Structure Evolution of Iron (Hydr)oxides under Nanoconfinement and Its Implication for Water Treatment.

In the development of nanoenabled technologies for large-scale water treatment, immobilizing nanosized functional materials into the confined space of suitable substrates is one of the most effective strategies. However, the intrinsic effects of nanoconfinement on the decontamination performance of nanomaterials, particularly in terms of structural modulation, are rarely unveiled. Herein, we investigate the structure evolution and decontamination performance of iron (hydr)oxide nanoparticles, a widely used material for water treatment, when confined in track-etched (TE) membranes with channel sizes varying from 200 to 20 nm. Nanoconfinement drives phase transformation from ferrihydrite to goethite, rather than to hematite occurring in bulk systems, and the increase in the nanoconfinement degree from 200 to 20 nm leads to a significant drop in the fraction of the goethite phase within the aged products (from 41% to 0%). The nanoconfinement configuration is believed to greatly slow down the phase transformation kinetics, thereby preserving the specific adsorption of ferrihydrite toward As(V) even after 20-day aging at 343 K. This study unravels the structure evolution of confined iron hydroxide nanoparticles and provides new insights into the temporospatial effects of nanoconfinement on improving the water decontamination performance.

Unveiling the Occurrence and Potential Ecological Risks of Organophosphate Esters in Municipal Wastewater Treatment Plants across China.

Organophosphate esters (OPEs) discharged from wastewater treatment plants (WWTPs) have attracted increasing concerns because of their potential risks to aquatic ecosystems. The identification of the structures of OPEs is a prerequisite for subsequent assessment of their environmental impacts, which could hardly be accomplished using traditional target analytical methods. In this study, we describe the use of suspect and nontarget screening techniques for identification of organophosphate triesters and diesters (tri-OPEs and di-OPEs) in the influent and effluent samples acquired from 25 municipal WWTPs across China. There are totally 33 different OPE molecules identified, 11 of which are detected in wastewater for the first time and 4 are new to the public. In all tested samples, di-OPEs account for a significant portion (53% on average) of the total OPEs (ng/L-µg/L). More importantly, most of the OPEs could not be eliminated after treatment in these WWTPs, while some of the di-OPEs even accumulate. The research priority of OPEs in the effluent based on ecological risk was also analyzed, and the results reflected a previously unrecognized exposure risk of emerging OPEs for aquatic living organisms. These findings present a holistic understanding of the environmental relevance of OPEs in WWTPs on a country scale, which will hopefully provide guidance for the upgrade of treatment protocols in WWTPs and even for the modification of governmental regulations in the future.

Interaction between Organic Compounds and Catalyst Steers the Oxidation Pathway and Mechanism in the Iron Oxide-Based Heterogeneous Fenton System.

In the past decades, extensive efforts have been devoted to the mechanistic understanding of various heterogeneous Fenton reactions. Nevertheless, controversy still remains on the oxidation mechanism/pathway toward different organic compounds in the classical iron oxide-based Fenton reaction, largely because the role of the interaction between the organic compounds and the catalyst has been scarcely considered. Here, we revisited the classic heterogeneous ferrihydrite (Fhy)/H2O2 system toward different organic compounds on the basis of a series of degradation experiments, alcohol quenching experiments, theoretical modeling, and intermediate analysis. The Fhy/H2O2 system exhibited highly selective oxidation toward the group of compounds that bear carboxyl groups, which tend to complex with the surface ≡Fe(III) sites of the Fhy catalyst. Such interaction results in a nonradical inner sphere electron transfer process, which seizes one electron from the target compound and features negligible inhibition by the radical quencher. In contrast, for the oxidation of organic compounds that could not complex with the catalyst, the traditional HO· process makes the main contribution, which proceeds via hydroxyl addition reaction and could be readily suppressed by the radical quencher. This study implies that the interaction between the organic compounds and the catalyst plays a decisive role in the oxidation pathway and mechanism of the target compounds and provides a holistic understanding on the iron oxide-based heterogeneous Fenton system.

Mn2O3 as an Electron Shuttle between Peroxymonosulfate and Organic Pollutants: The Dominant Role of Surface Reactive Mn(IV) Species.

The environmentally benign Mn oxides play a crucial role in the transformation of organic contaminants, either through catalytically decomposing oxidants, e.g., peroxymonosulfate (PMS), or through directly oxidizing the target pollutants. Because of their dual roles and the complex surface chemical reactions, the mechanism involved in Mn oxide-catalyzed PMS activation processes remains obscure. Here, we clearly elucidate the mechanism involved in the Mn2O3 catalyzed PMS activation process by means of separating the PMS activation and the pollutant oxidation process. Mn2O3 acts as a shuttle that mediates the electron transfer from organic substrates to PMS, accompanied by the redox cycle of surface Mn(IV)/Mn(III). Multiple experimental results indicate that PMS is bound to the surface of Mn2O3 to form an inner-sphere complex, which then decomposes to form long-lived surface reactive Mn(IV) species, without the generation of sulfate radicals (SO4•-) and hydroxyl radicals (HO•). The surface reactive Mn(IV) species are proposed to be responsible for the degradation of organic contaminants (e.g., phenol) and the formation of singlet oxygen (1O2), followed by the regeneration of the surface Mn(III) sites on Mn2O3. This study advances the fundamental understanding of the underlying mechanism involved in transition metal oxide-catalyzed PMS activation processes.

Singlet oxygen mediated iron-based Fenton-like catalysis under nanoconfinement.

For several decades, the iron-based Fenton-like catalysis has been believed to be mediated by hydroxyl radicals or high-valent iron-oxo species, while only sporadic evidence supported the generation of singlet oxygen (1O2) in the Haber-Weiss cycle. Herein, we report an unprecedented singlet oxygen mediated Fenton-like process catalyzed by ∼2-nm Fe2O3 nanoparticles distributed inside multiwalled carbon nanotubes with inner diameter of ∼7 nm. Unlike the traditional Fenton-like processes, this delicately designed system was shown to selectively oxidize the organic dyes that could be adsorbed with oxidation rates linearly proportional to the adsorption affinity. It also exhibited remarkably higher degradation activity (22.5 times faster) toward a model pollutant methylene blue than its nonconfined analog. Strikingly, the unforeseen stability at pH value up to 9.0 greatly expands the use of Fenton-like catalysts in alkaline conditions. This work represents a fundamental breakthrough toward the design and understanding of the Fenton-like system under nanoconfinement, might cause implications in other fields, especially in biological systems.

Molecular Origin of the Biologically Accelerated Mineralization of Hydroxyapatite on Bacterial Cellulose for More Robust Nanocomposites.

Biomineralization generates hierarchically structured minerals with vital biological functions in organisms. This strategy has been adopted to construct complex architectures to achieve similar functionalities, mostly under chemical environments mimicking biological components. The molecular origin of the biofacilitated mineralization process is elusive. Herein, we describe the mineralization of hydroxyapatite (HAp) accompanying the biological secretion of nanocellulose by Acetobacter xylinum. In comparison with mature cellulose, the newly biosynthesized cellulose molecules greatly accelerate the nucleation rate and facilitate the uniform distribution of HAp crystals, thereby generating composites with a higher Young modulus. Both simulations and experiments indicate that the biological metabolism condition allows the easier capture of calcium ions by the more abundant hydroxyl groups on the glucan chain before the formation of hydrogen bonding, for the subsequent growth of HAp crystals. Our work provides more insights into the biologically accelerated mineralization process and presents a different methodology for the generation of biomimetic nanocomposites.

Overturned Loading of Inert CeO2 to Active Co3 O4 for Unusually Improved Catalytic Activity in Fenton-Like Reactions.

In the past decades, numerous efforts have been devoted to improving the catalytic activity of nanocomposites by either exposing more active sites or regulating the interaction between the support and nanoparticles while keeping the structure of the active sites unchanged. Here, we report the fabrication of a Co3 O4 -CeO2 nanocomposite via overturning the loading direction, i.e., loading an inert CeO2 support onto active Co3 O4 nanoparticles. The resultant catalyst exhibits unexpectedly higher activity and stability in peroxymonosulfate-based Fenton-like reactions than its analog prepared by the traditional impregnation method. Abundant oxygen vacancies (Ov with a Co⋅⋅⋅Ov ⋅⋅⋅Ce structure instead of Co⋅⋅⋅Ov ) are generated as new active sites to facilitate the cleavage of the peroxide bond to produce SO4 .- and accelerate the rate-limiting step, i.e., the desorption of SO4 .- , affording improved activity. This strategy is a new direction for boosting the catalytic activity of nanocomposite catalysts in various scenarios, including environmental remediation and energy applications.

Dual-Functionalized MIL-101(Cr) for the Selective Enrichment and Ultrasensitive Analysis of Trace Per- and Poly-fluoroalkyl Substances.

The presence of per- and poly-fluoroalkyl substances (PFASs) even at trace levels poses a potential threat to ecological safety and human health. PFASs often require an extraction pretreatment for enrichment before detection and analysis, which is still challenged by the relatively low efficiency because of the limited specific interactions involved. Here, we deliberately introduced multiple interactions into the solid-phase microextraction (SPME) process via a dual-functional modification of MIL-101(Cr), i.e., amination and subsequent fluorination, which is then used as an adsorbent for the efficient enrichment of PFASs. In combination with ultra-high-performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS), ultrasensitive quantitative analysis is available for nine selected PFASs with high linearities above 0.9941 in the ranges of 0.5-1500 ng/L, low limits of detection of 0.004-0.12 ng/L, satisfactory repeatability and reproducibility with a relative standard deviation (RSD) < 11.6%, as well as excellent performance in complicated real water samples (recovery ratio of 76.2-108.6%). This work represents a rational design of a solid extractant with the desired structure and functionality for the selective enrichment and analysis of PFASs at trace concentrations in real applications.

Are Free Radicals the Primary Reactive Species in Co(II)-Mediated Activation of Peroxymonosulfate? New Evidence for the Role of the Co(II)-Peroxymonosulfate Complex.

The catalytic activation of peroxymonosulfate (PMS) is under intensive investigation with potentials as an alternative advanced oxidation process (AOP) in wastewater treatment. Among all catalysts examined, Co(II) exhibits the highest reactivity for the activation of PMS, following the conventional Fenton-like mechanism, in which free radicals (i.e., sulfate radicals and hydroxyl radicals) are reckoned as the reactive species. Herein, we report that the primary reactive species (PRS) is proposed to be a Co(II)-PMS complex (Co(II)-OOSO3-), while free radicals and Co(III) species act as the secondary reactive species (SRS) that play a minor role in the Co(II)/PMS process. This Co(II)-OOSO3- exhibits several intriguing properties including ability to conduct both one-electron-transfer and oxygen-atom-transfer reactions with selected molecules, both nucleophilic and electrophilic in nature, and strongly pH-dependent reactivity. This study provides novel insights into the chemical nature of the Co(II)-catalyzed PMS activation process.

Structural Evolution of Lanthanum Hydroxides during Long-Term Phosphate Mitigation: Effect of Nanoconfinement.

Lanthanum (La)-based materials are effective in removing phosphate (P) from water to prevent eutrophication. Compared to their bulky analogues, La(OH)3 nanoparticles exhibit a higher P removal efficiency and a more stable P removal ability when spatially confined inside the host. Consequently, the understanding of the nanoconfinement effects on the long-term evolution of La-P structures is crucial for their practical use in P sequestration and recycle, which, however, is still missing. Here, we describe an attempt to explore the evolution of La-P structures, the P environment, and the status of La(OH)3 nanoparticles confined in the nanopores of the D201 resin, compared to a nonconfined analogue, over a P adsorption period of 25 days in both simulated wastewater and the real bioeffluent. A combinative use of X-ray diffraction (XRD), cross-polarization nuclear magnetic resonance (CP-NMR), and X-ray photoelectron spectroscopy (XPS) techniques confirms the transition from La-P inner-sphere complexation to the formation of LaPO4·xH2O and finally to LaPO4 in both samples. Interestingly, the rate of structural transformation in the real bioeffluent is substantially reduced. Nevertheless, in both conditions, nanoconfinement results in a much faster rate and larger extent of the structural transition. Moreover, nanoconfinement also facilitates the reverse transformation of stable LaPO4 back to La(OH)3. Our work provides the scientific basis of nanoconfinement for the preferable use of La-based nanocomposites in P mitigation, immobilization, and recycle application.

Toward Selective Oxidation of Contaminants in Aqueous Systems.

The presence of diverse pollutants in water has been threating human health and aquatic ecosystems on a global scale. For more than a century, chemical oxidation using strongly oxidizing species was one of the most effective technologies to destruct pollutants and to ensure a safe and clean water supply. However, the removal of increasing amount of pollutants with higher structural complexity, especially the emerging micropollutants with trace concentrations in the complicated water matrix, requires excessive dosage of oxidant and/or energy input, resulting in a low cost-effectiveness and possible secondary pollution. Consequently, it is of practical significance but scientifically challenging to achieve selective oxidation of pollutants of interest for water decontamination. Currently, there are a variety of examples concerning selective oxidation of pollutants in aqueous systems. However, a systematic understanding of the relationship between the origin of selectivity and its applicable water treatment scenarios, as well as the rational design of catalyst for selective catalytic oxidation, is still lacking. In this critical review, we summarize the state-of-the-art selective oxidation strategies in water decontamination and probe the origins of selectivity, that is, the selectivity resulting from the reactivity of either oxidants or target pollutants, the selectivity arising from the accessibility of pollutants to oxidants via adsorption and size exclusion, as well as the selectivity due to the interfacial electron transfer process and enzymatic oxidation. Finally, the challenges and perspectives are briefly outlined to stimulate future discussion and interest on selective oxidation for water decontamination, particularly toward application in real scenarios.

Nanoconfinement-Mediated Water Treatment: From Fundamental to Application.

Safe and clean water is of pivotal importance to all living species and the ecosystem on earth. However, the accelerating economy and industrialization of mankind generate water pollutants with much larger quantity and higher complexity than ever before, challenging the efficacy of traditional water treatment technologies. The flourishing researches on nanomaterials and nanotechnologies in the past decade have generated new understandings on many fundamental processes and brought revolutionary upgrades to various traditional technologies in almost all areas, including water treatment. An indispensable step toward the real application of nanomaterials in water treatment is to confine them in large processable substrate to address various inherent issues, such as spontaneous aggregation, difficult operation and potential environmental risks. Strikingly, when the size of the spatial restriction provided by the substrate is on the order of only one or several nanometers, referred to as nanoconfinement, the phase behavior of matter and the energy diagram of a chemical reaction could be utterly changed. Nevertheless, the relationship between such changes under nanoconfinement and their implications for water treatment is rarely elucidated systematically. In this Critical Review, we will briefly summarize the current state-of-the-art of the nanomaterials, as well as the nanoconfined analogues (i.e., nanocomposites) developed for water treatment. Afterward, we will put emphasis on the effects of nanoconfinement from three aspects, that is, on the structure and behavior of water molecules, on the formation (e.g., crystallization) of confined nanomaterials, and on the nanoenabled chemical reactions. For each aspect, we will build the correlation between the nanoconfinement effects and the current studies for water treatment. More importantly, we will make proposals for future studies based on the missing links between some of the nanoconfinement effects and the water treatment technologies. Through this Critical Review, we aim to raise the research attention on using nanoconfinement as a fundamental guide or even tool to advance water treatment technologies.

Mn3 O4 /N-Doped Graphite Catalysts from Wastewater for the Degradation of Methylene Blue.

The accelerating research interest in graphene involving the use of Hummers method has generated non-negligible amount of wastewater containing residual graphite as well as Mn2+ . In this paper, we report the first example of using this wastewater as precursor to prepare Mn3 O4 /N-doped graphite (NG) composites through a facile solvothermal process. The mass fraction of Mn3 O4 in the composites was manipulated by adding various amounts of extra Mn2+ . The conversion of Mn2+ to Mn3 O4 nanoparticles and the N atoms doping were achieved by adding hydrazine hydrate and ammonia into the system. The as-obtained Mn3 O4 /NG composites were well characterized by SEM, TEM, EDS, Raman, XPS, TGA, XRD and N2 adsorption-desorption experiments and showed excellent catalytic performances as well as stability in the degradation of a model organic pollutant methylene blue (MB). Theoretical simulation was also carried out to illustrate the structural features of the Mn3 O4 /NG composite. This work presents a novel idea of designing functional materials from waste precursors.

N-Doped Carbon Nanofibrous Network Derived from Bacterial Cellulose for the Loading of Pt Nanoparticles for Methanol Oxidation Reaction.

The large-scale, low-cost preparation of Pt-based catalysts with high activity and durability for the methanol oxidation reaction is still challenging. The key to achieving this aim is finding suitable supporting materials. In this paper, N-doped carbon nanofibrous networks are prepared by annealing a gel containing two inexpensive and ecofriendly precursors, that is, bacterial cellulose and urea, for the loading of Pt nanoparticles. An undoped analogue is also prepared for comparison. Meanwhile, the effect of the annealing temperature on the performance of the catalysts is evaluated. The results show that the N doping and higher annealing temperature can improve the electron conductivity of the catalyst and provide more active sites for the loading of ultrafine Pt nanoparticles with a narrow size distribution. The best catalyst exhibits a remarkably high electrocatalytic activity (627 mA mg-1 ), excellent poison tolerance, and high durability. This work demonstrates an ideal Pt supporting material for the methanol oxidation reaction.

Highly Efficient Water Decontamination by Using Sub-10 nm FeOOH Confined within Millimeter-Sized Mesoporous Polystyrene Beads.

Millimeter-sized polymer-based FeOOH nanoparticles (NPs) provide a promising option to overcome the bottlenecks of direct use of NPs in scaled-up water purification, and decreasing the NP size below 10 nm is expected to improve the decontamination efficiency of the polymeric nanocomposites due to the size and surface effect. However, it is still challenging to control the dwelled FeOOH NP sizes to sub-10 nm, mainly due to the wide pore size distribution of the currently available polymeric hosts. Herein, we synthesized mesoporous polystyrene beads (MesoPS) via flash freezing to assemble FeOOH NPs. The embedded NPs feature with α-crystal form, tunable size ranging from 7.3 to 2.0 nm and narrow size distribution. Adsorption of As(III/V) by the resultant nanocomposites was greatly enhanced over the α-FeOOH NPs of 18 × 60 nm, with the iron mass normalized capacity of As(V) increasing to 10.3 to 14.8 fold over the bulky NPs. Higher density of the surface hydroxyl groups of the embedded NPs as well as their stronger affinity toward As(V) was proved to contribute to such favorable effect. Additionally, the as-obtained nanocomposites could be efficiently regenerated for cyclic runs. We believe this study will shed new light on how to fabricate highly efficient nanocomposites for water decontamination.

Fabrication of Novel Magnetic Nanoparticles of Multifunctionality for Water Decontamination.

Efficient and powerful water purifiers are in increasing need because we are facing a more and more serious problem of water pollution. Here, we demonstrate the design of versatile magnetic nanoadsorbents (M-QAC) that exhibit excellent disinfection and adsorption performances at the same time. The M-QAC is constructed by a Fe3O4 core surrounded by a polyethylenimine-derived corona. When dispersed in water, the M-QAC particles are able to interact simultaneously with multiple contaminants, including pathogens and heavy metallic cations and anions, in minutes. Subsequently, the M-QACs along with those contaminants can be easily removed and recollected by using a magnet. Meanwhile, the mechanisms of disinfection are investigated by using TEM and SEM, and the adsorption mechanisms are analyzed by XPS. In a practical application, M-QACs are applied to polluted river water 8000-fold greater in mass, producing clean water with the concentrations of all major pollutants below the drinking water standard of China. The adsorption ability of M-QAC could be regenerated for continuous use in a facile manner. With more virtues, such as low-cost fabrication and easy scaling up, the M-QAC have been shown to be a very promising multifunctional water purifier with rational design and to have great potential for real water purification applications.

Uniform, high aspect ratio fiber-like micelles and block co-micelles with a crystalline π-conjugated polythiophene core by self-seeding.

Monodisperse fiber-like micelles with a crystalline π-conjugated polythiophene core with lengths up to ca. 700 nm were successfully prepared from the diblock copolymer poly(3-hexylthiophene)-block-polystyrene using a one-dimensional self-seeding technique. Addition of a polythiophene block copolymer with a different corona-forming block to the resulting nanofibers led to the formation of segmented B-A-B triblock co-micelles by crystallization-driven seeded growth. The key to these advances appears to be the formation of a relatively defect-free crystalline micelle core under the self-seeding conditions.

A high-sensitivity lanthanide nanoparticle reporter for mass cytometry: tests on microgels as a proxy for cells.

This paper addresses the question of whether one can use lanthanide nanoparticles (e.g., NaHoF4) to detect surface biomarkers expressed at low levels by mass cytometry. To avoid many of the complications of experiments on live or fixed cells, we carried out proof-of-concept experiments using aqueous microgels with a diameter on the order of 700 nm as a proxy for cells. These microgels were used to test whether nanoparticle (NP) reagents would allow the detection of as few as 100 proteins per "cell" in cell-by-cell assays. Streptavidin (SAv), which served as the model biomarker, was attached to the microgel in two different ways. Covalent coupling to surface carboxyls of the microgel led to large numbers (>10(4)) of proteins per microgel, whereas biotinylation of the microgel followed by exposure to SAv led to much smaller numbers of SAv per microgel. Using mass cytometry, we compared two biotin-containing reagents, which recognized and bound to the SAvs on the microgel. One was a metal chelating polymer (MCP), a biotin end-capped polyaspartamide containing 50 Tb(3+) ions per probe. The other was a biotinylated NaHoF4 NP containing 15 000 Ho atoms per probe. Nonspecific binding was determined with bovine serum albumin (BSA) conjugated microgels. The MCP was effective at detecting and quantifying SAvs on the microgel with covalently bound SAv (20 000 SAvs per microgel) but was unable to give a meaningful signal above that of the BSA-coated microgel for the samples with low levels of SAv. Here the NP reagent gave a signal 2 orders of magnitude stronger than that of the MCP and allowed detection of NPs ranging from 100 to 500 per microgel. Sensitivity was limited by the level of nonspecific adsorption. This proof of concept experiment demonstrates the enhanced sensitivity possible with NP reagents in cell-by-cell assays by mass cytometry.

Investigating the evolution of reactive species in the CuO-mediated peroxymonosulfate activation process.

The utilization of copper oxide (CuO) as a catalyst in the peroxymonosulfate (PMS) activation process holds great promise for effectively degrading aqueous organic pollutants, while the relevant mechanism remains inadequately understood. In this study, we delve into the evolution pathways of reactive species in the CuO/PMS system through a comprehensive series of experimental analyses. Our findings indicate that various reactive species are generated in the CuO/PMS system with the specific sequence, where the decomposition of surface Cu(II)-OOSO3- leads to the formation of surface Cu(III) species, which are responsible for the subsequent generation of HO•. The reactivity of these reactive species and the sequence of their generation explain the distinct oxidation behaviors of pollutants with different values of ionization potential (IP). In addition, singlet oxygen (1O2) may be produced during the PMS activation process, while its involvement in the oxidation of substrates is deemed negligible. This investigation presents a novel perspective, enhancing our comprehension of the mechanism underlying transition metal-mediated PMS activation processes. ENVIRONMENTAL IMPLICATION: The removal of refractory organic contaminations in water constitutes a fundamental concern within the realm of environmental pollution management. Peroxymonosulfate activation induced by transition metal oxides has garnered significant recognition as a promising technological approach for the degradation of aqueous organic contaminants, while the underlying mechanism remains enigmatic. In this study, we systematically investigate the evolution pathways of reactive species in the CuO/peroxymonosulfate system to reveal the mystery of the reaction mechanism between CuO and peroxymonosulfate. The outcomes of our study contribute to enhancing the practical applicability of transition metal-triggered PMS activation processes.

Nanoconfinement-triggered oligomerization pathway for efficient removal of phenolic pollutants via a Fenton-like reaction.

Heterogeneous Fenton reaction represents one of the most reliable technologies to ensure water safety, but is currently challenged by the sluggish Fe(III) reduction, excessive input of chemicals for organic mineralization, and undesirable carbon emission. Current endeavors to improve the catalytic performance of Fenton reaction are mostly focused on how to accelerate Fe(III) reduction, while the pollutant degradation step is habitually overlooked. Here, we report a nanoconfinement strategy by using graphene aerogel (GA) to support UiO-66-NH2-(Zr) binding atomic Fe(III), which alters the carbon transfer route during phenol removal from kinetically favored ring-opening route to thermodynamically favored oligomerization route. GA nanoconfinement favors the Fe(III) reduction by enriching the reductive intermediates and allows much faster phenol removal than the unconfined analog (by 208 times in terms of first-order rate constant) and highly efficient removal of total organic carbon, i.e., 92.2 ± 3.7% versus 3.6 ± 0.3% in 60 min. Moreover, this oligomerization route reduces the oxidant consumption for phenol removal by more than 95% and carbon emission by 77.9%, compared to the mineralization route in homogeneous Fe2++H2O2 system. Our findings may upgrade the regulatory toolkit for Fenton reactions and provide an alternative carbon transfer route for the removal of aqueous pollutants.