TY - JOUR
T1 - Hf-Based MOF for Rapid and Selective Sensing of a Nerve Agent Simulant and an Aminophenol
T2 - Insights from Experiments and Theory
AU - Ghosh, Subhrajyoti
AU - Lipin, Raju
AU - Ngoipala, Apinya
AU - Ruser, Niklas
AU - Venturi, Diletta Morelli
AU - Rana, Abhijeet
AU - Vandichel, Matthias
AU - Biswas, Shyam
N1 - Publisher Copyright:
© 2023 American Chemical Society.
PY - 2023/9/11
Y1 - 2023/9/11
N2 - The metal-organic framework (MOF) Hf-DUT-52 was prepared with diamino functionality by the solvothermal method. This material displayed fluorometric sensing ability toward a nerve agent simulant (diethyl chlorophosphate (DCP)) and 3-diethylaminophenol (3-DEAP). It is the first-ever reported fluorescent MOF sensor for DCP and 3-DEAP. Apart from a fast response (<5 s), the sensor had a very low detection limit for both DCP and DEAP (limit of detection (LOD) values for DCP and 3-DEAP sensing were 9 and 125 nM, respectively). The obtained detection limit is the second lowest among all of the reported optical sensors for DCP. The sensor also displayed its capability to identify the presence of trace amount of DCP in various natural water specimens with good selectivity. Moreover, MOF@cotton composites were developed for visual, on-site, nanomolar-level detection of both targeted analytes. Furthermore, a MOF@PVA thin film was fabricated and successfully utilized for the detection of highly volatile and deadly poisonous DCP in the vapor phase. The sensor was also recyclable for up to five cycles without losing appreciable efficiency. Density functional theory (DFT)-based periodic and cluster calculations were performed to shed light on the sensing ability of the MOF by studying the interactions of DCP and DEAP with the MOF. Our theoretical results reveal the importance of linker defects and water chemisorption on the adsorption/complexation of the analytes at uncoordinated Hf sites.
AB - The metal-organic framework (MOF) Hf-DUT-52 was prepared with diamino functionality by the solvothermal method. This material displayed fluorometric sensing ability toward a nerve agent simulant (diethyl chlorophosphate (DCP)) and 3-diethylaminophenol (3-DEAP). It is the first-ever reported fluorescent MOF sensor for DCP and 3-DEAP. Apart from a fast response (<5 s), the sensor had a very low detection limit for both DCP and DEAP (limit of detection (LOD) values for DCP and 3-DEAP sensing were 9 and 125 nM, respectively). The obtained detection limit is the second lowest among all of the reported optical sensors for DCP. The sensor also displayed its capability to identify the presence of trace amount of DCP in various natural water specimens with good selectivity. Moreover, MOF@cotton composites were developed for visual, on-site, nanomolar-level detection of both targeted analytes. Furthermore, a MOF@PVA thin film was fabricated and successfully utilized for the detection of highly volatile and deadly poisonous DCP in the vapor phase. The sensor was also recyclable for up to five cycles without losing appreciable efficiency. Density functional theory (DFT)-based periodic and cluster calculations were performed to shed light on the sensing ability of the MOF by studying the interactions of DCP and DEAP with the MOF. Our theoretical results reveal the importance of linker defects and water chemisorption on the adsorption/complexation of the analytes at uncoordinated Hf sites.
UR - http://www.scopus.com/inward/record.url?scp=85170582310&partnerID=8YFLogxK
U2 - 10.1021/acs.inorgchem.3c01777
DO - 10.1021/acs.inorgchem.3c01777
M3 - Article
C2 - 37640009
AN - SCOPUS:85170582310
SN - 0020-1669
VL - 62
SP - 14632
EP - 14646
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 36
ER -