The development of versatile mesoporous silica nanomaterials (MSNSs) with suitable textural properties is essential for the targeted and precise delivery of therapeutic drugs for the treatment of various diseases. Especially, loading of highly toxic platinum-based drugs is essential to reduce their toxic side effects. However, loading platinum-based drugs such as carboplatin in high quantity in porous materials is extremely challenging owing to the high hydrophobicity and lack of functional groups for interacting with surfaces of MSNS. In this study, we report a facile synthesis of core-shell MSNS by employing a unique combination of triple surfactants - pluronic P123, cetyltrimethylammonium bromide (CTAB) and fluorocarbon-4 (FC-4) for targeted delivery of the carboplatin for the treatment of lung cancer. The highly hydrophobic FC-4 plays a vital role in tuning the self-assembly and thereby controls the size, morphology, textural properties and uniform pore size distribution of the MSNS. The optimised MSNS with the size range of 300–320 nm, uniform size distribution, high surface area and ordered structure was successfully synthesised. A high drug loading of 26.7% was achieved on both bare and amine functionalised MSNS with a steady release of up to 60% and 37%, respectively, in PBS. The targeting efficiency of the folic acid functionalised particles was established by confocal microscopy, which showed higher cellular uptake of these particles in A549 cells. The high carboplatin loading and targeting ability resulted in high cytotoxicity from the folic acid functionalised and drug-loaded MSNS samples in PC9 cells compared to non-targeted and bare MSNS samples. Overall, this study proposes a new single-step synthesis of core-shell MSNS with high drug loading capacity that can be used to deliver drugs in treating different types of cancers.

Sodalite is a common zeolite, which is often discarded or ignored due to its small pore size and poor adsorption capacity. In this study, two sodalite type materials, CSF-S and N-CSF-S, were synthesized using cellulose superfine fiber (CSF) as template. Its unique scaly structure not only enhances its adsorption capacity for Cd (II), but also improves its adsorption efficiency. At 298 K and the initial Cd (II) concentration of 100 mg/L, the adsorption equilibrium of CSF-S was achieved within 30 min, which is 98% shorter than that of traditional sodalite. The adsorption of Cd (II) by CSF-S and N-CSF-S is an endothermic process and at 298 K the adsorption capacity could be as high as 260.1 and 284.1 mg/L, respectively, which were 1.9 and 2.0 times of the original sodalite, far higher than the reported similar adsorbents, and competitive to over other types of adsorbents. In addition, with low zero points of charge CSF-S (pHzpc around 1) and N-CSF-S (pHzpc around 3) can effectively remove Cd(II) over a wide pH range, superior to most zeolitic sorbent materials. Therefore, this work proposes a simple and cost-effective synthesis method for the sodalite type sorbents with high Cd(II) adsorption capacity and rapid adsorption rate, and also provides some basis for the study of heavy metal adsorption materials in aqueous systems.

Adenosine triphosphate (ATP) and other nucleotides can be irreversibly bound to the metal-organic framework (MOF) MIL-101(Cr). Analysis of X-ray diffraction data suggests that the location of the adsorbed ATP molecule is in proximity of the Cr3 clusters. Solid-state NMR and DFT calculations indicate that ATP is bound to MIL-101(Cr) through linkages of the terminal phosphate group with Cr(III) of the framework. In the presence of Cu(II) ions, the MOF-supported nucleotides can function as stable and reusable enantioselective heterogeneous catalysts for reactions like Diels-Alder and Michael addition. Compared to the corresponding homogeneous nucleotide-based artificial metalloenzymes (ArMs), the MOF-supported nucleotide-based ArMs exhibit significantly enhanced activity and selectivity in certain cases, demonstrating their potential as a new class of enantioselective heterogeneous catalysts.

The standard faujasite Y series of Zeolyst International was tested in the catalytic cracking of 1,3,5-Triisopropylbenzene (TIPB) in a continuous-flow fixed-bed catalytic reactor. Textural properties, true density, XRD, TEM, ammonia TPD, and Brønsted acidity by the isopropylamine decomposition reaction were used to characterize the zeolites. TIPB conversion responds to the acidity available to the molecule rather than only mesoporosity. Deactivation behavior gives valuable information about accessibility. Criteria like the initial conversion or at another time are not enough for correctly ranking the catalysts; neither is the selectivity to benzene. TOF and TON are better criteria for classifying the catalysts than selectivity to a specific product like di-isomers. Zeolite CBV780 shows the highest TOF of the series, but zeolite CBV720 gives the highest TON. A good balance between acidity and mesoporosity provides the catalyst with increased activity in the TIPB cracking reaction.

Impregnation handlement can load highly dispersed CuO nanoparticles on the Fe-MFI zeolite and effectively enhances its catalytic activity in the tetracycline degradation reactions, but encounters serious re-usability problems. In this work, Fe-MFI zeolite-encapsulated copper oxide CuO@Fe-MFI was prepared via one-step hydrothermal synthesis and utilized as heterogeneous catalyst for the removal of tetracycline. The obtained 2CuO@1Fe-MFI zeolite presented a external surface area of 270 m2/g, which was almost 5.5 folds of 2CuO/1Fe-MFI zeolite obtained by impregnation handlement. In addition, there may be a near-neighbor effect between encapsulated CuO and framework iron evidenced by the shifts of UV–Vis absorption bands as well as binding energies for Fe 2p and Cu 2p. At pH = 7.0, 2CuO@1Fe-MFI zeolite attained the largest tetracycline removal rate of 99.6% within 20 min at experimental conditions: [TCE] = 50 mg/L, [Catalyst] = 0.5 g/L, [PMS] = 1.0 g/L, 323 K, and the biggest degradation rate constant of 2.42 min−1, which was almost 11.1 folds of that for 2CuO/1Fe-MFI zeolite. The large external surface area and near-neighbor effect together gave rise to the excellent tetracycline degradation performance for 2CuO@1Fe-MFI zeolite. On the same time, the obtained 2CuO@1Fe-MFI zeolite can be reused for more than five times. Quenching experiments and EPR characterizations demonstrated the reactive species for tetracycline removal over 2CuO@1Fe-MFI zeolite were •OH, SO4•−, •O2− and 1O2 species, and moreover 1O2 served as the major active species. Furthermore, possible tetracycline degradation pathways over 2CuO@1Fe-MFI zeolite were proposed.

In a world where capture and separation processes represent above 10% of global energy consumption, novel porous materials, such as Metal-Organic Frameworks (MOFs) used in adsorption-based processes are a promising alternative to dethrone the high-energy-demanding distillation. Shape and size tailor-made pores in combination with Lewis acidic sites can enhance the adsorbate-adsorbent interactions. Understanding the underlying mechanisms of adsorption is essential to designing and optimizing capture and separation processes. Herein, we analyze the adsorption behaviour of light hydrocarbons (methane, ethane, ethylene, propane, and propylene) in two synthesized copper-based MOFs, Cu-MOF-74 and URJC-1. The experimental and computational adsorption curves reveal a limited effect of the exposed metal centers on the olefins. The lower interaction Cu-olefin is also reflected in the calculated enthalpy of adsorption and binding geometries. Moreover, the diamond-shaped pores' deformation upon external stimuli is first reported in URJC-1. This phenomenon is highlighted as the key to understanding the adsorbent's responsive mechanisms and potential in future industrial applications.

SiO2 does not have magnetic elements; therefore, it behaves as a diamagnetic material with a possible paramagnetism due to oxygen vacancy defects. Incorporation of magnetic elements and pores into SiO2 films can add an additional functionality to its dielectric and insulating properties. Herein we report the incorporation of Co element into the mesoporous framework of SiO2 (Co–SiO2) thin films through chemical sol-gel based-spin coating processes. The thus obtained Co–SiO2 thin film exhibits transition in the magnetic properties, increase in the specific surface area and a decrease in the leakage current while maintaining better electric conductivity. For comparison, the bare mesoporous SiO2 (m-SiO2) films were prepared at identical conditions. Interestingly, a S-type shape on the isothermal magnetization measurements versus magnetic field (M vs. H) curves appeared at 5 K in case of the Co–SiO2 films, and a paramagnetic behavior was observed at 50 K and above. The temperature-dependent magnetization (M vs. T) measurements of the Co–SiO2 films also showed an increase of magnetization below 50 K. It is anticipated that Co substitutes Si although presence of the CoO and/or Co3O4 phases cannot be completely ruled out. These results support the idea that a ferromagnetic-like transition takes place in the Co-doped SiO2 films below 50 K due to Co doping. At the same time, a reduction in the leakage current density was determined in Co–SiO2, while maintaining better charge transfer in 1.0 M KOH for ion conducting devices.

Covalent Organic Frameworks (COFs) with uniform aperture size, high surface area and tunable structure have been proposed as a potential material in water treatment. In this work, we utilized methoxy based covalent organic frameworks (COF–OMe) at room temperature as a dual-role smart material. For one thing, it can respond to the pH of solutions by visual, colorimetric change. Due to the protonation effect of methoxy groups in its pore skeleton, the fluorescent intensity of COF–OMe went down and the color changed from yellow to black as the pH decreased reversibly. For another, the abundant pores and ordered conjugated structure endowed it with a large surface area and light absorption ability. Therefore, the light-triggered oxidase-mimic porous COF–OMe can be applied in the synergistic removal of organic pollutants with synergistic physical absorption and light degradation. The outstanding and sensitive response to pH, great removal efficiency and dual function made it applied in water treatment with great potential, achieving killing two birds with one stone.

The modified inverse micelle approach was used to create nickel-doped mesoporous manganese oxides (Ni-MM). These novel catalysts showed much higher reactivity to activating PMS than the pristine mesoporous manganese oxides, and 5% doping ratio (Ni/Mn) would lead to best degradation efficiency in the PMS/Ni-MM system. X-ray diffraction (XRD) displayed that the crystal composition of manganese oxides would be changed and scanning electron microscope (FESEM) presented that the surface morphology was transformed from spherical deconstruction to sponge-like particles since Ni was doped into MM. Mn2+, Mn3+ and Mn4+ were coexisted in 5%Ni-MM, and Ni in the material was +2. The operating conditions such as catalyst dosage, PMS dosage, TCH concentration and beginning pH. Under the ideal reaction conditions for 5%Ni-MM/PMS system, the TCH degradation efficiency could be 86.79% in 30 min, and it could be used in the pH range (3-11). In the presence of Cl−, SO42−, CO32−, PO43−, HCO3−, humic acid (HA) and natural water bodies, TCH degradation efficiencies could still be greater than 80%. Quenching experiments indicated that O2·-, 1O2, SO4·- and ·OH contributed to TCH degradation in the 5%Ni-MM/PMS system. The intermediates were identified by LC-MS, and the pathways for 5%Ni-MM/PMS system degradation of TCH were conjectured.

Metal organic frameworks (MOFs)-induced synthetic strategy has been proven a convenient and efficient way for preparing anatase-free hierarchical TS-1 zeolite in our previous study. Here, to further enhance the catalytic performance on 1-hexene, the MOFs-induced hydrothermal synthesis route is optimized by adjusting the amount of tetrapropylammonium hydroxide (TPAOH) and performing different degrees of silanization treatment. A low TPAOH dosage can ensure the synthesized samples have abundant and dense active framework Ti at the expense of partial hierarchical structure. Further deep silanization treatment created mesoporous structure ranging between 20 and 30 nm without affecting the content or distribution of active titanium. The obtained anatase-free hierarchical TS-1 sample Sil-0.150 possesses excellent 1-hexene conversion of >38%. Based on detailed NH3-TPD and Py-IR tests, the presence of high-density Lewis acid sites (LAS) leads to a decreased epoxy product selectivity of 91.5%, and the optimized MOFs-induced synthesis strategy may open up new perspectives for the design and application of high-performance TS-1 catalysts in selective epoxidation reactions of various alkenes.

A benzotrizole-based hyper-crosslinked polymer (HCP) was employed to load cobalt and prepare a novel metal-containing nitrogen-doped carbon catalyst for the selective hydrogenation of quinoline. The high porosity, large surface area and nitrogen-containing monomer of HCP made a positive contribution to metal loading. Owing to the excellent thermostability of HCP, the original porous texture of HCP was partially reserved during pyrolysis, which resulted in highly dispersive Co species in the N-doped carbon material. The remaining mesopores in Co@CN catalyst during thermal decomposition provided available diffusion channels for substrates, which facilitated their full contact with catalytic active sites and their effective conversion. The prepared Co@CN catalyst achieved a conversion rate of 100% and a selectivity of 100% in the hydrogenation of quinoline into 1, 2, 3, 4-tetra-hydroquinoline in water at 100 °C under 3 MPa H2. The as-synthesized catalyst had good reuse performance, exhibiting >95% conversion rate and >99% selectivity even after 12 cycles. Moreover, the catalyst could also be applied to the selective hydrogenation of a serial of quinoline derivatives. The study provided a useful strategy for constructing metal-doped carbon materials which might be applicable for other metals and other reactions.

Catalytic hydrogenation of CO2 or CO, obtained from biomass gasification, is the most used technology to produce renewable methanol. The main problem is that the reactions are controlled by equilibrium, achieving low conversions to methanol, leading to high purification costs and reagent recirculation rates. At 250 °C and 50 bar, the equilibrium conversion of CO2 is around 25%, and methanol selectivity is about 64%. The process can be improved by a sorption-enhanced reaction process (SERP), removing the reaction products in situ and overcoming the equilibrium. To carry out the process, adsorbents with high affinity to the products at high temperatures, like LTA zeolites, are required. Experimental data on methanol and water adsorption at reaction temperatures is quite scarce in the literature, and it is usually assumed that methanol is not adsorbed onto 4A and 3A zeolites. This information is required to design a SERP process with this adsorbent. In this work, the influence of sodium and potassium proportion on the adsorption of methanol and water on LTA zeolites is studied by measuring Henry's adsorption equilibrium constants and reciprocal diffusion time constants. Sodium LTA zeolites (4A) strongly adsorb water and methanol. Potassium-rich LTA zeolites (3A) have higher water/methanol selectivity than sodium-rich LTA zeolites.

The alkali leaching post-treatment method is a simple, economical and general route for introducing mesopores into SSZ-13, while the existing studies have rarely addressed the Al behavior between solution and zeolites framework during the alkali treatment. In this paper, a series of multi-cavity micro-mesoporous SSZ-13 were successfully prepared by using the alkali leaching post-treatment method at various treatment time. Extensive characterization illustrated that Al backfilling and zeolite framework reconstruction also existed during the NaOH treatment, besides the destruction of the zeolite framework due to the dissolution of Si and Al at the beginning of the reaction, and Al was preferentially backfilled into eight-membered ring (8 MR) to repair the zeolite framework and then filled into six-membered ring (6 MR) to reconstruct the zeolite framework. Concurrently, the amount of Brønsted acid (B acid) showed a decreasing-increasing-stabilizing trend during the progress. The catalytic activity and hydrothermal stability tests confirmed that multi-cavity micro-mesoporous SSZ-13 showed excellent catalytic activity for NH3 selective catalytic reduction (NH3-SCR) and good hydrothermal stability. This study provided basic guidance for the optimal design of the post-treatment alkali leaching route, which was highly significant for the development of hierarchically porous zeolites.

Here, we demonstrate a process that constructs highly active Pt–Sn alloy nanoparticles on Sn-Beta zeolite to create highly active and stable propane dehydrogenation catalysts. Sn-Beta zeolite was prepared by the dry-gel (DG) synthesis and dealumination-Sn incorporation (DA) method to stabilize Pt nanoparticles, respectively. Pt–Sn nanoalloy particles with ∼4 nm were formed constructed on Pt/Sn-Beta (DG) via interacting Pt with Sn from Sn-Beta (DG) zeolite, which is realized by series characterizations including high angle angular dark field-scanning transmission electron microscopy (HAADF-STEM) with Energy-dispersive X-ray spectroscopy (EDS), fourier transform infrared spectroscopy of CO (FT-IR-CO) and X-ray absorption spectroscopy (XAS). In contract to Pt/Sn-Beta (DG), Pt@Sn core-shell nanostructure was realized through the interaction of sufficient Sn species in channel of Sn-Beta (DA) with Pt metal. The as-prepared Pt/Sn-Beta (DG) exhibits superior catalytic performance with a turnover frequency (TOF) at 1.8 h−1 and a high propylene selectivity of 99.0% using 40 kPa propane and 60 kPa nitrogen gas at 550 °C. The stability of the Pt–Sn alloy structure and its resilience to sintering results in a promising one-pass durability over 7360 min.

In this research, a core-shell magnetic (Fe3O4, MNP) microporous organic network (MON) was first prepared, then Cu nanoparticles (NPs) were uniformly immobilized on the surface of the MON shell material. According to XPS and XRD analyses, the copper NPs are composed of metallic and oxide (CuO/Cu2O) components. TEM analysis showed that the size of the spherical Cu/CuO/Cu2O NPs immobilized on the MON surface is below 5 nm in diameter. XPS and photo PiFM analyses confirmed Cu NPs’ chelation by the amine groups on the surface of MON materials. MON-Cu/CuO/Cu2O as a heterogeneous nanocatalyst was tested for the synthesis of different carbonates via the CO2 fixation reaction. These compounds were successfully synthesized through the direct reaction between different epoxides and 0.5 MPa CO2 with yields up to 95%, in solvent-free conditions and with noticeable improvement in reaction times, reaching completion in as fast as 60 min.

P-doped tunnel-shaped carbon nitride is prepared for the first time using phosphonitrilic chloride trimer as P source and SBA-15 as template. The optimization experiments reveal that 20% P doped tunnel-shaped carbon nitride exhibited the best tetracycline hydrochloride (TC) degradation performance under visible light irradiation. The degradation rate constant is 0.23367 min−1, which is around 3 and 30 times faster than that of carbon nitride without P doping (0.07223 min−1) and without SBA-15 as template (0.00078 min−1). Radical capture experiment shows that h+ and ∙O2− are the main reactive radicals in the photocatalytic degradation process. The doped P element can increase the formation rate of ∙O2− and reduce the combination of photogenerated electron-hole pairs due to the presence of electron capture centers. The photocatalytic mechanism of P-doped tunnel-shaped carbon nitride is proposed, providing experimental data and theoretical basis for the practical application in polluted wastewater.

The objective of this paper was to study CO2 adsorption on the extremely porous ZIF-8 (Zn(mIm)2 with mIm = 2-methylimidazolate). The ZIF-8 was characterized via X-ray diffraction, scanning electron microscopy, TGA analysis and N2 adsorption-desorption isotherms. The adsorption isotherms were generated at different temperatures, namely, 273 K, 298 K, 323 K, and 353 K. Based on the experimental result, a new model was simulated and interpreted using a multilayer model with saturation. The physicochemical parameters that described the CO2 adsorption process were determined by physical statistical formalism. The characteristic parameters of the CO2 adsorption isotherm such as the number of carbon dioxide molecules per site (nCO2), the receptor site densities (DZIF-8), and the energetic parameters (ΔE1a, ΔE2a) were investigated. In addition, the thermodynamic functions that governed the adsorption process such as the internal energy (Eint), entropy (Sad) and Gibbs free energy (Gad) were determined by a statistical physics model. Thus, the results showed that CO2 adsorption on ZIF-8 was spontaneous and exothermic in nature.

In recent years, covalent organic frameworks (COFs) have garnered considerable attention as a captivating class of organic porous crystalline materials, characterized by their remarkable features such as well-ordered pore channels, and facile functionalization. In this review article, we provide a comprehensive overview of the latest breakthroughs in the field of covalent organic framework (COF) membranes achieved in the past few years. Specifically, we delve into the various fabrication methods employed for COF membranes, including the bottom-up approach (comprising interfacial polymerized method, solvothermal approach, continuous flow method, layer-by-layer self-assembly, chemical vapor deposition and electrophoretic deposition) and the top-down strategy. Moreover, we highlight the remarkable applications of COF membranes, encompassing areas such as water purification, chiral sieving, gas separation, proton conduction, and sensors. Finally, we analyze the existing challenges and opportunities that lie ahead in this field, with a view to providing a roadmap for future research endeavors.

Iron modified mesoporous silica structures were achieved from biomass-derived renewable molding agents (glyceryl monostearate and glycerol) and can become potential substitutes for conventional mesoporous catalysts synthesized from petrochemical-derived precursors. These materials were prepared by different methods (wet impregnation with iron contents of 2.5, 5, 10 and 20% w/w and direct incorporation using a molar ratio Si/Fe = 20) and characterized by XRD, N2 adsorption and desorption isotherms, UVvis-DR and ICP. By using these solid as heterogeneous catalysts in the wet oxidation reaction of the herbicide glyphosate with air under extremely mild reaction conditions (atmospheric pressure and room temperature), herbicide degradation/fragmentation levels of around 70% were achieved. The methodology employed for the synthesis played a key role in the development of the structure and dispersion of Fe species as well as in the stability of the catalytic system. In this way, an advanced technology with low environmental impact for the treatment of a pollutant of great concern at the global level was developed, which adds sustainability to the chemical industry from the use of residual glycerol and/or glyceryl monostearate in the catalyst synthesis.

This study examines the differences in using two primary methods for adsorbing trimethylphosphine oxide (TMPO) onto acid catalysts and their influence on the NMR spectra of TMPO-loaded zeolites. The findings show that TMPO molecules interact with both Brønsted and Lewis acid sites, and that the amount of (TMPO)2H+ dimers formed increases with the amount of TMPO added. The use of dichloromethane as a solvent inhibits the formation of dimers and crystalline TMPO but may lead to inaccurate estimations of acid site strength and quantification due to interactions with residual solvent molecules. The gas-phase method is preferred for adsorbing TMPO onto zeolites, but caution is needed to avoid forming a high number of dimers that ca pose challenges in the interpretation of the NMR spectra.