Sheng Zhong,Bin He,Shuang Wei,Ruirui Wang,Ruirui Zhang,Ruixia Liu
Electrocatalytic glycerol oxidation reaction to produce high-value organic chemicals has research significance for managing the overproduction of glycerol and handling the energy crisis. Herein, a copper-based self-supporting catalytic electrode with a dynamic Fe-O-Cu optimized coordination (Fe-CuO x /CF) was prepared. The oxygen-bridged asymmetric coordination structure (Fe-O-Cu) optimized the electronic configuration and promoted the formation of the crucial intermediate species. After Fe was embedded in the lattice of copper oxides, a remarkable enhancement in the adsorption capacity of OH - and glycerol was confirmed. As a result, Fe-CuO x /CF exhibited an excellent production capacity of formate, with high faradaic efficiency and selectivity values of 93.65 % and 95.10 %. Concurrent production of formate and high purity hydrogen was achieved in the double-electrode flow electrolyzer. This work provides guiding significance for the optimization of the catalytic coordination and the design of high-efficiency transition metal-based catalysts for electrooxidation of biomass platform molecules.
NH 2 -MIL-88B (Fe) (MOF) is a promising photocatalytic material for antitumor therapy because of its distinctive electronic structure. However, inadequate separation of photo-generated electrons and slow reaction rate in low/high-valence iron (Fe) cycles limit their clinical application. In the present study, “electronic storage station” as a ligand-to-metal charge transfer bridge bond was constructed to inhibit recombination of electron/hole under 650 nm laser irradiation. Cupric (Cu) ions and gallic acid (GA) were self-assembled into a MOF (denoted as CGMOF) to create an Fe O(GA) Cu bridge bond. GA, characterized by robust electron delocalization and abundant electron-donating groups, significantly enhances electron transfer efficiency for photodynamic therapy (PDT). CGMOF can respond to endogenous glutathione and release cuprous ions, accelerating the iron ion/ferrous ion cycles for chemodynamic therapy (CDT). The released Fe species can serve as T 2 -weighted magnetic resonance imaging contrast. Extended X-ray absorption fine structure spectra confirmed the presence of GA-containing Fe O Cu bonds in CGMOF. Furthermore, a series of photo-electrochemical tests confirmed that the formation of Fe O(GA) Cu bond prominently elevated the redox capacity and increased the carrier density of CGMOF by 2.74-fold compared to that of MOF. In addition, cinnamaldehyde was grafted onto CGMOF for tumor-responsive hydrogen peroxide self-supply. Concurrently, hyaluronic acid was surface-modified to achieve the targeted delivery of nano-photosensitizers. In summary, this study presents an innovative approach for engineering Fe-based metal–organic frameworks for synergetic PDT/CDT applications.
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