Investigation of Ester- and Amide-Linker-Based Porous Organic Polymers for Carbon Dioxide Capture and Separation at Wide Temperatures and Pressures.

Organic compounds, such as covalent organic framework, metal-organic frameworks, and covalent organic polymers have been under investigation to replace the well-known amine-based solvent sorption technology of CO2 and introduce the most efficient and economical material for CO2 capture and storage. Various organic polymers having different function groups have been under investigation both for low and high pressure CO2 capture. However, search for a promising material to overcome the issues of lower selectivity, less capturing capacity, lower mass transfer coefficient and instability in materials performance at high pressure and various temperatures is still ongoing process. Herein, we report synthesis of six covalent organic polymers (COPs) and their CO2, N2, and CH4 adsorption performances at low and high pressures up to 200 bar. All the presented COPs materials were characterized by using elemental analysis method, Fourier transform infrared spectroscopy (FTIR) and solid state nuclear magnetic resonance (NMR) spectroscopy techniques. Physical properties of the materials such as surface areas, pore volume and pore size were determined through BET analysis at 77 K. All the materials were tested for CO2, CH4, and N2 adsorption using state of the art equipment, magnetic suspension balance (MSB). Results indicated that, amide based material i.e. COP-33 has the largest pore volume of 0.2 cm(2)/g which can capture up to the maximum of 1.44 mmol/g CO2 at room temperature and at pressure of 10 bar. However, at higher pressure of 200 bar and 308 K ester-based compound, that is, COP-35 adsorb as large as 144 mmol/g, which is the largest gas capturing capacity of any COPs material obtained so far. Importantly, single gas measurement based selectivity of COP-33 was comparatively better than all other COPs materials at all condition. Nevertheless, overall performance of COP-35 rate of adsorption and heat of adsorption has indicated that this material can be considered for further exploration as efficient and cheaply available solid sorbent material for CO2 capture and separation.

A detailed study of cholinium chloride and levulinic acid deep eutectic solvent system for CO2 capture via experimental and molecular simulation approaches.

Choline chloride + levulinic acid deep eutectic solvent is studied as a suitable material for CO2 capturing purposes. The most relevant physicochemical properties of this solvent are reported together with the CO2 solubility as a function of temperature. The corrosivity of this solvent is studied showing better performance than amine-based solvents. A theoretical study using both density functional theory and molecular dynamics approaches is carried out to analyze the properties of this fluid from the nanoscopic viewpoint, and their relationship with the macroscopic behavior of the system and its ability for CO2 capturing. The behavior of the liquid-gas interface is also studied and its role on the CO2 absorption mechanism is analyzed. The reported combined experimental and theoretical approach leads to a complete picture of the behavior of this new sorbent with regard to CO2, which together with its low cost, and the suitable environmental and toxicological properties of this solvent, lead to a promising candidate for CO2 capturing technological applications.

Strategies of making TiO2 and ZnO visible light active.

In modern purification techniques employing semiconductor mediated photooxidation of toxic substances, zinc oxide (ZnO) and titanium dioxide (TiO2) are the most widely used metal oxides due to their unique blend of properties. However, the band edges of these semiconductors lie in the UV region which makes them inactive under visible light irradiation. Researchers have been interested in the modification of electronic and optical properties of these metal oxides for their efficient use in water and air purification under visible light irradiation. Visible light activity has been induced in TiO2 and ZnO by surface modification via organic materials/semiconductor coupling and band gap modification by doping with metals and nonmetals, co-doping with nonmetals, creation of oxygen vacancies and oxygen sub-stoichiometry. This paper encompasses the progress and developments made so far through these techniques in the visible light photocatalysis with TiO2 and ZnO. Recently, nitrogen doping in titania has been extensively carried out and therefore somewhat detailed discussion in this respect has been presented. Visible light activation of titania clusters encapsulated in zeolite-Y by nitrogen doping and incorporation of dye or organic sensitizers inside the zeolite framework, has also been highlighted in this review.

Photocatalytic degradation of organic dyes with manganese-doped ZnO nanoparticles.

Manganese-doped and undoped ZnO photocatalysts were synthesized via wet-chemical techniques. Doping of ZnO with manganese (Mn(2+)) was intended to create tail states within the band gap of ZnO. These can subsequently be used as efficient photocatalysts which can effectively degrade organic contaminants only with visible light irradiation. Photocatalysts prepared with these techniques, which were characterized with transmission electron microscopy (TEM), infrared spectroscopy (FTIR), photo-co-relation spectroscopy (PCS) and UV-vis-spectroscopy showed significant difference in the optical absorption of Mn-doped ZnO. Enhancement in optical absorption of Mn-doped ZnO indicates that it can be used as an efficient photocatalyst under visible light irradiation. The photo-reduction activities of photocatalysts were evaluated using a basic aniline dye, methylene blue (MB) as organic contaminant irradiated only with visible light from tungsten bulb. It was found that manganese-doped ZnO (ZnO:Mn(2+)) bleaches MB much faster than undoped ZnO upon its exposure to the visible light. The experiment demonstrated that the photo-degradation efficiency of ZnO:Mn(2+) was significantly higher than that of undoped ZnO and might also be better than the conventional metal oxide semiconductor such as TiO(2) using MB as a contaminant.