Emerging Doped Metal-Organic Frameworks: Recent Progress in Synthesis, Applications, and First-Principles Calculations.

Metal-organic frameworks (MOFs) are crystalline porous materials with a long-range ordered structure and excellent specific surface area and have found a wide range of applications in diverse fields, such as catalysis, energy storage, sensing, and biomedicine. However, their poor electrical conductivity and chemical stability, low capacity, and weak adhesion to substrates have greatly limited their performance. Doping has emerged as a unique strategy to mitigate the issues. In this review, the concept, classification, and characterization methods of doped MOFs are first introduced, and recent progress in the synthesis and applications of doped MOFs, as well as the rapid advancements and applications of first-principles calculations based on the density functional theory (DFT) in unraveling the mechanistic origin of the enhanced performance are summarized. Finally, a perspective is included to highlight the key challenges in doping MOF materials and an outlook is provided on future research directions.

Fabrication of an Fe-Doped ZIF-67 Derived Magnetic Fe/Co/C Composite for Effective Removal of Congo Red.

The dyes in printing and dyeing wastewater are harmful to the human body and the environment. It is essential to develop practical and effective adsorbents to deal with them. In this study, an Fe-doped, ZIF-67 derived Fe/Co/C composite material with strong magnetism was successfully synthesized. The effects of pH, initial concentration, and adsorption time on the properties of the adsorbent were investigated. To further improve the removal efficiency and enhance the practicality, potassium peroxymonosulfate (PMS) was added to the system due to its Fenton-like effect. Then, an Fe/Co/C composite was used with PMS to remove Congo red (CR) with a 98% removal of 250 mg·L-1. Moreover, for its high saturation magnetization of 85.4 emu·g-1, the Fe/Co/C composite can be easily recovered by applying a magnetic field, solving the problem that powdery functional materials are difficult to recover and, thus, avoiding secondary pollution. Furthermore, since the composite material was doped before carbonization, this synthetic strategy is flexible and the required metal elements can be added at will to achieve different purposes. This study demonstrates that this Fe-doped, ZIF-67 derived magnetic material has potential application prospects for dye adsorption.

High-efficient liquid exfoliation of 2D metal-organic framework using deep-eutectic solvents.

The exfoliation of bulk two-dimensional metal-organic framework (MOF) into few-layered nanosheets has attracted much attention recently. In this work, an environmental-friendly route has been developed for layered-MOF (MAMS-1) delamination using deep eutectic solvent (DES), which is more sustainable and efficient alternative than conventional organic solvents for MOF nanosheet preparation. Under sonication condition, DES as solvents, the highest exfoliation rate of MAMS-1 is up to 70% with two host layers via poly(vinylpyrrolidone) (PVP) surfactant-assisted method. The presence of tert-butyl exteriors and the atomically thickness endow the MOF nanosheets stable suspension for at least one month. Due to the 2D structure and excellent stability, MAMS-1 nanosheet (MAMS-1-NS) was chosen as a good candidate to encapsulate Eu3+ cations. The obtained Eu3+@MAMS-1-NS acts as a multi-responsive luminescent sensor through fluorescence quenching, and can specifically recognize Fe3+ (LOD = 0.40 µM, KSV = 1.05 × 105 M-l), Hg2+ (LOD = 0.038 µM, KSV = 5.78 × 106 M-l), Cr2O72- (LOD = 0.33 µM, KSV = 1.55 × 105 M-l) and MnO4- (LOD = 0.088 µM, KSV = 4.49 × 105 M-l). Compared with bulk Eu3+@MAMS-1, the sensitivity of Eu3+@MAMS-1-NS is greatly improved owing to its ultrathin nanosheet morphology and highly accessible active sites on the surface.

Catalytic Activation of Cobalt Doping Sites in ZIF-71-Coated ZnO Nanorod Arrays for Enhancing Gas-Sensing Performance to Acetone.

Developing acetone gas sensors with high sensitivity is crucially important for many applications including nonevasive diagnosis of diabetes. In the present work, cobalt doping is used to catalyze acetone gas-sensing reactions and hence to promote the sensitivity of acetone gas sensors. In order to achieve this, ZIF-71 metal-organic framework (MOF) is synthesized onto ZnO nanorod arrays with various concentrations of Co doping to form composite ZnO@ZIF-71(Co) sensors, which are then evaluated as sensing materials for acetone detection. Such sensors are shown to be sensitive to a trace amount of acetone (50 ppb) and have a massively enhanced response of about 100 times that for the undoped sensor at an optimal Co/Zn ratio and operating temperature. Fourier-transform infrared spectroscopy and temperature-programmed desorption with density functional theory calculations are also made to assist in elucidating the catalytic gas-sensing mechanism for the Co-doped composite sensors ZnO@ZIF-71(Co). It demonstrated that the introduced Co site in ZIF-71(Co) can activate oxygen catalytically and increase active oxygen released to the ZnO surface. Meanwhile, the Co sites also promote the decomposition of acetone. These two steps together affect the catalytic oxidation of gases and finally enhance the sensitivity. This work introduces the catalytic effect of the MOF into the gas-sensing mechanism and provides an idea for broadening the application of MOF catalysis.