TY - JOUR
T1 - MOF-on-MOF hybrid adsorbent for pipette-tip solid-phase extraction of organophosphate esters
AU - Pang, Long
AU - Feng, Haiyang
AU - Hu, Xingru
AU - Feng, Zhigao
AU - Kong, Ying
AU - Yuan, Weiwei
AU - Liu, Chao
N1 - Publisher Copyright:
© 2025 Elsevier B.V.
PY - 2025/8
Y1 - 2025/8
N2 - Organophosphate esters (OPEs) are ubiquitously employed as flame retardants in industries, making effective monitoring essential. This study presents a novel nano-hybrid composite adsorbent based on a MOF-on-MOF (MIL-125@ZIF-67) for the pipette-tip solid-phase extraction (PT-SPE) of nine OPEs with varying physicochemical properties. Comprehensive characterization verified the MIL-125@ZIF-67 composite formation, integrating advantageous properties of both constituent MOFs. Key extraction parameters, including extraction time, adsorbent mass, elution solvent type, and volume, were systematically optimized for maximum efficiency. When coupled with ultra-high-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS), the method demonstrated satisfactory linearity (10–2000 μg L−1), low limits of detection (0.006–0.022 ng L−1), and acceptable intra- and inter-day precisions (RSD ≤ 8.97 %; n = 6), respectively. Compared with ZIF-67, MIL-125, and MIL-125/ZIF-67 composite, the MIL-125@ZIF-67 demonstrated superior extraction performance for all nine OPEs due to its unique heterostructure along with hydrogen bonding interaction, hydrophobic interaction, π-π stacking interactions and C-H···π interactions. The developed PT-SPE-UPLC-MS/MS approach quantified OPE levels in environmental waters, demonstrating the practicability of MIL-125@ZIF-67 in sample preparation. The multifunctional potential of MOF-on-MOF nanohybrid material for sensitive screening of emerging pollutants provides a new paradigm for advanced applications in environmental monitoring and analytical nanotechnology.
AB - Organophosphate esters (OPEs) are ubiquitously employed as flame retardants in industries, making effective monitoring essential. This study presents a novel nano-hybrid composite adsorbent based on a MOF-on-MOF (MIL-125@ZIF-67) for the pipette-tip solid-phase extraction (PT-SPE) of nine OPEs with varying physicochemical properties. Comprehensive characterization verified the MIL-125@ZIF-67 composite formation, integrating advantageous properties of both constituent MOFs. Key extraction parameters, including extraction time, adsorbent mass, elution solvent type, and volume, were systematically optimized for maximum efficiency. When coupled with ultra-high-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS), the method demonstrated satisfactory linearity (10–2000 μg L−1), low limits of detection (0.006–0.022 ng L−1), and acceptable intra- and inter-day precisions (RSD ≤ 8.97 %; n = 6), respectively. Compared with ZIF-67, MIL-125, and MIL-125/ZIF-67 composite, the MIL-125@ZIF-67 demonstrated superior extraction performance for all nine OPEs due to its unique heterostructure along with hydrogen bonding interaction, hydrophobic interaction, π-π stacking interactions and C-H···π interactions. The developed PT-SPE-UPLC-MS/MS approach quantified OPE levels in environmental waters, demonstrating the practicability of MIL-125@ZIF-67 in sample preparation. The multifunctional potential of MOF-on-MOF nanohybrid material for sensitive screening of emerging pollutants provides a new paradigm for advanced applications in environmental monitoring and analytical nanotechnology.
KW - MIL-125@ZIF-67
KW - Organophosphate esters
KW - Pipette-tip solid-phase extraction
KW - Sensitive
UR - https://www.scopus.com/pages/publications/105009888524
U2 - 10.1016/j.microc.2025.114468
DO - 10.1016/j.microc.2025.114468
M3 - 文章
AN - SCOPUS:105009888524
SN - 0026-265X
VL - 215
JO - Microchemical Journal
JF - Microchemical Journal
M1 - 114468
ER -