A simple and fast route for the synthesis of metal-organic framework（MOF） particles was presented.Cu 3（BTC） 2（HKUST-1,BTC=1,3,5-benzenetricarboxylate）,one of the most well-known MOFs,was synthesized at room temp...A simple and fast route for the synthesis of metal-organic framework（MOF） particles was presented.Cu 3（BTC） 2（HKUST-1,BTC=1,3,5-benzenetricarboxylate）,one of the most well-known MOFs,was synthesized at room temperature via coordination modulation method.By adding different modulators（monocarboxylic acids） into the reaction system,the morphologies of HKUST-1 crystals were tuned from nano spheres to micro octahedrons at room temperature without any complex equipment.X-Ray diffractions and gas sorption measurements revealed highly crystalline particles with large Brunauer-Emmett-Teller（BET） surface areas（1116―1273 m^ 2 /g） and total pore volumes（0.62―0.73 cm^ 3 /g）.The significantly small particle sizes and high capacity of gas sorption are considered advantageous for envisaged application in practical industrial process.展开更多
Even though titanium-based metal-organic frameworks(Ti-MOFs)are promising as efficient photocata-lysts,the high reactivity of titanium ions makes the synthesis and structure determination of new Ti-MOFs quite challeng...Even though titanium-based metal-organic frameworks(Ti-MOFs)are promising as efficient photocata-lysts,the high reactivity of titanium ions makes the synthesis and structure determination of new Ti-MOFs quite challenging.In this study,we propose a chelating coordination modulation(CCM)method for the synthesis of Ti-MOF single crystals by using molecules with chelating coordination groups as the modu-lator.Thanks to this method,three Ti-MOFs(FIR-117-119)have been obtained and their structures were determined by single crystal X-ray diffraction(SCXRD),validating the universality of this approach.By cap-turing the intermediate and determining its single crystal structure,the role of the modulator in the growth of Ti-MOF single crystals is clarified:the use of a chelating coordination molecule as the modu-lator and a competitive ligand slows down the reaction rate by forming Ti-modulator key intermediates,which balance the formation of Ti-MOFs and growth of single crystals.Furthermore,FIR-119 exhibits excellent photocatalytic performance under visible light due to its good light absorption ability with a narrow bandgap.These results highlight the potential of the chelating coordination modulation method in the synthesis of new photoactive Ti-MOFs and their single crystals.展开更多
基金Supported by the National Natural Science Foundation of China(Nos.21173034,20907006)
文摘A simple and fast route for the synthesis of metal-organic framework（MOF） particles was presented.Cu 3（BTC） 2（HKUST-1,BTC=1,3,5-benzenetricarboxylate）,one of the most well-known MOFs,was synthesized at room temperature via coordination modulation method.By adding different modulators（monocarboxylic acids） into the reaction system,the morphologies of HKUST-1 crystals were tuned from nano spheres to micro octahedrons at room temperature without any complex equipment.X-Ray diffractions and gas sorption measurements revealed highly crystalline particles with large Brunauer-Emmett-Teller（BET） surface areas（1116―1273 m^ 2 /g） and total pore volumes（0.62―0.73 cm^ 3 /g）.The significantly small particle sizes and high capacity of gas sorption are considered advantageous for envisaged application in practical industrial process.
基金supported by the National Natural Science Foundation of China(21935010)the Natural Science Foundation of Fujian Province(2022J01505).
文摘Even though titanium-based metal-organic frameworks(Ti-MOFs)are promising as efficient photocata-lysts,the high reactivity of titanium ions makes the synthesis and structure determination of new Ti-MOFs quite challenging.In this study,we propose a chelating coordination modulation(CCM)method for the synthesis of Ti-MOF single crystals by using molecules with chelating coordination groups as the modu-lator.Thanks to this method,three Ti-MOFs(FIR-117-119)have been obtained and their structures were determined by single crystal X-ray diffraction(SCXRD),validating the universality of this approach.By cap-turing the intermediate and determining its single crystal structure,the role of the modulator in the growth of Ti-MOF single crystals is clarified:the use of a chelating coordination molecule as the modu-lator and a competitive ligand slows down the reaction rate by forming Ti-modulator key intermediates,which balance the formation of Ti-MOFs and growth of single crystals.Furthermore,FIR-119 exhibits excellent photocatalytic performance under visible light due to its good light absorption ability with a narrow bandgap.These results highlight the potential of the chelating coordination modulation method in the synthesis of new photoactive Ti-MOFs and their single crystals.
