Covalent organic frameworks （COFs）, established as an emerging class of crystalline porous polymers with high surface area, structural diversity, and esignability, attract much interest and exhibit potential applica...Covalent organic frameworks （COFs）, established as an emerging class of crystalline porous polymers with high surface area, structural diversity, and esignability, attract much interest and exhibit potential applications in catalysis. In this review, we summarize the use of COFs as a versatile platform to develop heterogeneous catalysts for a variety of chemical reactions. Catalytic COFs are categorized in accordance with the types of active sites, involving single functional active sites, bifunctional active sites, and metal nanoparticles （NPs） embedded in pores. Special emphasis is placed on the deliberate or incidental synthesis strategies, the stability, the heterogeneity, and the shape/size selectivity for COF catalysis. Moreover, a description of the application of COFs as photocatalysts and electrocatalysts is presented. Finally, the prospects of COFs in catalysis and remaining issues in this field are indicated.展开更多
Unveiling the pore-size performance of metal organic frameworks(MOFs)is imperative for controllable design of sophisticated catalysts.Herein,UiO-66 with distinct macropores and mesopores were intentionally created and...Unveiling the pore-size performance of metal organic frameworks(MOFs)is imperative for controllable design of sophisticated catalysts.Herein,UiO-66 with distinct macropores and mesopores were intentionally created and served as substrates to create advanced CdS/UiO-66 catalysts.The pore size impacted the spatial distribution of CdS nanoparticles(NPs):CdS tended to deposit on the external surface of mesoporous UiO-66,but spontaneously penetrated into the large cavity of macroporous UiO-66 nanocage.Normalized to unit amount of CdS,the photocatalytic reaction constant of macroporous CdS/UiO-66 over 4-nitroaniline reduction was~3 folds of that of mesoporous counterpart,and outperformed many other reported state-of-art CdS-based catalysts.A confinement effect of CdS NPs within UiO-66 cage could respond for its high activity,which could shorten the electron-transport distance of NPs-MOFs-reactant,and protect the active CdS NPs from photocorrosion.The finding here provides a straightforward paradigm and mechanism to rationally fabricate advance NPs/MOFs for diverse applications.展开更多
A new flexible 3D porous metal-organic framework （MOF） with 1D open nanotube, [Co2（/zs-CTAl）（dpe）（H20）2]n-6n（H20） （1） （CTA = cyclohexane-1,2,4,5-tetracarboxylic acid, dpe = 1,2-di（4-pyridyl） ethylene） ...A new flexible 3D porous metal-organic framework （MOF） with 1D open nanotube, [Co2（/zs-CTAl）（dpe）（H20）2]n-6n（H20） （1） （CTA = cyclohexane-1,2,4,5-tetracarboxylic acid, dpe = 1,2-di（4-pyridyl） ethylene） has been prepared and structurally character- ized. Meanwhile, each 1D nanotubes filled with 1D water chain with dimension of 13.711 ~ 12.275/~2. Compound 1 represents a new example that collapse/deform upon dehydration/hydration and shows adsorb 1-120 selectively over organic solvents.展开更多
基金supported by the National Natural Science Foundation of China (21473196, 21406215)the State Key Laboratory of Fine Chemicals, Dalian University of Technology (KF1415)the funding from Dalian Institute of Chemical Physics, Chinese Academy of Sciences (DICP_M201401)~~
文摘Covalent organic frameworks （COFs）, established as an emerging class of crystalline porous polymers with high surface area, structural diversity, and esignability, attract much interest and exhibit potential applications in catalysis. In this review, we summarize the use of COFs as a versatile platform to develop heterogeneous catalysts for a variety of chemical reactions. Catalytic COFs are categorized in accordance with the types of active sites, involving single functional active sites, bifunctional active sites, and metal nanoparticles （NPs） embedded in pores. Special emphasis is placed on the deliberate or incidental synthesis strategies, the stability, the heterogeneity, and the shape/size selectivity for COF catalysis. Moreover, a description of the application of COFs as photocatalysts and electrocatalysts is presented. Finally, the prospects of COFs in catalysis and remaining issues in this field are indicated.
文摘Unveiling the pore-size performance of metal organic frameworks(MOFs)is imperative for controllable design of sophisticated catalysts.Herein,UiO-66 with distinct macropores and mesopores were intentionally created and served as substrates to create advanced CdS/UiO-66 catalysts.The pore size impacted the spatial distribution of CdS nanoparticles(NPs):CdS tended to deposit on the external surface of mesoporous UiO-66,but spontaneously penetrated into the large cavity of macroporous UiO-66 nanocage.Normalized to unit amount of CdS,the photocatalytic reaction constant of macroporous CdS/UiO-66 over 4-nitroaniline reduction was~3 folds of that of mesoporous counterpart,and outperformed many other reported state-of-art CdS-based catalysts.A confinement effect of CdS NPs within UiO-66 cage could respond for its high activity,which could shorten the electron-transport distance of NPs-MOFs-reactant,and protect the active CdS NPs from photocorrosion.The finding here provides a straightforward paradigm and mechanism to rationally fabricate advance NPs/MOFs for diverse applications.
基金supported by the National Natural Science Foundation of China (20771090)State Key Program of National Natural Science Foundation of China (20931005)+1 种基金Major Research Plan of National Natural Science Foundation of China (91022004)Specialized Research Found for the Doctoral Program of Higher Education (20096101110005)
文摘A new flexible 3D porous metal-organic framework （MOF） with 1D open nanotube, [Co2（/zs-CTAl）（dpe）（H20）2]n-6n（H20） （1） （CTA = cyclohexane-1,2,4,5-tetracarboxylic acid, dpe = 1,2-di（4-pyridyl） ethylene） has been prepared and structurally character- ized. Meanwhile, each 1D nanotubes filled with 1D water chain with dimension of 13.711 ~ 12.275/~2. Compound 1 represents a new example that collapse/deform upon dehydration/hydration and shows adsorb 1-120 selectively over organic solvents.
