Damien Thirion

Charge-specific size-dependent separation of water-soluble organic molecules by fluorinated nanoporous networks

Molecular architecture in nanoscale spaces can lead to selective chemical interactions and separation of species with similar sizes and functionality. Substrate specific sorbent chemistry is well known through highly crystalline ordered structures such as zeolites, metal organic frameworks and widely available nanoporous carbons. Size and charge-dependent separation of aqueous molecular contaminants, on the contrary, have not been adequately developed. Here we report a charge-specific size-dependent separation of water-soluble molecules through an ultra-microporous polymeric network that features fluorines as the predominant surface functional groups. Treatment of similarly sized organic molecules with and without charges shows that fluorine interacts with charges favourably. Control experiments using similarly constructed frameworks with or without fluorines verify the fluorine-cation interactions. Lack of a σ-hole for fluorine atoms is suggested to be responsible for this distinct property, and future applications of this discovery, such as desalination and mixed matrix membranes, may be expected to follow.

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.

Covalent organic polymer framework with C–C bonds as a fluorescent probe for selective iron detection

A new carbon–carbon bonded nanoporous polymer network was synthesized via efficient and catalyst free Knoevenagel-like condensation polymerization in near quantitative yields. The obtained polymer network, Covalent Organic Polymer – COP-100 possesses strong fluorescent properties and designed solubility in polar aprotic solvents, which shows promise for use as a metal-sensing material in solution. COP-100 exhibited high selectivity towards Fe2+ and Fe3+ in the presence of other common metal cations (Al3+, Ag+, Cd2+, Co2+, Cr3+, Cu2+, Hg2+, Mg2+, Mn2+, Na+, Ni2+, Zn2+) as the fluorescence of the polymer was significantly quenched even at very low concentrations. In the range from 2.5 × 10−6 to 2 × 10−4 M, a linear fluorescence emission response with equipment limited detection minimum of 2.13 × 10−7 M and 2.45 × 10−7 M for Fe2+ and Fe3+, respectively, was observed. These results suggest that COP-100 is a promising material as a selective fluorescence sensor for iron ions.

High performance CO2 filtration and sequestration by using bromomethyl benzene linked microporous networks

Porous solid sorbents have been investigated for the last few decades to replace the costly amine solution and explore the most efficient and economical material for CO2 capture and storage. Covalent organic polymers (COPs) have been recently introduced as promising materials to overcome several issues associated with the solid sorbents such as thermal stability and low gas capturing capacity. Herein we report the synthesis of four COPs and their CO2, N2 and CH4 uptakes. All the presented COP materials were characterized by using an elemental analysis method, Fourier transform infrared spectroscopy (FTIR) and solid state nuclear magnetic resonance (NMR) spectroscopy techniques. The physical properties of the materials such as surface area, pore volume and pore size were determined by BET analysis at 77 K. All the materials were tested for CO2, CH4 and N2 adsorption through a volumetric method using magnetic sorption apparatus (MSA). Among the presented materials, COP-118 has the highest surface area of 473 m2 g−1 among the other four materials and has shown excellent performance by capturing 2.72 mmol g−1 of CO2, 1.002 mmol g−1 of CH4 and only 0.56 mmol g−1 of N2 at 298 K and 10 bars. However the selectivity of another material, COP-117-A, was better than that of COP-118. Nevertheless, the overall performance of the latter has indicated that this material can be considered for further exploration as an efficient and cheaply available solid sorbent compound for CO2 capture and separation.

Understanding the colorimetric properties of quinoxaline-based pi-conjugated copolymers by tuning their acceptor strength: a joint theoretical and experimental approach

A series of five new π-conjugated donor–acceptor–donor (DADn) copolymers are presented, combining a common donating unit (substituted propylenedioxythiophene, ProDOT-(OEtHx)) with five diphenyl-quinoxaline based acceptor units bearing substituents of increasing acceptor strength (OMe < H < F < COOMe < CN). The DADn copolymers, namely P3-X (X = OMe, H, F, COOMe, CN), have been studied in solid state by cyclic voltammetry to investigate their electronic properties during n- and p-doping processes and to determine their electrochemical band gap. UV-Vis spectroscopy reveals a dual-band absorption system in which both high energy and low energy band (HEB and LEB) positions and intensities are governed by the acceptor strength. Density functional theory (DFT) computations were performed on D–A–D trimer model compounds in order to understand the experimental results. A colorimetric study in the CIELAB color space revealed that the modulation of the acceptor strength with σ- or π-electron withdrawing/donating groups leads to shades of blue to green upon increasing the acceptor strength. The polymers can also switch to a grey color upon p-doping. Finally, a detailed discussion on color–structure relationship provides valuable insights on molecular design principles to render cyan and green colors.

Robust C–C bonded porous networks with chemically designed functionalities for improved CO2 capture from flue gas

Effective carbon dioxide (CO2) capture requires solid, porous sorbents with chemically and thermally stable frameworks. Herein, we report two new carbon–carbon bonded porous networks that were synthesized through metal-free Knoevenagel nitrile–aldol condensation, namely the covalent organic polymer, COP-156 and 157. COP-156, due to high specific surface area (650 m2/g) and easily interchangeable nitrile groups, was modified post-synthetically into free amine- or amidoxime-containing networks. The modified COP-156-amine showed fast and increased CO2 uptake under simulated moist flue gas conditions compared to the starting network and usual industrial CO2 solvents, reaching up to 7.8 wt % uptake at 40 °C.