Photocatalytic Degradation Pathway Research Articles

Bi2MoO6/ZnIn2S4 S-scheme heterojunction containing oxygen vacancies for photocatalytic degradation of organic pollutant

Photocatalytic removal of organic pollutants is a promising strategy to alleviate environmental pollution. In this study, S-scheme heterojunctions Bi2MoO6/ZnIn2S4 (BMO/ZIS) containing oxygen vacancies were synthesized by the solvothermal method. Oxygen vacancies improved the utilization of sunlight and accelerated the separation of charge carriers. The S-scheme charge transfer mechanism provided a channel for the directed migration of photogenerated charges. 10Bi2MoO6/ZnIn2S4 (10BMO/ZIS) efficiently degraded various organic pollutants with a small amount of photocatalyst (15 mg) under visible light irradiation. 10BMO/ZIS presented the highest RhB removal efficiency of 96.52 %, which was 7.02 and 3.67 times greater than Bi2MoO6 containing oxygen vacancies (BMO-Vo) and ZnIn2S4 (ZIS), respectively. Meanwhile, in various inorganic salt ion solutions, 10BMO/ZIS still exhibited high degradation performance. In addition, the photocatalytic degradation pathway was inferred, and the threat of degradation intermediates to the ecological environment was evaluated. This work contributes to a deeper understanding of the photocatalytic mechanisms of oxygen vacancy-modified heterojunction photocatalysts and offers insights for designing efficient environmental remediation photocatalysts.

Anchoring gadolinium oxide nanoparticles onto CuInZnS: Efficient photocatalytic tetracycline degradation and mechanism analysis

Photocatalysis technology is one of the potential methods to remit the growing issues of environmental pollution. It is of great significance to rationally design high performance antibiotic wastewater degradation catalysts in the whole pH range. In this experiment, Gd2O3 nanoparticles (GdO NPs) were successfully grown onto CuInZnS (CIZS) by a simple hydrothermal method. The introduction of GdO has obvious effects on the nanosheet thickness of CIZS, which reduces carrier transport distances and improves the active sites number of CIZS. What’s more, the SO4•- absorption and electron transfer ability are also greatly optimized. Under 300 W Xe light, tetracycline can be efficient degraded more than 93 % in the whole pH range, which presents absolute advantage compared to CIZS and GdO. Based on the combination of experimental characterization and density functional theory calculations, the proposed photocatalytic tetracycline degradation pathway and mechanism have been given. Moreover, the results of toxicity analysis proved that the CIZS-GdO catalyst could successfully reduce the toxicity of tetracycline wastewater. This work has reference value for the application of rare earth oxides in the field of photocatalysis at full pH range.

Insight into photocatalytic chlortetracycline degradation by WO3/AgI S-scheme heterojunction: DFT calculation, degradation pathway and electron transfer mechanism

The construction of S-scheme heterojunction with excellent redox ability holds promising prospects for photocatalytic environment remediation. However, the rationally design of the heterojunction interface to achieve efficient charge transfer still faces challenges. In this study, we fabricated a tight-contacted S-scheme heterojunction by in situ anchoring AgI nanoparticles onto WO3 nanoplates. The significant difference in Fermi energy levels between WO3 and AgI results in the formation of a space charge region around the interface and bending of the energy band, facilitating directional migration and spatial separation of charge carriers. This contributes to enhanced generation of superoxide radicals (•O2−) and holes (h+) active species, leading to a significant increase in chlortetracycline (CTC) degradation rate. The apparent rate constant for CTC removal using the WO3/AgI (WA-2) is approximately 15 times higher than that observed for pure WO3. Furthermore, WA-2 exhibits universal degradation effects on tetracycline (TC) and oxytetracycline (OTC). Molecular dynamics (MD) simulation reveals the synergistic adsorption effect of WO3 and AgI on CTC and reactive oxygen species molecules. Based on Fukui function calculation of CTC molecules and degradation intermediates, liquid chromatography-mass spectrometry (LC-MS) analysis, photocatalytic degradation pathway over WO3/AgI was determined to be sequential demethylation followed by dechlorination and decarbonylation. These findings provide valuable insights into high-performance S-scheme heterojunctions interface design and elucidation of pollutant degradation mechanism.

Mechanistic insights into the reaction pathway for efficient cationic dye photocatalytic degradation and the importance of the enhanced charge isolation over dual Z-scheme CeO2/BiOCl/Ag2WO4 photocatalyst

Fabricating a multi-component heterojunction system with enhanced charge isolation efficacy remains challenging. A photoactive CeO2/BiOCl/Ag2WO4 heterojunction was successfully constructed using a co-precipitation technique to degrade crystal violet and methylene blue dyes. It was found through a combination of characterization and experiments that the dual Z-scheme system not only augmented the charge isolation and migration efficiency but also maintained superior redox ability with extended visible light absorption capacity. In the CeO2/BiOCl/Ag2WO4 system, 97 % of methylene blue and 98 % of crystal violet were degraded in 75 min using 50 mg/L of ternary photocatalyst. The rate of reaction of CeO2/BiOCl/Ag2WO4 for methylene blue (0.0445 min−1) and crystal violet (0.05053 min−1) exhibited a multi-fold increase in comparison to the bare photocatalysts. The electron spin resonance (ESR) analysis has remarkably identified hydroxyl and superoxide radicals (•OH, •O2−) as the primary reactive species in the photodegradation process. Liquid chromatography-mass spectrometry analysis was utilized to obtain potential degradation pathways for methylene blue and crystal violet, respectively. The dual charge transferal mechanism by the ternary photocatalyst resulted in a significant increase in photocatalytic activity. It provided new perspectives on the principles guiding the rational development of a multicomponent system for environmental remediation.

Efficient photocatalytic degradation of 24 imidazolium ionic liquids in an N-ZnO/simulated sunlight irradiation system and its mechanism

An efficient nitrogen (N)-ZnO photocatalytic composite was synthesized and well characterized to demonstrate its superior photocatalytic performance as well as the degradation kinetics of 24 ILs in an N-ZnO/Xe lamp irradiation system, as well as the pathways and mechanisms of the photocatalytic degradation (PCD) of typical ionic liquids [OMIm]Br was systematically studied. To investigate the catalytic effect, nitrogen was synthesized from various inorganic and organic nitrogen compounds to ZnO. The NH4NO3-ZnO composite calcined at 300 °C with a molar ratio of NH4NO3 to Zn(NO3)2·6H2O of 10:1 exhibited superior catalytic performance as assessed by SEM, TEM, FT-IR, UVDRS, BET surface area, XPS, and XRD characterizations. After 24 h of exposure to Xe lamp irradiation, all 24 ILs were significantly degraded by the introduction of 0.125 g/L of catalyst, whereas simulated sunlight alone resulted in minimal degradation. The pseudo-first-order rate coefficients (k) for PCD were closely related to the carbon chain length of the alkyl substituents and the type of anion. Multiple linear regression analysis indicated no linear correlation between the parameters E, H°, Eth, and Cv° from the Gaussian calculation and k. Conversely, a positive correlation was observed for EHOMO (B=0.742, β = 1.282, P = 0.011), qH+ (B=1.040, β = 3.284, P = 0.006), and G° (B=0.001, β = 5.400, P = 0.007) with k. Mass spectrometry analysis revealed that the primary PCD pathway for [OMIm]Br involved C-N and/or C-C bond breaking, mono-, di-, and tri-hydroxylation, single and double oxygen transfer, and bromo-substitution reactions.

Highly efficient photocatalytic degradation of rhodamine B by immobilizing CdS quantum dots on ZnCr-layered double hydroxide nanosheets

The removal of Rhodamine B (RhB), a commonly encountered cationic dye in heavily contaminated wastewater streams, from wastewater effluents presents a significant challenge. Herein, we focus on developing an innovative ternary nanocomposite of zinc oxide nanoparticles, quantum dots of cadmium sulfide (CdS QDs), and zinc-chromium carbonate layered double hydroxide nanosheets (ZnCr–CO3-LDH NSs) via a sonochemical synthesis route. The synthesized ternary nanocomposite, CdS QDs@ZnO/ZnCr–CO3-LDH referred to as CZC-LDH, exhibits remarkable photodegradation performance of rhodamine B (RhB) dye under UV-A radiation. A comprehensive investigation into the photocatalytic efficiency and characteristics of CZC-LDH was conducted using various analytical techniques, including XRD, FESEM, DRS, XPS, HR-TEM, PL, and BET (surface area analysis). Results indicate that CZC-LDH demonstrates superior photocatalytic efficiency, achieving 98.26 % degradation of RhB within 3-h only. Moreover, the influence of different scavengers on CZC-LDH photocatalytic efficiency was evaluated to elucidate the plausible RhB photocatalytic degradation pathway. The as-prepared CZC-LDH exhibits exceptional photocatalytic performance, stability, and reusability, positioning it as a promising candidate to previously reported photocatalysts in literature.

MOF-derived In2O3/TiO2 S-scheme heterojunction for efficient photocatalytic degradation of tetracycline

It is challenging to engineer a photocatalyst that can degrade antibiotics efficiently. We have successfully developed a series of photocatalysts by annealing In-MOF (BUT-205) with TiO2, namely (a) In2O3/TiO2-I, (b) In2O3/TiO2-II, and (c) In2O3/TiO2-III. These catalysts, particularly In2O3/TiO2-III, exhibited superior efficiency in degrading tetracycline (TC) under visible light. The enhanced photocatalytic performance of In2O3/TiO2-III can be attributed to the formed S-scheme heterojunction, which promoting the separation of electron-hole pairs. The S-scheme heterojunction was confirmed by XPS, in-situ XPS, UV–vis diffuse reflectance spectroscopy, and Mott-Schottky plot, etc. Compared to pure TiO2 and In2O3, the In2O3/TiO2-III demonstrated an 18-fold and 3-fold higher degradation rate constant (k). Various factors affecting the degradation of TC were investigated, including pollutant concentration, catalyst type, solution pH, catalyst dosage, inorganic anions, inorganic cations, and radical species. Photoluminescence (PL) and transient photocurrent density evaluate the separation rate of electron-hole pairs, and EPR experiments (active species trapping) studies confirmed •O2− and h+ as the primary entities in TC photodegradation by In2O3/TiO2-III. HPLC/MS analysis revealed the photocatalytic degradation pathway. The MOF-derived photocatalysts efficiency in TC photoreduction results from the formed S-scheme heterojunction, making it a promising candidate for environmental remediation.

Synthesis of double Z-type heterojunction AgI/Ag6Si2O7/BiOI photocatalyst for antibiotics degradation and weakening toxicity

A novel ternary photocatalyst of AgI/Ag6Si2O7/BiOI was successfully synthesized using the ultrasonic co-precipitation method. The ratio of Ag6Si2O7, AgI and BiOI in the composite were screened and the reaction conditions were optimized. Under the optimal reaction conditions, the AgI/Ag6Si2O7/BiOI-65 % (1/3AI/AS/BI-65 %) catalyst exhibited excellent performance in degrading 20 mg/L norfloxacin (NOR) with a removal rate of up to 92.96 % and the apparent rate constant (0.01241 min−1) was approximately 12.048, 27.578, 3.866 and 1.693 times as high as that of Ag6Si2O7, AgI, BiOI and AgI/Ag6Si2O7, respectively. Meanwhile, the 1/3AI/AS/BI-65 % catalyst showed good universality, salt resistance and recycling stability for antibiotics. Additionally, the toxicity of degraded NOR to wheat was significantly reduced. High-performance liquid chromatography-mass spectrometry (HPLC-MS), free radical trapping experiments and electron paramagnetic resonance (EPR) analysis were employed to deduce possible photocatalytic mechanisms and degradation pathways for NOR. The results indicate that the improved photocatalytic activity can be attributed to the formation of a double Z-type heterojunction in the 1/3AI/AS/BI-65 % which effectively promotes charge carrier separation and enhances the visible light absorption capacity. This study provides new insights into treating antibiotics in sewage using BiOI based heterojunction catalyst.

Enhanced degradation of E2/EE2 by BiPO4/AgI/BC composite photocatalysts via BC-enhanced ·O2-

This study presents the synthesis of highly active BiPO4/AgI/BC composite photocatalysts via a green, simple, and low-cost ambient temperature precipitation method. The electron transfer rate and visible-light responsiveness can be effectively enhanced by utilizing BiPO4 compounded with the semiconductor AgI, which has a narrow bandgap and good visible-light responsiveness. Additionally, the introduction of biocarbon (BC) enhances the absorption and separation of photogenerated electrons and holes under visible light. Notably, the synthesized BP-AgI0.6-BC5 % could remove 99.16 % and 99.7 % of EE2 and E2, respectively, at a concentration of 3 mg/L after 40 min of light exposure. The capture experiments and electron paramagnetic resonance spectroscopy reveal that the main active substance in the system is ·O2-, with BC playing a crucial role in enhancing the ·O2- concentration in the system. The findings from phytotoxicity and antimicrobial tests reveal that BP-AgI0.6-BC5 % can efficiently degrade pollutants, producing degradation products that are substantially less toxic than the original pollutants. Moreover, it can remove more than 99.99 % of E. coli under both dark and light conditions, demonstrating excellent antimicrobial performance. Additionally, the photocatalytic mechanism and degradation pathway were examined in this study. Notably, the composite photocatalysts synthesized in this study achieved efficient degradation of EE2 and E2 under visible light conditions while exhibiting efficient bactericidal function. Furthermore, the room-temperature preparation method is conducive to industrial-scale production, highlighting a better prospect for practical applications.

Enhanced synergistic removal of tetracycline and uranium in wastewater using Defective-Enriched S-scheme hollow dodecahedron K3PW12O40@WS2 heterojunction

In aquatic environments, the coexistence and interaction of multiple the pollutants complicate remediation process. This study focuses on developing a defective-enriched S-scheme heterojunction of K3PW12O40@WS2 (KPW@WS2) with hollow structure for the simultaneous removal of tetracycline (TC) and hexavalent uranium (U(VI)) in wastewater. The internal electric field (IEF) within this heterojunction plays a crucial role in efficiently separating photo-generated carriers, creating high reduction and oxidation active sites. The band structure and optical properties suggest that WS2-Vs have a narrower band gap energy compared to conventional WS2, leading to improved charge carrier separation and transfer rates. Density functional theory (DFT) calculations support the reduced recombination of electron-hole pairs in WS2-Vs due to the presence of S vacancies. Experimental results reveal a synergistic effect between the removal of TC and U(VI), with a significant increase in the reaction rate constant for the reduction of U(VI) to 0.0426 min−1, 1.6 times higher than in a single U(VI) reduction system. Additionally, the reaction rate constant for the oxidation of TC also rises from 0.0573 to 0.0729 min−1. The study also delves into the photocatalytic mechanism, degradation pathways, and intermediate products. Overall, this research offers an innovative strategy for simultaneous pollutant removal and optimizing photocatalytic redox reactions to enhance solar energy utilization.

Halogen-functionalized covalent organic frameworks for photocatalytic Cr(VI) reduction under visible light

Covalent organic frameworks (COFs) are a type of novel organic catalysts which show great potential in the treatment of environmental contaminations. Herein, we synthesized three isoreticular halogen-functionalized (F, Cl and Br) porphyrin COFs for visible-light (420 nm ≤ λ ≤ 780 nm) photocatalytic reduction of Cr(VI) to Cr(III). Halogen substituents with tunable electronegativity can regulate the band structure and modulate the charge carrier kinetics of COFs. In the absence of any sacrificial reagent, the isoreticular COFs exhibited good photocatalytic reduction activity of Cr(VI). Particularly, the TAPP-2F showed nearly 100 % conversion efficiency and the highest reaction rate constants (k) on account of the strong electronegativity of F substituent. Experimental results and theoretical calculations showed that the conduction band (CB) potentials of COFs became more negative and charge carrier separation increased with the enhancement of electronegativity (Br < Cl < F), which could provide sufficient driving force for the photoreduction of Cr(VI) to Cr(III). The halogen substituents strategy for regulating the electronic structure of COFs can provide opportunities for designing efficient photocatalysts for environmental remediation. Meanwhile, the mechanistic insights reported in this study help to understand the photocatalytic degradation pathways of heavy metals.

Rice hull-derived biochar with photocatalytic activity for efficient degradation of oxytetracycline in water under sunlight

Photocatalytic degradation is an effective strategy for the removal of environmental pollutants. However, the development of low-cost and high-efficiency photocatalysts continues to present a significant challenge. This work reported the fabrication of a composite photocatalyst directly from waste biomass (rice hulls) in a single step, which efficiently degraded oxytetracycline (OTCs) under sunlight. The morphology, microstructures and photoelectric features of the fabricated materials were subjected to comprehensive investigation using characterization techniques. The results found that the improved photocatalytic activity in sunlight was attributed to the complexation of rice hull-derived biochar and nano-ZnO generated in the preparation, which exhibited favourable adsorption, conductivity characteristics and small bandgap. The photocatalytic efficiency was observed to reach 72.6 % in 120 min under the irradiation of a 100 W xenon lamp. The effect of natural waters, degradation kinetics and degradation TOC analysis were also examined. The dominant agent responsible for the degradation of OTCs was the •O2− radical. Furthermore, the principal photocatalytic degradation pathway of OTCs was identified with the assistance of UHPLC/MS.

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.

Photocatalytic degradation of p-aminobenzoic acid on N-biomass charcoal etched with Fe-Al-bilayer hydroxide: New insights through spectroscopic investigation

We investigated the photocatalytic property of etched iron‑aluminum layered double hydroxide (LDH) composites using urea-modified biochar (N-BC) carrier to degrade para-aminobenzoic acid (PABA), a refractory organic pollutant. The prepared FeAl-LDH@FeSx-N-BC composite exhibited excellent photocatalytic performance, attributed to the enhanced photogenerated charge-carrier separation by the etched LDH and the improved comparative surface areas by the doped N-BC. The composite photocatalytically degraded 96 % of PABA. The performance was affected by solute concentration, pH and photocatalyst dose. Adding p-benzoquinone and EDTA-2Na significantly decreased the degradation rate, suggesting that superoxide radicals and holes were co-involved in PABA degradation. The excellent PABA removal efficiency was consistent for three consecutive runs. The samples' reactive oxygen species was confirmed, as electron paramagnetic reverberation explained the photodegradation mechanism. Under xenon lamp irradiation, two PABA photocatalytic degradation pathways were proposed using Liquid Chromatograph Mass Spectrometer (LCMS) and density functional theory. As expected, FeAl-LDH@FeSx-N-BC showed excellent photocatalytic performance, expanding a new direction and possibility for future photocatalytic treatment of water pollutants.

Resource utilization of MSWI fly ash supporting TiO2/BiOCl nanocomposite for enhanced photocatalytic degradation of sodium isopropyl xanthate: Mechanism and performance evaluation

The removal of organic pollutants in water environments and the resource utilization of solid waste are two pressing issues around the world. Facing the increasing pollution induced by discharge of mining effluents containing sodium isopropyl xanthate (SIPX), in this work, municipal solid waste incineration fly ash (MSWI FA) was pretreated by hydrothermal method to produce stabilized FA, which was then innovatively used as support for the construction of FA/TiO2/BiOCl nanocomposite (FTB) with promoted photocatalytic activity under visible light and natural sunlight. When the content of FA was 20 wt% and the mass ratio of TiO2 to BiOCl was 4:6, a remarkable performance for the optimal FTB (20-FTB-2) was achieved. Characterizations demonstrated that TiO2 and BiOCl uniformly dispersed on FA contributing to high surface area and broad light adsorption of FTB, which exhibits excellent adsorption capacity and light response ability. Build in electric field formed in the interface of TiO2/BiOCl heterojunction revealed by density functional theory calculations accelerated the separation of photoinduced e− and h+, leading to high efficiency for SIPX degradation. The synergetic effect combined with adsorption and photocatalytic degradation endowed 20-FTB-2 superior SIPX removal efficiency over 99% within 30 min under visible light and natural sunlight irradiation. The photocatalytic degradation pathways of SIPX were determined through theoretical calculations and characterizations, and the toxic byproduct CS2 was effectively eliminated through oxidation of •O2−. For 20-FTB-2, reusability of photocatalyst was showed by cycle tests, also the concentrations of main heavy metals (Pb, Zn, Cu, Cr, and Cd) in the liquid phases released during photocatalyst preparation process (< 1 mg/L) and photodegradation process (< 8.5 μg/L) proved the satisfactory stability with low toxicity. This work proposed a novel strategy to develop efficient and stable support-based photocatalysts by utilizing MSWI FA and realize its resource utilization.

Synthesis of CuO, ZnO nanoparticles, and CuO-ZnO nanocomposite for enhanced photocatalytic degradation of Rhodamine B: a comparative study

Water pollution, arising from the presence of toxic dyes and chemicals, is a global challenge, urging the need for eco-friendly solutions in water decontamination. This study focused on the synthesis of copper oxide nanoparticles (CuO NPs), zinc oxide nanoparticles (ZnO NPs), and a bimetallic CuO-ZnO nanocomposite (CZ NC) through an environmentally friendly method employing Tragia involucrata L. leaf extract. Comprehensive analysis of structural and optical properties involved using various analytical techniques such as XRD, FT-IR, XPS, UV-DRS, PL, FE-SEM, EDAX, TEM, SAED, zeta potential, TGA, and BET. In comparison to pristine CuO and ZnO NPs, the CZ-NC demonstrated notably enhanced photocatalytic activity in the degradation of Rhodamine B dye (RhB). The optimum conditions for RhB degradation were found to be a pH of 9 and a catalyst dosage of 1 mg/mL for a concentration of 10 ppm. Under these conditions, CuO NPs, ZnO NPs, and CZ-NC demonstrated high efficiencies of 78%, 83%, and 96.1% respectively over 105 min. Through LC-HRMS, the identification of degradation products offered valuable insights into the pathway of photocatalytic degradation. Furthermore, toxicity analysis of intermediates, conducted through ECOSAR software, indicated the formation of non-toxic by-products (ChV/LC50/EC50 > 100) after the completion of the reaction. Furthermore, the recycled catalysts exhibited sustained stability for up to 4 cycles, with only a minor decrease in activity of up to 6.8%. This confirms their catalytic efficacy in purifying polluted water. This research significantly contributes to the progress of environmentally friendly nanocomposites, enhancing their efficacy in the realm of environmental remediation.

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.

One-pot vanadium-based organic frameworks for DEHP effective removal: Relationships between the synthetic strategy, characterization, adsorption and solar-driven photocatalytic activity

Metal-organic frameworks (MOFs) are promising photocatalysts, yet the incorporation of vanadium into MOFs is prospective to achieve broad visible-light response, functionalized and topography-selective photocatalysts. Herein, we developed a series of self-assembly and template-free vanadium-based frameworks (V-MOFs) via a one-pot synthesis method accelerating the efficient adsorption and solar-driven photocatalytic degradation of DEHP, where V ions were immobilized by -COO groups to form various favorable configurations and the monodispersed transient V3+/V4+/V5+ centers served as active sites facilitating the separation of photogenerated charges. The advantageous photoelectron leaping capability, electron-hole lifetime and catalytic active sites of the synthesized V-MOFs were verified. The Mantel test analysis was applied to obtain the optimal synthetic route by exploring the correlation among the synthesis factors, V-MOFs’ characterization, and DEHP adsorption-degradation properties, the resultant V1-BDA@ and V1-H3BTB@ exhibited outstanding photocatalytic degradation and adsorption performances with a total DEHP (20 ppm) removal rate of 98 % in 240 min. The effective attack sites on DEHP were explained by Fukui function, and the photocatalytic degradation pathway of DEHP by V1-H3BTB@ was furtherly revealed.

SU-101 for the removal of pharmaceutical active compounds by the combination of adsorption/photocatalytic processes

Pharmaceutical active compounds (PhACs) are some of the most recalcitrant water pollutants causing undesired environmental and human effects. In absence of adapted decontamination technologies, there is an urgent need to develop efficient and sustainable alternatives for water remediation. Metal–organic frameworks (MOFs) have recently emerged as promising candidates for adsorbing contaminants as well as providing photoactive sites, as they possess exceptional porosity and chemical versatility. To date, the reported studies using MOFs in water remediation have been mainly focused on the removal of a single type of PhACs and rarely on the combined elimination of PhACs mixtures. Herein, the eco-friendly bismuth-based MOF, SU-101, has been originally proposed as an efficient adsorbent-photocatalyst for the elimination of a mixture of three challenging persistent PhACs, frequently detected in wastewater and surface water in ng L−1 to mg·L−1 concentrations: the antibiotic sulfamethazine (SMT), the anti-inflammatory diclofenac (DCF), and the antihypertensive atenolol (At). Adsorption experiments of the mixture revealed that SU-101 exhibited a great adsorption capacity towards At, resulting in an almost complete removal (94.1 ± 0.8% for combined adsorption) in only 5 h. Also, SU-101 demonstrated a remarkable photocatalytic activity under visible light to simultaneously degrade DCF and SMT (99.6 ± 0.4% and 89.2 ± 1.4%, respectively). In addition, MOF-contaminant interactions, the photocatalytic mechanism and degradation pathways were investigated, also assessing the toxicity of the resulting degradation products. Even further, recycling and regeneration studies were performed, demonstrating its efficient reuse for 4 consecutive cycles without further treatment, and its subsequent successful regeneration by simply washing the material with a NaCl solution.

Innovative ternary composite photocatalyst: BiOCl/Bi12O17Cl2/Bi2O3 for sustainable water remediation

The presence of pollutants in aquatic environments is causing severe health effects on both humans and animals. To address this issue, it has become crucial to develop more efficient and environmentally friendly photocatalysts for the removal of persistent pollutant mixtures from water. In this context, photocatalysts containing more than two bismuth-based materials have rarely been explored for water remediation. With this in mind, we propose an innovative ternary composite, BiOCl-1/Bi12O17Cl2/Bi2O3, as a potentially sustainable visible light-active photocatalyst. Firstly, bismuth oxychloride has been prepared in the presence of ionic liquid, leading to the formation of BiOCl-1 with highly reactive {110} facets. Subsequently, the construction of the ternary composite has been accomplished using a facile and soft hydrothermal approach. The as-prepared BiOCl-1/Bi12O17Cl2/Bi2O3 composite has been successfully used in degrading binary mixtures of contaminants (i.e. ciprofloxacin, methylparaben or methyl orange), achieving an improved visible-light photocatalytic activity compared to single BiOCl-1 and other previously reported bismuth-based photocatalysts. In addition, the photocatalytic mechanism and degradation pathways have been elucidated through scavenger and electrochemical experiments, as well as chromatography-mass spectrometry (LC-MS) analysis, respectively.