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.

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.

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.

Self-carbon-thermal-reduction strategy for boosting the Fenton-like activity of single Fe-N4 sites by carbon-defect engineering.

Carbon-defect engineering in metal single-atom catalysts by simple and robust strategy, boosting their catalytic activity, and revealing the carbon defect-catalytic activity relationship are meaningful but challenging. Herein, we report a facile self-carbon-thermal-reduction strategy for carbon-defect engineering of single Fe-N4 sites in ZnO-Carbon nano-reactor, as efficient catalyst in Fenton-like reaction for degradation of phenol. The carbon vacancies are easily constructed adjacent to single Fe-N4 sites during synthesis, facilitating the formation of C-O bonding and lowering the energy barrier of rate-determining-step during degradation of phenol. Consequently, the catalyst Fe-NCv-900 with carbon vacancies exhibits a much improved activity than the Fe-NC-900 without abundant carbon vacancies, with 13.5 times improvement in the first-order rate constant of phenol degradation. The Fe-NCv-900 shows high activity (97% removal ratio of phenol in only 5 min), good recyclability and the wide-ranging pH universality (pH range 3-9). This work not only provides a rational strategy for improving the Fenton-like activity of metal single-atom catalysts, but also deepens the fundamental understanding on how periphery carbon environment affects the property and performance of metal-N4 sites.

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.

Single-Atom Fe Catalysts for Fenton-Like Reactions: Roles of Different N Species.

Recognizing and controlling the structure-activity relationships of single-atom catalysts (SACs) is vital for manipulating their catalytic properties for various practical applications. Herein, Fe SACs supported on nitrogen-doped carbon (SA-Fe/CN) are reported, which show high catalytic reactivity (97% degradation of bisphenol A in only 5 min), high stability (80% of reactivity maintained after five runs), and wide pH suitability (working pH range 3-11) toward Fenton-like reactions. The roles of different N species in these reactions are further explored, both experimentally and theoretically. It is discovered that graphitic N is an adsorptive site for the target molecule, pyrrolic N coordinates with Fe(III) and plays a dominant role in the reaction, and pyridinic N, coordinated with Fe(II), is only a minor contributor to the reactivity of SA-Fe/CN. Density functional theory (DFT) calculations reveal that a lower d-band center location of pyrrolic-type Fe sites leads to the easy generation of Fe-oxo intermediates, and thus, excellent catalytic properties.

Synthesis, characterization and performances of green rusts for water decontamination: A review.

In recent years, the application of green rusts (GRs) for water purification has received significant attention, but its full understanding has not been well achieved. Then, the comprehension about the synthesis and characteristics of GRs can highly favor their decontamination performances for the site-specific conditions. This review comprehensively summarized the synthesis, characteristics and performances of GRs including the GR (Cl-), GR (CO32-) and GR (SO42-) for sequestration of various aqueous pollutants (e.g., tetrachloride, Cr(VI), Se(VI), and U(VI), etc.). Generally, the different reactivity of GRs toward contaminants is strongly dependent on the GRs' characteristics (e.g., interlayer distance, specific surface area, and Fe(II) content) and solution chemistry (e.g., pH, background electrolytes, dissolved oxygen, and contaminant concentration, etc.). In addition, the reaction mechanisms of GRs with the contaminants involve the redox reactions, adsorption, catalytic oxidation, interlayer and octahedral incorporation, which can mutually or singly contribute to the decontamination to varying degrees. Particularly, this review addressed the transformation pathways of GRs under various solution chemistry conditions and clarified that the stability of GRs should be the key challenge for the real application. Finally, how to effectively use the GRs for water decontamination was proposed, which will significantly benefit the rational control of environmental pollution.

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.

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.

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.

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.

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.

Degradation of phosphonates in Co(II)/peroxymonosulfate process: Performance and mechanism.

The increased release of phosphonates to natural waters causes global concern due to their potential threat to the aquatic environment. It is curial to mineralize phosphonates to orthophosphate (PO43-) before they are thoroughly removed from wastewater via conventional biological treatment. In this study, we systematically investigated the performance and mechanism of degradation of phosphonates in Co(II)-triggered peroxymonosulfate (PMS) activation process. The degradation efficiency of various phosphonates is highly dependent on their coordination with Co(II). Using 1-hydroxyethane 1,1-diphosphonic acid (HEDP) as a target pollutant, the Co(II)/PMS process is effective in a broad solution pH range from 5.0 to 10.0. Multiple experimental results imply that Co(II)-PMS complex is the primary reactive species, while hydroxyl radicals (HO•), sulfate radicals (SO4•-), singlet oxygen (1O2) and Co(III) play as the secondary reactive species for the degradation of HEDP. The presence of Cl-, HCO3-, and natural organic matters (NOM) inhibits the degradation of HEDP. However, in real water samples, the selectivity and efficiency for HEDP removal in the Co(II)/PMS process are higher than that in free radicals-mediated advanced oxidation processes. This study not only sheds new lights on the mechanism of Co(II)-triggered PMS activation process, but also provides feasible technology for the degradation of phosphonates in wastewater.

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.

Free-standing SnS/carbonized cellulose film as durable anode for lithium-ion batteries.

Metal sulfides have recently attracted broad attention for lithium-ion batteries (LIB) owing to their high theoretical capacity and long lifetime. However, the inferior structural integrity and low electron conductivity of metal sulfides limit their practical applications. A feasible strategy is to distribute these materials in conductive carbonaceous substrates with shapeable morphology. Here we report the design of free-standing films of tin sulfide (SnS) nanosheets distributed uniformly on carbonized bacterial cellulose (CBC) nanofibers. The SnS/CBC composites possess three dimensional interconnected nanostructures, which is crucial for the high conductivity and high lithium storage capacity. LIB using SnS/CBC as anode exhibits a reversible capacity of 872 mA h g-1 at 100 mA g-1 after 100 cycles, and the capacity remains as high as 527 mA h g-1 at 2000 mA g-1 after 1000 cycles. The free-standing sulfide-based nanocomposites with unique nanostructure composition and flexibility could be utilized as promising electrode materials for future LIB systems.

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.

Enhanced production of methane in anaerobic water treatment as mediated by the immobilized fungi.

Anaerobic digestion of organic waste and wastewater represents an attractive sustainable bio-technology to produce methane as an alternative to fossil energy. In response to improvement of methane production via enhancing methanogenesis, current strategies of the addition of external biological/non-biological materials have to confront either the loss of materials, high cost and/or possible destruction of the microbial community. Here, we report the first case of using immobilized fungi Aspergillus sydowii 8L-9-F02 to optimize the microbial community, achieving remarkable improvement of the methane production in both batch test (1.5 times) and continuous flow operation (1.13-1.31 times). The crucial role of fungi is associated with the stimulation of enrichment of Methanosaeta and Methanobacterium for methanogenesis from 28.2 to 67.4% as well as the improved activity of enzyme F420. Moreover, fungi also increase the content of extracellular polymeric substances, facilitating the formation of bio-aggregates. This work provides a new pathway to enhance methanogenesis during anaerobic digestion of wastewater by using fungi as bio-enhancer.

Film-like bacterial cellulose/cyclodextrin oligomer composites with controllable structure for the removal of various persistent organic pollutants from water.

The adsorptive removal of persistent organic pollutants (POPs) is reckoned as a simple, convenient, and practical technology, especially in decentralized systems and remote areas. For this purpose, it is important to design new adsorbents, with controllable structure and convenient shape, for the highly efficient removal of POPs. In this study, we describe a strategy for film-like water purifier, prepared by loading cyclodextrin (CD) oligomer onto the ultrafine nanofibers of 3D bacterial cellulose. The optimum product exhibits remarkable removal ability toward various target pollutants such as phenol, bisphenol A (BPA), glyphosate and 2,4-Dichlorophenol (2,4-DCP), with capacities higher than most adsorbents including porous carbon based materials reported previously. Moreover, our sample demonstrated stable adsorption ability over a broad pH range and under more complex water conditions, and more importantly excellent reusability. A rough cost analysis highlights the commercial potential of our sample. We reckon our study provides new insight for the design of adsorbent with high yet stable adsorption ability and controllable structure. Furthermore, the product can be used to treat actual sewage with its convenient film-like shape and excellent performance, which improves its potential in complex systems and large-scale applications.