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Single-atom catalysts (SACs) with atomic dispersion active sites have exhibited huge potentials in peroxymonosulfate (PMS)-based Fenton-like chemistry in water purification. However, four-N coordination metal (MN4) moieties often suffer from such problems as low selectivity and narrow workable pH. How to construct SACs in a controllable strategy with optimized electronic structures is of great challenge. Herein, an innovative strategy (i.e., the "4 + 1" fabrication) was devised to precisely modulate the first-shell coordinated microenvironment of FeN4 SAC using an additional N (SA-FeN5). This leads to almost 100% selective formation of high-valent iron-oxo [Fe(IV)âO] (steady-state concentration: 2.00 × 10-8 M) in the SA-FeN5/PMS system. In-depth theoretical calculations unveil that FeN5 configuration optimizes the electron distribution of monatomic Fe sites, which thus fosters PMS adsorption and reduces the energy barrier for Fe(IV)âO generation. SA-FeN5 was then attached to polyvinylidene difluoride membrane for a continuous flow device, showing long-term abatement of the microcontaminant. This work furnishes a general strategy for effective PMS activation and selective high-valent metal-oxo species generation by high N-coordination number regulation in SACs, which would provide guidance in the rational design of superior environmental catalysts for water purification.
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The global ecological crisis of perfluoroalkyl and polyfluoroalkyl substances (PFASs) in drinking water has gradually shifted from long-chain to short-chain PFASs; however, the widespread established PFAS adsorption technology cannot cope with the impact of such hydrophilic pollutants given the inherent defects of solid-liquid mass transfer. Herein, we describe a reagent-free and low-cost strategy to reduce the energy state of short-chain PFASs in hydrophobic nanopores by employing an in situ constructed confined water structure in activated carbon (AC). Through direct (driving force) and indirect (assisted slip) effects, the confined water introduced a dual-drive mode in the confined water-encapsulated activated carbon (CW-AC) and completely eliminated the mass transfer barrier (3.27 to 5.66 kcal/mol), which caused the CW-AC to exhibit the highest adsorption capacity for various short-chain PFASs (C-F number: 3-6) among parent AC and other adsorbents reported. Meanwhile, benefiting from the chain length- and functional group-dependent confined water-binding pattern, the affinity of the CW-AC surpassed the traditional hydrophobicity dominance and shifted toward hydrophilic short-chain PFASs that easily escaped treatment. Importantly, the ability of CW-AC functionality to directly transfer to existing adsorption devices was verified, which could treat 21,000 bed volumes of environment-related high-load (~350 ng/L short-chain PFAS each) real drinking water to below the World Health Organization's standard. Overall, our results provide a green and cost-effective in situ upgrade scheme for existing adsorption devices to address the short-chain PFAS crisis.
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Single-atom Fenton-like catalysis has attracted significant attention, yet the quest for controllable synthesis of single-atom catalysts (SACs) with modulation of electron configuration is driven by the current disadvantages of poor activity, low selectivity, narrow pH range, and ambiguous structure-performance relationship. Herein, we devised an innovative strategy, the slow-release synthesis, to fabricate superior Cu SACs by facilitating the dynamic equilibrium between metal precursor supply and anchoring site formation. In this strategy, the dynamics of anchoring site formation, metal precursor release, and their binding reaction kinetics were regulated. Bolstered by harmoniously aligned dynamics, the selective and specific monatomic binding reactions were ensured to refine controllable SACs synthesis with well-defined structure-reactivity relationship. A copious quantity of monatomic dispersed metal became deposited on the C3N4/montmorillonite (MMT) interface and surface with accessible exposure due to the convenient mass transfer within ordered MMT. The slow-release effect facilitated the generation of targeted high-quality sites by equilibrating the supply and demand of the metal precursor and anchoring site and improved the utilization ratio of metal precursors. An excellent Fenton-like reactivity for contaminant degradation was achieved by the Cu1/C3N4/MMT with diminished toxic Cu liberation. Also, the selective ·OH-mediated reaction mechanism was elucidated. Our findings provide a strategy for regulating the intractable anchoring events and optimizing the microenvironment of the monatomic metal center to synthesize superior SACs.
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In the state-of-the-art membrane industry, membranes have linear life cycles and are commonly disposed of by landfill or incineration, sacrificing their sustainability. To date, little or no thought is given in the design phase to the end-of-life management of membranes. For the first time, we have innovated high-performance sustainable membranes, which can be closed-loop recycled after long-term usage for water purification. By synergizing membrane technology and dynamic covalent chemistry, covalent adaptable networks (CANs) with thermally reversible Diels-Alder (DA) adducts were synthesized and employed to fabricate integrally skinned asymmetric membranes via the nonsolvent-induced phase separation technique. Due to the stable and reversible features of CAN, the closed-loop recyclable membranes exhibit excellent mechanical properties and thermal and chemical stabilities as well as separation performance, which are comparable to or even higher than the state-of-the-art nonrecyclable membranes. Moreover, the used membranes can be closed-loop recycled with consistent properties and separation performance by depolymerization to remove contaminants, followed by refabrication into new membranes through the dissociation and reformation of DA adducts. This study may fill in the gaps in closed-loop recycling of membranes and inspire the advancement of sustainable membranes for a green membrane industry.
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Solar-driven clean water production is challenged by VOCs (volatile organic compounds), which pose health risks in distilled water. Herein, we developed a Cu/W18O49@Graphene photothermal-photocatalytic material addressing VOCs contamination. Plasmonic coupling between Cu and W18O49 enhances light absorption, and 1-2 layers of graphene encapsulation protects oxygen vacancies within W18O49 while facilitating hot electron extraction, effectively mitigating their ultrafast relaxation. Density functional theory calculations revealed enhanced VOCs adsorption on graphene. These synergies address oxygen vacancy decay in W18O49 and provide more active sites for gas-liquid-solid triphase photocatalytic reactions. Integrated with a three-dimensional floating evaporator substrate, the optimized Cu/W18O49@Graphene material achieved an effective water evaporation rate of 1.41 kg m-2 h-1 (efficiency of 88.6%), exceptional stability (>120 h), and remarkable 99% phenol removal under 1 sun irradiation (1 kW m-2). This work provides a promising solution to mitigate VOCs contamination in solar-driven water evaporation.
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Photocatalytic membranes can effectively integrate membrane separation and photocatalytic degradation processes to provide an eco-friendly solution for efficient water purification. It is of great significance to develop highly efficient photocatalytic membranes driven by visible light to ensure the long-term stability of membrane separation systems and the maximum utilization of solar energy. Metal-organic framework (MOF) is an emerging photocatalyst with a well-defined structure and tunable chemical properties, showing a broad application prospect in the construction of high-performance photocatalytic membranes. Herein, this work provides a comprehensive review of recent advancements in MOF-based photocatalytic membranes. Initially, this work outlines the main tailoring strategies that facilitate the enhancement of the photocatalytic activity of MOF-based photocatalysts. Next, this work introduces commonly used methods for fabricating MOF-based photocatalytic membranes. Subsequently, this work discusses the application and mechanisms of MOF-based photocatalytic membranes toward organic pollutant degradation, metal ion removal, and membrane fouling mitigation. Finally, challenges in developing MOF-based photocatalytic membranes and their practical applications are presented, while also pointing out future research directions toward overcoming these existing limitations.
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To address current energy crises and environmental concerns, it is imperative to develop and design versatile porous materials ideal for water purification and energy storage. The advent of covalent organic frameworks (COFs), a revolutionary terrain of porous materials, is underscored by their superlative features such as divinable structure, adjustable aperture, and high specific surface area. However, issues like inferior electric conductivity, inaccessible active sites impede mass transfer and poor processability of bulky COFs restrict their wider application. As a herculean stride forward, COF/graphene hybrids amalgamate the strengths of their constituent components and have in consequence, enticed significant scientific intrigue. Herein, the current progress on the structure and properties of graphene-based materials and COFs are systematically outlined. Then, synthetic strategies for preparing COF/graphene hybrids, including one-pot synthesis, ex situ synthesis, and in situ growth, are comprehensively reviewed. Afterward, the pivotal attributes of COF/graphene hybrids are dissected in conjunction with their multifaceted applications spanning adsorption, separation, catalysis, sensing, and energy storage. Finally, this review is concluded by elucidating prevailing challenges and gesturing toward prospective strides within the realm of COF/graphene hybrids research.
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MXene's configuration, whether it is aggregated or dispersed in a monolayer, determines the specific application areas and even greatly influences the intrinsic properties of MXene. However, how to desirably control MXene's configuration is challenging. Here, a simple, additive-free, chemical reaction-free, and scalable strategy to optionally and reversibly regulate MXene's ordered stacking and delamination of MXene aggregates (AM) is reported. Just by controlled freezing of MXene aqueous dispersions, the aggregation percentage, delamination percentage, and interlayer spacing of AM can be finely tuned. Experimental results reveal that the freezing-induced aggregation and delamination effects can be explained by the squeezing action of growing ice grains on the MXene excluded/concentrated between ice grains and the expanding action caused by the ice formation between AM lamellae, respectively. The dominance between them depends on the freezing parameter-influenced ice nucleation sites, numbers, and ice grain sizes. This work not only contributes to the preparation, storage, and practical applications of MXene, but also opens a new and green avenue for controlling materials' assembly structures.
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A new method to engineer hierarchically porous zeolitic imidazolate frameworks (ZIFs) through selective ligand removal (SeLiRe) is presented. This innovative approach involves crafting mixed-ligand ZIFs (ML-ZIFs) with varying proportions of 2-aminobenzimidazole (NH2-bIm) and 2-methylimidazole (2-mIm), followed by controlled thermal treatments. This process creates a dual-pore system, incorporating both micropores and additional mesopores, suggesting selective cleavage of metal-ligand coordination bonds. Achieving this delicate balance requires adjustment of heating conditions for each mixed-ligand ratio, enabling the targeted removal of NH2-bIm from a variety of ML-ZIFs while preserving their inherent microporous framework. Furthermore, the distribution of the initial thermolabile ligand plays a pivotal role in determining the resulting mesopore architecture. The efficacy of this methodology is aptly demonstrated through the assessment of hierarchically porous ZIFs for their potential in adsorbing diverse organic dyes in aqueous environments. Particularly striking is the performance of the 10%NH2-ZIF-2 h, which showcases an astonishing 40-fold increase in methylene blue adsorption capacity compared to ZIF-8, attributed to larger pore volumes that accelerate the diffusion of dye molecules to adsorption sites. This versatile technique opens new avenues for designing micro/mesoporous ZIFs, particularly suited for liquid media scenarios necessitating efficient active site access and optimal diffusion kinetics, such as purification, catalysis, and sensing.
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Due to the chemical stability of graphene, synthesis of carboxylated graphene still remains challenging during the electrochemical exfoliation of graphite. In this work, a spatially confined radical addition reaction which occurs in the sub-nanometer scaled interlayers of the expanded graphene sheets for the electrochemical synthesis of highly stable carboxylated graphene is reported. Here, formate anions act as both intercalation ions and co-reactant acid for the confinement of electro-generated carboxylic radical (âCOOH) in the sub-nanometer scaled interlayers, which facilitates the radical addition reaction on graphene sheets. The controllable carboxylation of graphene is realized by tuning the concentration of formate anions in the electrolyte solution. The high crystallinity of the obtained product indicates the occurrence of spatially confined âCOOH addition reaction between the sub-nanometer interlayers of expanded graphite. In addition, the carboxylated graphene have been used for water desalination and hydrogen/oxygen reduction reaction. Therefore, this work provides a new method for the in situ preparation of functionalized graphene through the electrolysis and its applications in water desalination and hydrogen/oxygen reduction reactions.
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Atomic thick 2D materials hold great potential as building blocks to construct highly permeable membranes, yet the permeability of laminar 2D material membranes is still limited by their irregularity sheep track-like interlayer channels. Herein, a supramolecular-mediated strategy to induce the regular assembly of high-throughput 2D nanofluidic channels based on host-guest interactions is proposed. Inspired by the characteristics of motorways, supramolecular-mediated ultrathin 2D membranes with broad and continuous regular water transport channels are successfully constructed using graphene oxide (GO) as an example. The prepared membrane achieves an ultrahigh water permeability (369.94 LMH bar-1) more than six times higher than that of the original membranes while maintaining dye rejection above 98.5%, which outperforms the reported 2D membranes. Characterization and simulation results show that the introduction of hyaluronate-grafted ß-cyclodextrin not only expands the interlayer channels of GO membranes but also enables the membranes to operate stably under harsh conditions with the help of host-guest interactions. This universal supramolecular assembly strategy provides new opportunities for the preparation of 2D membranes with high separation performance and reliable and stable nanofluidic channels.
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Wilderness adventure favored by many enthusiasts often endanger lives due to lacking freshwater or drinking contaminated water. Therefore, compared to the inefficient methods of filtration, steaming, and direct solar heating, it is of great meaningfulness to develop a solar-driven water purification device with efficiency, lightweight, portability, and multi-water-quality purification by taking full advantage of solar-driven interfacial evaporation. Here, a tent-inspired portable solar-driven water purification device consisting of Janus-structured bacterial cellulose aerogel (JBCA) solar evaporator and tent-type condensation recovery device is reported. For the JBCA solar evaporator, it is prepared from biomass bacterial cellulose (BC) as raw material and hydroxylated carbon nanotubes (HCNT) as photothermal material, and the Janus property is achieved by the assistance of hydrophobic and hydrophilic chemical cross-linking. It exhibits lightweight, unibody, high photothermal conversion, efficient evaporation, and multi-water-quality purification capability for representative seawater, urine, and bacterial river water. For the tent-type condensation recovery device, it is based on the prototype of tent and uses flexible ultra-transparent polyvinyl chloride (PVC) film as raw material. Thanks to the rational prototype and material selection, it displays outstanding portability and lightweight through the folding/unfolding method. Therefore, the designed tent-inspired portable solar-driven water purification device demonstrates great potential application in wilderness exploration.
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The development of a high-performing adsorbent that can capture both iodine vapor from volatile nuclear waste and traces of iodine species from water is an important challenge, especially in industrially relevant process conditions. This study introduces novel imidazopyridinium-based covalent organic frameworks (COFs) through post-modification of a picolinaldehyde-based imine COF. These COFs demonstrate excellent iodine adsorption capacity, adsorption kinetics, and a high stability/recyclability in both vapor and water phases. Notably, one imidazopyridinium COF exhibits gaseous iodine uptake of 21 wt.% under dynamic adsorption conditions at 150 °C and a relative humidity of 50%, surpassing the performance of the currently used silver-based zeolite adsorbents (Ag@MOR (17wt.%)). Additionally, the same imidazopyridinium COFs can efficiently remove iodine species at a low concentration from aqueous solution. Seawater containing triiodide ions treated under dynamic flow-through conditions resulted in decreased concentrations down to the ppb level. The adsorption mechanisms for iodine and polyiodide species are elucidated for the imine COF and imidazopyridinium COFs; involving halogen bonding, hydrogen bonding, and charge-transfer complexes.
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Freshwater scarcity threatens human survival, particularly in extreme environments like deserts, oceans, and space. Compatible atmospheric water harvesting and undrinkable water purification offer an affordable approach to solving freshwater scarcity in these extreme environments. Nonetheless, developing composite sorbent to attain efficient atmospheric water harvesting and undrinkable water purification remains challenging. Hence, a portable hybrid hygroscopic powder (HLC powder) consisting of hydroxypropyl chitosan, dibenzaldehyde-functional poly(ethylene glycol), lithium chloride (LiCl), and nano carbon black is proposed. The HLC powder with optimized LiCl load can capture moisture from the air, showing a high water uptake of 1.76 g g-1 at 34% relative humidity (RH) and appropriate over a wide humidity from 34% to 75% RH. pH-responsive sol-gel transition induced by Schiff base bonds transforms the HLC solution into hydrogel, inhibiting hydrated salt leakage. Meanwhile, to achieve efficient undrinkable water purification, the LiCl-free hybrid powder is utilized to convert the undrinkable water, including seawater, dye water, and human urine, to photothermal hydrogel evaporators with low evaporation enthalpies and high evaporation rates ranging from 1.81 to 2.05 kg m-2 h-1 under one sun. This strategy establishes a new path to conveniently obtaining freshwater, breaking hydrological restrictions.
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The main objective of this study was to assess the usefulness of the sweet cherry stones for the production of carbonaceous adsorbents by means of direct physical activation method, using conventional and microwave variant of heating. The adsorbents were characterized in terms of textural parameters, acidic-basic character of the surface, electrokinetic properties and their suitability for drinking water purification. Adsorption tests were carried out against three organic compounds - Triton X-100 (surfactant), bovine serum albumin (protein) and methylene blue (synthetic dye). Depending on the variant of heating applied during activation procedure, the obtained activated biochars differed significantly in terms of the elemental composition, acidic-basic properties as well as degree of specific surface development and the type of porous structure generated. Adsorption tests have showed that the efficiency of organic pollutants removal from aqueous solutions depends significantly not only on the type of the adsorbent and adsorbate applied, but also on the temperature and pH of the system. The sample prepared by microwave-assisted direct activation proved to be very effective in terms of all tested organic pollutants adsorption. The maximum sorption capacity toward Triton X-100, bovine serum albumin and methylene blue reached the level of 86.5, 23.4 and 81.1â mg/g, respectively.
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Poluentes Ambientais , Prunus avium , Purificação da Água , Adsorção , Azul de Metileno/química , Octoxinol , Soroalbumina Bovina , Purificação da Água/métodos , Cinética , Concentração de Íons de HidrogênioRESUMO
The increasing use of nanomaterials in consumer products is expected to lead to environmental contamination sometime soon. As water pollution is a pressing issue that threatens human survival and impedes the promotion of human health, the search for adsorbents for removing newly identified contaminants from water has become a topic of intensive research. The challenges in the recyclability of contaminated water continue to campaign the development of highly reusable catalysts. Although exfoliated 2D MXene sheets have demonstrated the capability towards water purification, a significant challenge for removing some toxic organic molecules remains a challenge due to a need for metal-based catalytic properties owing to their rapid response. In the present study, we demonstrate the formation of hybrid structure AuNPs@MXene (Mo2CTx) during the sensitive detection of Au nanoparticle through MXene sheets without any surface modification, and subsequently its applications as an efficient catalyst for the degradation of 4-nitrophenol (4-NP), methyl orange (MO), and methylene blue (MB). The hybrid structure (AuNPs@MXene) reveals remarkable reusability for up to eight consecutive cycles, with minimal reduction in catalytic efficiency and comparable apparent reaction rate constant (Kapp) values for 4-NP, MB, and MO, compared to other catalysts reported in the literature.
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Peracetic acid (PAA) oxidation catalyzed by metal-free carbons is promising for advanced water decontamination. Nevertheless, developing reaction-oriented and high-performance carbocatalysts has been limited by the ambiguous understanding of the intrinsic relationship between carbon chemical/molecular structure and PAA transformation behavior. Herein, we comprehensively investigated the PAA activation using a family of well-defined sp2/sp3 carbon hybrids from annealed nanodiamonds (ANDs). The activity of ANDs displays a volcano-type trend, with respect to the sp2/sp3 ratio. Intriguingly, sp3-C-enriched AND exhibits the best catalytic activity for PAA activation and phenolic oxidation, which is different from persulfate chemistry in which the sp2 network normally outperforms sp3 hybridization. At the electron-rich sp2-C site, PAA undergoes a reduction reaction to generate a reactive complex (AND-PAA*) and induces an electron-transfer oxidation pathway. At the sp3-C site adjacent to CâO, PAA is oxidized to surface-confined OH* and O* successively, which ultimately evolves into singlet oxygen (1O2) as the primary reactive species. Benefiting from the dual nonradical regimes on sp2/sp3 hybrids, AND mediates a sustainable redox recycle with PAA to continuously generate reactive species to attack water contaminants, meanwhile maintaining structural/chemical integrity and exceptional reusability in cyclic runs.
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Ácido Peracético , Ácido Peracético/química , Catálise , Nanodiamantes/química , Purificação da Água/métodos , Oxirredução , Poluentes Químicos da Água/química , Água/químicaRESUMO
Significant progress has been made previously in the research and development of graphene oxide (GO) membranes for water purification, but their biofouling behavior remains poorly understood. In this study, we investigated the biofilm formation and biofouling of GO membranes with different surface microstructures in the context of filtering natural surface water and for an extended operation period (110 days). The results showed that the relatively hydrophilic and smooth Fe(OH)3/GO membrane shaped a thin and spatially heterogeneous biofilm with high stable flux. However, the ability to simultaneously mitigate biofilm formation and reduce biofouling was not observed in the weakly hydrophilic and wrinkled Fe/GO and H-Fe(OH)3/GO membranes. Microbial analyses revealed that the hydrophilicity and roughness distinguished the bacterial communities and metabolic functions. The organic matter-degrading and predatory bacteria were more adapted to hydrophilic and smooth GO surfaces. These functional taxa were involved in the degradation of extracellular polymeric substances (EPS), and improved biofilm heterogeneity. In contrast, the weakly hydrophilic and wrinkled GO surfaces had reduced biodiversity, while unexpectedly boosting the proliferation of EPS-secreting bacteria, resulting in increased biofilm formation and aggravated biofouling. Moreover, all GO membranes achieved sustainable water purification during the entire operating period.
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Biofilmes , Incrustação Biológica , Grafite , Purificação da Água , Grafite/química , Membranas Artificiais , Óxidos/químicaRESUMO
Attention is widely drawn to the extracellular electron transfer (EET) process of electroactive bacteria (EAB) for water purification, but its efficacy is often hindered in complex environmental matrices. In this study, the engineered living materials with EET capability (e-ELMs) were for the first time created with customized geometric configurations for pollutant removal using three-dimensional (3D) bioprinting platform. By combining EAB and tailored viscoelastic matrix, a biocompatible and tunable electroactive bioink for 3D bioprinting was initially developed with tuned rheological properties, enabling meticulous manipulation of microbial spatial arrangement and density. e-ELMs with different spatial microstructures were then designed and constructed by adjusting the filament diameter and orientation during the 3D printing process. Simulations of diffusion and fluid dynamics collectively showcase internal mass transfer rates and EET efficiency of e-ELMs with different spatial microstructures, contributing to the outstanding decontamination performances. Our research propels 3D bioprinting technology into the environmental realm, enabling the creation of intricately designed e-ELMs and providing promising routes to address the emerging water pollution concerns.
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In water purification, the performance of heterogeneous advanced oxidation processes significantly relies upon the utilization of the catalyst's specific surface area (SSA). However, the presence of the structural "dead volume" and pore-size-induced diffusion-reaction trade-off limitation restricts the functioning of the SSA. Here, we reported an effective approach to make the best SSA by changing the traditional 3D spherule catalyst into a 2D-like form and creating an in situ micro-nanolinked structure. Thus, a 2D-like catalyst was obtained which was characterized by a mini "paddy field" surface, and it exhibited a sharply decreased dead volume, a highly available SSA and oriented flexibility. Given its paddy-field-like mass-transfer routine, the organic capture capability was 7.5-fold higher than that of the catalyst with mesopores only. Moreover, such a catalyst exhibited a record-high O3-to-·OH transition rate of 2.86 × 10-8 compared with reported millimetric catalysts (metal base), which contributed to a 6.12-fold higher total organic removal per catalyst mass than traditional 3D catalysts. The facile scale preparation, performance stability, and significant material savings with the 2D-like catalyst were also beneficial for practical applications. Our findings provide a unique and general approach for designing potential catalysts with excellent performance in water purification.