Microfluidic-Aerosol Hyphenated Synthesis of Metal-Organic Framework-Derived Hybrid Catalysts for CO2 Utilization.

A new and efficient technique is developed by combining the hyphenated microfluidic- and aerosol-based synthesis with the coupled differential mobility analysis for the effective and continuous synthesis and simultaneous analysis of metal-organic frameworks (MOFs)-derived hybrid nanostructured products. HKUST-1, a copper-based MOF, is chosen as the representative to fabricate Cu-based hybrid catalysts for reverse water-gas shift (RWGS) reaction, an effective route for CO2 utilization. The effect of precursor concentration and carrier selection on the properties of the resulting products, including mobility size distribution, crystallization degree, surface area, and metal dispersion are investigated, as well as the correlation between the material properties of the synthesized catalysts and their catalytic performance in RWGS reaction in terms of conversion ratio/rate, selectivity, and operational stability. The results indicate that the continuous microfluidic droplet system can successfully synthesize MOF colloids, followed by the continuous production of MOF-derived hybrid materials through the tandem aerosol spray-drying-reaction system. High catalytic activity and low initiate temperature toward RWGS (turnover frequency = 0.0074 s-1; 450 °C) are achievable. The work facilitates the production and the designed concept of relevant MOF-derived hybrid nanostructured catalysts in the continuous synthesis system and the enhancement of applications in CO2 capture and utilization.

Real-Time Quantifying Microdroplet Synthesis of Metal-Organic Framework Colloids Using Gas-Phase Electrophoresis.

A hyphenated electrospray-differential mobility analysis (ES-DMA) was developed for providing a high-resolution, real-time quantitative analysis on the metal-organic framework (MOF) colloids produced via the concept of microfluidic flow chemistry. Zeolitic imidazolate framework-8 was chosen as the representative MOF of the study. The results show that the physical size and number concentration of the MOF colloid were successfully characterized by the hyphenated ES-DMA during the microdroplet synthetic process, with 3 nm and 4% of measurement uncertainties, respectively. The effects of the synthetic temperature and the molar ratio of the organic linker to metal precursor were investigated, providing an opportunity for accurate control on the particle size (100-200 nm) of the microdroplet-synthesized MOF. The work demonstrates a powerful approach for the real-time quality assurance and material optimization in microdroplet synthesis of colloidal MOFs.