RESUMO
Defect-engineered metal-organic frameworks (MOFs) with outstanding structural and chemical features have become excellent candidates for specific separation applications. The introduction of structural defects in MOFs as an efficient approach to manipulate their functionality provides excellent opportunities for the preparation of MOF-based mixed matrix membranes (MMMs). However, the use of this strategy to adjust the properties and develop the separation performance of gas separation membranes is still in its early stages. Here, a novel defect-engineered MOF (quasi ZrFum or Q-ZrFum) was synthesized via a controlled thermal deligandation process and incorporated into a CO2-philic 6FDA-durene polyimide (PI) matrix to form Q-ZrFum loaded MMMs. Defect-engineered MOFs and fabricated MMMs were investigated regarding their characteristic properties and separation performance. The incorporation of defects into the MOF structure increases the pore size and provides unsaturated active metal sites that positively affect CO2 molecule transport. The interfacial compatibility between the Q-ZrFum particles and the PI matrix increases via the deligandation process, which improves the mechanical strength of Q-ZrFum loaded membranes. MMM containing 5â wt.% of defect-engineered Q-ZrFum exhibits excellent CO2 permeability of 1308 Barrer, which increased by 99 % compared to the pure PI membrane (656 Barrer) at a feed pressure of 2â bar. CO2/CH4 and CO2/N2 selectivity reached 44 and 26.6 which increased by about 70 and 16 %, respectively. This study emphasizes that defect-engineered MOFs can be promising candidates for use as fillers in the preparation of MMMs for the future development of membrane-based gas separation applications.
RESUMO
Fluorinated metal-organic frameworks (F-MOFs) as fast-growing porous materials have revolutionized the field of gas separation due to their tunable pore apertures, appealing chemical features, and excellent stability. A deep understanding of their structure-performance relationships is critical for the synthesis and development of new F-MOFs. This critical review has focused on several strategies for the precise design and synthesis of new F-MOFs with structures tuned for specific gas separation purposes. First, the basic principles and concepts of F-MOFs as well as their structure, synthesis and modification and their structure to property relationships are studied. Then, applications of F-MOFs in adsorption and membrane gas separation are discussed. A detailed account of the design and capabilities of F-MOFs for the adsorption of various gases and the governing principles is provided. In addition, the exceptional characteristics of highly stable F-MOFs with engineered pore size and tuned structures are put into perspective to fabricate selective membranes for gas separation. Systematic analysis of the position of F-MOFs in gas separation revealed that F-MOFs are benchmark materials in most of the challenging gas separations. The outlook and future directions of the science and engineering of F-MOFs and their challenges are highlighted to tackle the issues of overcoming the trade-off between capacity/permeability and selectivity for a serious move towards industrialization.
RESUMO
The presence of copper in aquatic environment is a serious threat for human health and ecosystem conservation. Adsorption is a powerful, operable and economic method for remediation of copper ions from aqueous phase. Carbohydrate biopolymers have emerged as promising, effective and environmental-friendly adsorbents for copper remediation. In part A of this review, different types of carbohydrate biopolymer adsorbents were surveyed focusing on prevalent and novel synthesis and modification methods. In current work (part B of the review), isothermal, thermodynamic and kinetic aspects of the copper adsorption by carbohydrate-based adsorbents as well as the regeneration and reusability of the biopolymer adsorbents are overviewed. Adsorption capacity, time required for equilibrium (adsorption rate), thermal-sensitivity of the adsorption, favorability extent, and sustainability of the adsorbents and adsorption processes are valuable and useful outcomes, resulted from the thermokinetic and reusability investigations. Such considerations are critical for the process design and scale up regarding technical, economical and sustainability of the adsorption process.
Assuntos
Cobre , Poluentes Químicos da Água , Adsorção , Biopolímeros , Carboidratos , Ecossistema , Concentração de Íons de Hidrogênio , Íons , Cinética , Termodinâmica , Poluentes Químicos da Água/análiseRESUMO
Copper is one of the most toxic heavy metals which must be eliminated from aqueous environments, according to the environmental standards. Carbohydrate biopolymers are promising candidates for synthesizing copper-adsorbent composites. It is due to unique properties such as having potential adsorptive functional sites, availability, biocompatibility and biodegradability, formability, blending capacity, and reusability. Different types of copper-adsorbent carbohydrate biopolymers like chitosan and cellulose with particular focus on the synthesizing and modification approaches have been tackled in this review. Composites, functionality and morphological aspects of the biopolymer adsorbents have also been surveyed. Further progress in the fabrication and application of biopolymer adsorbents would be achievable with special attention to some critical challenges such as the process economy, copolymer and/or (nano) additive selection, and the physicochemical stability of the biopolymer composites in aqueous media.