Palladium Nanoparticles Supported on Ce-Metal-Organic Framework for Efficient CO Oxidation and Low-Temperature CO2 Capture.

In this article, we report the lowest-temperature CO oxidation catalyst supported on metal-organic frameworks (MOFs). We have developed a facile, general, and effective approach based on microwave irradiation for the incorporation of Pd nanoparticle catalyst within Ce-MOF. The resulting Pd/Ce-MOF material is a unique catalyst that is capable of CO oxidation at modest temperatures and also of efficient uptake of the product CO2 gas at low temperatures. The observed catalytic activity of this material toward CO oxidation is significantly higher than those of other reported metal nanoparticles supported on MOFs. The high activity of the Pd/Ce-MOF catalyst is due to the presence of Ce(III) and Ce(IV) ions within the metal-organic framework support. The Pd nanoparticles supported on the Ce-MOF store oxygen in the form of a thin palladium oxide layer at the particle-support interface, in addition to the oxygen stored on the Ce(III)/Ce(IV) centers. Oxygen from these reservoirs can be released during CO oxidation at 373 K. At lower temperatures (273 K), the Pd/Ce-MOF has a significant CO2 uptake of 3.5 mmol/g.

From Azo-Linked Polymers to Microporous Heteroatom-Doped Carbons: Tailored Chemical and Textural Properties for Gas Separation.

Heteroatom-doped porous carbons with ultrahigh microporosity were prepared from a nitrogen-rich azo-linked polymer (ALP-6) as a precursor for gas separation applications. Direct carbonization and chemical activation of ALP-6 with ZnCl2 and KOH were successfully applied to obtain three different classes of porous carbons (ALPDCs). Synthetic processes were conducted at relatively mild temperatures (500-800 °C),which resulted in retention of appreciable levels of nitrogen content (4.7-14.3 wt %). Additionally, oxygen functionalities were found to be present in chemically activated samples. The resultant porous carbons feature a diverse range of textural properties with a predominant microporous nature in common. The highest CO2 uptake value of 5.2 mmol g(-1) at 1 bar and 298 K in ALPDCK600 was originated from well-developed porosity and basic heteroatoms (N and O) on the pore walls. The highest heteroatom doping level (12 wt % nitrogen and 20 wt % oxygen) coupled with the high level of microporosity (84%) for ALPDCK500 led to notable CO2/N2 (62) and CO2/CH4 (11) selectivity values and a high CO2 uptake capacity (1.5 mmol g(-1), at 0.15 bar) at 298 K. This study illustrates the effective use of a single-source precursor with robust nitrogen bonds in combination with diverse carbonization methods to tailor the chemical and textural properties of heteroatom-doped porous carbons for CO2 capture and separation applications.

CMK-3 nanoporous carbon as a new fiber coating for solid-phase microextraction coupled to gas chromatography-mass spectrometry.

CMK-3 nanoporous carbon was prepared and characterized as a highly porous fiber coating, with a highly ordered carbon framework, for solid-phase microextraction (SPME). The nanomaterial was immobilized onto platinum, stainless steel and copper metal wires for preparation of new SPME fibers. The copper-CMK-3 fiber showed superior properties and therefore was applied for extraction of some phenolic compounds in combination with GC-MS. For optimization of the extraction conditions, a simplex optimization method was used. The selected conditions were: sample volume 13 ml, extraction temperature 56°C, extraction time 7 min, ultrasonic time 5.5 min, pH 5 and salt concentration 8.9%. The selected fiber showed some selectivity towards the polar phenolic compounds and its extraction efficiency was better than a commercial PDMS fiber. Linear calibration curves with correlation coefficients better than 0.99 and detection limits in the range from 0.002 to 0.068 µg mL(-1) were obtained for the fiber. No significant change was observed in the extraction efficiency of the new SPME fiber over at least 40 extractions. The fiber was successfully used for the determination of phenolic compounds in natural water samples.

Multi-walled carbon nanotubes-ionic liquid-carbon paste electrode as a super selectivity sensor: application to potentiometric monitoring of mercury ion(II).

In this article a super selectivity potentiometric methodology, using an ion-selective electrode, for determination of mercury ion(II) in aqueous solution was investigated. For modification of the electrode a room temperature ionic liquid, 1-n-butyl-3-methylimidazolium tetrafluoroborate (BMIM·BF(4)), was applied as a super conductive binder, and Multi-walled carbon nanotubes (MWCNTs) was used in the composition of the carbon paste to improve conductivity and transduction of chemical signal to electrical signal. Moreover, incorporation of 1-(2-ethoxyphenyl)-3-(3-nitrophenyl)triazene (ENTZ) as an ionophore to this composition caused to significantly enhanced selectivity toward Hg(II) ions over a wide concentration range of 1.0×10(-4) to 5.0×10(-9) M with a lower detection limit of 2.5×10(-9) M (0.5 ppb) and a Nernstian slope of 29.3±(0.2) mV decade(-1) of Hg(II) activity. The electrode has a short response time (∼5s) and can be used for at least 55 days without any considerable divergence in potentials, and the working pH range was 2.0-4.3. Finally, the proposed electrode was successfully used as an indicator for potentiometric determination of Hg(II) in dental amalgam and water samples.