摘要
Although the selective hydrogenation ofα,β-unsaturated aldehyde to unsaturated alcohol(UOL)is an extremely important transformation,it is still a great challenge to achieve high selectivity to UOL due to thermodynamic favoring of the C=C hydrogenation over the C=O hydrogenation.Herein,we report that iridium nanoclusters(Ir NCs)confined within hollow MIL-101(Fe)expresses satisfied reaction activity(93.9%)and high selectivity(96.2%)for the hydrogenation of cinnamaldehyde(CAL)to cinnamyl alcohol(COL)under 1 bar H;atmosphere and room temperature.The unique hollow structure of MIL-101(Fe)benefits for the fast transport of reactant,ensuring the comparable reaction activity and better recyclability of Ir@MIL-101(Fe)than the counterparts which Ir NCs were on the surface of MIL-101(Fe).Furthermore,The X-ray photoelectron spectroscopy data indicates the electropositive Ir NCs,owing to the electron transfer from Ir to MIL-101(Fe),can interact with oxygen lone pairs,and Fourier transform infrared spectrum shows the Lewis acid sites in MIL-101(Fe)can strongly interact with C=O bond,which contributes to a high selectivity for COL.This work suggests the considerable potential of synergetic effect between hollow MOFs and metal nanoclusters for selective hydrogenation reactions.
基金
supported by National Key R&D Program of China(No.2018YFA0108300)
the Overseas High-level Talents Plan of China and Guangdong Province
the 100 Talents Plan Foundation of Sun Yat-sen University
the Fundamental Research Funds for the Central Universities
the Program for Guangdong Introducing Innovative and Entrepreneurial Teams(No.2017ZT07C069)
the NSFC Projects(Nos.21905315 and 22075321)。
