracycline was hazardous to human health and ecosystems. Ag2ZnGeO4/g-C3N4 heterojunction photocatalysts were successfully prepared by the wet impregnation method. The morphological structure and optical properties of the photocatalysts were measured by a series of characterization methods. Moreover, Ag2ZnGeO4/g-C3N4 with a loading ratio of 20 % exhibited excellent photocatalytic activity by exploring the Ag2ZnGeO4 loading, catalyst dosage, initial concentration, and initial pH of tetracycline. The degradation efficiency of 20 % Ag2ZnGeO4/g-C3N4 for 10 mg/L TC was 94.29 % at 0.2 g/L catalyst dosage, and the corresponding first-order reaction rate constant reached a maximum of 0.0199 min−1. In addition, according to the results of the trapping experiments, superoxide anion radical was the major active species. Eventually, a possible Z-scheme of the photocatalytic degradation mechanism was proposed. The heterojunction formed between Ag2ZnGeO4 and g-C3N4 could accelerate the transfer and separation of photogenerated carriers, enhancing the photocatalytic activity.

Bi-Doped and Bi Nanoparticles Loaded CeO2 Derived from Ce-MOF for Photocatalytic Degradation of Formaldehyde Gas and Tetracycline Hydrochloride.

Bi/CeO2 (BC-x) photocatalysts are successfully prepared by solvothermal loading Bi nanoparticles and Bi-doped CeO2 derived by Ce-MOF (Ce-BTC). Formaldehyde gas (HCHO) and tetracycline hydrochloride (HTC) are used to evaluate the photocatalytic activity of the synthesized Bi/CeO2. For BC-1000 photocatalyst, the degradation of HTC by 420nm < λ < 780nm light reaches 91.89% for 90min, and HCHO by 350nm < λ < 780nm light reaches 94.66% for 120min. The photocatalytic cycle experiments prove that BC-1000 has good cyclic stability and repeatability. The results of photoluminescence spectra, fluorescence lifetime, photocurrent response, and electrochemical impedance spectroscopy showed that the SPR (Surface Plasmon Resonance) effect of Bi nanoparticles acted as a bridge and promoted electron transfer and enhanced the response-ability of Bi/CeO2 to visible light. Bi-doping produced more oxygen vacancies to provide adsorption sites for adsorbing oxygen and generated more ·O2 - thus promoting photocatalytic reactions. The mechanism of photocatalytic degradation is analyzed in detail utilizing active free radical capture experiments and electron paramagnetic resonance (EPR) characterization. The experimental results indicate that ·O2 - and h+ active free radicals significantly promote the degradation of pollutants.

Construction of AgI/PCN-224 Z-scheme heterojunction for efficient photocatalytic degradation of tetracycline hydrochloride: Pathways, mechanism and theoretical calculations

The construction of heterojunction structures is pivotal in enhancing carrier separation and photocatalytic activity. Hence, AgI/PCN-224 (APN-x composites) Z-scheme heterojunctions were successfully synthesised using an in-situ precipitation method. The direction of electron migration and the band structures of APN-x were comprehensively investigated using a combination of experimental approaches and density functional theory (DFT) calculations. Owing to the extensive visible-light absorption capabilities of PCN-224 and the high efficiency of photogenerated carrier separation in the Z-scheme heterojunction, the optimally developed APN-3 photocatalyst demonstrated exceptional photodegradation efficiency for tetracycline hydrochloride (TCH). The removal rate of TCH by APN-3 within 120 min reached 91.56%, approximately 4.64 times higher than that achieved by pure AgI. The photocatalytic degradation mechanism was explored using free radical trapping experiments, electron spin resonance (ESR) technology and band structure analysis. Degradation pathways and intermediate products were investigated using liquid chromatography–tandem mass spectrometry (LC–MS).

Basic magnesium sulfate@TiO2 composite for efficient adsorption and photocatalytic degradation of 4-dodecylmorpholine in brine

More than 70% of the potash fertilizer globally is produced by the froth flotation process, in which 4-dodecylmorpholine (DMP) serves as a reverse flotation agent. As the potash fertilizer production rapidly rises, the increased DMP levels in discharged brine pose a threat to the production of high-value chemicals. In this paper, composite particles of basic magnesium sulfate@TiO2 (BMS@TiO2) were prepared using a simple and mild loading method. These particles were utilized for the adsorption and photocatalytic degradation of DMP in brine. Compared with normal powdered materials, the granular BMS@TiO2 in this study can be easily separated from liquid, and the degradation intermediates will not enter the brine without causing secondary pollution. BMS@TiO2 consists of 5·1·7 phase (5Mg(OH)2·MgSO4·7H2O) whisker clusters embedding 2.3% TiO2. The adsorption equilibrium of DMP on BMS@TiO2 particles was achieved through hydrogen bonding and pore interception with the adsorption capacity of approximately 5 mg g−1 after 6 h. The photodegradation efficiency of DMP adsorbed on BMS@TiO2 reached about 92% within 16 h, which is compared with that of pure TiO2 nanoparticles. Additionally, excellent stability and recyclability of BMS@TiO2 were also observed in five cycle tests of adsorption and photocatalytic degradation of DMP, and the possible photocatalytic degradation pathways and mechanism of DMP are proposed following molecular electrostatic potential analysis. This work provides a sustainable and environmentally friendly approach for eliminating organic micropollutants from water environments.