TY - JOUR
T1 - Sulfolane as a Solvent for Nano-MOF Synthesis
T2 - Enabling Prolonged Nucleation and Controlled Growth
AU - Yang, Saiyu
AU - Yin, Zicheng
AU - Chen, Xianchun
AU - Geng, Zhide
AU - Wang, Bo
AU - Zhou, Junwen
AU - Wang, Lu
N1 - Publisher Copyright:
© 2025 American Chemical Society.
PY - 2025/6/2
Y1 - 2025/6/2
N2 - Conventional methods for synthesizing nano-sized metal-organic frameworks (nano-MOFs) often rely on additives or extra conditions, overlooking the critical role of solvents. Here, we highlight tetramethylene sulfone (TMS, or sulfolane) as a versatile solvent for nano-MOF synthesis. TMS forms strong solvation structures with metal ions and inhibits ligand deprotonation, enabling control over particle size. Using TMS, we synthesized ZIF-65 [Zn(2-nIm)2, 2-nIm = 2-nitroimidazole], ZIF-8 [Zn(2-mIm)2, 2-mIm = 2-methylimidazole], UiO-66 [Zr6O4(OH)4(BDC)6, BDC = 1,4-dicarboxybenzene acid], and MOF-199 [Cu3(BTC)2, BTC = 1,3,5-benzenetricarboxylic acid] with significantly smaller particle sizes compared to traditional solvents like ethanol (EtOH). Systematic analysis on the growth of ZIF-65 revealed distinct growth behaviors: in TMS, slower kinetics allowed the coexistence of nucleation and growth over an extended period, leading to an increase in particle number while maintaining relatively constant size; in contrast, EtOH promoted rapid growth followed by Ostwald ripening, resulting in larger particles and reduced particle number over time. By adjusting reactant concentration, metal-to-ligand ratio, and reaction temperature, we achieved facile size modulation of ZIF-65 nanoparticles. This work underscores the importance of solvents in nano-MOF synthesis and offers a robust strategy for tailoring MOF particle size, advancing applications in catalysis, biomedicine, and beyond.
AB - Conventional methods for synthesizing nano-sized metal-organic frameworks (nano-MOFs) often rely on additives or extra conditions, overlooking the critical role of solvents. Here, we highlight tetramethylene sulfone (TMS, or sulfolane) as a versatile solvent for nano-MOF synthesis. TMS forms strong solvation structures with metal ions and inhibits ligand deprotonation, enabling control over particle size. Using TMS, we synthesized ZIF-65 [Zn(2-nIm)2, 2-nIm = 2-nitroimidazole], ZIF-8 [Zn(2-mIm)2, 2-mIm = 2-methylimidazole], UiO-66 [Zr6O4(OH)4(BDC)6, BDC = 1,4-dicarboxybenzene acid], and MOF-199 [Cu3(BTC)2, BTC = 1,3,5-benzenetricarboxylic acid] with significantly smaller particle sizes compared to traditional solvents like ethanol (EtOH). Systematic analysis on the growth of ZIF-65 revealed distinct growth behaviors: in TMS, slower kinetics allowed the coexistence of nucleation and growth over an extended period, leading to an increase in particle number while maintaining relatively constant size; in contrast, EtOH promoted rapid growth followed by Ostwald ripening, resulting in larger particles and reduced particle number over time. By adjusting reactant concentration, metal-to-ligand ratio, and reaction temperature, we achieved facile size modulation of ZIF-65 nanoparticles. This work underscores the importance of solvents in nano-MOF synthesis and offers a robust strategy for tailoring MOF particle size, advancing applications in catalysis, biomedicine, and beyond.
UR - http://www.scopus.com/inward/record.url?scp=105005186234&partnerID=8YFLogxK
U2 - 10.1021/acs.inorgchem.5c01354
DO - 10.1021/acs.inorgchem.5c01354
M3 - Article
AN - SCOPUS:105005186234
SN - 0020-1669
VL - 64
SP - 10645
EP - 10652
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 21
ER -