A 2D Acridine-Based Covalent Organic Framework for Selective Detection and Efficient Extraction of Gold from Complex Aqueous-Based Matrices.

Developing candidate materials which possess the ability of both selective detection and efficient capture of precious metal gold is highly desirable for environment and economy. However, most of reported materials only focus on single function, which seriously restricts their practical application as probes or adsorbents. Herein, a two dimensional (2D) acridine-based covalent organic framework (TpDa-COF) is prepared via the linkage of imine bonds for gold detection and adsorption. The synthesized COF can achieve both fluorescence and colorimetric dual sensing for Au3+ in a low concentration range (0.1-1.5 ppm) with the limit of detection (LOD) of 0.036 ppm. Impressively, the selectivity of TpDa-COF for the detection of Au3+ is admirable (Fe3+, Fe2+ and Cu2+ for negligible influence on its fluorescence). In addition, TpDa-COF exhibits ultrahigh adsorption capacity of 982.5 mg ⋅ g-1 for gold at pH=4, which is attributed the synergistic effect of both selective coordination and reductive process of Au(III) to Au(0). Meanwhile, both positive entropy change (ΔS=76.07 J ⋅ mol-1 ⋅ K-1) and high distribution coefficient (Kd=12484.8 mL ⋅ g-1) confirm the good affinity between TpDa-COF framework and gold. This work gives us a new insight to prepare COF with pyridine nitrogen sites for gold detection and adsorption.

Rapid Detection and Selective Extraction of Au(III) from Electronic Waste Using an Oxime Functionalized MOF-on-MOF Heterostructure.

Gold is not only a precious resource for many industries but also a global contaminant as a result of the discharge of gold-containing waste. Designing appropriate materials for the detection and extraction of gold is of great significance for the economy and environment. However, most reports only focus on sensing or adsorption for gold because of the difficulty of combining two functions in a single material. Herein, an oxime-functionalized MOF-on-MOF heterostructure (MOF-808@ZIF-90-XE) for the simultaneous detection and recovery of Au3+ is first demonstrated. The constructed hybrid material exhibits good stability, ultra-fast response time (3.6 s) as well as excellent sensitivity for the detection of Au3+ . Experimental characterizations and theoretical calculations suggest that dynamic quenching and competitive adsorption may be possible sensing mechanisms. In addition, MOF-808@ZIF-90-XE shows outstanding selectivity and admirable adsorption capacity (1575 mg g-1 ) for the capture of Au3+ owing to high surface area and abundant active adsorption sites. This paper provides a new strategy by designing a hybrid MOF-on-MOF heterostructure for the detection and extraction of gold.

Numerical Recognition System and Ultrasensitive Fluorescence Sensing Platform for Al3+ and UO22+ Based on Ln (III)-Functionalized MOF-808 via Thiodiglycolic Acid Intermediates.

Continuous accumulation of Al3+ in the human body and unintended leakage of UO22+ have posed a great threat to human health and the global environment; thus searching an efficient probe for the detection of Al3+ and UO22+ is of great importance. Herein, we designed and synthesized two hydrolytically stable Eu3+- and Tb3+-functionalized MOF materials Eu@MOF-808-TDA and Tb@MOF-808-TDA via thiodiglycolic acid (TDA) intermediates by the postsynthetic modification method. Among them, Tb@MOF-808-TDA was applied to construct numerical recognition systems of multiples of three and four by the combination of fluorescent signals, hierarchical cluster analysis, and logical gates. In addition, Tb@MOF-808-TDA exhibits good selectivity and sensitivity for the detection of Al3+ and UO22+. The detection limit is calculated to be 0.085 ppm for Al3+ and 0.082 ppm for UO22+ in aqueous solutions, which is lower than or close to that of latest reported Ln-MOFs. Moreover, the probe shows excellent hydrolytic stability and luminescence stability in the pH range of 4-11, further providing solid evidence for the practical application of Tb@MOF-808-TDA. More importantly, a mixed matrix hydrogel PVA-Tb@MOF-808-TDA was prepared to achieve the visual detection of Al3+, which broadens the potential in real-world sensing applications.

Flumequine-mediated fluorescent zeolitic imidazolate framework functionalized by Eu3+ for sensitive and selective detection of UO22+, Ni2+ and Cu2+ in nuclear wastewater.

Currently, antibiotics and heavy metal contaminants have posed a great threat for ecological security and human health. Herein, the lanthanide functionalized ZIF (named ZIF-90-PABA-Eu) is constructed by coordinating with Eu3+ via p-aminobenzoic acid intermediate. Due to the excellent fluorescence properties, the novel fluorescent probe can selectively monitor flumequine based on "turn on" mode. Furthermore, the obtained new material (named ZIF-90-PABA-Eu-Flu) can be used as "turn off" sensor for selective detection of both radioactive and nonradioactive heavy metal ions (UO22+, Ni2+ and Cu2+) which are the main component of nuclear industrial wastewater. ZIF-90-PABA-Eu-Flu shows ultra-short fluorescence response time (3 s) and ultra-low limit of detection (9.0 × 10-3, 1.3 × 10-2 and 6.1 × 10-4 ppm) for three metal ions, which may be attributed to its good affinity with UO22+, Ni2+ and Cu2+. Moreover, principal component analysis (PCA) is applied to distinguish the three metal ions. Additionally, the possible sensing mechanism is investigated by the UV-vis spectra, luminescence lifetimes and theoretical calculation analysis. Based on these results, ZIF-90-PABA-Eu possesses promising potential in practical application and provides insight for the design of novel probes to continuously monitor flumequine, radioactive and nonradioactive heavy metal ions.

Efficient uranium adsorbent with antimicrobial function constructed by grafting amidoxime groups on ZIF-90 via malononitrile intermediate.

Herein, a dual-function Zeolitic Imidazole Frameworks (ZIFs) ZIF-90 grafted with malononitrile by Knoevenagel reaction and following with an amidoximation reaction to form an efficient U (VI) adsorbent (ZIF-90-AO). The strong chelation power of amidoxime groups (AO) with uranium and ZIF-90's mesoporous structure afforded ZIF-90-AO high maximum uranium adsorption capacity of 468.3 mg/g (pH = 5). In addition, the factors affecting uranium adsorption process were investigated by a batch of adsorption tests under different adsorption conditions. ZIF-90-AO displayed good selectivity to UO22+ in the solution containing multiple co-existing ions and good regeneration property. More importantly, ZIF-90-AO showed excellent antimicrobial property against both E. coli and S. aureus. Therefore, ZIF-90-AO is a U-adsorbent with great application value for removing U (VI) from wastewater due to the high U (VI) adsorption capacity in weak acid condition and good anti-biofouling properties.