Modulating metal-organic framework structure by metal ion stimulation for photocatalytic CO2 reduction reaction
A 2D Cd-based metal-organic framework with moderate coordination bond strength and adequate frame-work flexibility was obtained by self-assembly,namely {[Cd(HL)(BPY)0.5(H2O)]·2H2O}n(1),where H3L=4,4',4"-(nitri-lotris(methylene))tribenzoic acid,BPY=4,4'-bipyridine.Due to the unique structural features,under the stimulation of metal ions(Zn2+/Ni2+/Co2+),1 gradually transforms into the MOF structures dominated by the corresponding metal ions(2,3,and 4).During this process,with the exchanges of Cd2+→Zn2+,Cd2→Ni2+,and Cd22→Co2+,the free Cd2+and L3-in the channel of 1 fuse with the backbone,leading to the channel space expansion and secondary building unit(SBU)transformation to form a tunable backbone.The photocatalytic CO2 reduction results show that the new structures obtained by ion exchange do not have a great improvement in catalytic efficiency,but have a great increase in product selectivity(3 demonstrated 100％CO selectivity).CCDC:2299888,1;2299889,2;2299890,3;2299891,4.
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