Per- and polyfluoroalkyl substances (PFAS) are persistent global contaminants, posing challenges to predicting their environmental fate. The solid-liquid distribution coefficient (logKd) is a key parameter for PFAS mobility, but current machine learning (ML) models often overlook its susceptibility to real-world water chemistry. To address this, we introduce the Phys-ML Sorp Framework, a novel multiscale approach integrating molecular dynamics (MD) simulations with ML to enhance logKd prediction. We quantified physically informed microscopic features from MD simulations, including radius of gyration (Rg), solvent accessible surface area (SASA), and a novel effective activity coefficient (logγ) that uniquely captures solute conformational responses by incorporating MD-derived Rg into an extended Debye-Hückel equation, offering a physically meaningful measure of nonideal solution effects. Leveraging 499 PFAS partitioning observations in pure water and calcium chloride (CaCl2) systems, our model achieved superior predictive performance (RPD = 2.90, RMSE = 0.32). The incorporation of MD-derived microscopic features resulted in a 14.62% improvement in RPD and a 13.52% reduction in RMSE over models relying solely on macroscopic parameters. SHAP analysis revealed molecular weight (MW, 0.32), SASA (0.28), logKow (0.23), Rg (0.08), and logγ (0.07) as dominant factors. This framework not only advances environmental pollutant modeling but also establishes a robust, mechanistically informed approach for enhanced environmental risk assessment.

The inadequate efficiency of extracellular electron transfer (EET) between electroactive microorganisms (EAMs) and abiotic electrodes represents a fundamental limitation on the energy conversion efficiency of bioelectrochemical systems (BES). Most current strategies aimed at enhancing EET focus on optimizing isolated components-either materials or microorganisms-often neglecting the multiscale regulation of the biotic-abiotic interface. This oversight hinders efforts to fundamentally overcome the thermodynamic and kinetic constraints associated with the EET process. Metal-organic frameworks (MOFs), characterised by their precisely tunable pore structures and designable redox-active centres, offer promising materials for reconfiguring synergistic biotic-abiotic interfaces and addressing these challenges. However, direct evidence for MOF-microbe orbital coupling remains limited, making it a key research gap rather than a confirmed mechanism. We systematically examine the latest advancements in the coupling system of MOFs and EAMs. We analyse the functional evolution of MOFs, which transition from serving as passive protective shells for microorganisms to acting as active regulators of extracellular electron transfer in EAMs. Furthermore, we elucidate the synergistic regulatory mechanisms inherent in this coupling system. Unlike existing reviews that predominantly summarise synthesis methods and performance characterisation results of MOFs, this review critically addresses the core challenges and engineering barriers encountered in the practical application of this system within real-world environments, with a particular focus on interface engineering. We integrate practical applications of this system across several cutting-edge fields and reveal the underlying principles of interface engineering that enhance system stability and resistance by comparing the constitutive relations of various coupled systems. Finally, in light of the current challenges faced by these biohybrid systems, we delineate potential avenues for future breakthroughs.

Spatial nanoconfinement is known to influence catalytic reactions, but in many studies it is treated merely as a binary parameter, either present or absent. This work demonstrates that the confinement environments of reactants can be precisely controlled and leveraged to tune the electronic properties of active sites. By varying the pyrolysis temperature, a series of Fe cluster catalysts with distinct confinement environments were synthesized within a carbon nitride matrix. This directly shifted the d-band center of the Fe sites. The optimally confined catalyst, FeNC-700, exhibits an upshifted d-band center that steers peroxymonosulfate activation away from radical pathways and toward a synergistic combination of singlet oxygen (1O2) and electron transfer process (ETP). This creates a self-reinforcing cycle: ETP drives 1O2 production, and rapid 1O2 consumption in turn sustains the ETP, resulting in 13.4-fold faster pollutant degradation. Through detailed characterization and theoretical calculations, a direct correlation among confinement environments, d-band position, and reaction pathway was established. This work shows that nanoconfinement is not just a fixed property of a catalyst but a tunable parameter during synthesis that can be meticulously designed to achieve desired catalytic behavior.

Various co-catalysts were employed in peracetic acid-based (PAA) Fenton-like systems, and the co-catalytic performance, Fe(III) reduction ability and electron transfer property were compared. As a superior co-catalyst, molybdenum boride (MoB) facilitated the complete activation of PAA by Fe(II), while effectively suppressing PAA self-decomposition. The self-renewal surface facilitated the continuous exposure of low-valence species, thereby promoting the Fe(III)/Fe(II) circulation. Theoretical calculations revealed that the (112) crystal plane of MoB demonstrated a more pronounced reduction capability toward both FeOH2+ and FeOH2+ species. Importantly, the Bader charge analysis revealed that Mo predominantly acted a donor of reducing electrons during the reduction processes, whereas B demonstrated a synergistic mechanism involving both electrons transfer and the attraction of Fe(III) species. Additionally, residual peroxides exhibited potential ecological risks, as they inhibited crop and zebrafish growth even at trace concentration. The experimental results demonstrated that MoB exhibited promising co-catalytic performance within the reaction device, highlighting the application potential of PAA-based Fenton-like processes when integrated with a dual sites molybdenum-based co-catalyst.

Spin-state engineering of atomic active sites is pivotal in selective singlet oxygen (1O2) generation during Fenton-like catalysis. Dual-atom catalysts (DACs) offer flexibility in spin-state regulation, while precisely regulating spin states remains challenging. Here, a CoCe dual-atom catalyst (CoCe-N/C) with a moderate spin state was designed for efficient 1O2 generation in peroxymonosulfate (PMS) activation. The incorporation of Ce adjacent to Co-N4 moieties distorted the symmetry of the ligand field and reduced the crystal field splitting energy (Delta), thus inducing spin crossover of the Co configuration from a low-spin state (LS Co3+: t62ge0g) to a medium-spin state (MS Co3+: t52ge1g). The MS electron configurations of CoCe-N/C facilitated the orbital overlap with PMS and significantly reduced the 1O2 generation barrier, resulting in Rhodamine B (RhB) elimination kinetics 12.3 times higher than that of Co-N/C. Simultaneously, the electron buffer of neighbouring Ce enabled the conversion of Co3+/Co2+via Ce4+/Ce3+ cycling to be stabilized and expedited, achieving strong anti-interference and dynamic-degradation capabilities in continuous-flow filtration systems for water purification. This study presents a novel strategy for spin-state modulation of DACs in 1O2-based Fenton-like reactions.

In metal-organic framework (MOF)-derived single-atom catalysts (SACs), pyrolyzed organic linkers function as both carbon precursors and coordination shell providers for the metal centers. Therefore, the judicious selection of organic linkers, such as those containing pyridine N (2-methylimidazole) or O (terephthalic acid), can readily “encode” the coordination microenvironment at the final single-atom site. Guided by this linker-encoding principle, we tailor these organic linkers within MOFs to construct two SACs (70-Fe-ZIF-8-900 and 8-Fe-MOF-5-900) with distinct optimal Fe loadings (0.94% and 0.03%, respectively), which achieve precise control over structural morphology and coordination environment. Remarkably, 8-Fe-MOF-5-900 with Fe-C1O3 sites, despite its ultralow Fe loading, exhibits phenol degradation activity 2.69 times higher than that of 70-Fe-ZIF-8-900 in the peroxymonosulfate (PMS) system, underscoring exceptional atomic utilization efficiency. The tailored electronic configuration, featuring an elevated d-band center and increased electron density around iron, enhances PMS activation and induces a singlet oxygen-driven mechanism. Quantitative structure-activity relationship models reveal strong linear correlations (R2 = 0.716-0.855) between the catalytic rate constant and key electronic-structure descriptors in 8-Fe-MOF-5-900/PMS system, demonstrating high predictability for oxidation activity. Overall, this work offers a conceptual framework for designing advanced oxidation processes with controllable redox reactivity, tunable selectivity, and 1O2-dominated catalytic pathways.

Antimony contamination in mining-impacted river basins poses persistent environmental risks, yet the microbial processes governing antimony redox transformation under anoxic sediments remain poorly understood. Here, we report that photoelectrons generated by naturally occurring dissolved organic matter can support microbial antimonate reduction. Natural dissolved organic matter exhibits sustained photocurrent responses under illumination. In anoxic microcosms, indigenous sediment communities achieve 50-70% antimonate reduction with photoelectron supply, thereby constraining purely abiotic reduction or alternative electron-donor explanations under our experimental conditions. Multi-omics further identify non-phototrophic taxa (e.g., Sphingomonas and Bosea) with elevated antimony reduction/detoxification pathways and respiratory electron-transfer components under photoelectron exposure. The consistent presence of photosensitive dissolved organic matter and candidate taxa across mining-impacted sediments suggests broader environmental relevance. These findings indicate that photosensitive dissolved organic matter may provide a photoelectron flux that influences microbial antimony redox transformations in anoxic sediments.

Transitioning advanced oxidation processes (AOPs) from deep mineralization to pollutant polymerization represents a promising strategy toward low-carbon water decontamination. Single-atom catalysts (SACs), with their well-defined active sites, offer a unique platform to establish precise structure-activity relationships and elucidate polymerization mechanisms. Herein, we synthesized Fe SACs with an Fe & horbar;N1O3 configuration that exhibit superior activity in activating peroxymonosulfate (PMS) for phenol removal, achieving a rate constant of 0.204 min-1 and a total organic carbon removal efficiency of 82.05%. Mechanistic studies reveal that phenol removal followed a nonradical singlet oxygen-driven polymerization pathway mediated by Fe active sites. The generated singlet oxygen possesses moderate redox potential, which drives surface-absorbed phenol oxidation on support to form phenoxyl radicals through electrophilic attack, subsequently triggering the formation of high-molecular-weight chains (<= 11 units). In-depth theoretical calculations unveil that the asymmetric Fe & horbar;N1O3 site exhibits a strong internal electric field and a moderate d-band center. This electronic configuration enables enhanced PMS adsorption for sustained singlet oxygen generation and confers resistance to intermediate poisoning based on the Sabatier principle, thereby driving a continuous polymerization process. This fundamental mechanistic insight, bridging single-atom coordination engineering with reaction selectivity control, provides a transformative blueprint for designing low-carbon, high-value water decontamination technologies centered on resource recovery.

The production scalability and increasing demand for black phosphorus nanosheets (BPNSs) inevitably lead to environmental leakage. Although BPNSs' ecotoxicological effects have been demonstrated, their indirect health risks, such as inducing increased resistance in pathogenic bacteria, are often overlooked. This study explores the influence of BPNSs on the horizontal gene transfer of antibiotic resistance genes (ARGs) facilitated by the RP4 plasmid, which carries multiple resistance genes. The results indicated that BPNSs exhibited concentration-dependent hormesis-like effects on bacterial conjugation gene transfer. Specifically, at sub-inhibitory concentrations (0.0001-1 mg/L), BPNSs promoted both intra- and intergeneric conjugative transfer, demonstrating an initial increase followed by a decline, with transfer rates rising by 1.5-3.1-fold and 1.5-3.3-fold, respectively. BPNSs were found to induce reactive oxygen species (ROS) production, increase malondialdehyde levels, and trigger the SOS response, enhancing plasmid uptake. Additionally, BPNSs increased membrane permeability by forming pores and upregulating outer membrane porins (OMPs) genes. At higher BPNSs concentrations (0.1-1 mg/L), conjugative frequency was inhibited due to the disruption of the cellular antioxidant system and changes in the adsorption process. These findings underscore the influence of BPNSs on the conjugative transfer of ARGs, complementing current knowledge of the biotoxicity and potential ecological risks associated with BPNSs.

The hybrid capacitive deionization (HCDI) technology has demonstrated improved efficiency compared to conventional capacitive deionization (CDI). Prussian blue analogues (PBAs) possess high capacity and rapid ion transfer capability, recognized as promising materials for HCDI electrodes. PBAs with a more uniform morphology and smaller particle size could enhance contact with the electrolyte, and facilitate rapid ion transport. It has been observed that adding manganese can reduce the particle size of these materials and lead to a more uniform structure. In this study, nickel-based Prussian blue analogues were modified with varying manganese doping ratios to enhance desalination properties. The optimal desalination performance was achieved when the atomic ratio of manganese to nickel was 3:7 (MNP-3), yielding a maximum deionization rate of 20.59 mg & sdot;(g & sdot;min)-1 and a high desalination capacity of 58.82 mg & sdot;g-1 in batch mode testing at an applied voltage of 1.2 V in a 500 mg & sdot;L-1 NaCl feed solution. Furthermore, MNP-3 exhibited higher specific capacitance and smaller transfer resistance than the undoped material, which were advantageous for sodium ion storage. This study emphasizes the impact of particle size on HCDI performance, providing valuable insights for future HCDI application studies.

Eutrophication of water bodies caused by cyanobacteria is a headache in water treatment nowadays, and the treatment of harvested cyanobacteria creates another difficult problem. Fortunately, cyanobacteria can produce biochar (BC) through pyrolysis, but the catalytic performance of BC is clearly unsatisfactory. Metal-organic frameworks, materials with multiple active centers, are naturally combined with BC for superior functional materials. In this study, ZnS-NC/BC was obtained by in situ growth of ZIF-8 on cyanobacteria-derived biochar and subsequent sulfur-doped pyrolysis. Characterization indicated that ZIF-8 was successfully uniformly loaded onto the BC substrate and transformed into ZnS-loaded N-doped graphitic carbon during the subsequent pyrolysis process. In the performance evaluation, ZnS-NC/BC-1 showed excellent peroxymonosulfate activation performance and 4-chlorophenol (4-CP) removal capability. Subsequently, it turned out that 1O2 dominated the degradation of 4-CP in the system. Furthermore, it was exciting to note that the system exhibited good resistance to various factors, including pH, inorganic anions, and humic acids. In addition, the removal of 4-CP and dissolved organic matter proceeded well even in natural water and sewage effluent. The degradation pathway of 4-CP was confirmed by density functional theory (DFT) and liquid chromatography-mass spectrometry (LC-MS) to be two, namely the degradation pathway and the polymerization pathway. In addition, the toxicity of the intermediates showed a general trend of detoxification, proving the toxicological feasibility. In conclusion, a feasible solution for the synergistic development of solid waste and water treatment was provided.

Partial nitrification (PN) is of practical significance for achieving autotrophic nitrogen removal with impressive economic and environmental benefits. While most studies focused on the selective suppression of nitrite-oxidizing bacteria, maintaining stable ammonia oxidation as the primary source of nitrite remains equally critical but largely underexplored. Herein, we identified Nitrosomonas eutropha as the keystone species dominating ammonia oxidation in free ammonia treatment-based PN systems, comprising over 40% of the nitrifier community. Combined metagenomic and metaproteomic analyses revealed that N. eutropha orchestrated multiple cellular processes and reallocated intracellular resources to adapt to the PN niche. Specifically, enhanced primary metabolism and stress response systems within N. eutropha were observed, alongside significant upregulation of the protein synthesis machine, such as ribosomal proteins and translation factors. Notably, overexpression of the cell division protein FtsA was detected, which is known to disrupt Z-ring formation and inhibit cell division. These results suggest a protein synthesis-centered survival strategy, wherein N. eutropha maintained robust protein synthesis capacity while retarding propagation. This strategy differs fundamentally from conventional microbial stress responses, which typically involve the downregulation of protein synthesis to conserve resources. These findings provide multidimensional insights into the survival strategies of Nitrosomonas in PN systems, with practical implications for both understanding molecular responses to environmental stress and optimizing engineering strategies for autotrophic nitrogen removal.

Singlet oxygen (1O2), with its unique electrophilic character and prolonged lifetime, stands out among reactive oxygen species (ROS) for selectively targeting electron-rich contaminants in advanced oxidation processes (AOPs). Despite advances in materials engineering for steering peroxymonosulfate (PMS) toward 1O2-dominated pathways, systematic studies on metal nanoparticle (NP)-driven 1O2 production remain scarce, which possess unique electronic and steric structures. A critical limitation of metal NPs is their susceptibility to metal leaching under reactive conditions, which not only degrades catalytic activity and long-term stability but also raises concerns about secondary environmental pollution. Here, we reported for the first time that zinc-iron oxide (ZnFeOx) NPs encapsulated within a conductive carbon shell and anchored on MOF-5-derived carbon nanosheets via a nanoconfinement strategy, which could behave as robust and stable catalysts towards efficient PMS activation to produce 1O2 with 90.36 % selectivity. Benefiting from the 1O2-dominated mechanism, Fe-MOF-5-900/ PMS system exhibited a wide pH adaptation (3-11) and high resistance to inorganic anions. In-depth theoretical calculations revealed that the introduction of Fe on MOF-5-derived carbon nanosheets displayed enhanced adsorption between PMS molecules compared with MOF-5-derived carbon. Mechanistic studies established that 1O2 predominantly originated from the self-reaction of SO5 center dot- radicals, mediated by Fe-active sites through PMS activation.

Metal-organic frameworks (MOFs) derivatives catalysts prepared with MOFs exhibit excellent performance in the Electro-Fenton (EF) process. However, the direct use of MOFs derivatives catalysts will face the problem of difficult recycling, and previous coated MOFs derivatives EF electrodes have suffered from catalysts shedding during the reaction process. Herein, Fe/Co bimetallic nanoparticle derived from Co-doped MIL-88B(Fe) was wrapped with cellulose to produce a hydrogel electrode (CoFe2O4/Co3Fe7@CH). The three-dimensional network skeleton of cellulose hydrogel (CH) provided loading conditions for the catalysts, and its well-developed pore structure promoted substance adsorption and exchange, which increased the stability of the electrode without affecting the catalytic efficiency. Furthermore, the Co-doping facilitated the generation of Fe0 and enhanced the chemical composition of the catalyst, thereby accelerating electron transfer and promoting the generation of diverse active substances. The CoFe2O4/Co3Fe7@CH/EF system could remove 91.1 % of tetracycline (TC) within 60 min, and it could be adapted to different current density, pH, and aqueous environments. The results exhibited that both free radical (center dot OH, center dot O2 ) and non-free radical (1O2, high-valent metal oxygen species) resulted in TC degradation. The possible degradation pathways of TC and toxicity analysis showed that most of the intermediates were less toxic than TC. In conclusion, this work provided the theoretical basis and technical support for the development of hydrogel as an EF electrode and novel EF process.

Sludge foaming can promote sludge drying efficiency. In the foaming process, sludge protein plays a critical role due to its amphiphilic properties. However, the existing alkaline hydrolysis can generate sufficient solubilized proteins but unable to adjust their properties suitable for subsequent foaming. In response to this issue, acid pretreatment, thermal pretreatment, and enzymes of α-amylase, neutral protease (NP), and alkaline protease were applied in combination with alkaline hydrolysis. Among all methods, the enzymatic hydrolysis of 10 ‰ NP (NP10) within 2.0 h optimally adjust the proteins hydrophilic/hydrophobic, reducing foaming time by 36.7 %, drying time by 19.7 %, and energy consumption by 21.1 %. The NP pretreatment followed by alkaline hydrolysis achieved a controllable hydrolysis of proteins, with NP10 reaching the highest ratio of polypeptides to proteins at 0.4 ± 0.02, which is desirable in sludge foaming. Meanwhile, the plastein reaction was observed in NP group, characterized by increased aggregated strands and decreased α-helix/(β-sheet + random coil) in protein secondary structures, which can improve the hydrophobicity of protein hydrolysate. Two-dimensional correlation spectroscopy analysis confirmed the highest reaction activity of aggregated strands with NP. In sludge drying, the NP10 enhanced the value of effective moisture diffusivity by 51.1 % during the second falling rate period, and significantly decreased the resistance to internal moisture migration in sludge matrix. This work offered a synergistic strategy for efficient sludge foaming and drying by tuning the hydrophilic/hydrophobic balance of protein hydrolysate, and provided a deep understanding on sludge protein properties in relevant treatment processes.

Perfluorooctane sulfonate (PFOS) is a highly persistent and cytotoxic emerging pollutant that accumulates in sludge. Clarifying its effects on anaerobic digestion and its cytotoxicity on functional microbial metabolism is essential for evaluating the ecological risks it may pose during sludge disposal. This study investigated the effects of PFOS on methane production, microbial community responses and functional adaptations during anaerobic digestion. The results showed that environmentally relevant concentrations of PFOS had minimal effects on methane production. However, as PFOS accumulate at higher concentration, the cumulative methane production was decreased by 10% compared to the control. This reduction was primarily attributed to the inhibition of methanogens by PFOS, especially Methanosarcina, which was reduced by over 50% compared to the control. Cellular activity tests demonstrated that PFOS induced excessive reactive oxygen species and disrupted the cell membrane integrity. Further metabolic potential mining of biomarkers in F0 and F5 revealed that microorganisms enriched in functional genes associated with bacterial chemotaxis, quorum sensing and EPS metabolism were more likely to gain survival advantages under PFOS stress. This study reveals the cytotoxic mechanism of PFOS on microorganisms, deepens the understanding of microbial adaptations in anaerobic digester, and provides a theoretical basis for assessing the ecological risk of PFOS.

Camellia oleifera cake (COC) is a by-product of the Camellia oleifera oil collection process, which is rich in nutrients such as polysaccharide and protein. This study represents the first use of COC as a microbial medium substitute and its potential for producing bioflocculants. The COC was used to culture Paenibacillus polymyxa GA1, and its colony counts was more than one order of magnitude higher than that in the traditional fermentation medium, increasing from 0.6 x 107 CFU/mL to 1.8 x 108 CFU/mL. The bioflocculant produced by GA1 had a flocculation efficiency of 98.9 +/- 0.4 % on kaolin suspension, which remained unchanged when the volume of acetone used in extracting the bioflocculant was reduced by 75 %. Chlorella vulgaris was harvested with the bioflocculant and the harvesting efficiency reached 95.6 +/- 0.2 %, even without improving the pH. The above results demonstrate the potential of COC as an alternative medium.

Three-dimensional electrode technology (3D technology), featuring dispersed particulate electrodes is rapidly advancing in the separation of pollutants. However, in contrast to the electrochemical oxidation performance, the design of particulate electrodes for electrochemical reduction remains relatively underexplored. This study introduced a bionic particle electrode (BC@SA-Nafion) with high reducibility and selectivity, and integrated it into a 3D system. Specifically, the selective electro-induced reduction capacity of BC@SA-Nafion was examined using Cr(VI) as a model pollutant. The electrochemical reactivity of BC@SA-Nafion was found to be dependent on the amount of biochar (BC) incorporated. Furthermore, the selectivity for Cr(VI) could be fine-tuned by adjusting the Nafion content, thereby addressing the efficiency decline at lower Cr(VI) concentrations. In the 3D system, the Cr(VI) removal rate reached up to 99 % under optimal conditions (pH 2, 2 V cm(-1) , 30 min). The density functional theory calculations indicated that the selectivity of BC@SA-Nafion for Cr(VI) was dependent on the presence of fluorine bonds. The reduction of Cr(VI) mainly relied on direct electron transfer provided, with superoxide (& sdot;O- 2) also playing a role. Post-treatment with the 3D technology resulted in negligible phytotoxicity of the wastewater. This study introduced a novel strategy for enhancing the selectivity of particle electrodes, thereby expanding the application of the particle electrode and advancing sustainable water treatment technologies.

Most current photoelectrodes used in photoelectrocatalytic technology exhibited problems such as a high leaching rate of metal ions, resulting in poor stability and secondary pollution. Herein, we prepared a composite flexible nanocellulose hydrogel photoelectrode loaded with ZIF-8 (ZIF-8@(C-TOCNF/Agar)). ZIF-8@(C-TOCNF/ Agar) photoelectrode combined the excellent chemical stability of ZIF-8 and the good support properties of nanocellulose hydrogel, which could improve the deficiencies in practical applications. The ZIF-8@(C-TOCNF/ Agar) photoelectrode showed 95% degradation of tetracycline (TC) within 60 min under the irradiation of visible light with a reaction rate constant of 0.0489 min(-1). The photoelectrode enhanced the photogenerated electron generation and separation, while the free radical (center dot O-2(-)) and non-free radical (h(+) and O-1(2)) pathways could accelerate the TC degradation. Subsequently, liquid chromatograph-mass spectrometer (LC-MS) and phytotoxicity tests were used to detect the toxicity of the intermediates of the TC degradation process. The feasibility of the ZIF-8@(C-TOCNF/Agar) photoelectrode was further confirmed by applying it for the efficient removal of real wastewater. In this research, an economical and environmentally friendly technique for getting ready for flexible photoelectrodes was proposed, which provided a regulatory strategy for the synthesis and modification of photoelectrodes with a wide range of applications.

Periodate (PI, IO4 )-based advanced oxidation processes (AOPs) provide an economical and sustainable approach to alleviate water pollution challenges. Developing efficient and stable activators for PI is the focus of current research. Herein, S/Fe-co-doped magnetic porous carbon material (S/Fe-ZIF-950) was prepared by introducing exogenous S atoms using Fe-doped zeolitic imidazolate framework-8 (Fe-ZIF-8) as a precursor, which showed the most superior performance (100 % within 10 min) in activating PI to remove p-chlorophenol (4-CP). Quenching tests, electron spin resonance and electrochemical characterizations revealed that IO3 center dot, 1 O 2 , center dot O2 dominated the 4CP degradation process with Fe3C and ZnS as the main active sites. The synergistic effect of S and Fe was the main reason for the enhanced degradation performance of 4-CP in S/Fe-ZIF-950/PI system, among which the reducing S2 could effectively promote the regeneration of Fe(II), thus facilitating the continuous generation of active species. Combined with LC-MS results and density functional theory (DFT) calculations, possible degradation routes of 4-CP in the S/Fe-ZIF-950/PI system were presented. Moreover, toxicity assessment showed that the S/Fe-ZIF-950/PI system exhibited low biotoxicity and no toxic iodine by-products were formed. In addition, S/Fe-ZIF-950/PI system demonstrated excellent activity, good stability, outstanding reusability and durability in a variety of complex water environments. This study investigated the activation mechanism of S/Fe-co-doped porous carbon materials on PI, which shed a new light on the catalytic activation of PI by heteroatom-doped Fe-loaded carbon-based materials.