Rabindra Dubadi

Mechanochemical synthesis of ordered mesoporous carbons with tunable mesopores and well-developed irregular microporosity is investigated. This synthesis was carried out by the self-assembly of ecofriendly chemicals such as tannin and glyoxal used as carbon precursors, and triblock copolymer as a soft templating agent. The structural properties of the resulting carbons were tailored by using different block copolymers (Pluronic F127, and P123) as soft templates. The various weight ratios of tannin and block copolymer were employed to tune the textural properties of these carbons. The tannin: Pluronic F127 ratios (1:0.75, 1:1, 1:1.1) gave the ordered mesoporous carbons among a wide variety of the samples studied. The ordered mesoporosity was not observed in the case of Pluronic P123 templated mesoporous carbons. The CO₂-activated carbon samples obtained for both Pluronic templates showed a high specific surface area (close to 900 m²/g), large pore volume (about 0.6–0.7 cm³g⁻¹), narrow pore size distribution, and high CO₂ uptake of about 3.0 mmol g⁻¹ at 1 bar pressure and ambient temperature.

In this study, the facile and sustainable synthesis of highly microporous carbons is explored to reduce the extensive use of harsh activating agents and solvents. The role of potassium citrate (PC) as a greener activating agent in addition to the conventional ZnCl₂ is investigated in the mechanochemical solvent-free preparation of highly microporous carbon materials from chestnut tannin (CT), a biomass-type carbon precursor. A small amount of potassium citrate as a chemical activator coupled with CO₂ activation at 700 °C afforded carbons with higher specific surface area (1256 m² g⁻¹) and larger micropore volume (0.54 cm³ g⁻¹) as compared to the carbons activated with both PC and ZnCl₂. The high microporosity of the PC-activated carbon materials, significantly enlarged after CO₂ activation from micropore volume of 0.16 to 0.54 cm³ g⁻¹, makes them favorable for CO₂ adsorption, as evidenced by high adsorption capacity of 3.55 mmol g⁻¹ at ambient conditions (25 °C, 1 bar). This study shows that the solvent-free mechanochemical processing of tannin in the presence of PC is a promising method for obtaining highly microporous carbon materials.

Although it has no known biochemical role in living organisms, bismuth has been used to treat syphilis, diarrhea, gastritis and colitis for almost a century due to its nontoxic nature to mammalian cells. When prepared via a top-down sonication route from a bulk sample, bismuth subcarbonate (BiO)₂CO₃ nanoparticles (NPs) with an average size of 5.35 ± 0.82 nm exhibit broad-spectrum potent antibacterial activity against both the gram-positive and gram-negative bacteria including methicillin-susceptible Staphylococcus aureus (DSSA), methicillin-resistant Staphylococcus aureus (MRSA), drug-susceptible Pseudomonas aeruginosa (DSPA) and multidrug-resistant Pseudomonas aeruginosa (DRPA). Specifically, the minimum inhibitory concentrations (MICs) are 2.0 µg/mL against DSSA and MRSA and 0.75 µg/mL against DSPA and DRPA. In sharp contrast to ciprofloxacin, AgNPs and meropenem, (BiO)₂CO₃ NPs show no sign of developing Bi-resistant phenotypes after 30 consecutive passages. On the other hand, such NPs can readily overcome the resistance to ciprofloxacin, AgNPs and meropenem in DSPA. Finally, the combination of (BiO)₂CO₃ NPs and meropenem shows a synergistic effect with the fractional inhibitory concentration (FIC) index of 0.45.

γ-Alumina with incorporated metal oxide species (including Fe, Cu, Zn, Bi, and Ga) was synthesized by liquid-assisted grinding—mechanochemical synthesis, applying boehmite as the alumina precursor and suitable metal salts. Various contents of metal elements (5 wt.%, 10 wt.%, and 20 wt.%) were used to tune the composition of the resulting hybrid materials. The different milling time was tested to find the most suitable procedure that allowed the preparation of porous alumina incorporated with selected metal oxide species. The block copolymer, Pluronic P123, was used as a pore-generating agent. Commercial γ−alumina (S_BET = 96 m²·g⁻¹), and the sample fabricated after two hours of initial grinding of boehmite (S_BET = 266 m²·g⁻¹), were used as references. Analysis of another sample of γ-alumina prepared within 3 h of one-pot milling revealed a higher surface area (S_BET = 320 m²·g⁻¹) that did not increase with a further increase in the milling time. So, three hours of grinding time were set as optimal for this material. The synthesized samples were characterized by low-temperature N₂ sorption, TGA/DTG, XRD, TEM, EDX, elemental mapping, and XRF techniques. The higher loading of metal oxide into the alumina structure was confirmed by the higher intensity of the XRF peaks. Samples synthesized with the lowest metal oxide content (5 wt.%) were tested for selective catalytic reduction of NO with NH₃ (NH₃-SCR). Among all tested samples, besides pristine Al₂O₃ and alumina incorporated with gallium oxide, the increase in reaction temperature accelerated the NO conversion. The highest NO conversion rate was observed for Fe₂O₃-incorporated alumina (70%) at 450 °C and CuO-incorporated alumina (71%) at 300 °C. The CO₂ capture was also studied for synthesized samples and the sample of alumina with incorporated Bi₂O₃ (10 wt.%) gave the best result (1.16 mmol·g⁻¹) at 25 °C, while alumina alone could adsorb only 0.85 mmol·g⁻¹ of CO₂. Furthermore, the synthesized samples were tested for antimicrobial properties and found to be quite active against Gram-negative bacteria, P. aeruginosa (PA). The measured Minimum Inhibitory Concentration (MIC) values for the alumina samples with incorporated Fe, Cu, and Bi oxide (10 wt.%) were found to be 4 µg·mL⁻¹, while 8 µg·mL⁻¹ was obtained for pure alumina.

There is an increased interest in porous materials due to their unique properties such as high surface area, enhanced catalytic properties, and biological applications. Various solvent-based approaches have been already used to synthesize porous materials. However, the use of large volume of solvents, their toxicity, and time-consuming synthesis make this process less effective, at least in terms of principles of green chemistry. Mechanochemical synthesis is one of the effective eco-friendly alternatives to the conventional synthesis. It adopts the efficient mixing of reactants using ball milling without or with a very small volume of solvents, gives smaller size nanoparticles (NPs) and larger surface area, and facilitates their functionalization, which is highly beneficial for antimicrobial applications. A large variety of nanomaterials for different applications have already been synthesized by this method. This review emphasizes the comparison between the solvent-based and mechanochemical methods for the synthesis of mainly inorganic NPs for potential antimicrobial applications, although some metal-organic framework NPs are briefly presented too.