The metal−organic framework MIL-53(Al) serves as a model system in this study. Its formation mechanism in N,N-dimethylformamide (DMF) is elucidated through simultaneous FTIR and Raman spectroscopy and turbidity measurements collected under in-situ synthesis conditions in a custom-designed solvothermal reactor coupled with reaction sampling. Different synthesis steps are followed over synthesis time including a prenucleation building unit (PNBU) consisting of one linker molecule and one aluminum atom, the assembly of the PNBUs to MIL-53 nuclei in solution, the decomposition of DMF to formic acid and dimethylammonium, and finally the precipitation of the crystalline MOF phase. The rearrangement of the PNBU to form MIL-53 is identified as the rate-limiting reaction step responsible for the long induction time at low temperatures (<80 °C). MOF nucleation and particle growth is followed directly in-situ through a novel methodcomparison of the temporal evolution of the respective FTIR and Raman bands. Analysis of the particles isolated after various synthesis times indicates that MIL-53(H 2 BDC) of low crystalline long-range order is formed initially, which quickly rearranges to form more ordered, crystalline particles with DMF inside of the pores (MIL-53(DMF)). It is to be expected that the synthesis steps elucidated herein can be generalized to the solvothermal synthesis of other metal−organic framework structures from metal salts and organic acid linkers.
The fovea centralis is a closely-packed vertical array of inverted-cone photoreceptor cells located in the retina that is responsible for high acuity binocular vision. The cones are operational in well-lit environments and are responsible for trapping the impinging illumination. We present the vertical light-funnel silicon array as a light-trapping technique for photovoltaic applications that is bio-inspired by the properties of the fovea centralis. We use opto-electronic simulations to evaluate the performance of light-funnel solar cell arrays. Light-funnel arrays present ~65% absorption enhancement compared to a silicon film of identical thickness and exhibit power conversion efficiencies that are 60% higher than those of optimized nanowire arrays of the same thickness although nanowire arrays consist of more than 2.3 times the amount of silicon. We demonstrate the superior absorption of the light-funnel arrays as compared with recent advancements in the field. Fabrication of silicon light-funnel arrays using low-cost processing techniques is demonstrated.
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