Achieving Sub-ppm Sensitivity in SO2 Detection with a Chemically Stable Covalent Organic Framework.

We report the inaugural experimental investigation of covalent organic frameworks (COFs) to address the formidable challenge of SO2 detection. Specifically, an imine-functionalized COF (SonoCOF-9) demonstrated a modest and reversible SO2 sorption of 3.5 mmol g-1 at 1 bar and 298 K. At 0.1 bar (and 298 K), the total SO2 uptake reached 0.91 mmol g-1 with excellent reversibility for at least 50 adsorption-desorption cycles. An isosteric enthalpy of adsorption (ΔHads) for SO2 equaled -42.3 kJ mol-1, indicating a relatively strong interaction of SO2 molecules with the COF material. Also, molecular dynamics simulations and Møller-Plesset perturbation theory calculations showed the interaction of SO2 with π density of the rings and lone pairs of the N atoms of SonoCOF-9. The combination of experimental data and theoretical calculations corroborated the potential use of this COF for the selective detection and sensing of SO2 at the sub-ppm level (0.0064 ppm of SO2).

CYCU-3: an Al(III)-based MOF for SO2 capture and detection.

The Al(III)-based MOF CYCU-3 exhibits a relevant SO2 adsorption performance with a total uptake of 11.03 mmol g-1 at 1 bar and 298 K. CYCU-3 displays high chemical stability towards dry and wet SO2 exposure. DRIFTS experiments and computational calculations demonstrated that hydrogen bonding between SO2 molecules and bridging Al(III)-OH groups are the preferential adsorption sites. In addition, photoluminescence experiments demonstrated the relevance of CYCU-3 for application in SO2 detection with good selectivity for SO2 over CO2 and H2O. The change in fluorescence performance demonstrates a clear turn-on effect after SO2 interaction. Finally, the suppression of ligand-metal energy transfer along with the enhancement of ligand-centered π* → π electronic transition was proposed as a plausible fluorescence mechanism.

SO2 capture and detection with carbon microfibers (CMFs) synthesised from polyacrylonitrile.

SO2 emissions not only affect local air quality but can also contribute to other environmental issues. Developing low-cost and robust adsorbents with high uptake and selectivity is needed to reduce SO2 emissions. Here, we show the SO2 adsorption-desorption capacity of carbon microfibers (CMFs) at 298 K. CMFs showed a reversible SO2 uptake capacity (5 mmol g-1), cyclability over ten adsorption cycles with fast kinetics and good selectivity towards SO2/CO2 at low-pressure values. Additionally, CMFs' photoluminescence response to SO2 and CO2 was evaluated.

APTES functionalization in SBA-15: the effect on SO2 capture and detection applications.

The development of adsorbents for air pollutant remediation and effective monitoring is of interest. Then, the effect of the APTES functionalization ratio on the impact of the adsorption and detection of SO2 molecules was evaluated. The higher APTES functionalization material (SBA-15_6.1APTES) shows a high uptake of 1.15 mmol g-1 at 0.001 bar and 298 K. Fluorescence, time-resolved photoluminescence, and quantum yield experiments revealed a turn-on effect specifically for SO2 molecules, indicating high selectivity, suggesting host-to-guest energy transfer. Attractively, XPS measurement provided an understanding of the mechanism, suggesting hydrogen bonding and dipole-dipole interactions as the main interactions between SO2 molecules and SBA-15_6.1APTES. DFT calculations were performed to confirm these interactions. Furthermore, this study highlights the application of SBA-15 materials with different amino modifications for SO2 treatment and provides insight into the interaction mechanism using experimental techniques.

MFM-300(Sc): a chemically stable Sc(III)-based MOF material for multiple applications.

Developing robust multifunctional metal-organic frameworks (MOFs) is the key to advancing the further deployment of MOFs into relevant applications. Since the first report of MFM-300(Sc) (MFM = Manchester Framework Material, formerly known as NOTT-400), the development of applications of this robust microporous MOF has only grown. In this review, a summary of the applications of MFM-300(Sc), as well as some emerging advanced applications, have been discussed. The adsorption properties of MFM-300(Sc) are presented systematically. Particularly, this contribution is focused on acid and corrosive gas adsorption. In addition, recent applications for catalysis based on the outstanding hemilabile Sc-O bond character are highlighted. Finally, some new research areas are introduced, such as host-guest chemistry and biomedical applications. This highlight aims to showcase the recent advances and the potential for developing new applications of this promising material.

Detection of SO2 using a chemically stable Ni(II)-MOF.

The MOF-type Ni2(dobpdc) shows a high chemical stability towards SO2, high capacity for SO2 capture at low pressure (4.3 mmol g-1 at 298 K and up to 0.05 bar), and exceptional cycling performance. Fluorescence experiments demonstrated the SO2 detection properties of Ni2(dobpdc) with a remarkable SO2 detection selectivity. Finally, time-resolved photoluminescence experiments provided a plausible mechanism of SO2 detection by this Ni(II)-based MOF material.

SU-101: a Bi(III)-based metal-organic framework as an efficient heterogeneous catalyst for the CO2 cycloaddition reaction.

A non-porous version of SU-101 (herein n-SU-101) was evaluated for the CO2 cycloaddition reaction. The findings revealed that open metal sites (Bi3+) are necessary for the reaction. n-SU-101 displays a high styrene oxide conversion of 96.6% under mild conditions (3 bar and 80 °C). The catalytic activity of n-SU-101 demonstrated its potential application for the cycloaddition of CO2 using styrene oxide.

Modulated self-assembly of three flexible Cr(III) PCPs for SO2 adsorption and detection.

Modulated self-assembly protocols are used to develop facile, HF-free syntheses of the archetypal flexible PCP, MIL-53(Cr), and novel isoreticular analogues MIL-53(Cr)-Br and MIL-53(Cr)-NO2. All three PCPs show good SO2 uptake (298 K, 1 bar) and high chemical stabilities against dry and wet SO2. Solid-state photoluminescence spectroscopy indicates all three PCPs exhibit turn-off sensing of SO2, in particular MIL-53(Cr)-Br, which shows a 2.7-fold decrease in emission on exposure to SO2 at room temperature, indicating potential sensing applications.

Reversible and efficient SO2 capture by a chemically stable MOF CAU-10: experiments and simulations.

The adsorption of sulphur dioxide (SO2) in CAU-10 is obtained with the use of advanced experimental and computational tools to gain insight into the molecular mechanisms responsible for the adsorption of SO2. It is shown that the adsorption by CAU-10 is highly energy efficient and that van der Waals interactions are the driving force that controls adsorption in this system.