Temperature dependent NIR emitting lanthanide-PMO/silica hybrid materials

Two materials - a mesoporous silica (MS) and a periodic mesoporous organosilica (PMO) functionalized with dipyridyl-pyridazine (dppz) units were grafted with near-infrared (NIR) emitting lanthanide (Nd3+, Er3+, Yb3+) complexes in an attempt to obtain hybrid NIR emitting materials. The parent materials: dppz-vSilica and dppz-ePMO were prepared by a hetero Diels-Alder reaction between 3,6-di(2-pyridyl)-1,2,4,5- tetrazine (dptz) and the double bonds of either ethenylene-bridged PMO (ePMO) or vinyl-silica (vSilica) and subsequent oxidation. The dppz-vSilica is reported here for the first time. The prepared lanthanide-PMO/silica hybrid materials were studied in depth for their luminescence properties at room temperature and chosen Nd3+ and Yb3+ samples also at low temperature (as low as 10 K). We show that both the dppz-vSilica and dppz-ePMO materials can be used as "platforms" for obtaining porous materials showing NIR luminescence. To obtain NIR emission these materials can be excited either in the UV or Vis region (into the pi -> pi* transitions of the ligands or directly into the f-f transitions of the Ln(3+) ions). More interestingly, when functionalized with Nd3+ or Yb3+ beta-diketonate complexes these materials showed interesting luminescence properties over a wide temperature range (10-360 K). The Yb3+ materials were investigated for their potential use as ratiometric temperature sensors

Tuning component enrichment in amino acid functionalized (organo)silicas

A straightforward procedure to synthesize cysteine functionalized materials with tailored support properties has been developed. It allows tuning the hydrophobicity of the material via the incorporation of aliphatics, aromatics or silica in the framework structure. The aldol condensation of 4-nitrobenzaldehyde and acetone, as a probe reaction for the catalytic activity of the produced materials, exhibited a remarkable interplay between the reactant, solvent, traces of water and support hydrophobicity. A selective enrichment in the catalyst pores of specific bulk phase molecules is believed to be the key to achieve the targeted catalyst performance

Facile synthesis of cooperative acid-base catalysts by clicking cysteine and cysteamine on an ethylene-bridged periodic mesoporous organosilica

A periodic mesoporous organosilica (PMO) that contains ethylene bridges was functionalized to obtain a series of cooperative acid-base catalysts. A straightforward, single-step procedure was devised to immobilize cysteine and cysteamine on the support material by means of a photoinitiated thiol-ene click reaction. Likewise, PMO materials capped with hexamethyldisilazane (HMDS) were used to support both compounds. This resulted in different materials in which the amine site was promoted by carboxylic acid groups, surface silanol groups, or both. The catalysts were tested in the aldol reaction of 4-nitrobenzaldehyde and acetone. It was found that silanol groups have a stronger promoting effect on the amine than the carboxylic acid group. The highest turnover frequency (TOF) was obtained for an amine-functionalized material that contained only silanol promoting sites. The loading of the active sites also had a significant effect on the activity of the catalysts, which was rationalized on the basis of a computational study

Metalporphyrin on PMO catalysts for the conversion of CO2 to cyclic carbonates

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L-proline functionalized modualted Zr-MOFs for the aldol reaction

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Titania-functionalized diatom frustules as photocatalyst for indoor air purification

Diatom frustules were extracted from the species Thalassiosira pseudonana and functionalized with titania to be used as photocatalysts in the abatement of acetaldehyde. The synthetic procedure is water-based and environmentally friendly. The synthesis parameters were optimized to give the highest possible photocatalytic activity. The optimized material, visualized with TEM and STEM-EDX, shows the TiO2 nanoparticles grafted inside the frustule pores, as well as on the silica surface. The titania particles, stabilized by the frustules, are 2.5 times more active than the P25 benchmark material. The photocatalyst is then tested in conditions of elevated relative humidity, to simulate indoor air. The catalytic activity only shows a minor decrease at 50% relative humidity, which is a better result than for the P25 benchmark. When tested over an extended period of time, the photocatalyst only shows a minor decrease in activity

The Tsunami’s CSR Effect: MNEs and Philanthropic Responses to the Disaster

This paper contributes to the literature on CSR and International Business by linking firm internationalization to corporate philanthropy. Considering the 2004 Tsunami disaster as a highly relevant case of an international societal issue, we analyze the characteristics of the corporate response to the disaster among Fortune Global 500 firms. We find that home region, degree of internationalization, firm size and profitability most strongly influenced the propensity of firms to donate as well as the value of their donations

PMO-immobilized Au-I-NHC complexes : heterogeneous catalysts for sustainable processes

A stable periodic mesoporous organosilica (PMO) with accessible sulfonic acid functionalities is prepared via a one-pot-synthesis and is used as solid support for highly active catalysts, consisting of gold(I)-N-heterocyclic carbene (NHC) complexes. The gold complexes are successfully immobilized on the nanoporous hybrid material via a straightforward acid-base reaction with the corresponding [Au(OH)(NHC)] synthon. This catalyst design strategy results in a boomerang-type catalyst, allowing the active species to detach from the surface to perform the catalysis and then to recombine with the solid after all the starting material is consumed. This boomerang behavior is assessed in the hydration of alkynes. The tested catalysts were found to be active in the latter reaction, and after an acidic work-up, the IPr*-based gold catalyst can be recovered and then reused several times without any loss in efficiency

Titania-functionalized diatom frustules as photocatalysts for indoor air purification

Diatoms are single-celled algae, which produce a porous silica skeleton. These so-called frustules can take on a large variation of shapes and sizes. In this study, the Thalassiosira Pseusonana algae species was selected and its frustules were functionalized with titania nanoparticles. The synthesis method used was an impregnation with titanyl sulfate (TiOSO4) in water, which makes the procedure more environmentally friendly than when using the more common titanium alkoxides or chlorides. The immobilized titania nanoparticles could be visualized by TEM measurements, which showed that the NP are well dispersed on the silica surface (Figure 1). The samples were used as photocatalyst in the oxidative decomposition of gaseous acetaldehyde, which is a common indoor air pollutant. The titania nanoparticles immobilized on the diatom frustules were 2.5 times more active than P25, which is the most common titania benchmark in photocatalysis. The titania-functionalized frustules also performed well in humid conditions and over a prolonged period of time, which are both important factors to consider for applications in indoor air pollution