Browse
Submit Data
Databases
API
Help

Dataset Information

10 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Site-isolated manganese carbonyl on bipyridine-functionalities of periodic mesoporous organosilicas: efficient CO₂ photoreduction and detection of key reaction intermediates.

ABSTRACT: Well-defined and fully characterized supported CO₂ reduction catalysts are developed through the immobilization of an earth abundant Mn complex on bpy-PMO (bpy = bipyridine; PMO = Periodic Mesoporous Organosilica) platform materials. The resulting isolated Mn-carbonyl centers coordinated to bipyridine functionalities of bpy-PMO catalyze the photoreduction of CO₂ into CO and HCOOH with up to ca. 720 TON in the presence of BIH (1,3-dimethyl-2-phenyl-2,3-dihydro-1H-benzoimidazole), used as the electron donor. A broad range of photochemical conditions (varying solvents, sacrificial electron donors, photosensitizer type and concentration, catalyst loading as well as the Mn loading within the PMO) are investigated, demonstrating high activity even for simple organic dyes and Zn-porphyrin as photosensitizers. Spectroscopic and catalytic data also indicate that site isolation of the Mn complex in the PMO framework probably inhibits bimolecular processes such as dimerisation and disproportionation and thus allows the spectroscopic observation of key reaction intermediates, namely the two meridional isomers of the carbonyl complexes and the bipyridine radical anion species.

SUBMITTER: Wang X

PROVIDER: S-EPMC5857931 | biostudies-literature |

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Similar Datasets

A facile template route to periodic mesoporous organosilicas nanospheres with tubular structure by using compressed CO2.

Project description:Periodic mesoporous organosilicas (PMOs) nanospheres with tubular structure were prepared with compressed CO2 using cationic and anionic mixed surfactant (CTAB/SDS) and triblock copolymer Pluronic P123 as bi-templates. TEM, N2 adsorption-desorption, solid NMR, and FTIR were employed to characterize the obtained materials. Compressed CO2 severed as acidic reagent to promote the hydrolysis of organosilicas, and could tune the morphology and structure of the obtained PMOs nanomaterials simple by adjusting the CO2 pressure during the synthesis process. Rhodamine B (RB) and Ibuprofen (IBU), as the model dye and drug, were loaded into the prepared nanomaterials to reveal its adsorption and desorption ability. Furthermore, different molars of the surfactant (CTAB/SDS) and organosilane precursor (BTEB) were investigated to show the effect of the surfactant concentration on the morphology and structure of the PMOs prepared with compressed CO2, and some different structures were obtained. A possible mechanism for the synthesis of PMOs with tubular structure using compressed CO2 was proposed based on the experimental results.

| S-EPMC5357914 | biostudies-literature

Synthesis and Characterization of Novel Pyridine Periodic Mesoporous Organosilicas and Its Catalytic Activity in the Knoevenagel Condensation Reaction.

Project description:The preparation of novel organic-inorganic hybrid mesoporous organosilica containing pyridinedicarboxamide functional groups uniformly distributed inside the nanostructured pore walls has been addressed. The mesoporosity and uniformity of the synthesized nanomaterials were characterized by different techniques such as nitrogen adsorption/desorption measurements and powder X-ray diffraction (PXRD). Additionally, the presence of the pyridinedicarboxamide in the pore walls of the nanomaterials was assessed by Fourier-transform infrared spectroscopy (FT-IR), as well as 29Si and 13C solid-state cross-polarization and magic angle spinning nuclear magnetic resonance (CP/MAS-NMR). The Knoevenagel condensation of aldehydes with active methylene compounds was carried out over the pyridinedicarboxamide functionalized mesoporous organosilica, which has been proven to be an efficient heterogeneous basic catalyst in the presence of ethanol as solvent. The catalytic activity of the investigated materials was investigated in the Knoevenagel condensation between malononitrile and several benzaldehyde derivatives exhibiting a high conversion (>90%) and excellent selectivity toward the final condensation products under very mild reaction conditions. Furthermore, the catalyst stability is noteworthy as it could be recycled and reused at least twelve times without any significant change in the performance.

| S-EPMC7084680 | biostudies-literature

Preparation of Palladium-Supported Periodic Mesoporous Organosilicas and their Use as Catalysts in the Suzuki Cross-Coupling Reaction.

Project description:Three periodic mesoporous materials, i.e., two organosilicas with either ethylene or phenylene bridges and one silica, have been used as supports for Pd nanoparticles. All Pd-supported samples (1.0 wt%) were prepared by the incipient wetness method and subsequently reduced in an H₂ stream at 200 °C. Both hydrogen chemisorption and temperature programmed reduction experiments revealed significant differences depending on the support. Pd2+ species were more reducible on the mesoporous organosilicas than on their silica counterpart. Also, remarkable differences on the particle morphology were observed by transmission electron microscopy. All Pd-supported samples were active in the Suzuki cross-coupling reaction between bromobenzene and phenylboronic acid.

| S-EPMC5452325 | biostudies-other

Dual metal nanoparticles within multicompartmentalized mesoporous organosilicas for efficient sequential hydrogenation.

Project description:Controlling localization of multiple metal nanoparticles on a single support is at the cutting edge of designing cascade catalysts, but is still a scientific and technological challenge because of the lack of nanostructured materials that can not only host metal nanoparticles in different sub-compartments but also enable efficient molecular transport between different metals. Herein we report a multicompartmentalized mesoporous organosilica with spatially separated sub-compartments that are connected by short nanochannels. Such a unique structure allows co-localization of Ru and Pd nanoparticles in a nanoscale proximal fashion. The so designed cascade catalyst exhibits an order of magnitude activity enhancement in the sequential hydrogenation of nitroarenes to cyclohexylamines compared with its mono/bi-metallic counterparts. Crucially, an interesting phenomenon of neighboring metal-assisted hydrogenation via hydrogen spillover is observed, contributing to the significant enhancement in catalytic efficiency. The multicompartmentalized architectures along with the revealed mechanism of accelerated hydrogenation provide vast opportunity for designing efficient cascade catalysts.

| S-EPMC8371113 | biostudies-literature

Periodic Mesoporous Organosilica Nanoparticles for CO2 Adsorption at Standard Temperature and Pressure.

Project description:(1) Background: Due to human activities, greenhouse gas (GHG) concentrations in the atmosphere are constantly rising, causing the greenhouse effect. Among GHGs, carbon dioxide (CO2) is responsible for about two-thirds of the total energy imbalance which is the origin of the increase in the Earth's temperature. (2) Methods: In this field, we describe the development of periodic mesoporous organosilica nanoparticles (PMO NPs) used to capture and store CO2 present in the atmosphere. Several types of PMO NP (bis(triethoxysilyl)ethane (BTEE) as matrix, co-condensed with trialkoxysilylated aminopyridine (py) and trialkoxysilylated bipyridine (Etbipy and iPrbipy)) were synthesized by means of the sol-gel procedure, then characterized with different techniques (DLS, TEM, FTIR, BET). A systematic evaluation of CO2 adsorption was carried out at 298 K and 273 K, at low pressure. (3) Results: The best values of CO2 adsorption were obtained with 6% bipyridine: 1.045 mmol·g-1 at 298 K and 2.26 mmol·g-1 at 273 K. (4) Conclusions: The synthetized BTEE/aminopyridine or bipyridine PMO NPs showed significant results and could be promising for carbon capture and storage (CCS) application.

| S-EPMC9268279 | biostudies-literature

Tuning molecular adsorption in SBA-15-type periodic mesoporous organosilicas by systematic variation of their surface polarity† †Electronic supplementary information (ESI) available. See DOI: 10.1039/d0sc00168f

Project description:Adsorption of organic molecules from solution into mesoporous organosilicas is modulated by the relative polarity of the surface. Surface polarity plays a key role in controlling molecular adsorption at solid–liquid interfaces, with major implications for reactions and separations. In this study, the chemical composition of periodic mesoporous organosilicas (PMOs) was varied by co-condensing Si(OEt)4 with organodisilanes, to create a homologous series of materials with similar surface areas, pore volumes, and hydroxyl contents. Their relative surface polarities, obtained by measuring the fluorescence of a solvatochromic dye, cover a wide range. In this series of PMO materials, EPR spectra of tethered nitroxide radicals show monotonically decreasing mobility as larger fractions of the radicals interact strongly with increasingly non-polar surfaces. The surface properties of the materials also correlate with their affinities for organic molecules dissolved in various solvents. The most polar PMO has negligible affinity for phenol, p-cresol, or furfural when these molecules are dissolved in water. However, stronger solute–surface interactions and favor adsorption as the surface polarity decreases. The trend is reversed for furfural in benzene, where weaker solvent–surface interactions result in higher adsorption on polar surfaces. In DMSO, furfural adsorption is suppressed due to the similar strengths of solute-surface and solvent–surface interactions. Thus, the polarity of the surface relative to the solvent is critical for molecular adsorption. These findings show how adsorption/desorption can be precisely and systematically tuned by appropriate choice of both solvent and surface, and contribute to a predictive strategy for the design of catalytic and separations processes.

| S-EPMC7643544 | biostudies-literature

Facile fabrication of mesoporous silica micro-jets with multi-functionalities.

Project description:Self-propelled micro/nano-devices have been proved as powerful tools in various applications given their capability of both autonomous motion and on-demand task fulfilment. Tubular micro-jets stand out as an important member in the family of self-propelled micro/nano-devices and are widely explored with respect to their fabrication and functionalization. A few methods are currently available for the fabrication of tubular micro-jets, nevertheless there is still a demand to explore the fabrication of tubular micro-jets made of versatile materials and with the capability of multi-functionalization. Here, we present a facile strategy for the fabrication of mesoporous silica micro-jets (MSMJs) for tubular micromotors which can carry out multiple tasks depending on their functionalities. The synthesis of MSMJs does not require the use of any equipment, making it facile and cost-effective for future practical use. The MSMJs can be modified inside, outside or both with different kinds of metal nanoparticles, which provide these micromotors with a possibility of additional properties, such as the anti-bacterial effect by silver nanoparticles, or biochemical sensing based on surface enhanced Raman scattering (SERS) by gold nanoparticles. Because of the high porosity, high surface area and also the easy surface chemistry process, the MSMJs can be employed for the efficient removal of heavy metals in contaminated water, as well as for the controlled and active drug delivery, as two proof-of-concept examples of environmental and biomedical applications, respectively. Therefore, taking into account the new, simple and cheap method of fabrication, highly porous structure, and multiple functionalities, the mesoporous silica based micro-jets can serve as efficient tools for desired applications.

| S-EPMC5708346 | biostudies-literature

Solid State Photoreduction of Silver on Mesoporous Silica to Enhance Antifungal Activity.

Project description:A solid-state Ultraviolet-photoreduction process of silver cations to produce Ag0 nanostructures on a mesoporous silica is presented as an innovative method for the preparation of efficient environmental anti-fouling agents. Mesoporous silica powder, contacted with AgNO3, is irradiated at 366 nm, where silica surface defects absorb. The detailed characterization of the materials enables us to document the silica assisted photo-reduction. The appearance of a Visible (Vis) band centered at 470 nm in the extinction spectra, due to the surface plasmon resonance of Ag0 nanostructures, and the morphology changes observed in transmission electron microscopy (TEM) images, associated with the increase of Ag/O ratio in energy dispersive X-ray (EDX) analysis, indicate the photo-induced formation of Ag0. The data demonstrate that the photo-induced reduction of silver cation occurs in the solid state and takes place through the activation of silica defects. The activation of the materials after UV-processing is then tested, evaluating their antimicrobial activity using an environmental filamentous fungus, Aspergillus niger. The treatment doubled inhibitory capacity in terms of minimal inhibitory concentration (MIC) and biofilm growth. The antimicrobial properties of silver-silica nanocomposites are investigated when dispersed in a commercial sealant; the nanocomposites show excellent dispersion in the silicon and improve its anti-fouling capacity.

| S-EPMC8465249 | biostudies-literature

Single PEDOT Catalyst Boosts CO2 Photoreduction Efficiency.

Project description:Atmospheric pollution demands the development of solar-driven photocatalytic technologies for the conversion of CO2 into a fuel; state-of-the-art cocatalyst systems demonstrate conversion efficiencies currently unattainable by a single catalyst. Here, we upend the status quo demonstrating that the nanofibrillar conducting polymer poly(3,4-ethylenedioxythiophene) (PEDOT) is a record-breaking single catalyst for the photoreduction of CO2 to CO. This high catalytic efficiency stems from a highly conductive nanofibrillar structure that significantly enhances surface area, CO2 adsorption and light absorption. Moreover, the polymer's band gap is optimized via chemical doping/dedoping treatments using hydrochloric acid, ammonia hydroxide, and hydrazine. The hydrazine-treated PEDOT catalyst exhibits 100% CO yield under a stable regime (>10 h) with a maximum rate of CO evolution (3000 μmol gcat -1 h-1) that is 2 orders of magnitude higher than the top performing single catalyst and surpassed only by three other cocatalyst systems. Nanofibrillar PEDOT provides a new direction for designing the next generation of high-efficiency photoreduction catalysts.

| S-EPMC8554841 | biostudies-literature

Fabrication of ultrasmall WS2 quantum dots-coated periodic mesoporous organosilica nanoparticles for intracellular drug delivery and synergistic chemo-photothermal therapy.

Project description:IntroductionThe consolidation of different therapies into a single nanoplatform has shown great promise for synergistic tumor treatment. In this study, a multifunctional platform by WS2 quantum dots (WQDs)-coated doxorubicin (DOX)-loaded periodic mesoporous organosilicas (PMOs-DOX@WQDs) nanoparticles were fabricated for the first time, and which exhibits good potential for synergistic chemo-photothermal therapy.Materials and methodsThe structure, light-mediated drug release behavior, photothermal effect, and synergistic therapeutic efficiency of PMOs-DOX@WQDs to HCT-116 colon cancer cells were investigated. The thioether-bridged PMOs exhibit a high DOX loading capacity of 66.7 ?g mg-1. The gating of the PMOs not only improve the drug loading capacity but also introduce the dual-stimuli-responsive performance. Furthermore, the as-synthesized PMOs-DOX@WQDs nanoparticles can efficiently generate heat to the hyperthermia temperature with near infrared laser irradiation.ResultsIt was confirmed that PMOs-DOX@WQDs exhibit remarkable photothermal effect and light-triggered faster release of DOX. More importantly, it was reasonable to attribute the efficient anti-tumor efficiency of PMOs-DOX@WQDs.ConclusionThe in vitro experimental results confirm that the fabricated nanocarrier exhibits a significant synergistic effect, resulting in a higher efficacy to kill cancer cells. Therefore, the WQD-coated PMOs present promising applications in cancer therapy.

| S-EPMC5896670 | biostudies-literature