ABSTRACT
Metal-organic frameworks (MOFs), a diverse and rapidly expanding class of crystalline materials, present many opportunities for various applications. Within this class, the amino-functionalized Zr-MOF, namely, UiO-66-NH2, stands out due to its distinctive chemical and physical properties. In this study, we report on the new unique property where UiO-66-NH2 nanocrystals exhibited enhanced fluorescence upon heating, which was persistently maintained postcooling. To unravel the mechanism, the changes in the fluorescence signal were monitored by steady-state fluorescence spectroscopy, lifetime measurements, and a fluorescence microscope, which revealed that upon heating, multiple mechanisms could be contributing to the observed enhancement; the MOFs can undergo disaggregation, resulting in a fluorescent enhancement of the colloidally stable MOF nanocrystals and/or surface-induced phenomena that result in further fluorescence enhancement. This observed temperature-dependent photophysical behavior has substantial applications. It not only provides pathways for innovations in thermally modulated photonic applications but also underscores the need for a better understanding of the interactions between MOF crystals and their environments.
ABSTRACT
Surface -functionalised silica networks are advanced adsorbents. They have been given much attention for treating wastewater using the adsorption technique due to the silanol reactivity, resulting in strong binding affinities towards many pollutants. This review discusses the removal of anionic azo dyes utilising various functional groups such as amines, surfactants, polymers, macrocyclic, and other chelating groups functionalised on silica's surface. This review also reveals the steadily increasing interest in surface-functionalised silicas as adsorbents, emphasising the scholarly advancements in this field as a platform for future research. For that, adsorption capacities with different experimental conditions have been compared. The possible adsorption mechanisms, rate-limiting step, and factors affecting the anionic azo dye adsorption process have been comprehensively discussed. This review discloses that adsorbent characteristics such as porosity and functional groups, besides structural properties of an anionic azo dye, significantly affect adsorption. The adsorption process followed the Langmuir isotherm and pseudo-second-order models, with a predominantly spontaneous and endothermic nature. Multiple interactions, including electrostatic interaction, π-π interactions, and hydrogen bonding, are observed between dyes and functionalised silicas, indicating the adsorption process's complexity. Regeneration and cost-economic analysis are also presented to provide a roadmap for sustainable improvements. Chemical and biological regeneration techniques restore > 80% of the spent functionalised silicas. There is a significant opportunity to improve their efficiencies and regenerability, resulting in surface-functionalised silicas being used commercially instead of only in the laboratory. Finally, future research has been proposed by identifying current research gaps, particularly concerning the application of functionalised silicas in wastewater treatment.
