Synthesizing 2D metal–organic frameworks (2D MOFs) in high yields and rational tailoring of the properties in a predictable manner for specific applications is extremely challenging. Now, a series of porphyrin‐based 2D lanthanide MOFs (Ln‐TCPP, Ln=Ce, Sm, Eu, Tb, Yb, TCPP=tetrakis(4‐carboxyphenyl) porphyrin) with different thickness were successfully prepared in a household microwave oven. The as‐prepared 2D Ln‐TCPP nanosheets showed thickness‐dependent photocatalytic performances towards photooxidation of 1,5‐dihydroxynaphthalene (1,5‐DHN) to synthesize juglone. Particularly, the Yb‐TCPP displayed outstanding photodynamic activity to generate O2− and 1O2. This work not only provides fundamental insights into structure designing and property tailoring of 2D MOFs nanosheets, but also pave a new way to improve the photocatalytic performance.
Novel metal-organic gels (MOGs) consisting of iron (Fe) as the central ion and 1,10-phenanthroline-2,9-dicarboxylic acid (PDA) as the ligand were synthesized by a mild facile strategy. The Fe(III)-containing metal-organic xerogels (Fe-MOXs), obtained after removing the solvents in MOGs, were found to exhibit outstanding performance in the catalysis of luminol chemiluminescence (CL) for the first time even in the absence of extra oxidants such as hydrogen peroxide. The possible CL mechanism was discussed according to the electro/optical measurements, including electron paramagnetic resonance (EPR), UV-vis absorption, and CL spectra, as well as the effects of radical scavengers on Fe-MOXs-catalyzed luminol CL system, suggesting that the CL emission of luminol might originate from the intrinsic oxidase-like catalytic activity of Fe-MOXs on the decomposition of dissolved oxygen. Additionally, the potential practical application of the resulting luminol-Fe-MOXs system was evaluated by the quantitative analysis of dopamine. Good linearity over the range from 0.05 to 0.6 μM was obtained with the limit of detection (LOD, 3σ) of 20.4 nM and acceptable recoveries ranging from 98.6 to 105.4% in human urine. These results may open up the promising application of novel metal-organic gels as highly effective catalysts in the field of chemiluminescence.
Until now, despite much progress in the study of metal-organic gels (MOGs), the modification of transition-metal containing MOGs with noble metal nanoparticles (NPs) is far from fully developed. Herein, iron-based MOGs nanosheet hybrids with gold NPs (AuNPs) immobilization were first synthesized by a facile in situ grown strategy at ambient conditions. It is found that the as-prepared AuNPs/MOGs (Fe) hybrids exhibited enhanced mimicking peroxidase-like activity, making them endowed with outstanding performance in chemiluminescence (CL) field in the presence of HO. The remarkable CL enhancement by AuNPs/MOGs (Fe) hybrids was attributed to the modification of AuNPs on MOGs (Fe) nanosheets, which could synergistically accelerate the CL reaction by speeding up the generation of OH, O, and O. Accordingly, a sensitive CL detection of organophosphorus pesticides was successfully achieved by the AuNPs/MOGs (Fe) hybrids CL enhancing system in the range of 5-800 nM with a detection limit of 1 nM. We envision that this highly active and novel enzyme mimetic catalyst can be applicable to other extended AuNPs/MOGs (Fe) hybrid-based CL systems for sensitive detection of various analytes.
Metal organic gels (MOGs) have emerged as a new class of smart soft materials with superb luminescence properties and have attracted tremendous attention in various aspects. However, the electrochemiluminescence (ECL) behavior of MOGs has not been reported yet. In this work, cathode electrochemiluminescence (ECL) emission of terbium(III) organic gels (TOGs) was reported for the first time with potassium persulfate (KSO) as an efficient coreactant. TOGs were synthesized by a facile one-step strategy, mixing terbium ions (Tb) and the ligand 4'-(4-carboxyphenyl)-2,2':6',2''-terpyridine (Hcptpy) at room temperature. The possible strong green ECL emission mechanism was discussed in detail and ascribed to the external coreactant enhancement and internal antenna effect enhancement. Moreover, the promising application of TOGs in analytical chemistry was clarified by the ECL on-off detection of tetracycline. This remarkable discovery of ECL emission of TOGs may pioneer the application of MOGs in ECL fields.
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