Degradation Of Pollutants Research Articles

Multifunctional, Novel Zinc-Pyrrole Polymeric MOF as Free Standing, Binder Free Supercapacitor Electrode and Photocatalyst for Organic Pollutant Degradation

Multifunctional, Novel Zinc-Pyrrole Polymeric MOF as Free Standing, Binder Free Supercapacitor Electrode and Photocatalyst for Organic Pollutant Degradation

Review of Bio-Inspired Green Synthesis of Titanium Dioxide for Photocatalytic Applications

Titanium dioxide (TiO2) is an important photocatalyst that is widely studied for environmental applications, especially for water treatment by degradation of pollutants. A range of methods have been developed to produce TiO2 in the form of nanoparticles and thin films. Solution-based synthesis methods offer the opportunity to tune the synthesis through a choice of reagents, additives and reaction media. In particular, the use of biomolecules, such as proteins and amino acids, as bio-inspired additives in TiO2 synthesis has grown over the last decade. This review provides a discussion of the key factors in the solution-based synthesis of titania, with a focus on bio-inspired additives and their interaction with Ti precursors. In particular, the role of bio-inspired molecular and biomolecular additives in promoting the low-temperature synthesis of titania and controlling the phase and morphology of the synthesised TiO2 is discussed, with a particular focus on the interaction of TiO2 with amino acids as model bio-inspired additives. Understanding these interactions will help address the key challenges of obtaining the crystalline TiO2 phase at low temperatures, with fast kinetics and under mild reaction conditions. We review examples of photocatalytic applications of TiO2 synthesised using bio-inspired methods and discuss the ways in which bio-inspired additives enhance photocatalytic activity of TiO2 nanomaterials. Finally, we give a perspective of the current challenges in green synthesis of TiO2, and possible solutions based on multi-criteria discovery, design and manufacturing framework.

Rape straw biochar-assisted preparation of flower-like BiOCl with enriched oxygen vacancies for efficient photocatalytic CO2 reduction and pollutants degradation

Utilizing photocatalytic technology to transform CO2 into high added value chemical products has represented an effective strategy for alleviating the climate problems that have arisen due to excessive CO2 emissions. As a typical bismuth-based photocatalyst, BiOCl has garnered widespread attention due to its unique layered structure and low toxicity. However, the low light utilization efficiency and the rapid recombination of e−/h+ pairs severely hinder the practical application of BiOCl. Introducing oxygen vacancies (OVs) into BiOCl has been demonstrated to be one of the effective strategies for enhancing the photocatalytic performance of BiOCl. However, introduction of OVs through a mild and cost-effective approach remains a significant challenge. In this work, we developed a strategy for introducing OVs on BiOCl, which indues the growth of BiOCl into flower-like spherical structures and introduction of abundant OVs through addition of rape straw biochar (RC) under hydrothermal conditions. The synergistic interaction of RC and OVs endows with BiOCl more active sites as well as higher photogenerated carriers (e−/h+) separation efficiency. When the mass ratio of RC to BiOCl is 0.5 % (RC-0.5), the sample demonstrates the best performance, conversion of CO2 to CO on the sample is 4.0 μmol g−1 h−1, which is 3.08 times higher than that on the reference BiOCl. Additionally, versatility of the photocatalysts was further evaluated through photocatalytic degradation of rhodamine B (RhB) and perfluorooctanoic acid (PFOA). The degradation rate constant of RhB and PFOA on the RC-0.5 sample is 0.0642 min−1 and 0.00566 min−1, respectively, which is 2.26 times and 0.43 times higher than that on the reference BiOCl. Total organic carbon (TOC) experiments demonstrate that RhB can be effectively mineralized into CO2, H2O and small molecules on the photocatalyst. The main reactive species involved in the photocatalytic degradation process were investigated through active free radical trapping experiments and electron paramagnetic resonance (EPR). This work provides a viable strategy for the development of high-performance BiOCl photocatalysts for environmental applications.

Enhanced activation of sulfite by CoFe2O4-loaded with WS2 nanosheet with smooth surface for elimination and detoxification of metronidazole

In this study, cobalt ferrite-loaded tungsten disulfide (CoFe2O4@WS2) with different loading ratios was prepared by coprecipitation as a catalyst for activating sulfite in the degradation of metronidazole (MNZ) for the first time. Characterization analysis revealed that the heterogeneous catalyst possesses favorable surface properties and catalytic stability. The CoFe2O4@WS2/Na2SO3 (2:1) system exhibited the best catalytic performance under optimal conditions, achieving an impressive MNZ degradation efficiency of up to 95 % within 20 min. Quenching experiments and electron paramagnetic resonance tests indicated that oxysulfur radicals (SO3•−, SO4•− and SO5•−),1O2, •O2− and •OH generated during Na2SO3 activation and participates in the degradation of MNZ to varying degrees, while the redox cycles of Co2+/Co3+ and Fe2+/Fe3+ on the catalyst surface facilitated electron transfer, thereby promoting radical generation. Importantly, the synergistic effect between highly active W (Ⅳ) sites and unsaturated S on the catalyst surface effectively enhanced ion valence state recycling among various metal ions, ensuring continuous decomposition of sulfite, thereby facilitating sustained generation of ROS and the degradation of MNZ, confirming that WS2 played an excellent co-catalysis role. MNZ was degraded into various intermediates through three distinct pathways before ultimately mineralizing into inorganic small molecules. Toxicity analysis results indicated that the intermediate toxicity diminished with the reaction, reducing potential risks to aquatic ecosystem. Furthermore, findings demonstrated that the catalyst has excellent anti-interference ability, recyclability and low ion leaching rate. This study provides a novel approach for the efficient degradation of multiple organic pollutants using sulfites with promising application in practical water treatment.

A Review of the Mechanisms of Single-Atom-Based Advanced Oxidation Processes for the Degradation of Persistent Organic Pollutants in Water Environments

A Review of the Mechanisms of Single-Atom-Based Advanced Oxidation Processes for the Degradation of Persistent Organic Pollutants in Water Environments

Electro-coagulation technique using iron [Fe] and aluminium [Al] for microplastics removal from fashion industry wastewater, Thailand

The textile sector is considered as the 3rd largest source of water pollution and land degradation during 2020. of the world’s water pollution is linked with textile production and utilisation. Textile washing releases 14 million tons of microplastics, according to European Environmental Agency estimates. Wastewater Treatment Plant [WWTP] has declared everyday normal releases of more than 4 million MP particles because of its tiny size (<5mm) and low thickness (<1.2 g/cm3). Electrochemistry for the removal of tinny pollutants is recognised as an efficient treatment mechanism. The main aim of this research paper is to identify the efficiency of electro-coagulation technology using Fe and Al as anode and cathode in microplastic removal from Thailand’s textile industries. Results show the maximum 100% microplastic removal efficiency with pH 10 at a current density of 30 A/m2 within 60 minutes of the current supply. This paper helps to understand the role of electro-coagulation in Thailand textile wastewater plants and adopt the best available technique for microplastic removal.

Novel strategies for enhancing energy metabolism and wastewater treatment in algae-bacteria symbiotic system through carbon dots-induced photogenerated electrons: The definitive role of accelerated electron transport

The nitrogen removal efficiency of the algae-bacteria symbiotic system (ABSS) remains challenging due to competition for light capture and insufficient electron donors in aquaculture wastewater. To overcome this bottleneck issue, we first identified and reported the introduction of photogenerated electrons into ABSS by coupling them with carbon dots (CDs). The energy metabolism (21.52 %-56.25 %) and pollutant degradation efficiency (89.36 %-96.42 %) of ABSS/CDs surpassed the biochemical limit observed in traditional ABSS. Notably, the addtion of CDs facilitated an opening of the plastoquinone-pool (PQ-pool) valve and accelerated electron transfer rates, enabling photogenerated electrons to selectively target light-harvesting complexs as activation sites, thereby mobilizing photosynthesis and respiratory system activity to enhance nicotinamide adenine dinucleotide reduced (NADH) and adenosine triphosphate (ATP) production while promoting tricarboxylic acid (TCA) and Calvin cycle processes. In simulated swine wastewater treatment, ABSS/CDs achieved higher removal rates for the chemical oxygen demand (COD), total nitrogen (TN) and ammonium-nitrogen (NH4+-N) (100 %, 99.23 % and 98.62 % respectively) compared to pure culture systems alone. Network-based analysis revealed that ABSS/CDs improved microbial community structure stability within the photobioreactor while demonstrating efficient coupling between fungi, nitrifying bacteria, and denitrifying bacteria for enhanced performance in nitrogen removal processes. The upregulation of nitrogen metabolism and PQ-pool genes maintains efficient electron transport rates and contributes to nitrogen removal. This study expands our understanding of the physiological aptitudes of ABSS and provides valuable insights into applying CDs photoelectrons for enhanced wastewater treatment.

Bibliometric Analysis of Research Status, Hotspots, and Prospects of UV/PS for Environmental Pollutant Removal

There are various methods for environmental organic pollutant degradation and removal, among which ultraviolet/persulfate has drawn significant attention due to its excellent oxidizing properties, high maneuverability, and less formation of by-products. To comprehensively assess the development of ultraviolet/persulfate, a bibliometric analysis was conducted based on relevant literature indexed by Web of Science from 2002 to 2024. The findings revealed a growing number of publications, with China, Iran, and the United States being the top three countries with the highest total number of publications. Robust regional collaborations were evident. Additionally, Chinese and American scholars presented more significant activity in this field, and their publications exhibited higher quality. Furthermore, the current research hotspots, as indicated by keywords, primarily focused on the degradation mechanism of ultraviolet/persulfate and the reaction kinetic model simulation. Bibliometric results underscored that ultraviolet/persulfate, as an effective and environmentally friendly disinfection technology, possessed substantial potential for controlling diverse environmental pollutants, such as antibiotics, dyes, natural organic substances, heavy metals, microorganisms, and so on. Future research might concentrate on developing new catalytic composites and optimization of the photoactivation system. The practical application still needs to be investigated due to the complexity of the water matrix. The revival of microorganisms and the variation of toxicity should be considered further.

Iron–Cobalt Bimetallic Metal–Organic Framework-Derived Carbon Materials Activate PMS to Degrade Tetracycline Hydrochloride in Water

Organic pollutants entering water bodies lead to severe water pollution, posing a threat to human health. The activation of persulfate advanced oxidation processes using carbon materials derived from MOFs as substrates can efficiently treat wastewater contaminated with organic pollutants. This research uses NH2-MIL-101(Fe) as a substrate, doped with Fe2+ and Co2+, to prepare Fe/Co-CNs through a one-step carbonization method. The surface morphology, pore structure, and chemical composition of Fe/Co-CNs were investigated using characterization techniques such as XRD, SEM, TEM, XPS, FT-IR, BET, and Raman. A comparative study was conducted on the performance of catalysts with different Fe/Co ratios in activating PMS for the degradation of organic pollutants, as well as the effects of various influencing factors (the dosage of Fe/Co-CNs, the amount of peroxymonosulfate (PMS), the initial pH of the solution, the TC concentration, and inorganic anions) on the catalyst’s activation of persulfate for TC degradation. Through radical quenching experiments and post-degradation XPS analysis, the active radicals in the FeCo-CNs/PMS system were investigated to explain the possible mechanism of TC degradation in the Fe/Co-CNs/PMS system. The results indicate that Fe/Co-CNs-2 (with a Co2+ doping amount of 20%) achieves a degradation rate of 93.34% for TC (tetracycline hydrochloride) within 30 min when activating PMS, outperforming other Co2+ doping amounts. In addition, singlet oxygen (1O2) is the main reactive species in the reaction system.

Flower-Shaped MnFe2O4@MoS2 Nanocomposite Activated H2O2 for Efficient Degradation of Tetracycline: Performance Evaluation, Mechanism and Degradation Pathway

The limited utilization of H2O2 restricts the practical application of heterogeneous Fenton oxidation technology. In this study, the flower-shaped MnFe2O4@MoS2 nanocomposite was prepared by two-step hydrothermal treatment, constructing MnFe2O4@MoS2/H2O2 system for the degradation of tetracycline (TC). Under optimized conditions, MnFe2O4@MoS2/H2O2 system fully degraded 20 mg·L−1 of TC within 60 min, and the corresponding utilization of H2O2 was also as high as 95.7%. Meanwhile, this system not only exhibited excellent cycling stability for the degradation of TC but also had good anti-interference ability against actual water sources, inorganic cations and anions and natural organic compounds. The efficient activation of H2O2 in MnFe2O4@MoS2/H2O2 system mainly relied on the redox cycling of Fe(II)/Fe(III) and Mn(II)/Mn(III) mediated by MoS2; meanwhile, the oxygen vacancies caused by redox cycling also accelerated activation of H2O2, resulting in the production of a large number of active species (·OH, ·O2− and 1O2) for rapid degradation of pollutants. The vulnerable atomic sites of TC were confirmed through theoretical calculation, and four degradation pathways of TC in MnFe2O4@MoS2/H2O2 system were proposed. Finally, the toxicity analysis confirmed that the toxicity of degradation intermediates was developing towards low toxicity. This study provided new insights into the wide application of heterogeneous Fenton systems in wastewater treatment.

High-efficiency and stable Z-scheme heterojunction of Co9S8 anchored by g-C3N4 for peroxymonosulfate activation

Photocatalytic technology and peroxymonosulfate (PMS) based advanced oxidation technology have been proven to be simple and effective strategies for recalcitrant organic pollutants degradation. In this work, we designed and prepared a coupled photocatalytic and advanced oxidation system for sulfamethazine (SMR) antibiotics degradation. Firstly, a series of Z-scheme Co9S8/g-C3N4 heterojunction photocatalysts are prepared by a simple two-step method and further work as PMS activators. The prepared Co9S8/g-C3N4 photocatalysts exhibit a great improvement in electron-hole pairs migration and visible-light response due to heterojunction formation. In addition, the g-C3N4 acts as a substrate to anchor the Co9S8 nanoparticle, which suppresses the Co9S8 leaching and prevents the Co9S8 oxidation. Consequently, the Co9S8/g-C3N4/PMS system displayed an improved SMR degradation ability (93 % for Co9S8/g-C3N4/PMS vs. 86 % for Co9S8/g-C3N4). After the fourth cyclic degradation experiment, the Co9S8/g-C3N4/PMS system still maintained a comparatively high degradation rate. Considering its good properties and better degradation performance, we propose that the synergistic effect of photocatalytic technology and PMS possess a promising prospect for application in environmental treatment.

In Situ Constructed Magnetic Core‐Shell Hydrogen‐Bonded Organic Framework‐on‐Metal–Organic Framework Structure: an Efficient Catalyst for Peroxymonosulfate Activation

AbstractZeolite imidazole‐based framework (ZIF‐67), a notable class of metal–organic frameworks (MOFs), shows promise in activating peroxymonosulfate (PMS) for pollutant degradation due to its uniformly distributed cobalt ions. However, its nanoparticle form and the elution of cobalt ions during use cause challenges in recycling and the risk of secondary pollution. In this study, a magnetic core‐shell hydrogen‐bonded organic framework (HOF) on the MOF (HOF‐on‐Fe3O4/ZIF‐67) is successfully prepared. The porous HOF shell not only protects the active sites and mitigates cobalt ion leaching but also reduces mass transfer limitations, ensuring sustained catalytic performance. The magnetic Fe3O4 core enhances electron transfer between cobalt ions, boosts catalytic efficiency, and facilitates easy separation and recycling. This core‐shell structure effectively activates PMS, achieving 100% removal of Rhodamine B, a model wastewater dye, within 10 min (Rh B = 50 mg L−1, HFZ = 150 mg L−1, PMS = 1.5 mm, pH = 7, room temperature). Furthermore, under the protection of the HOF shell, cobalt ion leaching is minimized to a negligible value (0.14 mg L−1) after 5 cycles of use. The research provides fresh perspectives into the development of core‐shell composite materials with improved performance and recyclability in wastewater treatment.

Development of photoactive ZnS-SiO2 composites on biogenic silica matrix for organic pollutant degradation.

Sulfide ZnS-SiO2 composite photocatalysts with biogenic silica matrix were prepared by sol-gel method based on wet gel and xerogel. FT-IR, SEM, XRD, EDXRF, UV-Vis, and XPS methods were systematically used to characterize the obtained materials. The use of support allowed to obtain stable porous (SBET = 79-105 m2g-1; Vpore = 0.25-0.17 cm3·g-1) ZnS-SiO2 photocatalysts in aqueous solutions. Zn2+ content in methyl orange solution after its degradation was 0.4 MPC. ZnS-SiO2 composites had 3.68-3.70eV band gap. The obtained materials were photoactive under different irradiation conditions (sunlight, UV-light, Xenon light, visible light) due to effective separation of charge carriers (e- and h+). Methyl orange degradation degree under UV light excitation was 35-88%, under sunlight - 11-30%. ZnS-SiO2 composite synthesized using silica xerogel showed a greater photoactivity due to a presence of cone-shaped or cylindrical pores with one open end in its structure and a higher content of ZnS photoactive component. A comparative study of photocatalytic performance of methyl orange degradation by ZnS-SiO2 under UV irradiation was investigated using radical scavengers. •O2- was main active species during MO degradation under UV irradiation, and electrons played additional role during the photocatalytic process.

Trimetallic MOF–derived Fe–Mn–Sn oxide heterostructure enabling exceptional catalytic degradation of organic pollutants

Developing efficient and environmentally benign heterogeneous catalysts that activate peroxymonosulfate (PMS) for the degradation of persistent organic contaminants remains a challenge. Metal–organic frameworks (MOFs)–derived metal oxide catalysts in advanced oxidation processes (AOPs) have received considerable attention research fraternity. Herein, we report an innovative magnetic trimetallic MOF-derived Fe-Mn-Sn oxide heterostructure (FeMnO@Sn) with adjustable morphology, size and Sn content, prepared through an impregnation–calcination strategy. The formation of a novel magnetic Fe2O3/Fe3O4/Mn3O4 heterostructure induces the generation of abundant Fe2+ and Mn2+ sites on the FeMnO@Sn surface. Meanwhile, the introduction of SnO2 into the Fe2O3/Fe3O4/Mn3O4 heterostructure facilitates the cleavage of the OO bond in adsorbed PMS. The synergy among the different functionalities of each metal oxide plays a vital role in the swift and effective degradation of pollutants. In addition, the uniquely designed catalyst exhibits magnetic properties that facilitate easy recycling and repeated use, thereby meeting environmental protection requirements. Overall, this research highlights the design of heterogeneous catalysts for the effective activation of PMS and provides valuable insights for the advancement of future environmental catalysts.

TiO2 Catalysts Co-Modified with Bi, F, SnO2, and SiO2 for Photocatalytic Degradation of Rhodamine B Under Simulated Sunlight

The organic pollutants discharged from industrial wastewater have caused serious harm to human health. The efficient photocatalytic degradation of organic pollutants under sunlight shows promise for industrial applications and energy utilization. In this study, a modified TiO2 photocatalyst doped with bismuth (Bi) and fluorine (F) and composited with SnO2 and SiO2 was prepared, and its performance for the degradation of Rhodamine B (RhB) under simulated sunlight was evaluated. Through the optimization of the doping levels of Bi and F, as well as the ratio of SnO2 and SiO2 to TiO2, the optimal catalyst reached degradation efficiency of 100% for RhB within 20 min under simulated sunlight, with a first-order reaction rate constant of 0.291 min−1. This value was 15, 41, 6.5, and 3.3 times higher than those of TiO2/SnO2, Bi/TiO2, Bi-TiO2/SnO2, and F/Bi-TiO2/SnO2, respectively. The active species detection showed that h+ was the most crucial active species in the process. The role of Bi and F addition and SnO2-SiO2 compositing was investigated by characterization. Bi formed a chemical bonding with TiO2 by doping into TiO2. The absorbance intensity in the UV and visible light regions was improved by SnO2 and F modification. Composite with SiO2 led to a larger surface area that allowed for more RhB adsorption sites. These beneficial modifications greatly enhanced the photocatalytic activity of the catalyst.

S-scheme3D/3D Bi0/BiOBr/P Doped g-C3 N4 with Oxygen Vacancies (Ov) for Photodegradation of Pharmaceuticals: In-situ H2O2 Production and Plasmon Induced Stability.

Complications accompanying photocatalyst stability and recombination of exciton charges in pollutants degradation has been addressed through the construction of heterojunctions, especially S-scheme heterojunction with strong and distinctive redox centres. Herein, an S-scheme BiOBr (BOR) and g-C3N4PO4 (CNPO) catalyst (BORCNPO) with oxygen vacancy (Ov) was synthesized for levofloxacin (LVX) and oxytetracycline (OTC) photodegradation under visible light. The 3D/3D BORCNPO catalyst possessed C-O-Br bridging bonds for efficient charge transfer during the fabrication of S-scheme heterojunction. In-situ H2O2 formation affirmed by potassium titanium (IV) oxalate spectrophotometric method improved the mineralization ability of BORCNPO7.5 catalyst. Bi0 surface plasmon resonance (SPR) enhanced formation and involvement of ⋅O2 - and the stability of the catalyst which increased reaction rate with increasing cycling experiments. XPS and radical trapping experiments supported the S-scheme charge transfer mechanism formation with high degradation rate of LVX which was 3 times higher than OTC degradation rate. Mineralization of pollutants and their intermediates were demonstrated with florescence excitation and emission matrix (FEEM) and quadruple time of flight high performance liquid chromatography (QTOF-HPLC). This work advances development of highly stable and efficient catalysts for photodegradation of pollutants through the formation of S-scheme heterostructure.

Highly efficient Zn(O,S)/Mo(O,S)2 oxysulfide heterostructure photocatalyst for organic pollutant degradation

Environment and energy are presently some of the highest priority topics for mankind that need to be addressed. Organic pollutants are toxic and carcinogenic for human and aquatic life hence their presence in water even in low concentrations can cause serious health problems. Photodegradation of organic pollutants by utilizing oxide-based heterostructure photocatalysts is the promising approach to carry out remediation efficiently ascribed to the advanced optoelectronic and structural superiority of oxide photocatalysts. The Zn(O,S)/Mo(O,S)2 composites were synthesized via a facile solvothermal method at low temperatures. Several methods were used to characterize the composite morphology, structure, electrical conductivity, chemical composition, and optical characteristics. The heterostructured Zn(O,S)/Mo(O,S)2 oxysulfide was employed successfully in the photocatalytic degradation of organic pollutants. Among the as-prepared samples, the 30-ZnMoOS composite catalyst was found to have the highest photodegradation performance on various organic dye pollutants. The photocatalytic activity of the as-synthesized Zn(O,S)/Mo(O,S)2 samples was assessed on the photodegradation of different kinds of organic dyes under visible light irradiation. The photocatalytic degradation efficiency of 30-ZnMoOS composite over 10 ppm neutral red (NR), methylene blue (MB), rhodamine B (Rh B), and methyl orange (MO) was found to be 99.6 %, 99.9 %, 99.5 %, and 98.8 % within 40, 45, 180, and 180 min, respectively, under visible light illumination. In the present photocatalytic system, the superoxide (.O2-) anions, hydroxyl (.OH) radicals, and holes (h+) are proposed to be the direct reactive species causing the photodegradation of organic dyes.

Synthesis of Novel Fe-CNs-P/S Carbon Materials for Sustainable Water Treatment: Activation of Persulfate for Efficient Tetracycline Degradation

This study presents a novel Fe-CNs-P/S carbon composite material, synthesized by doping elements P and S into NH2-MIL-101 (Fe) using the carbonization method. The material’s application in sustainable water treatment was evaluated, focusing on its effectiveness in activating persulfate for pollutant degradation. The research thoroughly investigates the synthesis process, structural characteristics, and performance in degrading pollutants. The results indicate that Fe-CNs-P/S-5 with 50% P and S co-doping is higher than that of other samples, where the degradation rate of TC in 30 min is as high as 98.11% under the optimum conditions, that is temperature at 25 °C, 0.05 g/L of catalyst concentration, and 0.2 g/L of PMS concentration. The composite material demonstrates robust versatility and stability, maintaining high degradation efficiency across multiple organic pollutants, with no significant reduction in catalytic performance after four cycles. Furthermore, the free radical quenching experiments display that the singlet oxygen 1O2 is the main active species. It is demonstrated that the doping of P and S play a role in the enhancement of PMS activation over the Fe-CNs-P/S catalyst. This material demonstrates remarkable efficacy in treating a range of organic contaminants and exhibits excellent reusability, presenting a promising approach for enhancing sustainability in water treatment applications.

PH dependence of reactive oxygen species generation and pollutant degradation in Fe(II)/O2/tripolyphosphate system

It has been reported that tripolyphosphate (TPP) can effectively enhance the activation of O2 by Fe(II) to remove organic pollutants in the environment. However, the influence of solution pH on the generation and conversion of reactive oxygen species (ROS) and their degradation of pollutants in the Fe(II)/O2/TPP system needs further investigation. In this study, we demonstrated that O2•– and •OH were the main ROS responsible for degradation in the system at different pH conditions, and their formation rates were calculated using a steady-state model. Experiments combined with density functional theory (DFT) calculations showed that the p-nitrophenol (PNP) degradation pathway in the Fe(II)/O2/TPP system is regulated by solution pH. Specifically, at pH = 3, the existence of Fe(II) in the solution is dominated by [Fe(II)(HTPP)2]2−, which leads to a rapid conversion from O2 and HO2• to generate •OH, and PNP is primarily oxidatively degraded. However, at pH = 5/7, [Fe(II)(TPP)2]4− is taking the lead with which O2•– is accumulated in the solution due to the slow conversion to •OH in this condition, and the PNP is mainly reductively degraded. This study proposes a new strategy to achieve the targeted oxidative/reductive removal of different types of pollutants by simply varying the solution pH in the Fe(II)/O2/TPP system.

Prussian Blue Analogue‐Based Materials: Synthesis and Their Application in Peroxymonosulfate Activation for Wastewater Treatment

Peroxymonosulfate (PMS) based advanced oxidation processes (AOPs) are effective in degrading refractory organic pollutants in water. The unique internal chemical tunability of Prussian blue analogues (PBAs), a type of metal‐organic framework materials (MOFs), makes them promising catalysts for PMS‐AOPs. However, the pristine PBA is limited in practical application due to its structural instability and easy leaching of metal ions. To this end, various methods have been developed to enhance the catalytic performance of PBAs. In this paper, the recent advances in the modification and composite strategies of PBA catalysts are systematically reviewed. PBA modification by the regulation of synthesis conditions and post‐synthesis treatment, along with composite strategies involving metal and non‐metal based materials are introduced. The structural morphology improvement, physical and chemical property adjustment, vacancy design and crystal surface modulation of PBAs induced by these modification and composite strategies are discussed in depth. In addition, the performance of the modified and composite catalysts to activate PMS for organic pollutant degradation is demonstrated. The radical pathway via SO4•‐, •OH and O2•‐, non‐radical pathway through 1O2, electron transfer process and high‐valence metal‐oxygen species, or a combination of radical and non‐radical pathways are revealed in PMS‐AOPs with PBAs and their derivatives as catalysts.