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
Single-helical or double-helical structures are common in living organisms.Helical assembly has been found in the artificial nanoparticles,but how they do so remains poorly understood.Here,we exploit atomically precis...Single-helical or double-helical structures are common in living organisms.Helical assembly has been found in the artificial nanoparticles,but how they do so remains poorly understood.Here,we exploit atomically precise Au_(6)Cu_(6)bimetallic nanoparticles(or called nanoclusters)as building blocks to construct a single-helical Au_(12)Cu_(12)superstructure in an operative path,thereby providing access to currently elusive mechanistic pathways.We propose that the thermodynamically viable linearto-bent process at a couple of Au_(6)Cu_(6)nanoclusters imparted by the organic ligands seems to be critical for the helical-nanostructured arrangement of Au_(12)Cu_(12).This study could help to offer a new design rule for the exquisitely helical structure assembled from the artificial nanoparticles.展开更多
The optimization of catalysts for CO_(2) hydrogenation that is carried out in a traditional fixed-bed reactor predominantly focuses on pursuing various nanoparticles at the nanoscale.Much less is known about how heter...The optimization of catalysts for CO_(2) hydrogenation that is carried out in a traditional fixed-bed reactor predominantly focuses on pursuing various nanoparticles at the nanoscale.Much less is known about how heterogeneous catalysts can be exploited to precisely control the reaction pathways of CO_(2) conversion at the atomic level.展开更多
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.
基金National Natural Science Foundation of China,Grant/Award Number:22101128the Fundamental Research Funds for the Central Universities+1 种基金Foshan Science and Technology Innovation Project,Grant/Award Number:2018IT100363Programs for high-level entrepreneurial and innovative talents introduction of Jiangsu Province。
文摘Single-helical or double-helical structures are common in living organisms.Helical assembly has been found in the artificial nanoparticles,but how they do so remains poorly understood.Here,we exploit atomically precise Au_(6)Cu_(6)bimetallic nanoparticles(or called nanoclusters)as building blocks to construct a single-helical Au_(12)Cu_(12)superstructure in an operative path,thereby providing access to currently elusive mechanistic pathways.We propose that the thermodynamically viable linearto-bent process at a couple of Au_(6)Cu_(6)nanoclusters imparted by the organic ligands seems to be critical for the helical-nanostructured arrangement of Au_(12)Cu_(12).This study could help to offer a new design rule for the exquisitely helical structure assembled from the artificial nanoparticles.
基金supported by the National Natural Science Foundation of China(nos.21773109 and 91845104)the Scientific and Technological Innovation Foundation of Shunde Graduate School,USTB(no.BK19BE024)the Introduction Program of High-Level Entrepreneurial and Innovative Talents in Jiangsu Province.
文摘The optimization of catalysts for CO_(2) hydrogenation that is carried out in a traditional fixed-bed reactor predominantly focuses on pursuing various nanoparticles at the nanoscale.Much less is known about how heterogeneous catalysts can be exploited to precisely control the reaction pathways of CO_(2) conversion at the atomic level.
