Solar-Driven Ammonia Production through Engineering of the Electronic Structure of a Zr-Based MOF.

As a hydrogen carrier and a vital component in fertilizer production, ammonia (NH3) is set to play a crucial role in the planet's future. While its industrial production feeds half of the global population, it uses fossil fuels and emits greenhouse gases. To tackle this issue, photocatalytic nitrogen fixation using visible light is emerging as an effective alternative method. This strategy avoids carbon dioxide (CO2) emissions and harnesses the largest share of sunlight. In this work, we successfully incorporated a 5-nitro isophthalic acid linker into MOF-808 to introduce structural defects and open metal sites. This has allowed modulation of the electronic structure of the MOF and effectively reduced the band gap energy from 3.8 to 2.6 eV. Combination with g-C3N4 enhanced further NH3 production, as these two materials possess similar band gap energies, and g-C3N4 has shown excellent performance for this reaction. The nitro groups serve as acceptors, and their integration into the MOF structure allowed effective interaction with the free electron pairs on N-(C)3 in the g-C3N4 network nodes. Based on DFT calculations, it was concluded that the adsorption of N2 molecules on open metal sites caused a decrease in their triple bond energy. The modified MOF-808 showed superior performance compared with the other MOFs studied in terms of N2 photoreduction under visible light. This design concept offers valuable information about how to engineer band gap energy in MOF structures and their combination with appropriate semiconductors for solar-powered photocatalytic reactions, such as N2 or CO2 photoreduction.

Sulfonated Zinc Phthalocyanine Coating as an Efficient and Ecofriendly Corrosion Inhibitor for Copper Surfaces: An In Silico Led Design and Its Experimental Validation.

The current study highlights the successful integration of an in silico design with experimental validation to create a highly effective corrosion inhibitor for copper (Cu) surfaces. The synthesized sulfonated zinc phthalocyanine (Zn-Pc) is electrochemically characterized and demonstrates an impressive 97% inhibition efficiency, comparable to the widely used industrial corrosion inhibitor, BTA, for Cu surfaces. The corrosion inhibition is comprehensively analyzed through potentiodynamic polarization and impedance spectroscopy techniques, supported by their respective equivalent circuits. Furthermore, the sample undergoes thorough characterization using scanning electron microscopy, energy-dispersive X-ray analysis, X-ray photoelectron spectroscopy, contact angle measurements, and atomic force microscopy. Density functional theory calculations reveal that sulfonated Zn-Pc exhibits the highest interaction energy, underscoring its exceptional inhibition properties. These results open possibilities for utilizing computational methods to design and optimize corrosion inhibitors for protection of Cu surfaces.

Jute sticks biomass delignification through laccase-mediator system for enhanced saccharification and sustainable release of fermentable sugar.

Jute sticks obtained after the extraction of jute fiber are an excellent biomass feedstock with a significant amount of carbohydrates that makes it an attractive resource for sustainable energy generation. However, the high lignin content in the jute stick hinders the cellulosic component of the cell wall from enzymatic hydrolysis.This work demonstrates the lignin degradation of jute stick biomass by Trametes maxima laccase in the presence of mediator Hydroxybenzotriazole and improvement in its subsequent saccharification. Lignin component in jute stick is reduced by 21.8% in a single reaction treatment with laccase-mediator compared to the untreated jute stick sample used as control. The yield of fermentable sugar is increased by 19.5% that verifies enhanced saccharification after lignin removal. Delignification of jute stick was corroborated through different analytical techniques. The Pyrolysis gas chromatography/mass spectrometry results further confirms abundance of S lignin unit in the jute stick compared to the H and G unit and modification in lignin polymer as a change in the syringyl-to-guaiacyl ratio. Hence, this work demonstrates that jute stick can be effectively delignified using biocatalyst-mediator system and utilized as biomass source, thus contributing in circular bio-economy through waste valorization.