Facile synthesis of size controllable dendritic mesoporous silica nanoparticles.

The synthesis of highly uniform mesoporous silica nanospheres (MSNs) with dendritic pore channels, particularly ones with particle sizes below 200 nm, is extremely difficult and remains a grand challenge. By a combined synthetic strategy using imidazolium ionic liquids (ILs) with different alkyl lengths as cosurfactants and Pluronic F127 nonionic surfactants as inhibitors of particle growth, the preparation of dendritic MSNs with controlled diameter between 40 and 300 nm was successfully realized. An investigation of dendritic MSNs using scanning electron microscopy (SEM), transmission electron microscopy (TEM), and nitrogen physisorption revealed that the synthesis of dendritic MSNs at larger size (100-300 nm) strongly depends on the alkyl lengths of cationic imidazolium ILs; while the average size of dendritic MSNs can be controlled within the range of 40-100 nm by varying the amount of Pluronic F127. The Au@MSNs can be used as a catalyst for the reduction of 4-nitrophenol by NaBH4 into 4-aminophenol and exhibit excellent catalytic performance. The present discovery of the extended synthesis conditions offers reproducible, facile, and large-scale synthesis of the monodisperse spherical MSNs with precise size control and, thus, has vast prospects for future applications of ultrafine mesostructured nanoparticle materials in catalysis and biomedicine.

Stripping of acetone from water with microfabricated and membrane gas-liquid contactors.

Stripping of acetone from water utilizing nitrogen as a sweeping gas in co-current flow was conducted in a microfabricated glass/silicon gas-liquid contactor. The chip consisted of a microchannel divided into a gas and a liquid chamber by 10 µm diameter micropillars located next to one of the channel walls. The channel length was 35 mm, the channel width was 220 µm and the microchannel depth 100 µm. The micropillars were wetted by the water/acetone solution and formed a 15 µm liquid film between them and the nearest channel wall, leaving a 195 µm gap for gas flow. In addition, acetone stripping was performed in a microchannel membrane contactor, utilizing a hydrophobic PTFE membrane placed between two microstructured acrylic plates. Microchannels for gas and liquid flows were machined in the plates and had a depth of 850 µm and 200 µm respectively. In both contactors the gas/liquid interface was stabilized: in the glass/silicon contactor by the hydrophilic micropillars, while in the PTFE/acrylic one by the hydrophobic membrane. For both contactors separation efficiency was found to increase by increasing the gas/liquid flow rate ratio, but was not affected when increasing the inlet acetone concentration. Separation was more efficient in the microfabricated contactor due to the very thin liquid layer employed.

A comparative study on selective adsorption of metal ions using aminated adsorbents.

It is well-known that chitosan consists of amino groups for the chelation of metal ions while NH2-MCM-41 has excellent adsorption selectivities for metals. This work compares both adsorption capacities and selectivities of chitosan and NH2-MCM-41. It has been found that chitosan has adsorption capacities of 1.76 mmol/g, 1.03 mmol/g and 1.30 mmol/g for Cu2+, Ni2+ and Zn2+ respectively whereas NH-MCM-41 has adsorption capacity of 1.52mmol/g, 0.8mmol/g and 0.83mmol/g for Cu, Ni and Zn. The higher adsorption capacity in chitosan is attributed to its higher loading of amine groups. The single component adsorption isotherms were well-fitted using Freundlich model. The binary adsorptions of Cu2+-Zn2+ and Ni2+-Zn2+ systems showed similar adsorption selectivities for both adsorbents. However, chitosan has no preferential adsorption for Ni2+-Zn2+ system while NH2-MCM-41 has a good selectivity towards Zn2+. It is believed that the difference can be attributed to the heterogeneous surface of chitosan due to its organic nature. The multi-component adsorptions were best described by a multicomponent extended Freundlich model. Despite the surface functional group, this work indicates the importance of the adsorbent support on selective adsorption.

Facile large-scale synthesis of monodisperse mesoporous silica nanospheres with tunable pore structure.

Mesoporous silica nanoparticles (MSNs) are experiencing rapid development in the biomedical field for imaging and for use in heterogeneous catalysis. Although the synthesis of MSNs with various morphologies and particle sizes has been reported, synthesis of a pore network with monodispersion control below 200 nm is still challenging. We achieved this goal using mild conditions. The reaction occurred at atmospheric pressure with a templating sol-gel technique using cetyltrimethylammonium (CTA(+)) as the templating surfactant and small organic amines (SOAs) as the mineralizing agent. Production of small pore sizes was performed for the first time, using pure and redispersible monodispersed porous nanophases with either stellate (ST) or raspberry-like (RB) channel morphologies. Tosylate (Tos(-)) counterions favored ST and bromide (Br(-)) RB morphologies at ultralow SOA concentrations. Both anions yielded a worm-like (WO) morphology at high SOA concentrations. A three-step formation mechanism based on self-assembly and ion competition at the electrical palisade of micelles is proposed. Facile recovery and redispersion using specific SOAs allowed a high yield production at the kilogram scale. This novel technique has practical applications in industry.

Mononuclear-dinuclear equilibrium of grafted copper complexes confined in the nanochannels of MCM-41 silica.

Following the structural concept of copper-containing proteins in which dinuclear copper centers are connected by hydroxide bridging ligands, a bidentate copper(II) complex has been incorporated into nano-confined MCM-41 silica by a multistep sequential grafting technique. Characterization by a combination of EPR spectroscopy, X-ray photoelectron spectroscopy (XPS), UV/Vis spectroscopy, IR spectroscopy , and solid-state (13)C and (29)Si cross-polarization magic-angle spinning (CP-MAS) NMR suggests that dinuclear Cu complexes are bridged by hydroxide and other counterions (chloride or perchlorate ions), similar to the situation for EPR-undetectable [Cu(II)···Cu(II)] dimer analogues in biological systems. More importantly, a dynamic mononuclear-dinuclear equilibrium between different coordination modes of copper is observed, which strongly depends on the nature of the counterions (Cl(-) or ClO(4)(-)) in the copper precursor and the pore size of the silica matrix (the so-called confinement effect). A proton-transfer mechanism within the hydrogen-bonding network is suggested to explain the dynamic nature of the dinuclear copper complex supported on the MCM-41 silica.

Precious metal recovery by selective adsorption using biosorbents.

Silk sericin and chitosan biosorbents are low cost and highly efficient biosorbents derived from waste biomass. Both biosorbents displayed good capacity and excellent selectivity for gold adsorption. Silk sericin and chitosan adsorbed respectively 1 and 3.3mmolg(-1) of gold and have K(d) values of 450 and 34,000, respectively. Experimental evidence showed that gold adsorbed on the amide groups of the silk sericin, while gold and copper adsorbed on the amino groups of chitosan via charge-interactions and complexation. Binary (Au-Cu), five (Au-Co-Ni-Cu-Zn) and six (Au-Pd-Co-Ni-Cu-Zn) component separations consistently showed that silk sericin has better selectivity (Sel(Au)>2.4) than chitosan. It is possible to recover gold at 99.5% purity by silk sericin and 90% if the solution contained palladium.

Selective mesoporous adsorbents for Ag+/Cu2+ separation.

Three different approaches, including (1) manipulating the site chemistry, (2) controlling the spacing between neighbouring sites and (3) altering the adsorbates by the use of chelates, were successfully used to prepare MCM-41 adsorbents with excellent selectivity for silver adsorption from solutions containing copper.

Efficient approach for Cd2+ and Ni2+ removal and recovery using mesoporous adsorbent with tunable selectivity.

Cadmium pollution from the manufacture and disposal of NiCd batteries remains an important problem in developing countries. Among the available remedial technologies, adsorption is popular because of its low cost and simplicity. The mesoporous NH2-MCM-41 displays good adsorption capacities for cadmium and nickel ions. This work demonstrated for the first time the use of the competition between complexant and sorbentto create high adsorption selectivity. The selectivity was manipulated by the judicious use of a chelating agent, thus achieving on-demand 100% selectivity for either Cd2+ or Ni2+ adsorption. Single and binary components adsorption studies, carried out with different metals and EDTA concentrations, solution compositions and pH, showed that NH2-MCM-41 adsorbs only cadmium with a capacity of 0.56 mmol g(-1) from binary mixtures at [EDTA]/[M2+] = 0.5 and pH 5. The NH2-MCM-41 displays 100% selectivityfor nickel adsorption at [EDTA]/[M2+] = 0.5 and pH 2 with a measured adsorption capacity of 0.50 mmol g(-1). Pure Cd2+ and Ni2+ solutions were recovered by a simple acid wash, and the regenerated adsorbent could be reused without lost of performance (i.e., adsorption capacity and selectivity).

A rational approach in the design of selective mesoporous adsorbents.

Two MCM-41 derived adsorbents have been tailor-made for the separation of silver and copper ions using the hard-soft, acid-base (HSAB) principle as the design guideline. NH2-MCM-41 containing "hard" Lewis base adsorption sites (i.e., RNH2) was prepared for the adsorption of the "hard" Lewis acid, Cu2+, and SH-MCM-41 with a grafted "soft" thiolpropyl base was prepared for the selective removal of Ag+, a "soft" Lewis acid. Single- and binary-component adsorption studies were conducted at different metal concentrations, solution compositions, and pH values. The experimental results showed that SH-MCM-41 has excellent affinity and capacity for silver adsorption and adsorbed only the silver ions with copper remaining in the solution. The selectivity was not affected by the metal concentration and composition, anion, and pH. Under similar experimental conditions, NH2-MCM-41 selectively adsorbed copper from the binary solution. The selectivity of NH2-MCM-41 remained for the copper at different pH values, although the adsorption capacity diminished at lower pH values. The type of anions used affected copper adsorption on NH2-MCM-41 with an increased copper uptake in the presence of the sulfate ions. A simple Freundlich adsorption model was sufficient to describe metal adsorption on SH-MCM-41 and NH2-MCM-41, and the LeVan and Vermeulen model was successfully used to predict the adsorption capacity and selectivity for binary-component adsorptions.

An investigation of gold adsorption from a binary mixture with selective mesoporous silica adsorbents.

Gold-selective adsorbents were prepared from mesoporous MCM-41 silica by grafting organic amine groups (i.e., RNH2, R2NH, and R3N; R=propyl). NH2-MCM-41, NRH-MCM-41, and NR2-MCM-41 displayed strong affinity for gold and at 1 mmol/g loading adsorbed 0.40, 0.33, and 0.20 mmol/g of gold. Copper and nickel were not adsorbed on these adsorbents. Grafting surface chemical moieties introduces heterogeneity on an otherwise uniform MCM-41 pore surface and metal adsorption is best described by the Freundlich adsorption model. A series of binary adsorption equilibrium studies with NH2-MCM-41 containing 2.2 mmol RNH2/g shows that NH2-MCM-41 adsorbs only gold from solutions containing copper and nickel with an adsorption capacity of 0.6 mol of Au/mol of RNH2 (1.1 mmol of Au/g of NH2-MCM-41). Copper and nickel were not adsorbed by NH2-MCM-41 regardless of the solution concentration, composition, and pH (i.e., 2 to 4) in the presence of gold. The LeVan and Vermeulen adsorption model based on a single component Freundlich isotherm and corrected for the anion effect accurately predicted the binary adsorptions. The adsorbed gold was completely recovered by a simple acid wash and the recovered gold solution is 99% pure. The regenerated NH2-MCM-41 remained 100% selective for gold removal and exhibited the same adsorption capacity even after several uses.

Zeolite micropattern for biological applications.

A facile method was established using composition-gradient pattern on zeolite surface to guide the deposition and formation of chemical and biomolecular patterns with features as small as five microns.