Fine-tuning covalent organic frameworks for structure-activity correlation via adsorption and catalytic studies.

In applications utilizing Covalent Organic Frameworks (COFs) for adsorption, the interplay between crystallinity (vis-à-vis surface area) and active sites still remains ambiguous. To address this, the present study introduces three isoreticular COFs-COP-N18 (covalent organic polymer with short-range order), COF-N18 (COF having long-range order), and COF-N27 (semicrystalline COF with pyridyl heteroatoms)-to explore this duality. Through systematic variations in structural order, pore volume, and pore-wall nitrogen content, we aim to establish a structure-activity relationship (SAR) for these COFs via adsorption and catalysis, using CO2 and I2 as probes. Our investigation highlights the positive influence of crystallinity, surface area, and pore volume in adsorption as well as catalysis. However, the presence of heteroatoms manifests complex behavior in CO2 adsorption and CO2 cycloaddition reactions with epoxides. COF-N18 and COF-N27 showed comparable CO2 uptake capacities at different temperatures (273, 293, and 313 K) and ∼1 bar pressure. Additionally, CO2 cycloaddition reactions were performed with substrates possessing different polarities (epichlorohydrin, 1,2-epoxydodecane) to elucidate the role of COF surface polarity. Further investigation into iodine adsorption was performed to understand the impact of COF structural features on the modes of adsorption and adsorption kinetics. Improvements in COF-crystallinity results in faster average iodine uptake rate at 80% (K80% = 1.79 g/h) by COF-N18. Whereas, heteroatom doping slows down iodine adsorption kinetics (0.35 g/h) by prolonging the adsorption process up to 72 h. Overall, this study advances our understanding of COFs as adsorbents and catalysts, providing key insights into their SAR while emphasizing structural fine-tuning as a key factor for impactful environmental applications.

Systematic Thiol Decoration in a Redox-Active UiO-66-(SH)2 Metal-Organic Framework: A Case Study under Oxidative and Reductive Conditions.

The practical applicability of thiolated metal-organic frameworks (MOFs) remains challenging due to their low crystallinity and transient stability. Herein, we present a one-pot solvothermal synthesis process using varying ratios of 2,5-dimercaptoterephthalic acid (DMBD) and 1,4-benzene dicarboxylic acid (100/0, 75/25, 50/50, 25/75, and 0/100) to prepare stable mixed-linker UiO-66-(SH)2 MOFs (ML-U66SX). For each variant, the effects of different linker ratios on the crystallinity, defectiveness, porosity, and particle size have been discussed in detail. In addition, the impact of modulator concentration on these features has also been described. The stability of ML-U66SX MOFs was investigated under reductive and oxidative chemical conditions. The mixed-linker MOFs were used as sacrificial catalyst supports to highlight the interplay of template stability on the rate of the gold-catalyzed 4-nitrophenol hydrogenation reaction. The release of catalytically active gold nanoclusters originating from the framework collapse decreased with the controlled DMBD proportion, resulting in a 59% drop in the normalized rate constants (9.11-3.73 s-1 mg-1). In addition, post-synthetic oxidation (PSO) was used to further probe the stability of the mixed-linker thiol MOFs under harsh oxidative conditions. Following oxidation, the UiO-66-(SH)2 MOF underwent immediate structural breakdown, unlike other mixed-linker variants. Along with crystallinity, the microporous surface area of the post-synthetically oxidized UiO-66-(SH)2 MOF could be increased from 0 to 739 m2 g-1. Thus, the present study delineates a mixed-linker strategy to stabilize the UiO-66-(SH)2 MOF under harsh chemical conditions through meticulous thiol decoration.

Geographical Appraisal of COVID-19 in West Bengal, India.

Study shows that COVID-19 cases, deaths and recoveries vary in macro level. Geographical phenomena may act as potential controlling factor. The present paper investigates spatial pattern of COVID-19 cases and deaths in West Bengal (WB), India and assumes Kolkata is the source region of this disease in WB. Thematic maps on COVID related issues are prepared with the help of QGIS 3.10 software. As on 15th January 2021, WB has 564032 number of COVID-19 cases which is 0.618% to the total population of the state. However, the COVID-19 case for India is 0.843% and for world is 1.341% to its total population. Lorenz Curve shows skewed distribution of the COVID-19 cases in WB. 17 (90%) districts hold 84.11% of the total population and carry 56.30% of the total COVID-19 cases. However, the remaining two districts-Kolkata and North 24 Parganas-hold remaining 43.70% COVID-19 cases. Correlation coefficient with COVID-19 cases and Population Density, Urban Population and Concrete Roof of their house are significant at 1% level of significance.