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The copper nanoparticles stabilized by nanocrystalline MIL-101 framework (Cu/nano-MIL-101) was reproducibly prepared by following double solvent method combined with liquid phase chemical reduction technique. The characterization of the resulting new material was done by using various analytical techniques including ICP-OES, P-XRD, N-2-adsorption-desorption, XPS, FE-SEM, SEM-EDX, BFTEM and HAADF-STEM; the summation of their results reveals that the formation of well-dispersed and very small sized (0.8 nm) copper nanoparticles within nanocrystalline MIL-101 framework. The catalytic performance of Cu/nano-MIL-101 in terms of activity and stability was tested in the hydrolytic dehydrogenation of methylamine borane (CH3NH2BH3), which has been considered as one of the attractive materials for the efficient chemical hydrogen storage. Cu/nano-MIL-101 catalyzes the hydrolytic dehydrogenation of methylamine borane with high activity (turnover frequency; TOF = 257 mot H-2/mol Cu x h) and conversion ( > 99%) under air at room temperature. Moreover, these nano-MIL-101 framework stabilized copper nanoparticles show great durability against to sintering and leaching, which make Cu/nano-MIL-101 reusable nanocatalyst in the hydrolytic dehydrogenation of methylamine-borane. Cu/nano-MIL-101 nanocatalyst retains 83% of its inherent activity at complete conversion even at 10th recycle in the hydrolytic dehydrogenation of methylamine borane.

Herein we show that a previously unappreciated combination of CrAuPd alloy nanoparticles and amine-grafted silica support facilitates the liberation of CO-free H-2 from dehydrogenation of formic acid with record activity in the absence of any additives at room temperature. Furthermore, their excellent catalytic stability makes them isolable and reusable heterogeneous catalysts in the formic acid dehydrogenation.

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