BACKGROUND:Foliar application of RNA interference (RNAi)-based products offers a promising strategy for protecting crops against insect pests. This approach involves the direct spraying of exogenous double-stranded RNA (dsRNA) to silence specific target genes in pests. However, its practical efficacy is constrained by the environmental degradation of the dsRNA, rapid degradation by gut nucleases, inefficient cellular internalization and limited endosomal escape. The integration of nanotechnology with RNAi has emerged as a promising frontier in sustainable pest control, offering improved dsRNA stability, enhanced cellular delivery, and the potential to reduce conventional pesticide use. In this study, we explored the use of a positively charged covalent organic framework (COF)-based nanocarrier functionalized with polyethylenimine (PEI) and polyethylene glycol (PEG) for dsRNA delivery. RESULTS:The resulting COF-PEI-PEG@dsRNA complexes effectively resisted degradation by nuclease-rich midgut extracts. Moreover, COF-PEI-PEG facilitated efficient dsRNA delivery into Drosophila S2 and Lepidopteran Sf9 cells, resulting in significant improvement in target gene knockdown. In vivo, COF-PEI-PEG@dsRNA significantly enhanced RNAi efficacy in Leptinotarsa decemlineata and Drosophila suzukii, although no improvement was observed in Spodoptera exigua. CONCLUSION:Collectively, our findings highlight the potential of COF-PEI-PEG as effective dsRNA delivery platforms, offering a novel and versatile tool to enhance RNAi-based insect management and fundamental entomological research. © 2026 Society of Chemical Industry.
Open metal sites (OMS) serve as crucial active sites in numerous applications, including hydrogen isotope separation, highlighting the importance of developing targeted synthesis strategies for OMS-containing frameworks. Unlike defect-engineered approaches that generate disordered OMS, synthesizing frameworks with an ordered distribution of OMS remains highly challenging yet is essential for efficient separation. Guided by the topological simplification process-which abstracts connectivity while overlooking coordination geometry-this study introduces a strategy to construct metal-organic frameworks (MOFs) with ordered OMS by reducing linker symmetry. By employing bent linkers with lower axial symmetry, rather than linear linkers of equivalent topological connectivity, OMF-2 (OMF = Open-Metal Framework) was synthesized, a pcu 8-connected framework featuring four OMS per cluster, thereby validating the approach. Remarkably, OMF-2 demonstrates exceptional hydrogen isotope separation performance, with an ideal adsorbed solution theory (IAST) selectivity of 7.7, a cryogenically programmed desorption (CPD) selectivity of 6.6, and a breakthrough test selectivity of 2.3 for D2/H2. The ordered arrangement of OMS within the pore windows enhances both chemical affinity quantum sieving (CAQS) and kinetic quantum sieving (KQS) effects. This work establishes a new pathway for the targeted synthesis of MOFs with both ordered OMS structural features and strong application potential.
Ozone-assisted catalytic oxidation (OzCO) has emerged as a promising alternative to conventional catalytic oxidation (CCO) for the elimination of volatile organic compounds (VOCs), offering efficient conversion at lower temperatures. In this work, a series of monometallic (Cu/HAP, Mn/HAP) and bimetallic (CuzMn/HAP, z = 0.5, 1, 2) catalysts were synthesized by wet impregnation using hydroxyapatite (HAP) as support and systematically evaluated for propane (C3H8) OzCO. Comprehensive physicochemical characterization demonstrated that Cu-Mn interactions improved metal dispersion, reducibility, oxygen mobility, and the concentration of surface-adsorbed oxygen species. Mn/HAP exhibited the highest C3H8 conversion, whereas Cu/HAP showed the greatest CO2 selectivity. The bimetallic catalysts displayed clear synergistic effects, with Cu1Mn/HAP achieving the optimal balance between C3H8 conversion and CO2 selectivity. Mechanistically, MnOx species facilitated O(3 )decomposition to generate active oxygen species, while CuOx species rather enhanced the further oxidation of CO into CO2. The Cu1Mn/HAP catalyst exhibited optimal performance at intermediate space times and temperatures, high O3 partial pressures, and low C3H8 partial pressures. Water vapor inhibited C3H8 conversion at 80 degrees C but enhanced CO2 selectivity, with the effect being reversible and less pronounced at higher temperatures. Overall, Cu1Mn/HAP demonstrated robust performance, highlighting its potential as an efficient catalyst for low-temperature C3H8 OzCO.
Developing cost-effective photocatalysts for H2O2 production is essential for sustainable chemistry. Here, we employ the exceptionally inexpensive industrial precursor melamine to synthesize two triazine-based covalent organic frameworks (COFs), MA-COF-2 and MA-COF-3. By modulating hydroxyl functionalization in the aldehyde monomers, we successfully induce beta-ketoenamine tautomerism within the frameworks. The higher hydroxyl density in MA-COF-3 drives a more exhaustive enol-to-keto conversion, which promotes the spatial separation of HOMO-LUMO orbitals and effectively suppresses photogenerated charge recombination. Consequently, MA-COF-3 achieves a superior H2O2 production rate of 21.59 mmol g-1 h-1, which is 3.6-fold higher than the performance of MA-COF-2 (5.98 mmol g-1 h-1) and ranks among the top tier of reported COF-based photocatalysts. This work demonstrates a cost-efficient strategy to bypass the dependence on expensive building blocks, offering a scalable blueprint for the industrial-scale photosynthesis of H2O2 using readily available organic materials.
Covalent organic frameworks (COFs) have shown promising potential in electrochemical applications due to their highly tunable chemical structures and large surface areas. However, the limited charge-transfer properties of conventional COFs restrict their electrocatalytic performance. In this work, sulfur species were introduced into the COF framework via sulfurization to enhance the electrochemical properties. The effects of sulfurization on the electrochemical performance of COFs were systematically evaluated in both cathodic and anodic systems, revealing significant improvements in cathodic H2O2 generation and anodic tetracycline degradation. Furthermore, sulfurization markedly optimized the interfacial properties of the electrodes, leading to enhanced charge accumulation at the electrode-electrolyte interface and facilitating electron transport within the framework, thereby improving overall electrocatalytic efficiency and activity. When applied in a practical two-electrode system, the sulfurized COF enabled synergistic tetracycline degradation and hydrogen peroxide production, achieving approximately 93% tetracycline removal in 4 h at 2.4 V while maintaining excellent electrode stability. These results demonstrate its potential for sustainable water treatment applications.
Volatile organic compounds (VOCs) such as toluene are major atmospheric pollutants with significant health and environmental impacts. This study investigates toluene abatement in dry air by post-plasma catalysis (PPC) using Cu, Mn, and Cu-Mn mixed oxides supported on hydroxyapatite (Hap) at catalyst bed temperatures of 100-200 degrees C. The catalysts were prepared by wet impregnation and tested in a non-thermal plasma (NTP) reactor, where toluene (150 ppmv) was introduced into air. The NTP provided preliminary toluene activation and oxidative species to enhance catalytic oxidation. During catalytic oxidation, all samples showed no catalytic activity. In contrast, plasma alone enabled significant toluene conversion (55%) and mineralization (12%). Plasma combined with Hap exhibited strong synergy, boosting conversion and mineralization to 80% and 46% (CO2/CO = 1.4) at 200 degrees C and 350 J L- 1. This demonstrated the intrinsic catalytic role of Hap and provided a baseline for assessing the effect of metal impregnation. Metal loading further enhanced PPC performance. The best results were obtained at 100 degrees C, with 2.5 wt% metal loading. The performance trends indicate that Cu-containing catalysts mainly enhance toluene adsorption/activation, whereas MnOx promotes oxidation/by-product conversion and strongly suppresses O3 slip, consistent with redox-active Mn species. The optimal MnCuHap (Mn:Cu = 1:2) catalyst achieved 100% toluene conversion, 59% mineralization (CO2/CO = 1.9), and 95% ozone removal at 350 J L- 1.The synergy between NTP and the MnCuHap catalyst highlights the potential of this configuration for efficient VOC abatement and provides a benchmark for future PPC studies.
In this work we developed two different thiazole-linked Covalent Organic Frameworks (COFs) from their imine analogues for the recovery of gold from electronic waste. These gold ions are reduced through a dual-function mechanism: either directly by the COF framework itself or by photocatalytically generated electrons under light irradiation. Two COF systems were investigated: one based on pyrene (Tfpy-PDA) and another on a triazole-triazine core (TTT-TAPB). Initially synthesized with imine linkages, these COFs underwent a post-synthetic modification to convert the imine bonds into more robust thiazole rings. This transformation introduced sulfur atoms, significantly enhancing the gold adsorption performance, recyclability, stability and photophysical properties. Specifically, the thiazole-linked TTT-TAPB-S COF achieved a very high gold adsorption capacity of 3533 mg g-1 in dark conditions. Upon light irradiation, the adsorption capacities increased for both imine and thiazole variants, reaching a record high of 7980 mg g-1 for the thiazole-linked Tfpy-PDA-S COF. Demonstrating practical utility, these materials effectively removed up to 98% of gold from complex CPU waste leachates with high selectivity and exhibited excellent stability and recyclability.
The Guerbet reaction is a valuable route for producing beta-alkylated alcohols with high added value. Here we demonstrate that copper on covalent triazine frameworks (CTFs) are remarkable catalysts for the conversion of 1-octanol into 2-hexyl-1-decanol. Three different CTFs with tunable porosity and tailored coordinating groups were explored, demonstrating how the interplay between nanoscale pores dimensions and chelating sites affect the catalytic performance. Under optimized conditions, 2-hexyl-1-decanol yields approaching 80% were achieved within 4 h at 200 degrees C using a copper loading of only 0.17 mol %. The high activity of the catalyst is evidenced by TON values exceeding 2200. The mesoporous nature of the nanostructured support was found to be fundamental for enhanced activity, likely due to reduced diffusional restrictions, while triazine-pyridine coordination ensured sustained activity. The best-performing catalyst combined these features and maintained catalytic performance over six reuse cycles. This study establishes copper containing CTFs as a versatile platform for Guerbet alcohol production, uniting nanoscale structural control with high activity, stability, and reusability.
Climate-change-driven increases in wildfire and fire incidents make fire-borne soot an escalating risk for tangible cultural heritage. Water-sensitive, porous gypsum plaster presents one of the most difficult surfaces to clean after flame-generated soot contamination because conventional methods can under-clean, abrade the surface, or drive soot into the pore network. Here we develop an atmospheric-pressure atomic oxygen (AO) cleaning technology and dose-controlled treatment framework for targeted, non-contact removal of soot from gypsum plaster. AO was generated by a non-equilibrium 13.56 MHz helium plasma source and delivered remotely as a chemically ablating effluent, enabling selective oxidation without direct plasma-surface contact. Compared with representative cleaning methods, AO removed carbonaceous contamination by preferential oxidation to volatile products. Under optimized low-power, high-flux conditions, AO achieved near-complete visual recovery with minimal substrate impact and preserved submicron topography. The results provide a reproducible, solvent-free framework for cleaning highly sensitive heritage surfaces.
A non-thermal plasma based treatment strategy is proposed to prepare CoCeOx catalysts using metal-organic frameworks (MOFs) as precursor, which were synthesized by a simple NaOH-mediated method through an organometallic reaction of Co2 + /Ce4+ ions and benzimidazole in the presence of polyvinylpyrrolidone. The obtained catalysts exhibited large specific surface areas and retained the morphological and structural features of the MOF precursors. The activity of the catalysts in the degradation of acetone was investigated using a post-plasma catalytic (PPC) setup and a possible degradation pathway, using the CoCeOx catalyst, was proposed. The synergy between Co and Ce ions resulted in a better activity of the CoCeOx catalysts compared to the CoOx catalysts and an increased specific surface area of the CoCeOx catalysts. Among all CoCeOx catalysts studied, the Co0.7Ce0.3Ox catalyst exhibited the highest acetone removal efficiency, whereas a further increase in the Ce content led to a decrease in the conversion when the Co/Ce ratio exceeded 7:3. DFT calculations reveal that Co doped CeO2 surface is conducive to capturing acetone and Co3O4 surface helps to decompose O3 and form active oxygen. DRIFTS analyses prompt that acetic acid, which are the main intermediates, are difficult to decompose only by catalysts, while they can be effectively decomposed with the addition of plasma. This study thus offers a novel low temperature strategy in synthesizing Co and Ce based bimetallic oxide catalysts for efficient plasma-catalytic degradation of volatile organic compounds.
Covalent triazine frameworks (CTFs) have emerged as robust materials with high thermal and chemical stability, tunable porosity, and significant potential for sustainable applications in catalysis, adsorption, and gas storage and separation. Recent advances have focused on enhancing their intrinsic basicity through the incorporation of alkali oxides, which, although effective, exhibit limited moisture stability. For many practical applications, developing strongly basic, water-tolerant CTFs remains a critical challenge. In this work, magnesium oxideimpregnated covalent triazine frameworks (MgO@CTFs) were successfully synthesized through a sequential process involving the wet impregnation of magnesium salts onto CTFs, followed by thermal decomposition. The synthesis procedure was optimized by investigating the best ratio of the metal salt precursor to support, as well as the type of metal precursor. Impregnation of MgO at 5 wt% provided the best compromise between enhanced basicity and retention of porosity. The materials were thoroughly characterized to confirm their structure, composition, and porosity. Their catalytic performance was evaluated in the production of 2-hexyl-2-decenal from octanal, achieving over 80 % conversion at 170 degrees C within 4 h, as well as in the propanolysis of 4-nitrophenylacetate (4-NPA) and paraoxon-ethyl. Remarkably, reaction rates improved by factors of 4.5 (4-NPA) and 300 (paraxon) compared to the respective spontaneous reaction. DTF studies indicate that the CTF framework interacts with propanol and paraoxon-ethyl, facilitating the interaction between the reactive species. This study presents an effective strategy to introduce stable basic sites into CTFs without compromising their porosity or stability, expanding their applicability in base-catalyzed reactions and other advanced applications.
This work describes the design of reproducible mock-ups with controlled soot deposition, created to support comparative cleaning tests within the EU Horizon MOXY project. The latter develops atmospheric, plasma-generated, monoatomic oxygen as a cleaning method to remove (amongst others) fire-born soot from heritage objects. A literature review highlights the complexity of soot while revealing a lack of focus on the representativeness of artificial soot in previous studies. We benchmarked two approaches: (I) indirect/cold application of pre-fabricated soot and (II) direct/hot application via ongoing combustion. The results demonstrate that direct combustion yields soot with markedly different physical and chemical characteristics. Chemical analysis (Raman, XRPD, TGA, EGA-MS, XPS) and microscopic imaging (3D optical, SEM) revealed differences in composition, morphology, and deposition behaviour on substrates like paper, silk, paint and plaster. We selected the ‘smoke drum’ method as the most practical and reproducible approach for mimicking fire-born soot in heritage cleaning research.
Enhancing intrinsic activity and increasing catalytic site density are two widely employed strategies to improve catalytic performance. Although typically considered independently, their interplay remains poorly understood. Here, two UiO-66 metal-organic frameworks (MOFs) with distinct catalytic site densities-linker-defective UiO-66L and cluster-defective UiO-66C-are synthesized and systematically compared. Despite a higher density of open Zr catalytic sites, UiO-66L exhibited lower catalytic activity than UiO-66C across four model reactions, performing similarly to defect-free UiO-66. Although defect engineering is expected to enlarge pore connectivity, diffusion-ordered spectroscopy (DOSY) and molecular dynamics (MD) simulations surprisingly reveal that UiO-66C exhibits similar diffusion rates to defect-free UiO-66, while UiO-66L shows significantly slower diffusion. This discrepancy is attributed to self-adsorption of reactants at the high-density catalytic sites, which induces local diffusion resistance even in the presence of expanded channels. These findings reveal a performance trade-off between catalytic site density and intrinsic activity, establishing a critical threshold beyond which further increases in site density can hinder rather than enhance catalysis.
Ozone-assisted catalytic oxidation (OzCO) and conventional catalytic oxidation (CCO) of alkanes such as propane and methane were investigated over Mn/Hydroxyapatite at 50-450 degrees C using the innovative LoPOx setup, which enables precise control of the reactor total pressure. Utilizing ozone as the oxidant decreased the required oxidation temperature by up to 300 degrees C compared to CCO, enabling full propane conversion below 100 degrees C, with a maximum CO2 selectivity amounting to 85%. Kinetic analysis revealed distinct propane OzCO stages, transitioning from OzCO-driven conversion (<100 degrees C) to gas-phase ozonation (100-200 degrees C), followed by gas-phase ozonation and CCO (200-400 degrees C), and ultimately CCO (>400 degrees C). A comparative assessment of propane and methane oxidation revealed that, despite the presence of highly reactive oxygen species, the high C-H bond dissociation energy of methane significantly limited its oxidation. Consequently, although the presence of O-3 effectively enabled low-temperature propane oxidation, it was insufficient for methane abatement under similar conditions.
Titanium-based metal-organic frameworks (Ti-MOFs) hold great potential for applications in photocatalysis and other fields, owing to Ti's abundant reserves, low toxicity, and excellent photocatalytic and redox activity. However, Ti's strong affinity for oxygen often leads to Ti-MOFs being fully coordinated with ligands, which limits their catalytic and separation performance. Defect engineering provides an effective strategy to enhance the functionality of MOFs by introducing structural imperfections. Despite this, the synthesis of new Ti-MOFs and the incorporation of defects remain challenging due to the complex hydrolysis and reaction processes of Ti precursors and the uncertainty of Ti cluster formation. This review categorizes Ti-MOFs according to their diverse cluster structures, which play a key role in the development of new frameworks and defect engineering. It also examines various defect construction methods and their applications. Finally, insights from defect-engineered Zr-MOFs are discussed to inspire future advancements in the synthesis and application of defective Ti-MOFs.
In this study, we explore, for the first time, the use of a new pyridine-covalent triazine framework (py-CTF), containing both nitrogen and oxygen, as a metal-free catalyst in a post-plasma catalytic (PPC) system for abatement of toluene, a common volatile organic compound (VOC). The PPC system was evaluated under varying specific energy densities (SEDs) from 100 to 400 J/L and catalyst temperatures ranging from room temperature to 200 °C. Our findings reveal that combining py-CTF with non-thermal plasma significantly enhanced toluene removal efficiency compared to both plasma alone and catalyst alone systems. A remarkable toluene removal efficiency of 97.2
Luminescent metal‐organic frameworks (MOFs) have interesting applications as light‐emitting devices and optical (temperature) sensors. Bismuth‐based MOFs (Bi‐MOFs) are not heavily explored yet but are highly promising in this regard. A robust defect‐engineered Bi‐MOF (namely, Bi‐TATAB) is prepared under acid‐modulator‐free solvothermal conditions. Next, a series of lanthanide (Ln)‐doped Bi‐MOFs is obtained by incorporating either one or two Ln 3+ ions (Ln 3+ = Eu 3+ , Tb 3+ , Eu 3+ /Tb 3+ , Dy 3+ , or Sm 3+ ) using a facile one‐pot method. The resulting doped analogues show high crystallinity and porosity, good thermal resistance, and highly tunable luminescent properties. The color of the emitted light can be tuned by varying the dopant ions and their ratios. Thus, three white‐light‐emitting materials, including Eu 3+ or Eu 3+ /Tb 3+ , are developed. The new material (Eu 0.025 Tb 0.05 Bi 0.925 ‐TATAB) exhibits temperature sensing capability over a broad temperature range (10–360 K). Two ratiometric temperature sensors are constructed based on two thermometry modes proposed for this MOF: I Tb / I Eu and I Bi‐MOF / I Eu under single‐wavelength excitation. Intriguingly, the latter system is among the most sensitive cryogenic MOF‐based thermometers reported to date, with a maximum relative sensitivity ( S r ) value of 8.84% K −1 (at 60 K). This material is the first example of a Ln/Bi‐MOF platform with cryogenic temperature sensing properties.
The arsenic-based micropollutant, p-arsanilic acid (p-ASA), utilized as an additive in animal feed for decades, poses a significant threat to both human health and environmental safety. To address this, we developed a defect-engineered bimetallic MOF, UiO(Zr, Eu)-66-(NH2)2. This MOF shows high sensitivity and selectivity for detecting and capturing low concentrations ofp-ASA in water. This newly synthesized material is extremely sensitive top-ASA with a very low limit of detection (LOD = 0.72 mu g L-1), even in the presence of interfering species like Cl-, NO3-, humic acid, and others. Besides, UiO(Zr, Eu)-66-(NH2)2 exhibits a theoretical adsorption capacity of 189 mg g-1 forp-ASA pollutant, and an experimental adsorption affinity of 4.40 x 105 mL g-1 for 2 mg L-1 p-ASA in water. Density functional theory calculations reveal that the defect sites in UiO(Zr, Eu)-66-(NH2)2 provide the unsaturated Zr centers, forming a stable bidentate binuclear Zr-O-As coordination mode. Additionally, pi-pi stacking and hydrogen bonding strengthen the interaction between UiO(Zr, Eu)-66-(NH2)2 and p-ASA. These synergistic effects enable UiO(Zr, Eu)-66-(NH2)2 to achieve high adsorption capacity and selectivity toward low-concentrations p-ASA in water.
Covalent organic frameworks (COFs) have emerged as photocatalytic materials with bandgaps in the visible region. Imine-based COFs, which have been extensively explored, often suffer from limited stability and poor conjugation, hindering their photocatalytic activities. The chemical and hydrolytic stability and the photo- catalytic performance of COFs is drastically enhanced by constructing 2D COFs that are fully conjugated in the x, y plane, that have alternating donor-acceptor (D-A) units for better charge separation and that have enhanced conjugation in the z-axis by p-orbital overlap by using highly planar building blocks. In this study, we introduce three highly crystalline sp(2) COFs that are able to photocatalyticlly reduce highly toxic Cr (VI) species to much less toxic and easily removable Cr (III) residues, while simultaneously oxidizing water borne organic pollutants. One of them, the TEB-COF, with the integration of the acetylene group, exhibited excellent photocatalytic activity due to its superior planarity and extended conjugation. TEB-COF is able to completely remove the model dye Rhodamine B and Cr (VI) (10 mg/L) in less than 30 min. This research provides valuable insights into the development of recyclable metal-free photocatalysts for wastewater treatment.