Pores Of Mesoporous Silica Research Articles

DOPO chemically modified mesoporous silica composites: Preparation, flame retardancy, and thermodynamic properties

AbstractOrganic flame retardant 9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene‐10‐oxide (DOPO) was used to decorate the pores of mesoporous silica (m‐SiO2) nanospheres to prepare a new composite flame retardant (DK‐SiO2). The content of DOPO in DK‐SiO2 is about 17 wt%. Due to the chemical bonding, DK‐SiO2 not only enhances the flame retardant performance, but also effectively avoids adverse effects of DOPO on the glass transition temperature and mechanical properties of epoxy resin (EP). At 9 wt% loading, the limiting oxygen index of the EP increased from 25.7 to 31.2, and successfully passed the UL‐94 V‐0 rating. Besides, DK‐SiO2 can significantly reduce the peak heat release rate, total heat release, and total smoke production of EP, with reductions of 26%, 32%, and 20.8%, respectively. Compared with the simple blended sample, DK‐SiO2 not only has better flame retardant performance but also shows significant advantages in thermodynamic properties. The glass transition temperature, impact, and tensile strength, as well as storage and flexural modulus have been improved. This excellent flame retardant performance is mainly attributed to the gas‐condensed synergistic flame retardant mechanism between DOPO and m‐SiO2. The good thermodynamic performance is due to the excellent dispersion of DK‐SiO2 nanospheres in the EP.

Mesoporous silica-encapsulated nitrogen-doped fluorescent carbon dots modified polydopamine composites for monitoring non-steroidal anti-inflammatory drugs

A one-pot hydrothermal process incorporated nitrogen-doped fluorescent carbon dots (N-FCDs) into the pores of mesoporous silica (m-SiO2). Under weakly alkaline conditions, the m-SiO2/N-FCDs were further functionalized with dopamine to develop m-SiO2/N-FCDs modified polydopamine (m-SiO2/N-FCDs/PDA). The m-SiO2/N-FCDs/PDA exhibited emission at a wavelength of 520 nm (λexc. = 440 nm) and demonstrated excellent quenching efficiency in the presence of NSAIDs (aspirin, diclofenac, ketoprofen, naproxen, and ibuprofen) with a detection limit of 0.045 – 1.43 nM. Furthermore, the m-SiO2/N-FCDs/PDA was utilized to detect NSAIDs in tap and river water and pharmaceutical commercial tablets showing high recoveries of 90.96–100.41 % with RSD < 4.

Colorimetric and Photothermal Dual-Modal Switching Lateral Flow Immunoassay Based on a Forced Dispersion Prussian Blue Nanocomposite for the Sensitive Detection of Prostate-Specific Antigen.

Prostate-specific antigen (PSA) is a key marker for a prostate cancer diagnosis. The low sensitivity of traditional lateral flow immunoassay (LFIA) methods makes them unsuitable for point-of-care testing. Herein, we designed a nanozyme by in situ growth of Prussian blue (PB) within the pores of dendritic mesoporous silica (DMSN). The PB was forcibly dispersed into the pores of DMSN, leading to an increase in exposed active sites. Consequently, the atom utilization is enhanced, resulting in superior peroxidase (POD)-like activity compared to that of cubic PB. Antibody-modified DMSN@PB nanozymes serve as immunological probes in an enzymatic-enhanced colorimetric and photothermal dual-signal LFIA for PSA detection. After systematic optimization, the LFIA based on DMSN@PB successfully achieves a 4-fold amplification of the colorimetric signal within 7 min through catalytic oxidation of the chromogenic substrate by POD-like activity. Moreover, DMSN@PB exhibits an excellent photothermal conversion ability under 808 nm laser irradiation. Accordingly, photothermal signals are introduced to improve the anti-interference ability and sensitivity of LFIA, exhibiting a wide linear range (1-40 ng mL-1) and a low PSA detection limit (0.202 ng mL-1), which satisfies the early detection level of prostate cancer. This research provides a more accurate and reliable visualization analysis methodology for the early diagnosis of prostate cancer.

Reaction-Initiated Single-Molecule Tracking of Mass Transfer in Core-Shell Mesoporous Silica Particles.

Understanding the host-guest interactions in porous materials is of great importance in the field of separation science. Probing it at the single-molecule level uncovers the inter- and intraparticle inhomogeneity and establishes structure-property relationships for guiding the design of porous materials for better separation performance. In this work, we investigated the dynamics of host-guest interactions in core-shell mesoporous silica particles under in situ conditions by using a fluorogenic reaction-initiated single-molecule tracking (riSMT) approach. Taking advantage of the low fluorescence background, three-dimensional (3D) tracking of the dynamics of the molecules inside the mesoporous silica pore was achieved with high spatial precision. Compared to the commonly used two-dimensional (2D) tracking method, the 3D tracking results show that the diffusion coefficients of the molecules are three times larger on average. Using riSMT, we quantitatively analyzed the mass transfer of probe molecules in the mesoporous silica pore, including the fraction of adsorption versus diffusion, diffusion coefficients, and residence time. Large interparticle inhomogeneity was revealed and is expected to contribute to the peak broadening for separation application at the ensemble level. We further investigated the impact of electrostatic interaction on the mass transfer of molecules in the mesoporous silica pore and discovered that the primary effect is on the fraction rather than their diffusion rates of resorufin molecules undergoing diffusion.

Very Large Pore Mesoporous Bioactive Silicate Glasses: Comparison of Behavior toward Classical Mesoporous Bioactive Glasses in Terms of Drug Loading/Release and Bioactivity.

Considering the increase in patients who suffer from osteoporosis and the bone defects that occur in these patients, bone tissue regeneration is a promising option to solve this problem. To achieve a synergistic effect between the synthesis of a proper structure and bioactive/pharmaceutical activity, ions with a physiological effect can be added to silica structures, such as Ca2+, thanks to its bioactive behavior, and Ga3+ for its antibacterial and anticancer action. In this work, the synthesis of large pore mesoporous silica (LPMS), potential bioactive glasses containing Ca2+ and Ga3+, has been studied. Corresponding structures, in terms of composition, have been synthesized following the Sol-Gel EISA (Evaporation Induced Self-Assembly) process (obtaining Classical Mesoporous Silica, MS). Pore structure characterization of LPMSs and MSs has been performed using N2 adsorption/desorption and Hg-porosimetry, showing the presence of pores for LPMSs in the range of 20-60 and 200-600 nm. Nisin, a polycyclic antibacterial peptide, has been used for load tests. The load and release tests performed highlight a higher loading and releasing, doubled for LPMSs if compared to MSs. To confirm the maintenance of the structure of LPMSs and their mechanical strength and resistance, scanning electron microscopy images were acquired before and after release tests. Ca and Ga release in SBF has been studied through inductively coupled plasma-optical emission spectroscopy (ICP-OES), showing a particularly high release of these ions performed with LPMSs. The bioactive behavior of Ca-containing structures has been confirmed using FT-IR (Fourier-transform infrared spectroscopy), SEM-EDS (Scanning Electron Microscope-Energy Dispersive Spectroscopy), and X-ray powder diffraction (XRDP). In conclusion, LPMSs showed better loading and releasing properties compared with classical MS and better release in terms of active ions. In addition, it has also been demonstrated that LPMSs have bioactive behavior (a well-known characteristic of MSs).

One-pot, degradable, silica nanocarriers with encapsulated oligonucleotides for mitochondrial specific targeting

Mutations in nuclear and mitochondrial genes are responsible for severe chronic disorders such as mitochondrial myopathies. Gene therapy using antisense oligonucleotides is a promising strategy to treat mitochondrial DNA (mtDNA) diseases by blocking the replication of the mutated mtDNA. However, transport vehicles are needed for intracellular, mitochondria-specific transport of oligonucleotides. Nanoparticle (NP) based vectors such as large pore mesoporous silica nanoparticles (LP) often rely on surface complexation of oligonucleotides exposing them to nucleases and limiting mitochondria targeting and controlled release ability. In this work, stable, fluorescent, hollow silica nanoparticles (HSN) that encapsulate and protect oligonucleotides in the hollow core were synthesized by a facile one-pot procedure. Both rhodamine B isothiocyanate and bis[3-(triethoxysilyl)propyl]tetrasulfide were incorporated in the HSN matrix by co-condensation to enable cell tracing, intracellular-specific degradation and controlled oligonucleotide release. We also synthesized LP as a benchmark to compare the oligonucleotide loading and release efficacy of our HSN. Mitochondria targeting was enabled by NP functionalization with cationic, lipophilic Triphenylphosphine (TPP) and, for the first time a fusogenic liposome based carrier, previously reported under the name MITO-Porter. HSN exhibited high oligonucleotide incorporation ratios and release dependent on intracellular degradation. Further, MITO-Porter capping of our NP enabled delayed, glutathione (GSH) responsive oligonucleotide release and mitochondria targeting at the same efficiency as TPP functionalized NP. Overall, our NP are promising vectors for anti-gene therapy of mtDNA disease as well as many other monogenic disorders worldwide.Graphical

From Basic Research on Supported-Metal Catalysts to their Practical Applications for Reduction of Food Waste

Abstract Supported metal catalysts are one of the most important heterogeneous catalysts, and they are widely used in chemical processes such as naphtha reforming, purification of exhaust gas from automobiles and so on. However, rational design of supported metal catalysts is still a target in heterogeneous catalysis. The author had a hypothesis that metal nanoparticles in ordered pores of zeolite or mesoporous silica may exhibit novel catalytic properties. Based on this idea, we used micropores of zeolites to accommodate metal carbonyl clusters, and then mesoporous silica to prepare metal nanoparticles. First, we studied ship-in-bottle synthesis of Rh carbonyl clusters in zeolite and its reactivity. Rh6(CO)16 was synthesized in NaY zeolite accompanied with formation of a mononuclear Rh(CO)2, which acted as a carrier of 13CO in 12CO-13CO exchange reaction. Then we worked on synthesis of platinum nanoparticles in mesoporous silica, and found that high activity in preferential oxidation of CO in hydrogen and in low-temperature oxidation of ethylene. The high catalytic performance in ethylene oxidation has led to practical application of platinum/silica catalysts for preservation of fruits and vegetables, resulting in reduction of food waste. This article describes the development process of this research.

Atomic insights into the heterogeneity and the interface interactions of nanoconfined aqueous electrolyte solution

The structure and properties of nanoconfined electrolyte (nano electrolyte) solutions are important subjects in biochemistry, electrochemistry, separation science, etc. In the present work, neutron scattering and data driven reverse Monte Carlo were employed to quantitatively reveal the microstructure of aqueous CaCl2 solution in mesoporous silica MCM-41 at the atomic level. The electrolyte solution distributes in-homogeneously in the pores of mesoporous silica along the radial direction, which can be divided into the core, the transition, and the interface regions. The hydrogen bond structure of water in nano electrolytes is strengthened in the core region, analogous to that of nano water confined in nanochannels, and the ion association was enhanced in the transition region. The structure of the solution in the interface region was analogous to the bulk electrolyte solution under high pressure because of the confinement and interface effects. When the package ratio of nano electrolyte solution is insufficient, small amount of solution quasi-monolayer adsorb on the internal surface of mesoporous silica, the majority solution preferentially forms clusters with different sizes to adhere to the wetted interface. The anomalous hydrogen-bonding structure and ion association found in the present work improve our understanding of nanoconfined electrolyte solutions.

Grafting of Crown Ether and Cryptand Macrocycles on Large Pore Stellate Mesoporous Silica for Sodium Cation Extraction.

Regulation of the sodium cations level in the case of renal failure diseases is a very challenging task for clinicians, and new pollutant extractors based on nanomaterials are emerging as potential treatments. In this work, we report different strategies for the chemical functionalization of biocompatible large pore mesoporous silica, denoted stellate mesoporous silica (STMS), with chelating ligands able to selectively capture sodium. We address efficient methods to covalently graft highly chelating macrocycles onto STMS NPs such as crown ethers (CE) and cryptands (C221) through complementary carbodiimidation reactions. Regarding sodium capture in water, C221 cryptand-grafted STMS showed better capture efficiency than CE-STMS due to higher sodium atom chelation in the cryptand cage (Na+ coverage of 15.5% vs. 3.7%). The sodium selectivity was hence tested with C221 cryptand-grafted STMS in a multi-element aqueous solution (metallic cations with the same concentration) and in a solution mimicking peritoneal dialysis solution. Results obtained indicate that C221 cryptand-grafted STMS are relevant nanomaterials to extract sodium cations in such media and allow us to regulate their levels.

Application of a hybrid large pore mesoporous silica functionalized with β-cyclodextrin as sorbent in dispersive solid-phase extraction. Toward sustainable sample preparation protocols to determine polyphenolic compounds in Arbutus unedo L. fruits by UHPLC-IT-MS/MS

A quick, sensitive and selective analytical reversed-phase method using ultra-high performance liquid chromatography coupled to an ion-trap mass spectrometry detector (UHPLC-IT-MS/MS) was employed for the simultaneous determination of nine phenolic compounds (PCs) in strawberry tree (SBT) berries. The sample treatment included a solid-liquid extraction followed by a dispersive solid-phase extraction (dSPE) procedure using a hybrid large pore mesoporous silica (LP-MS) functionalized with β-cyclodextrin (β-CD) as sorbent material. For this purpose, the initial synthesized LP-MS was modified with β-CD following three different synthetic routes, obtaining three new functionalized materials (denoted LP-MS-β-CD-R1, LP-MS-β-CD-R2 and LP-MS-β-CD-R3). All synthesized materials were comprehensively characterized, showing excellent textural properties, and they were also tested as sorbent materials in the extraction of PCs by comparison of SPE and dSPE procedures. The LP-MS-β-CD-R2 as sorbent material in the dSPE procedure showed the best potential to extract and purify the target PCs, being more effective than the other materials and compared with the SPE procedure. The performance of the proposed dSPE-UHPLC-IT-MS/MS method was validated in terms of selectivity, linearity, LOD, LOQ, trueness, precision, and matrix effect, achieving good analytical method performance and demonstrating its feasibility and practicality for the quantification of PCs in SBT fruits. The analysis of the investigated SBT berries revealed, mainly, high contents of arbutin reaching concentrations up to 5979 µg/g dry weight, followed by catechin (661 µg/g dry weight). Arbutin was, undoubtedly, the major PC determined in all SBT berry samples analyzed, being the most prominent and showing a high concentration compared to that of other polyphenols determined in other red berries.

Immunoregulatory effects on RAW264.7 cells and subacute oral toxicity of ultra-large pore mesoporous silica nanoparticles loading Lycium barbarum polysaccharides

As a drug delivery carrier, ultra-large pore mesoporous silica nanoparticles (UCMS) are more flexible and sturdier than traditional drug delivery systems, which enable protect drugs and proteins from the destruction of gastrointestinal acid environment and enzymes. The purpose of this study was to develop ultra-large pore mesoporous silica nanoparticles loading Lycium barbarum polysaccharides (LBP-UCMS) as a novel and safe immunopotentiator, thence immune effect on macrophages and subacute oral toxicity of LBP-UCMS were investigated. UCMS were prepared successfully through a silica sol-gel reaction, followed by physical agitation to obtain LBP-UCMS. Various techniques were used to characterize the structure and morphology of LBP-UCMS, resulting in the successful loading of LBP into UCMS. As innate immune cells, macrophages play an important role. In vitro study demonstrated the immune-enhancing activity of LBP-UCMS on RAW264.7, including enhancement phagocytosis of macrophages, up-regulation the expression of costimulatory molecules CD80, CD86 and MHCII, and stimulation the production of cytokines (TNF-α, IL-1β and IL-6). For the evaluation of LBP-UCMS safety, mice were administered LBP-UCMS for 14 consecutive days. The results of in vivo study showed that oral administration of LBP-UCMS (200, 400 and 800 mg/kg) for 14 days was safe. Hence, UCMS is an effective and safety platform for delivery of LBP for improving the effect of its clinical application.

Adsorption of 17α-methyltestosterone onto silica-based porous materials: Effect of porosity and functionalization, reversible kinetics, and the coexistence of tannic acid

This study investigated the impacts of porosity and the surface functional groups of silica-based porous materials on the adsorption of 17α-methyltestosterone (MT) in low concentration ranges (μg L−1), including the role of coexisting tannic acid (TA). The reversible adsorption kinetics of MT revealed that it was preferentially adsorbed by the mesoporous cylindrical pores of Santa Barbara Amorphous-15 (SBA-15) rather than by the wormhole-like pores of hexagonal mesoporous silica and the micropores of NaY. Furthermore, the increasing pore diameter of SBA-15 from 5.8 nm to 19.9 nm (SBA-CHX) could inhibit reverse desorption and maintain the accessibility of MT through the internal surface area. Due to its high hydrophobicity, the grafted triethoxyoctyl- group had an influential role in hydrophobic partitioning, enhancing the adsorption of MT, especially when grafted on the extended pores of SBA-CHX. The adsorption mechanisms of MT on silica-based adsorbents might involve hydrophobic partitioning, π–π interaction, hydrogen bonding, and ion-dipole interaction. The presence of TA could enhance the selective adsorption of MT onto hydrophobic functionalized SBA-15 s via the increase of hydrophobic partitioning. In conclusion, the large pore diameter of SBA-15 (above 5.8 nm) and grafting with the triethoxyoctyl- group could provide the highest MT adsorption capacity and effectively reject the coexisting TA.

The Effect of Nanoconfinement on Deliquescence of CuCl2 Is Stronger than on Hydration.

The hydration of salts has gained particular interest within the frame of thermochemical energy storage. Most salt hydrates expand when absorbing water and shrink when desorbing, which decreases the macroscopic stability of salt particles. In addition, the salt particle stability can be compromised by a transition to an aqueous salt solution, called deliquescence. The deliquescence often leads to a conglomeration of the salt particles, which can block the mass and heat flow through a reactor. One way of macroscopically stabilizing the salt concerning expansion, shrinkage, and conglomeration is the confinement inside a porous material. To study the effect of nanoconfinement, composites of CuCl2 and mesoporous silica (pore size 2.5-11 nm) were prepared. Study of sorption equilibrium showed that the pore size had little or no effect on the onsets of (de)hydration phase transition of the CuCl2 inside the silica gel pores. At the same time, isothermal measurements showed a significant lowering of the deliquescence onset in water vapor pressure. The lowering of the deliquescence onset leads to its overlap with hydration transition for the smallest pores (<3.8 nm). A theoretical consideration of the described effects is given in the framework of nucleation theory.

High-Capacity Mesoporous Silica Nanocarriers of siRNA for Applications in Retinal Delivery.

The main cause of subretinal neovascularisation in wet age-related macular degeneration (AMD) is an abnormal expression in the retinal pigment epithelium (RPE) of the vascular endothelial growth factor (VEGF). Current approaches for the treatment of AMD present considerable issues that could be overcome by encapsulating anti-VEGF drugs in suitable nanocarriers, thus providing better penetration, higher retention times, and sustained release. In this work, the ability of large pore mesoporous silica nanoparticles (LP-MSNs) to transport and protect nucleic acid molecules is exploited to develop an innovative LP-MSN-based nanosystem for the topical administration of anti-VEGF siRNA molecules to RPE cells. siRNA is loaded into LP-MSN mesopores, while the external surface of the nanodevices is functionalised with polyethylenimine (PEI) chains that allow the controlled release of siRNA and promote endosomal escape to facilitate cytosolic delivery of the cargo. The successful results obtained for VEGF silencing in ARPE-19 RPE cells demonstrate that the designed nanodevice is suitable as an siRNA transporter.

Molecular-scale insights into confined clindamycin in nanoscale pores of mesoporous silica.

Clindamycin is an antibiotic used to treat a variety of bacterial infections. The sustained release of clindamycin from the drug carrier is an important strategy to prolong the effective antibacterial duration. In this work, the microstructure and dynamics of clindamycin confined into the nanopores of mesopore silica with different pore sizes were studied using molecular dynamics simulation. It is found that there is a layering behavior for clindamycin distribution as a function of distance from the pore surface to the pore center with preferred location near the surface of the nanopore. The radial distribution function between carbonyl oxygen and the silanol groups shows the highest intensity of the first peak with the preferred orientation of carbonyl oxygen pointing toward the pore surface, which suggests the strong interaction between the carbonyl oxygen and the silanol groups on the pore surface. The higher local diffusion coefficients for the clindamycin molecules near the pore surface can be found. In addition, the presence of water can lead to the shift of clindamycin distribution away from the surface and promote the local diffusion of clindamycin near the pore surface. The information in this work will provide the microscopic understanding for the design of the drug carriers for the controlled release of clindamycin.

Sintering-resistant and highly active Au/SBA-15 catalyst for carbon monoxide oxidation

The low thermal stability of gold-based catalysts is a significant obstacle to their practical application, especially under demanding conditions, such as those prevailing in automotive exhaust gas converters. In this work, we demonstrate that it is possible to strongly anchor 2–3 nm size gold nanoparticles inside the pores of SBA-15 mesoporous silica. The Au/SBA-15 catalyst showed high thermal stability, even at a temperature of 700–800 °C. The gold was evenly distributed inside the SBA-15 mesopores using the adsorption of the [Au(en)2]Cl3 complex (en = ethylenediamine) in an alkaline environment. Due to the very small size of gold nanoparticles, the obtained catalyst was highly active in low-temperature CO oxidation. The high resistance of Au particles to sintering can be explained by the confinement effect and the strong metal-support interaction, induced during the catalyst precursor decomposition under an oxygen-free atmosphere at 400 °C. The carbonaceous layer, formed from ethylenediamine ligands decomposition, plays an essential role in stabilizing gold nanoparticles inside the SBA-15 pores. We believe that our findings may contribute to solving the problem of carbon monoxide emission during engine start-up.

Aptamer-Gated Mesoporous Silica Nanoparticles for N Protein Triggered Release of Remdesivir and Treatment of Novel Coronavirus (2019-nCoV).

Since the 2019-nCoV outbreak was first reported, hundreds of millions of people all over the world have been infected. There is no doubt that improving the cure rate of 2019-nCoV is one of the most effective means to deal with the current serious epidemic. At present, Remdesivir (RDV) has been clinically proven to be effective in the treatment of SARS-CoV-2. However, the uncertain side effects make it important to reduce the use of drugs while ensuring the self-healing effect. We report an approach here with targeted therapy for the treatment of SARS-CoV-2 and other coronaviruses illness. In this study, mesoporous silica was used as the carrier of RDV, the nucleocapsid protein (N protein) aptamer was hybridized with the complementary chain, and the double-stranded DNA was combined with gold nanoparticles as the gates of mesoporous silica pores. When the RDV-loaded mesoporous silica is incubated with the N protein, aptamer with gold nanoparticles dissociate from the complementary DNA oligonucleotide on the mesoporous silica surface and bind to the N protein. The releasing of RDV was determined by detecting the UV-vis absorption peak of RDV in the solution. These results show that the RDV delivery system designed in this work has potential clinical application for the treatment of 2019-nCoV.

Cationic Molybdenum Imido Alkylidene N‐Heterocyclic Carbene Complexes Confined in Mesoporous Silica: Tuning Transition States Towards Z‐Selective Ring‐Opening Cross‐Metathesis

AbstractWe recently reported a method for selective macro(mono)cyclization of dienes utilizing catalysts confined inside the pores of mesoporous silica, which we believe occurs due to suppression of oligomerization due to pore size. We hypothesized, however, that the system of cationic molybdenum imido alkylidene N‐heterocyclic carbene (NHC) catalysts immobilized selectively inside the mesopores of silica materials could address much more subtle selectivity differences, such as E/Z selectivity in ring‐opening/cross‐metathesis (ROCM). Upon investigation, we observed that surface‐bound cationic molybdenum imido alkylidene NHC catalysts indeed display an increased Z‐selectivity, especially during the early stages of the reaction. This effect was present when the catalyst was confined inside a pore, as well as when the catalyst was bound to non‐porous silica, which led us to conclude it is an effect caused by the catalyst being bound directly to the surface of a silica material where the proximity of the catalyst to the surface governs the transition state. Kinetic investigations revealed that significant post‐metathesis olefin isomerization occurs, the amount of which seems to be governed by the rate of diffusion of the product away from the active catalyst, with smaller pore sizes resulting in higher Z‐selectivity at higher conversion, attributable to faster diffusion of the product out of the pore than diffusion back into the pore.

Synthesis of Mesoporous Silica Adsorbent Modified with Mercapto–Amine Groups for Selective Adsorption of Cu2+ Ion from Aqueous Solution

In a sol–gel co-condensation, a mesoporous silica hybrid integrated with (3-mercaptopropyl)trimethoxysilane (TMPSH) was prepared and then reacted with allylamine via a post-surface functionalization approach. Approximately 15 mol% of TMSPSH was introduced into the mesoporous silica pore walls along with tetraethyl orthosilicate. The mercapto ligands in the prepared mesoporous silica pore walls were then reacted with allylamine (AM) to form the mercapto–amine-modified mesoporous silica adsorbent (MSH@MA). The MSH@MA NPs demonstrate highly selective adsorption of copper (Cu2+) ions (~190 mg/g) with a fast equilibrium adsorption time (30 min). The prepared adsorbent shows at least a five times more efficient recyclable stability. The MSH@MA NPs adsorbent is useful for selective adsorption of Cu2+ ions.

Amine-Modified Small Pore Mesoporous Silica as Potential Adsorbent for Zn Removal from Plating Wastewater

The removal of Zn from wastewater generated from the Zn-based electroplating manufacturing process is essential because the regulation limit of Zn concentration in wastewater is becoming stricter in Japan. However, achieving this through conventional methods is difficult, especially for small and medium enterprises in the plating industry. Therefore, a suitable Zn-removal method with a low cost but high performance and Zn selectivity is required. The application of adsorbents is one possible solution. Mesoporous silica (MS) is a well-known adsorbent with controllable pore size, high specific surface area (SSA), high acid resistance, and ease of surface modification. In this study, we modified the surfaces of MSs with different initial pore sizes by amino groups and investigated their Zn removal performances. The effect of pore size on amine modification using (3-aminopropyl)triethoxysilane and on adsorption performance in a single system was investigated along with Zn adsorption selectivity in the Zn–Ni binary system. Amine-modified MS prepared from MS with an initial pore size of 1.9 nm showed drastically lower performance compared to those prepared from MS with an initial pore size larger than 2.8 nm. Zn-selectivity in the Zn–Ni binary system, containing equal amounts of Zn and Ni, was found to reach a maximum of 21.6 when modifying MS with an initial pore size of 2.8 nm.