Catalytic Materials Research Articles

Heterogeneous Catalytic Materials for Carbon dioxide Transformation: Efficient Carboxylation Cyclization to Cyclic Carbonates and Oxazolidinones

The exacerbation of environmental issues is increasingly attributed to the anthropogenic emissions of carbon dioxide (CO2) . CO2 is a cost‐effective and readily available C1 source. The conversion of CO2 into value‐added organic chemicals, such as cyclic carbonate and 2‐oxazolidinone, through carboxylation cyclization reactions shows promise in reducing carbon emissions and combating climate change. The use of catalysts can facilitate this process, with heterogeneous catalysts emerging as favorable due to their advantages of easy recovery and structural stability. This paper provides a comprehensive review of heterogeneous catalysts that have been utilized for the carboxylation cyclization of CO2 to afford cyclic carbonates and oxazolidinones in recent years. The catalysts include metal organic frameworks, covalent organic frameworks, super‐crosslinked polymers, conjugated microporous polymers, porous ionic organic polymers, and composite materials. We give a detailed synthesis route for each type of catalysts. Furthermore, the characteristics of the catalysts, such as BET specific surface area, CO2 adsorption capacity, and catalytic performance, is summarized and analyzed to offer insights for improving heterogeneous catalysts for CO2 conversion via carboxylation cyclization reactions in future research.

Applications of Ferric Oxide in Water Splitting by Electrolysis: A Comprehensive Review.

In water electrolysis, the use of an efficient catalyst derived from earth-abundant materials which is cost-effective and stable is essential for the economic sustainability of hydrogen production. A wide range of catalytic materials have been reported upon so far, among which Fe2O3 stands out as one of the most credible candidates in terms of cost and abundance. However, Fe2O3 faces several limitations due to its poor charge transfer properties and catalytic ability; thus, significant modifications are essential for its effective utilization. Considering the future of water electrolysis, this review provides a detailed summary of Fe2O3 materials employed in electrolytic applications with a focus on critically assessing the key electrode modifications that are essential for the materials' utilization as efficient electrocatalysts. With this in mind, Fe2O3 was implemented in a heterojunction/composite, doped, carbon supported, crystal facet tuned system, as well as in metal organic framework (MOF) systems. Furthermore, Fe2O3 was utilized in alkaline, seawater, anion exchange membrane, and solid oxide electrolysis systems. Recently, magnetic field-assisted water electrolysis has also been explored. This comprehensive review highlights the fact that the applicability of Fe2O3 in electrolysis is limited, and hence, intense and strategically focused research is vital for converting Fe2O3 into a commercially viable, cost-effective, and efficient catalyst material.

Electrode Materials for NO Electroreduction Based on Dithiolene Metal–Organic Frameworks: A Theoretical Study

To quickly and efficiently screen catalytic materials with both activity and selectivity for the nitric oxide reduction reaction (NORR), we adopted a strategy that considers the activity of the side reaction hydrogen evolution reaction (HER) first. It can be seen that Fe3(THT)2 (THT = triphenylene-2,3,6,7,10,11-hexathiol) has extremely excellent HER activity, with a Gibbs free energy change (ΔG) of 0.007 eV. Based on the relationship between ΔG and theoretical exchange current density, all TM3(THT)2 can be divided into two regions: one is the absolute values of ΔG greater than 1 eV, the other is the absolute values of ΔG greater than 0 eV and less than 1eV. Obviously, the candidates with the absolute values of ΔG greater than 1 eV have poor HER performance, but this precisely provides the possibility of obtaining NORR catalytic materials with both excellent selectivity and activity. Subsequent calculation results show that the maximum ΔG change of the rate-determining step of Ta3(THT)2 is unexpectedly only 0.05 eV. Therefore, Ta3(THT)2 may be regarded as the NORR catalytic material with both excellent performance and selectivity. Based on the electron transfer and partial density of states (PDOS) analysis, it can be seen that Ta plays a crucial role in the activation stage of NO. The approach that considers the activity of the side reaction HER first may provide a new idea for rapidly screening highly selective and active NORR catalysts.

A Photo-Assisted Zinc-Air Battery with MoS2/Oxygen Vacancies Rich TiO2 Heterojunction Photocathode.

Converting solar energy into electrochemical energy is a sustainable strategy, but the design of photo-assisted zinc-air battery (ZAB) with efficient utilization of sunlight faces huge challenges. Herein, a photo-assisted ZAB of a three-electrode system using MoS2/oxygen vacancies-rich TiO2 heterojunction as charge cathode and Fe, N-doped carbon matrix (FeNC) as discharge cathode is constructed, where MoS2 is chosen as solar light-responsive catalytic material and TiO2 acts as electron transport layer and hole blocking layer, arising from a train of thought for efficient charging under sunlight irradiation and light-independent discharging. The introduction of oxygen vacancies in TiO2 facilitates the temporary trapping of carriers and triggers rapid carrier transfer at the interface of the heterojunction, which hinders the recombination of photogenerated holes, thereby facilitating their further participation in the oxygen evolution reaction. Moreover, FeNC exhibits superior oxygen reduction reaction performance due to strong d-π interactions. As a result, the well-built ZABs deliver a low charge voltage (0.71 V) under illumination at 0.1 mA cm-2, and a high power density (167.6mW cm-2) in dark. This work paves a special way for the development of ZABs by directly harvesting solar energy in charging and efficiently discharging regardless of lighting conditions.

The tunable double-layer self-supporting Sb-Ni(OH)2 catalyst for boosting electrocatalytic water splitting

Green hydrogen preparation by electrolysis of water is key to driving the energy transition revolution. The development of low-cost, highly active and highly selective catalysts is a top priority for the commercial application from electrolytic water. This paper presents the synthesis of Sb-doped Ni(OH)2 nanosheets growing in situ on Ni foam, which serves as a self-supporting electrode. A straightforward one-step hydrothermal technique was employed to craft a dual-layer catalyst with a tunable morphology. Under the 1 M KOH conditions, Sb-Ni(OH)2-2.5/NF emerged as a bifunctional electrocatalyst, demonstrating an impressive HER performance of 159 mV (η10) and an OER performance of 430.8 mV (η50). The Sb-Ni(OH)2-2.5/NF also demonstrated remarkable stability by 3000 CV cycling tests. The Sb-Ni(OH)2-2.5/NF catalytic material prepared in this paper under laboratory conditions has a simple and inexpensive synthesis method, which helps to move electrolytic water catalysts from the laboratory to industry.

High‐Pressure Cell for In Situ Grazing Incidence XAS Characterization of Model Catalysts on Planar Supports

AbstractThe growing interest in physically deposited model catalysts for uncovering complex structure‐activity relationships is spurred by the possibility of depositing nanoparticles of precise atomic structure and composition using cluster‐beam sources. However, the limitations accompanying these synthesis techniques, such as low deposition rates and flat sample geometry, present a challenge for in situ structural characterization using bulk‐sensitive methods, such as X‐ray absorption spectroscopy (XAS), especially at elevated pressures (1–100 bar). To overcome this challenge, we constructed an in situ XAS cell operating in a grazing incidence (GI) geometry. The GIXAS cell was used to investigate the structure of cluster‐beam‐generated Pd and Au0.3Ag0.7 nanoparticles under CO2‐to‐methanol hydrogenation conditions (230 °C, 20 bar, CO2:H2=1 : 3). These nanoparticles, with metal loading of 0.96–10 μg cm−2, demonstrated stability and resistance to sintering upon activation in H2 at 120 °C and catalytic conditions, revealed by in situ XAS. The promising results from our work will help bridge the gap in the investigation of model catalytic materials produced by gas‐phase cluster deposition at industrially relevant pressures and temperatures, which is vital for a mechanistic understanding of catalytic processes.

Engineered Multifunctional BioHJzyme via Tuning D‐Band Center for Postoperative Infected Wound Regeneration of Tumor Resection

AbstractThe catalytic therapy for abundant •OH, 1O2, and •O2− provides an efficient tactic and methodology for rapid tumor/bacteria killing, whereas the limitation is focused on the catalytic efficiency owing to the in‐built energy band of catalytic materials. Thus, d‐band center tuning BioHJzyme is devised, which is composed of zinc tellurate/manganese dioxide anchored by glucose oxidase (GOx) with anti‐tumor and anti‐bacteria properties for postoperative infected wound regeneration of tumor. The GOx depletes glucose to produce H2O2, intercepting the glucose metabolism. The D‐BioHJzyme can catalyze the produced H2O2 to highly lethal •OH with POD‐mimetic activity owing to the tunned d‐band center strategy decreasing the adsorption energy of the intermediate in the catalytical process, while the oxygen originated from H2O2 and Mn2+ can be catalyzed into 1O2. The GPx‐mimetic activity of it can impair the antioxidant system of tumor. In vivo studies show that the BioHJzyme exhibits robust abilities against bacteria and tumors by •OH/1O2 production and promotes the apoptosis owing the Te. Besides, the BioHJzyme can accelerate cutaneous regeneration by M1/M2 regulation and the angiogenesis/collagen deposition. This work enlightens a powerful platform for the remedy of postoperative infected wound regeneration of tumor resection using an engineered BioHJzyme.

Oxidation of Geraniol on Vermiculite—The Influence of Selected Parameters on the Oxidation Process

Geraniol is a compound belonging to the group of monoterpenes that finds many applications in organic syntheses, medicine and cosmetics. The following properties of geraniol and its derivatives are of particular interest in medicine: its anti-inflammatory, antioxidant, antimicrobial and anticancer effects. The geraniol oxidation process was carried out using a mineral of natural origin—vermiculite. Vermiculite is a catalyst that perfectly fits into modern trends in the organic industry, where the aim is to use cheap, renewable and relatively easily available catalytic materials (vermiculite is found on continents including Africa, North America, South America, Australia and Asia). Preliminary studies on the oxidation process of geraniol on vermiculite was carried out in a glass apparatus using molecular oxygen supplied by means of a bubbler and magnetic stirrer with a heating function. During the oxidation process of geraniol on vermiculite, the influence of the following parameters was examined: the temperature, amount of catalyst and reaction time. The main parameters of the process, on the basis of which the most favorable process conditions were selected, were the selectivity of the transformation to 2,3-epoxygeraniol, citral and 2,3-epoxycitral, and the conversion of geraniol. The composition of the post-reaction mixtures was determined qualitatively and quantitatively using the gas chromatography method. In addition, vermiculite was subjected to instrumental tests, such as XRD, SEM, EDX, FTIR and UV-VIS. Moreover, the specific surface area, pore volume and pore volume distribution were estimated on the basis of N2 sorption at −196 °C and also the acid-site concentration in vermiculite was established.

Eco-Friendly Facile Conversion of Waste Eggshells into CaO Nanoparticles for Environmental Applications.

Amongst the many types of food waste, eggshells contain various minerals and bioactive materials, and they can become hazardous if not properly disposed of. However, they can be made useful for the environment and people by being converted to environmentally friendly catalytic materials or environmental purification agents. Simple calcination can enhance their properties and thereby render them suitable for catalytic and environmental applications. This work aimed to prepare CaO from waste eggshells and examine its effectiveness in photocatalytic pollution remediation, electrocatalytic activity, optical sensing, and antibacterial activities. As opposed to other techniques, this calcination process does not require any chemical reagents due to the high purity of CaCO3 in eggshells. Calcium oxide nanoparticles were prepared by subjecting waste eggshells (ES) to high-temperature calcination, and the synthesized CaO nanoparticles were characterized for their structural, morphological, chemical, optical, and other properties. Furthermore, their photocatalytic degradation of methylene blue dye and antibacterial efficiency against Escherichia coli and Staphylococcus aureus were investigated. It was found that the green-converted CaO can be efficiently used in environmental applications, showing good catalytic properties.

Nano-Metal-Organic Frameworks and Nano-Covalent-Organic Frameworks: Controllable Synthesis and Applications.

Nanoscale framework materials have received much attention due to their diverse morphologies as well as good properties, and synthetic methods to construct different dimensions have been reported. Therefore, the study of the relationship between different sizes, dimensions and properties has become a hot research topic. This article provides a comprehensive examination of the controllable synthesis strategies of nano-metal-organic frameworks (nano-MOFs) and nano-covalent-organic frameworks (nano-COFs) and their applications in energy storage and catalysis. Commences with an overview of the synthetic evolution of nanoscale framework materials, which have garnered attention due to their exceptional specific surface area, regular pores, and tunable structural functionality. Various preparation methods for 0D, 1D, 2D and 3D nanostructures are then highlighted. These synthesis strategies not only improve the stability and activity of the materials, but also provide a basis for the design of novel energy storage and catalytic materials. Furthermore, the article presents an overview of the recent advancements in the field of energy storage and catalysis, with a particular focus on the applications of nano-MOFs/COFs in zinc-, lithium-, and sodium-based batteries as well as supercapacitors. ​.

Polyoxometalates@Metal-Organic Frameworks: Synthesis Strategies, Nanostructure Modulation and Application in Biomass Conversion.

Polyoxometalates@metal-organic frameworks (POMs@MOFs) have attracted much attention as multifunctional materials in biomass catalysis. Individual POMs and MOFs are hindered by their respective defects, such as poor stability and single catalytic active site, which make it difficult to realize large-scale applications. However, the combination of POMs and MOFs can be used to maximize the catalytic advantages of each. MOFs with high specific surface area and rich pore structure can effectively stabilize and uniformly disperse POMs, while the introduction of POMs also provides more catalytic possibilities for POMs@MOFs. Therefore, POMs@MOFs with ultra-high porosity, large specific surface area and excellent acid catalytic activity have unique catalytic advantages in the field of biomass catalytic conversion. In this work, we provide an overview of the current development of POMs@MOFs in the field of biomass catalysis. The synthesis strategies of POMs@MOFs are summarized and discussed, highlighting the in-situ synthesis methods. We focus on the nanostructure engineering of POMs@MOFs, and explore the "structure-property" relationship in depth. In addition, the representative work of POMs@MOFs in the catalysis of biomass derivatives is summarized. Filially, the prospects, and challenges for the future development of POMs@MOFs in the field of biomass catalysis are also presented.

Breaking the Passivation Effect for MnO2 Catalysts in Li−S Batteries by Anion‐Cation Doping

AbstractTransition metal oxides (TMOs) are recognized as high‐efficiency electrocatalyst systems for restraining the shuttle effect in lithium‐sulfur (Li−S) batteries, owing to their robust adsorption capabilities for polysulfides. However, the sluggish catalytic conversion of Li2S redox and severe passivation effect of TMOs exacerbate polysulfide shuttling and reduce the cyclability of Li−S batteries, which significantly hinders the development of TMOs electrocatalysts. Here, through the anion‐cation doping approach, dual incorporation of phosphorus and molybdenum into MnO2 (P,Mo‐MnO2) was engineered, demonstrating effective mitigation of the passivation effect and allowing for the simultaneous immobilization of polysulfides and rapid redox kinetics of Li2S. Both experimental and theoretical investigations reveal the pivotal role of dopants in fine‐tuning the d‐band center and optimizing the electronic structure of MnO2. Furthermore, this well‐designed configuration processes catalytic selectivity. Specifically, P‐doping expedites rapid Li2S nucleation kinetics by minimizing reaction‐free energy, while Mo‐doping facilitates robust Li2S dissolution kinetics by mitigating decomposition barriers. This dual‐doping approach equips P,Mo‐MnO2 with robust bi‐directional catalytic activity, effectively overcoming passivation effect and suppressing the notorious shuttle effect. Consequently, Li−S batteries incorporating P,Mo‐MnO2‐based separators demonstrate favorable performance than pristine TMOs. This design offers rational viewpoint for the development of catalytic materials with superior bi‐directional sulfur electrocatalytic in Li−S batteries.

Breaking the Passivation Effect for MnO2 Catalysts in Li-S Batteries by Anion-Cation Doping.

Transition metal oxides (TMOs) are recognized as high-efficiency electrocatalyst systems for restraining the shuttle effect in lithium-sulfur (Li-S) batteries, owing to their robust adsorption capabilities for polysulfides. However, the sluggish catalytic conversion of Li2S redox and severe passivation effect of TMOs exacerbate polysulfide shuttling and reduce the cyclability of Li-S batteries, which significantly hinders the development of TMOs electrocatalysts. Here, through the anion-cation doping approach, dual incorporation of phosphorus and molybdenum into MnO2 (P,Mo-MnO2) was engineered, demonstrating effective mitigation of the passivation effect and allowing for the simultaneous immobilization of polysulfides and rapid redox kinetics of Li2S. Both experimental and theoretical investigations reveal the pivotal role of dopants in fine-tuning the d-band center and optimizing the electronic structure of MnO2. Furthermore, this well-designed configuration processes catalytic selectivity. Specifically, P-doping expedites rapid Li2S nucleation kinetics by minimizing reaction-free energy, while Mo-doping facilitates robust Li2S dissolution kinetics by mitigating decomposition barriers. This dual-doping approach equips P,Mo-MnO2 with robust bi-directional catalytic activity, effectively overcoming passivation effect and suppressing the notorious shuttle effect. Consequently, Li-S batteries incorporating P,Mo-MnO2-based separators demonstrate favorable performance than pristine TMOs. This design offers rational viewpoint for the development of catalytic materials with superior bi-directional sulfur electrocatalytic in Li-S batteries.

Renaissance of Chlorine Evolution Reaction: Emerging Theory and Catalytic Materials

Chlorine (Cl2) is one of the most important commodity chemicals that has found widespread utility in chemical industry. Most Cl2 is currently produced via the chlorine evolution reaction (CER) at the anode of chlor–alkali electrolyzers, for which precious group‐metal‐based mixed metal oxides (MMOs) have been used for more than half a century. However, MMOs suffer from the use of platinum‐group metals, which are costly and scarce, and the selectivity issue arises from the parasitic oxygen evolution reaction. Over the last decade, the field of CER catalysis has seen dramatic advances in both the theory and discovery of new catalysts. Theoretical approaches have enabled a fundamental understanding of CER mechanisms and provided catalyst design principles. The exploration of new materials has led to the discovery of CER catalysts other than MMOs, including non‐PGM‐based oxides, atomically dispersed single‐site catalysts, and organic molecules, with some of which following novel reaction pathways. This minireview provides an overview of the recent advances in CER electrocatalyst research and suggests future directions for this revitalized field.

Renaissance of Chlorine Evolution Reaction: Emerging Theory and Catalytic Materials.

Chlorine (Cl2) is one of the most important commodity chemicals that has found widespread utility in chemical industry. Most Cl2 is currently produced via the chlorine evolution reaction (CER) at the anode of chlor-alkali electrolyzers, for which precious group-metal-based mixed metal oxides (MMOs) have been used for more than half a century. However, MMOs suffer from the use of platinum-group metals, which are costly and scarce, and the selectivity issue arises from the parasitic oxygen evolution reaction. Over the last decade, the field of CER catalysis has seen dramatic advances in both the theory and discovery of new catalysts. Theoretical approaches have enabled a fundamental understanding of CER mechanisms and provided catalyst design principles. The exploration of new materials has led to the discovery of CER catalysts other than MMOs, including non-PGM-based oxides, atomically dispersed single-site catalysts, and organic molecules, with some of which following novel reaction pathways. This minireview provides an overview of the recent advances in CER electrocatalyst research and suggests future directions for this revitalized field.

Enhanced synergistic catalysis of bisphenol A in river water using an anti-aging photocatalytic membrane

Bisphenol A (BPA), as an endocrine disruptor, poses a potential threat to ecosystems and human health in aquatic environments. Membrane catalytic systems can accelerate the degradation of BPA and facilitate its conversion into harmless compounds. Nevertheless, the complex nature of the water environments and the limited stability of catalysts often result in challenges such as catalyst aging and deactivation. Herein, an anti-aging multifunctional AgFeO2 catalytic material with electron transfer membrane support was prepared for synergistic catalysis of low-energy LED light (12 W) excitation and peroxydisulfate (PDS) activation. The anti-aging photocatalytic membrane completely degraded 10 ppm of BPA within 30 min, and did not show significant aging after the long-term synergistic catalytic process. In addition, actual river water was employed to assess the aging process and catalytic efficiency in a practical environment. A 60.79 cm2 photocatalytic membrane completely purified 10 L of BPA polluted river water, while the total organic carbon content decreased by 50 %. This was mainly due to the synergistic catalytic effect of the membrane, which boosted photoelectron transfer through electron transfer shortcuts, thereby enhancing persulfate activation. Overall, the multifunctional membrane provides an effective strategy for achieving a long-lasting catalytic effect and controlling photocatalyst aging in practice.

Synthesis of Au/Co3O4/PVA hybrid nanocomposites via eco-friendly method based on pulsed laser ablation process for water treatment

A portable nanostructured nanocomposite film, based on cobalt oxide and gold nanoparticles (NPs) embedded in a polyvinyl alcohol structure (PVA), Au/Co3O4/PVA, was prepared via a novel way based on pulsed laser ablation to be applied as an effective catalytic degradation material for a hazardous chemical structure as nitro compounds. Au/Co3O4/PVA was investigated by the techniques of UV–Vis, FT-IR, SEM, and XRD. From XRD, the decrease in crystallinity of PVA is attributed to the intermolecular hydrogen bonding between PVA and Au/Co3O4. In addition, there are five interplanar peaks, with three shared peaks by both phases and one unique peak for each phase of Au and Co3O4. From FT-IR, the modes observed at a 500–1200 cm-1 wavenumber range correspond to the stretching vibration modes of Au/Co3O4. From UV–VIS, as the embedding of Co3O4 on Au-PVA structure increases, the energy band gap is shifted to a lower value. This is due to the embedding of Co3O4 NPs. From SEM, in the case of embedding PVA with Au NPs, the bright semi-spherical shape of the nanostructured materials has a bright semi-spherical light area. Moreover, in the case of the embedded PVA with Co3O4 NPs, the faint semi-spherical form of the nanostructured materials is discernible. Besides, the catalytic activity performance is tested for the degradation of 4-nitrophenol, which reveales that the reaction followed first-order kinetics, as indicated by linear regression analysis. The results shows that the sample completely convertes 4-nitrophenol to 4-aminophenol within 6 min.

Functionalized construction of multiple active centers for durability controlling during catalytic combustion of chlorinated aromatic hydrocarbons

The catalytic combustion of chlorine-containing VOCs primarily encounters the bottleneck of catalyst poisoning by chlorine, thereby impeding the further industrial application of this technology. The development of multi-active catalytic materials for discerning chlorine fixation, chlorine transfer, deep oxidation during elimination of chlorine-containing VOCs can mitigate catalyst chlorination and enhance stability. Herein, we utilizing LDHs as catalyst precursors and successfully synthesized flower-like Co2FexCr1-xOy catalyst with different functionalized reaction centers. The addition of Cr improved the surface lattice oxygen, oxygen vacancies, and acid sites of catalyst. The removal efficiency of CB can be achieved >90 % at 247 °C (WHSV = 33000 mL · g−1·h−1). The fixation of dissociated chlorine contributed by Cr not only enhances oxidation performance and directional adsorption of chlorine, but also improves carbon deposition resistance and catalyst sintering resistance significantly. Compared with Co2Fe1Oy, Co2Fe0.67Cr0.33Oy catalyst achieves a remarkable threefold reduction in surface carbon deposition. The DFT calculation revealed that water dissociation energy over the Co site is −0.72 eV, which is significantly lower than Fe (−0.59 eV) and Cr (−0.17 eV), facilitating water dissociation and subsequently removes a substantial amount of accumulated chlorine on Cr to form HCl. With the help of In situ DRIFT and GC/MS analysis, we found the efficient removal of chlorine atoms enhances the exposure of active sites on the catalyst surface with hydrolyzed hydroxyl group, which facilitating the conversion of aromatic hydrocarbons into a greater quantity of maleate and carboxylate species. This phenomenon is beneficial for the subsequent mineralization process of chlorobenzene. This work provide valuable insights for multi-active site catalysis mechanism in practical applications aimed at eliminating chlorinated organic waste gases from industrial emissions.

EGCG mildly reduced single atom Co-MXene catalytic membrane: Catalytic and antioxidant properties

As a 2D nanomaterial with high hydrophilic and co-catalytic properties, MXene has been widely studied in the field of membrane separation and advanced oxidation. However, its susceptibility to oxidation in catalytic environments poses a significant challenge to its long-term stability and performance. Therefore, constructing an oxidation-resistant MXene catalytic membrane technology and ensuring its excellent flux and catalytic performance are important for the practical application of MXene membranes. Herein, we prepared a cobalt monoatomic intercalated M/E0.1-Co catalytic separation membrane by mild reduction of epigallocatechin-3-gallate (EGCG). EGCG not only connects the MXene lamellae during filtration through strong hydrogen bonding, but also protects the chemical stability of the MXene substrate through its antioxidant ability. Furthermore, the trace amount of EGCG in the confined domain space also promotes the rate-limiting step of the transition from the high-valent state to the low-valent state in Co single-atom catalysis. The stability of the catalytic separation layer was ensured along with a 100% degradation performance of sulfamethoxazole. This study establishes a bridge between the catalytic oxidation and chemical stability of a wide range of MXene-based materials nowadays and provides a viable proposal for the practical application of long-term utilized MXene materials in catalysis.

ZIFs@MIL-101/urea-derived magnetic FeCo nitrogen-rich carbon as an effective and stable catalyst for peroxymonosulfate activation

High efficiency and stability are key issues in heterogeneous metal catalytic materials/peroxymonosulfate (PMS) systems during wastewater degradation. However, catalytic materials that are difficult to recover and metal leaching can cause secondary contamination of water bodies. Herein, we designed the magnetic FeCo nitrogen-rich carbon (FeCo-NC) obtained by layer-by-layer encapsulation, followed by urea encapsulation of in situ grown MOF-in-MOF and carbonization. The CoFe2O4 crystalline nature of FeCo-NC was confirmed by X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM), and selected angle electron diffraction (SAED) results, which is responsible for the magnetic properties of FeCo-NC. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) present that the material's morphology transforms from dodecahedral ZIF-67 to spindle-shaped ZIF-67@MIL-101 and then to octahedral FeCo-NC. Compared with FeCo-C and ZIF-67@MIL-101, the removal efficiency of FeCo-NC was maintained at 78.6 % after 10 consecutive cycles, with only a 17 % loss of raw material. The Fe and Co leaching amounts in the FeCo-NC/PMS system were approximately 0.6 and 0.1 mg/L, respectively, much lower than China's Fe and Co emission standards. FeCo-NC characterization and TC degradation results demonstrated that magnetic CoFe2O4 nanoparticles formed on the surface or inside the FeCo-NC could effectively inhibit metal (Fe and Co) loss and be easily regenerated in multiple degradation cycles. The mechanism and degradation routes in the FeCo-NC/PMS/ TC system, including the radical/nonradical pathways, Fe/Co valence change, and electron transfer, were further investigated by electron paramagnetic resonance experiments, electrochemical analyses, in situ Raman spectroscopy, and HPLC–MS experiments.