Production of aromatic compounds such as benzene, toluene, and xylene (BTX) from CO2 has emerged as a promising strategy for realizing sustainable, non-fossil-based compounds while addressing CO2 emissions. Herein, we investigate the synergistic effect between the modulated Fe-based catalyst active site and MFI zeolite with different pore levels. The result demonstrates the critical role of Cu doping and CO reduction in stabilizing olefin-producing active phases. Meanwhile, the increase in multi-level porosity in MFI obtained by a templated, solvent-free method enhanced the aromatic selectivity due to the reduction of diffusion constraints, shown by 46.72% conversion with 48.18% BTX selectivity in aromatic products.
The fundamental reaction mechanism, especially the synergistic effect between metal-support interaction and surface acidity of support are highly promising for liquid organic hydrogen carrier hydrogenation (LOHC) reaction but challenging for Ni-based catalysts. In this work, Ni nanoparticles (NPs) (2.1 nm) were highly dispersed on Al-SBA-15 support (Ni@Al-SBA-15(20)) via solid-state grinding method by fully considering the confinement effect of template P123, abundant silanols and alumina. Our results demonstrated that compared with Ni@SBA-15, the conversion rate over Ni@Al-SBA-15(20) catalyst containing acidic sites for N-ethylcarbazole(NEC) hydrogenation enhanced to 100%, the yield of 12H-NEC increased from 78.43% to 94.03%, and the hydrogen capacity reached to 5.58 wt.%. The excellent activity is attributed to highly dispersed and smaller sized Ni NPs, relatively uniform mesoporous structure and large amount of acid centers. Dual acid complementary mechanism based on strong metal-support interaction (SMSI), the Brønsted acid sites on the carrier acts as a receiver and transporter of hydrogen radicals to promote the hydrogen overflow effect. In addition, the Lewis acid sites acts as an adsorption center for NEC thereby facilitating a rapid and efficient organic liquid hydrogen storage process. The current work provides a novel strategy for developing high-performance Ni-based catalysts with exceptional Ni NPs dispersion, and activity with excellent stability for LOHC applications. The methodology highlights the importance of support acidity engineering and nanoconfinement effects in catalytic design.
The production and synthesis of carbon/metal oxide nanomaterials derived from metal-organic frameworks with a suitable porous structure and composition is significant for use as environmentally friendly catalysts in various organic transformations. In this work, the synthesis and characterization of a catalyst based on a nitrogen-doped porous carbon substrate containing cobalt oxide nanoparticles using the pyrolysis of a natural polymer (cellulose) and ZIF-67 composite is reported. It was found that this heterogeneous catalyst is fully recyclable and is very efficient for the reduction reaction of nitroaromatic compounds. In this study, the MNC (Micropore, nitrogen, carbon)/Co3O4 catalyst was designed and synthesized at temperatures of 600, 700, and 800 °C using cellulose/zeolitic metal-organic framework precursor. Several physical and chemical techniques, such as FT-IR, XRD, Raman spectroscopy, N2 ADS-DES, FE-SEM, AAS, EDS, MAP, and TEM, were used to characterize the structure and properties of the catalyst. The studies conducted show that the composite pyrolyzed at 700 °C shows higher catalytic activity than the other two temperatures.
Adsorption-based CO2 separation using porous solids is increasingly investigated for flue gas treatment, biogas and natural gas sweetening, hydrogen purification, direct air capture, and selected CO2-containing petrochemical streams. This review focuses on adsorption-based CO2 separation from gas streams by integrating recent findings in experimental studies, simulations and modeling works, and selected pilot and industrially relevant examples to clarify how porous adsorbents can be linked to practical cyclic CO2 capture systems. The review is organized around a structure-mechanism-process (SMP) selection logic that links the dominant adsorption mechanism required by a given gas stream to a suitable adsorbent class and cyclic process and applies it across five representative CO2-containing streams. Porous solids, including zeolites and metal-organic frameworks (MOFs), are emphasized as promising materials owing to their extensive surface area, adjustable pore structures, and selective adsorption capabilities. The study reviews the adsorption characteristics of popular zeolites (4A, 5A, 13X) under diverse conditions and assesses their reported performance in relation to industrial CO2 removal requirements. Also, key parameters such as adsorption capacity, regeneration energy, and selectivity are discussed in this review. Moreover, the performance of adsorbents in key adsorption process configurations was examined, including pressure swing adsorption (PSA), vacuum swing adsorption (VSA), temperature swing adsorption (TSA), and hybrid schemes (e.g., PVSA, TVSA).Key challenges include the absence of a practical adsorbent-selection framework, limited hydrothermal and contaminant tolerance, regeneration-energy penalties for strongly binding sorbents, shaping and mechanical robustness, and scalable synthesis. Future progress will depend on the combined optimization of adsorbent chemistry, morphology, and process configuration to achieve practical, economically viable CO2 capture solutions. By systematically linking adsorption mechanisms, materials design, and process engineering, adsorption-based CO2 capture holds promise for advancing from laboratory-scale studies to practical, energy-efficient industrial implementation.
Enzymes serve as green and efficient biocatalysts yet suffer from poor stability, difficult recycling, and low tolerance to harsh environments, severely restricting their industrial applications. Metal-organic frameworks (MOFs) have emerged as superior carriers for enzyme immobilization owing to their ultrahigh specific surface area, tunable pore structure, abundant surface functional groups, and designable framework composition. This review systematically summarizes the latest advances in enzyme immobilization using MOFs, covering four major immobilization strategies: physical adsorption, covalent conjugation, cross-linking, and pore encapsulation (including in-situ encapsulation and post-encapsulation). We focus on how rational design of MOF supports—such as morphology control, pore-size modulation, and surface functionalization—boosts enzyme loading, activity retention, thermal stability, solvent resistance, and reusability. The applications of MOF-enzyme composites are comprehensively reviewed across biocatalytic synthesis, biomedical therapy, biosensing, and environmental remediation (pollutant degradation). Despite remarkable progress, key challenges remain including mass-transfer limitations, activity loss during immobilization, insufficient stability under extreme conditions, and difficulties in scalable production. Finally, we discuss future directions toward hierarchical porous MOFs, stimuli-responsive systems, multi-enzyme cascade nanoreactors, green and biodegradable MOFs, and industrial-scale implementations. This review aims to establish a structure–performance relationship between MOF design and enzymatic performance, providing a theoretical roadmap for developing next-generation high-performance immobilized enzyme systems with tailored functionalities.
Silica aerogels possess ultrahigh porosity and a large specific surface area, yet their intrinsic fragility limits their practical implementation in load-bearing or cyclic adsorption applications. Herein, we report a double-network strategy for fabricating mechanically robust silica–poly(2-acrylamido-2-methylpropanesulfonic acid) composite aerogels. Initially, a rigid methyl-modified silica skeleton was constructed via sol–gel processing. Subsequently, the impregnation-polymerization of AMPS within the pore network was performed to form a spatially entangled secondary polymer network within the silica pores. The TDB-Pamps(2M) composite exhibited markedly enhanced mechanical performance (maximum compressive stress of 97.4 MPa at approximately 89% strain and apparent compressive modulus: 77.0 MPa) and was therefore selected for iodine vapor capture, reaching an iodine uptake of approximately 133.3 mg/g within 720 min, retaining ∼131 mg/g after five adsorption–desorption cycles and 140.85 mg/g after 48 h. In aqueous systems, the TDB-Pamps(1M) composite, which offered a higher specific surface area (577 m2/g) and larger pore volume (1.5 cm3 /g), was selected for dye adsorption studies and displayed high selectivity for methylene blue, attaining a theoretical Langmuir maximum adsorption capacity of 333.79mg/g while the experimentally observed removal efficiency exceeded ∼98% under optimized conditions. Combined experimental analysis and density functional theory calculations reveal that MB adsorption is governed by cooperative noncovalent interactions, including hydrogen bonding, van der Waals/hydrophobic interactions, and electrostatic attraction (ion pairing) between MB+ and surface sulfonate groups. Overall, this work highlights a scalable route for preparing strong, high-surface-area aerogel adsorbents with durable performance in gas and liquid-phase capture.
In the last decades, metal-organic frameworks (MOFs) have emerged as promising adsorbents in fields like atmospheric water harvesting and carbon capture. Despite their excellent sorption performance, most MOFs have yet to make their way from research laboratories into industrial processes. A big hurdle for the industrial application of MOFs is their microcrystalline nature, which leads to processing issues and high pressure drops in flow-based systems. In this study, we present a direct ink writing based 3D printing approach that combines MOF powders with carbons to produce hierarchically porous electrically conductive monolithic MOF@carbon composites with a tunable shape. Two MOFs, namely CAU-10-H and CALF-20 were combined with graphite and activated carbon (AC) respectively, to yield CAU-10@graphite and CALF-20@AC monoliths with quadratic macropore channels. The monoliths have a size of ca. 30 x 30 × 50 mm3 with high MOF loadings of 47.2 wt %. PXRD and sorption analysis showed, that the microporosity and crystallinity of both MOFs remained intact after the 3D printing process. Investigations of their CO2 adsorption capacity using static and dynamic methods resulted in uptake values of 0.5 and 1.4 mmol/g at 25 °C and 0.3 bar CO2 partial pressure for CAU-10@graphite and CALF-20@AC, respectively. Joule heating was used to internally heat the monoliths to over 60 °C, reducing the CO2 desorption time by up to a third.
This study reports the performance of trimethyl stearyl ammonium–modified montmorillonite nanoclay (MMT-TmSA) for the removal of the anionic adsorbate Mordant Orange 1 (MO1) from aqueous solutions, with particular emphasis on refining the energetic interpretation of the Dubinin–Radushkevich (D–R) isotherm. The organoclay adsorbent was characterized using SEM, EDX, XRD, and FTIR techniques. The pseudo-second-order model best described the adsorption kinetics. Thermodynamic analysis indicated an endothermic process (ΔH = 37.8 kJ/mol), with increasing temperature favoring adsorption. Equilibrium studies revealed a maximum experimental adsorption capacity of 76.48 mg/g at 300 K and 89.94 mg/g at 320 K. Six variants of the D–R isotherm model were evaluated for the MMT-TmSA/MO1 system; among them, two variants employing the initial absorbate concentration as the reference provided the best fit based on both linear and nonlinear regression analyses. The adsorption capacity predicted by these variants closely matched the experimental values. A proportional relationship () between the characteristic adsorption free energy (E) and the mean sorption energy (Es) derived from the D–R isotherm is proposed. Energetic analysis, corroborated by molecular modeling results, indicated an ion-exchange mechanism dominated by Coulomb electrostatic interactions with secondary van der Waals contributions. Moreover, an extended energy interval of E = 8–42 kJ/mol is highlighted for the ion-exchange processes, thereby challenging the commonly cited 16 kJ/mol threshold. Chemometric optimization identified optimal adsorption conditions, and the feasibility of a hybrid adsorption–ultrafiltration process was also demonstrated.
Two-dimensional (2D) nanomaterials have emerged as promising electrocatalysts for CO2 reduction reaction (CO2RR) owing to their high specific surface area, tunable active sites, and excellent electrical conductivity. This review systematically summarizes recent advances in 2D nanomaterials, including graphene, COFs, MOFs, metals/metal oxides, and MXenes, for electrocatalytic CO2RR. We comprehensively discuss optimization strategies encompassing heteroatom doping, defect engineering, morphological control, single/dual-atom loading, and heterostructure construction. The activity enhancement mechanisms and selectivity regulation toward C1 and C2+ products are highlighted. Furthermore, current challenges including ambiguous active site identification, insufficient long-term stability, and scale-up difficulties are critically analyzed. Ultimately, this work offers a systematic design roadmap for next-generation 2D electrocatalysts, aiming to facilitate the development of efficient, selective, and sustainable CO2 conversion technologies to support the global pursuit of carbon neutrality.
Metal-organic frameworks (MOFs) have emerged as highly tunable porous platforms for molecular recognition, selective enrichment, and controlled delivery of structurally diverse bioactive molecules. Traditional Chinese Medicine (TCM)-derived antiviral bioactive compounds, including flavonoids, alkaloids, terpenoids, and polysaccharides, possess promising biological activities but often suffer from poor aqueous solubility, limited physicochemical stability, and insufficient bioavailability. This review provides a molecular recognition-guided perspective on the transition from selective enrichment to controlled delivery of TCM-derived antiviral bioactive molecules using MOF-based systems. We discuss how MOF structural features, including pore architecture, surface functionality, defect engineering, and framework stability, regulate host–guest interactions, molecular encapsulation, and release behavior. Recognition mechanisms involved in selective extraction, such as pore confinement, hydrogen bonding, π-π interactions, electrostatic interactions, and coordination interactions, are critically evaluated as potential design principles for developing precision delivery platforms. However, selective adsorption does not directly guarantee therapeutic effectiveness, as successful translation requires balancing binding affinity, guest diffusion, release kinetics, framework degradation, and biological compatibility. Current challenges, including the limited use of authentic TCM extracts, insufficient quantitative relationships between adsorption properties and delivery outcomes, and the lack of systematic antiviral validation, are also discussed. This review highlights molecular recognition as a common chemical basis connecting selective enrichment and precision delivery, providing a conceptual framework for the rational design of emerging MOF-based antiviral platforms.
Combination photo-chemodynamic therapy (PDT/CDT) represents a promising anticancer strategy that synergistically generates reactive oxygen species (ROS) through light activation and Fenton-like reactions. However, the therapeutic efficacy of ROS is often compromised by overexpressed glutathione (GSH) and the ultra-short lifetime of hydroxyl radicals (•OH). To address these challenges, we developed a novel mesoporous silica-based nanosystem integrating a Fenton catalyst Cu(II), oxygen-vacancy-rich tungsten oxide (WO3-x), and the photosensitizer zinc phthalocyanine. The nanosystem enhances oxidative damage through Cu(II)-mediated GSH depletion and WO3-x-facilitated adsorption and stabilization of •OH via oxygen vacancy trapping, in addition to the synergistic PDT/CDT effect. Following conjugation with a mitochondria-targeting ligand, the nanosystem was evaluated in vitro and in vivo, achieving a cell inhibitory rate of 80% and a tumor growth inhibition rate of 73.9%, demonstrating high therapeutic efficacy. These results indicate that the as-synthesized multifunctional nanosystem with enhanced oxidative capacity holds great promise as a PDT/CDT nanoagent for tumor ablation.
The direct valorization of spent fluid catalytic cracking (FCC) catalysts into high-value zeolitic materials remains challenging because conventional conversion routes generally require alkali activation, complex pretreatments, or organic structure-directing agents. Herein, we report a direct and reproducible synthesis of HEU-type zeolite from non-alkali-activated spent FCC catalyst through a K+-directed seed-assisted hydrothermal strategy. In this approach, KOH serves as the sole alkali source, while synthetic HEU seeds promote nucleation and regulate framework formation. The optimized synthesis conditions (2.3 K2O: Al2O3: 8.0 SiO2: 440 H2O, 13 wt% seed loading, 160 °C, 72 h) yield highly crystalline HEU zeolite without the use of organic structure-directing agent (OSDA) or alkali activation. Systematic investigation of the crystallization field reveals that K+ plays a critical structure-directing role by stabilizing the building units required for HEU formation, whereas seed crystals shorten the induction period and accelerate nucleation. After Na+ exchange, the resulting Na-FCC-HEU exhibits excellent Pb2+ adsorption performance, including >99.8% removal efficiency at a low solid-to-liquid ratio of 1/1000, rapid adsorption equilibrium within 35 min, broad pH tolerance (3–7), strong resistance toward competing ions, and a maximum adsorption capacity of 215.1 mg g−1 at 80 °C. The superior adsorption behavior originates from the low Si/Al ratio and abundant exchangeable sites of FCC-derived HEU. This work provides a sustainable route for converting industrial waste into functional zeolitic materials and offers new insights into the crystallization chemistry of HEU zeolite.
Tetracycline (TC) contamination in aquatic environments poses severe ecological and health risks, necessitating the development of high-performance adsorbents. Focusing on resolving the poor accessibility and inadequate pore architectures of phenolic hydroxyl-functionalized hyper-cross-linked polymers (HCPs), we proposed a copolymerization strategy to synthesize several HCPs with resorcinol and benzene as monomers. By optimizing their molar ratio, a synergistic enhancement of specific surface area, hierarchical porosity, and accessibility were realized. The optimal HCP-B3 exhibited an exceptional TC adsorption capacity of 441 mg g−1, far higher than HCP-RE (97 mg g−1) and most conventional porous polymers (typically <100 mg g−1). Systematic investigations revealed that the adsorption followed the Freundlich isotherm, driven by physical hydrogen bond and π···π interactions. Furthermore, HCP-B3 demonstrated wide antibiotic adaptability and maintained 92% adsorption capacity after five cycles. This work provided a rational design principle and fundamental insights into the structure–property-performance relationship for porous polymers as antibiotic absorbents.
In this paper, the hollow coral-like ordered mesoporous MCM-41-C zeolites were synthesized by hydrothermal method, and their synthesis conditions were thoroughly investigated. Then, xwt%Al-MCM-41-C catalysts feature with hollow coral-like morphology were prepared by impregnation method, and used for the catalytic conversion of γ-valerolactone (GVL) to butene. The results showed that the introduction of Al species not only did not destroy the original special microscopic morphological structure of the MCM-41-C, but also co-existed on the surface and skeleton of the catalyst, resulting in a large number of weak acid sites. The optimal 7wt%Al-MCM-41-C catalyst has a specific surface area of 708.56 m2 g−1. The content of weak acid was 0.7262 mmol g−1. At 300 °C, the GVL conversion and butene yield over the catalyst can reach 99.10% and 92.26%, respectively, within just 90 min of reaction. Meanwhile, the 7 wt%Al-MCM-41-C catalysts also demonstrated excellent catalytic cycle stability, and the butene yield remained above 90% after the 4th cycle.
