Seed‐assisted low alkalinity gel system was developed to explore the organic‐free synthesis of MORzeolite.MOR nanoassemblies with Si/Al ratio(SAR)up to 9.4 and high solid yield(84–94%)weresuccessfully obtained unde...Seed‐assisted low alkalinity gel system was developed to explore the organic‐free synthesis of MORzeolite.MOR nanoassemblies with Si/Al ratio(SAR)up to 9.4 and high solid yield(84–94%)weresuccessfully obtained under controlled low alkalinity conditions.Characterization results demonstratethat the acid strength increases in parallel with the SAR,while the total acid amount and theproton distribution in the main channels and the side pockets are similar for the samples.The protondistribution in the H‐MOR is not straightforwardly related to the Na+distribution in theas‐synthesized MOR,implying the transfer of the protons among the oxygen sites of framework Tatom.Relative to low‐silica samples I‐5.3 and I‐7.4,sample I‐9.4 displays the best mass transferperformance and accessibility of the acid sites by pyridine due to its relatively low Al density andmild dealumination degree.Correspondingly,sample I‐9.4(pyridine‐modified catalyst)shows thebest activity with ca.100%selectivity of methyl acetate(MAc)in the DME carbonylation reaction.The high steady MAc yield(6.8 mmol/g/h)over sample I‐9.4 suggests the promising application ofMOR nanoassemblies synthesized by this economical organic‐free strategy.展开更多
Converting CO_(2)into carbonaceous fuels via photocatalysis represents an appealing strategy to simultaneously alleviate the energy crisis and associated environmental problems,yet designing with high photoreduction a...Converting CO_(2)into carbonaceous fuels via photocatalysis represents an appealing strategy to simultaneously alleviate the energy crisis and associated environmental problems,yet designing with high photoreduction activity catalysts remains a compelling challenge.Here,combining the merits of highly porous structure and maximum atomic efficiency,we rationally constructed covalent triazine-based frameworks(CTFs)anchoring copper single atoms(Cu-SA/CTF)photocatalysts for efficient CO_(2)conversion.The Cu single atoms were visualized by high-angle annular dark-field scanning transmission electron microscopy(HAADF-STEM)images and coordination structure of Cu-N-C2 sites was revealed by extended X-ray absorption fine structure(EXAFS)analyses.The as-prepared Cu-SA/CTF photocatalysts exhibited superior photocatalytic CO_(2)conversion to CH4 performance associated with a high selectivity of 98.31%.Significantly,the introduction of Cu single atoms endowed the CuSA/CTF catalysts with increased CO_(2)adsorption capacity,strengthened visible light responsive ability,and improved the photogenerated carriers separation efficiency,thus enhancing the photocatalytic activity.This work provides useful guidelines for designing robust visible light responsive photoreduction CO_(2)catalysts on the atomic scale.展开更多
文摘Seed‐assisted low alkalinity gel system was developed to explore the organic‐free synthesis of MORzeolite.MOR nanoassemblies with Si/Al ratio(SAR)up to 9.4 and high solid yield(84–94%)weresuccessfully obtained under controlled low alkalinity conditions.Characterization results demonstratethat the acid strength increases in parallel with the SAR,while the total acid amount and theproton distribution in the main channels and the side pockets are similar for the samples.The protondistribution in the H‐MOR is not straightforwardly related to the Na+distribution in theas‐synthesized MOR,implying the transfer of the protons among the oxygen sites of framework Tatom.Relative to low‐silica samples I‐5.3 and I‐7.4,sample I‐9.4 displays the best mass transferperformance and accessibility of the acid sites by pyridine due to its relatively low Al density andmild dealumination degree.Correspondingly,sample I‐9.4(pyridine‐modified catalyst)shows thebest activity with ca.100%selectivity of methyl acetate(MAc)in the DME carbonylation reaction.The high steady MAc yield(6.8 mmol/g/h)over sample I‐9.4 suggests the promising application ofMOR nanoassemblies synthesized by this economical organic‐free strategy.
基金the National Natural Science Foundation of China(Nos.51672047,21707173,and 21701168)Dalian high level talent innovation project(No.2019RQ063)+2 种基金the National Natural Science Foundation of Fujian Province(Nos.2019J01648 and 2019J01226)Open project Foundation of State Key Laboratory of Structural Chemistry,Fujian Institute of Research on the Structure of Matter,Chinese Academy of Sciences(No.20200021)the Youth Talent Support Program of Fujian Province(No.00387077).
文摘Converting CO_(2)into carbonaceous fuels via photocatalysis represents an appealing strategy to simultaneously alleviate the energy crisis and associated environmental problems,yet designing with high photoreduction activity catalysts remains a compelling challenge.Here,combining the merits of highly porous structure and maximum atomic efficiency,we rationally constructed covalent triazine-based frameworks(CTFs)anchoring copper single atoms(Cu-SA/CTF)photocatalysts for efficient CO_(2)conversion.The Cu single atoms were visualized by high-angle annular dark-field scanning transmission electron microscopy(HAADF-STEM)images and coordination structure of Cu-N-C2 sites was revealed by extended X-ray absorption fine structure(EXAFS)analyses.The as-prepared Cu-SA/CTF photocatalysts exhibited superior photocatalytic CO_(2)conversion to CH4 performance associated with a high selectivity of 98.31%.Significantly,the introduction of Cu single atoms endowed the CuSA/CTF catalysts with increased CO_(2)adsorption capacity,strengthened visible light responsive ability,and improved the photogenerated carriers separation efficiency,thus enhancing the photocatalytic activity.This work provides useful guidelines for designing robust visible light responsive photoreduction CO_(2)catalysts on the atomic scale.
