Aluminum porphyrin complexes are heavy-metal-free and soil-tolerant green catalysts for the copolymerization of CO2 and propylene oxide（PO）, but they suffer from relatively poor poly（propylene carbonate）（PPC） se...Aluminum porphyrin complexes are heavy-metal-free and soil-tolerant green catalysts for the copolymerization of CO2 and propylene oxide（PO）, but they suffer from relatively poor poly（propylene carbonate）（PPC） selectivity. Herein, steric hindrance porphyrin ligand was used to enhance the PPC selectivity. Typically, a bulky anthracene-like group was incorporated into the porphyrin ring to form 5,10,15,20-tetra（1,2,3,4,5,6,7,8-octahydro-1,4：5,8-dimethanoanthracen-9-yl）porphyrin, the aluminum porphyrin complex with this ligand, in combination with bis（triphenylphosphine）iminium chloride as a co-catalyst, produced completely alternate PPC. Additionally, the obtained PPC showed high regioselectivity, with a head-to-tail linkage content（HT） of 92%. Therefore, we demonstrated that introduction of bulky steric ligand into the porphyrin ring could reduce the propylene oxide homopolymerization activity leading to excellent PPC selectivity, and improve regioselectivity for the PO ring-opening during the copolymerization.展开更多
Pre-existing（multiple）shear bands were introduced into the ductile Zr56Co28Al16 and Zr65Ni10Cu15Al10bulk metallic glasses（BMGs）through the lateral-deformation,respectively.It was found that the pre-exiting shear b...Pre-existing（multiple）shear bands were introduced into the ductile Zr56Co28Al16 and Zr65Ni10Cu15Al10bulk metallic glasses（BMGs）through the lateral-deformation,respectively.It was found that the pre-exiting shear bands can further enhance the compressive plasticity of ductile BMGs.According to the serration analysis on the plastic deformation of the as-cast and the pre-deformed samples,the serration events in the stress-strain curves during deformation display a self-organized critical（SOC）behavior.Compared with the as-cast BMGs,a larger power-law scaling exponent calculated based on serrated flow behaviors becomes larger for the pre-deformed BMGs,implying that the shear banding stability of BMGs is effectively enhanced.This should be caused by the pronounced interactions of shear bands during plastic deformation for the pre-deformed BMGs.However,by introducing a large amount of multiple shear bands into the glassy matrix,it also becomes easier for shear bands to propagate along the pre-existing shear bands,leading to a lower cut-off elastic energy density for the pre-deformed BMGs.More multiple shear bands with stronger interactions for the pre-deformed BMGs could provide a larger chance to activate the shear-band cracking but less local elastic energies are remained for the subsequent crack-linking.展开更多
基金financially supported by the National Natural Science Foundation of China(No.51673193)Key Project for Frontier Research(2016)Youth Innovation Promotion Association Chinese Academy of Sciences
文摘Aluminum porphyrin complexes are heavy-metal-free and soil-tolerant green catalysts for the copolymerization of CO2 and propylene oxide（PO）, but they suffer from relatively poor poly（propylene carbonate）（PPC） selectivity. Herein, steric hindrance porphyrin ligand was used to enhance the PPC selectivity. Typically, a bulky anthracene-like group was incorporated into the porphyrin ring to form 5,10,15,20-tetra（1,2,3,4,5,6,7,8-octahydro-1,4：5,8-dimethanoanthracen-9-yl）porphyrin, the aluminum porphyrin complex with this ligand, in combination with bis（triphenylphosphine）iminium chloride as a co-catalyst, produced completely alternate PPC. Additionally, the obtained PPC showed high regioselectivity, with a head-to-tail linkage content（HT） of 92%. Therefore, we demonstrated that introduction of bulky steric ligand into the porphyrin ring could reduce the propylene oxide homopolymerization activity leading to excellent PPC selectivity, and improve regioselectivity for the PO ring-opening during the copolymerization.
基金financially supported by the National Natural Science Foundation of China(51501104,51501103,and 51371108)the Young Scholars Program of Shandong University(Weihai)
文摘Pre-existing（multiple）shear bands were introduced into the ductile Zr56Co28Al16 and Zr65Ni10Cu15Al10bulk metallic glasses（BMGs）through the lateral-deformation,respectively.It was found that the pre-exiting shear bands can further enhance the compressive plasticity of ductile BMGs.According to the serration analysis on the plastic deformation of the as-cast and the pre-deformed samples,the serration events in the stress-strain curves during deformation display a self-organized critical（SOC）behavior.Compared with the as-cast BMGs,a larger power-law scaling exponent calculated based on serrated flow behaviors becomes larger for the pre-deformed BMGs,implying that the shear banding stability of BMGs is effectively enhanced.This should be caused by the pronounced interactions of shear bands during plastic deformation for the pre-deformed BMGs.However,by introducing a large amount of multiple shear bands into the glassy matrix,it also becomes easier for shear bands to propagate along the pre-existing shear bands,leading to a lower cut-off elastic energy density for the pre-deformed BMGs.More multiple shear bands with stronger interactions for the pre-deformed BMGs could provide a larger chance to activate the shear-band cracking but less local elastic energies are remained for the subsequent crack-linking.
