Despite the recent progress on controllable synthesis of alkynyl-protected Au nanoclusters,the effective synthetic means are very limited and the cluster formation process still remains puzzling.Here,we develop a nove...Despite the recent progress on controllable synthesis of alkynyl-protected Au nanoclusters,the effective synthetic means are very limited and the cluster formation process still remains puzzling.Here,we develop a novel synchronous nucleation and passivation strategy to fabricate Au36(PA)24(PA=phenylacetylenyl) nanoclusters with high yield.In Au36(PA)24formation process,Au22(PA)18as key intermediate was identified.Meanwhile,Au22(PA)18can be synthesized under a low amount of reductant,and by employing more reductants,Au22(PA)18can turn into Au36(PA)24eventually.Moreover,the structure evolution from Au22(PA)18to Au36(PA)24is proposed,where four Au13cuboctahedra can yield one Au28kernel.Finally,the ratiocination is verified by the good accordance between the predicted intermediate/product ratio and the experimental value.This study not only offers a novel synthetic strategy,but also sheds light on understanding the structural evolution process of alkynyl-protected Au nanoclusters at atomic level.展开更多
It remains elusive to realize the distinct catalysis of isomeric catalysts because it becomes challenging to identify structural isomers in the polydisperse nanoparticles.Herein we investigate catalysis of two geometr...It remains elusive to realize the distinct catalysis of isomeric catalysts because it becomes challenging to identify structural isomers in the polydisperse nanoparticles.Herein we investigate catalysis of two geometric isomers for 36-gold-atom nanoclusters with different Au cores arrangements but the same thiolate ligands,thereby providing access to isomer catalysts readily participate in a desired reaction.Compared to the Au_(36)(SR)_(24)with a one-dimensional(1D)layout of Au4 tetrahedral units,the Au_(36)(SR)_(24)with a two-dimensional(2D)layout of Au4 tetrahedral units is more effective for the intramolecular hydroamination of alkyne.Our study suggests that the exposed Au sties of the two Au_(36)(SR)_(24)catalysts favor different reaction intermediates and pathways.The intramolecular H transfer leads to intermediates with the C-N and with C=N for the 1D and 2D Au_(36)(SR)_(24)respectively,and hence the different on-site and off-site pathways for the successive reaction steps account for the different performances of the two Au_(36)(SR)_(24)catalysts.展开更多
基金This work was supported by Guangdong Natural Science Funds for Distinguished Young Scholars(2015A030306006)Guangzhou Science and Technology Plan Projects(201804010323)+1 种基金the fundamental funds for central universities(SCUT,2018ZD022)the National Natural Science Foundation of China(21971070).
文摘Despite the recent progress on controllable synthesis of alkynyl-protected Au nanoclusters,the effective synthetic means are very limited and the cluster formation process still remains puzzling.Here,we develop a novel synchronous nucleation and passivation strategy to fabricate Au36(PA)24(PA=phenylacetylenyl) nanoclusters with high yield.In Au36(PA)24formation process,Au22(PA)18as key intermediate was identified.Meanwhile,Au22(PA)18can be synthesized under a low amount of reductant,and by employing more reductants,Au22(PA)18can turn into Au36(PA)24eventually.Moreover,the structure evolution from Au22(PA)18to Au36(PA)24is proposed,where four Au13cuboctahedra can yield one Au28kernel.Finally,the ratiocination is verified by the good accordance between the predicted intermediate/product ratio and the experimental value.This study not only offers a novel synthetic strategy,but also sheds light on understanding the structural evolution process of alkynyl-protected Au nanoclusters at atomic level.
基金supports from Fundamental Research Funds for the Central Universities,Programs for high-level entrepreneurial and innovative talents introduction of Jiangsu Province,and Scientific and Technological Innovation Foundation of Shunde Graduate School of USTB(No.BK19BE024).
文摘It remains elusive to realize the distinct catalysis of isomeric catalysts because it becomes challenging to identify structural isomers in the polydisperse nanoparticles.Herein we investigate catalysis of two geometric isomers for 36-gold-atom nanoclusters with different Au cores arrangements but the same thiolate ligands,thereby providing access to isomer catalysts readily participate in a desired reaction.Compared to the Au_(36)(SR)_(24)with a one-dimensional(1D)layout of Au4 tetrahedral units,the Au_(36)(SR)_(24)with a two-dimensional(2D)layout of Au4 tetrahedral units is more effective for the intramolecular hydroamination of alkyne.Our study suggests that the exposed Au sties of the two Au_(36)(SR)_(24)catalysts favor different reaction intermediates and pathways.The intramolecular H transfer leads to intermediates with the C-N and with C=N for the 1D and 2D Au_(36)(SR)_(24)respectively,and hence the different on-site and off-site pathways for the successive reaction steps account for the different performances of the two Au_(36)(SR)_(24)catalysts.
