Brønsted Acid-Functionalized Ionic Co(II) Framework: A Tailored Vessel for Electrocatalytic Oxygen Evolution and Size-Exclusive Optical Speciation of Biothiols.
ACS Appl Mater Interfaces
; 14(26): 29773-29787, 2022 Jul 06.
Article
de En
| MEDLINE
| ID: mdl-35728309
ABSTRACT
Metal-organic frameworks (MOFs) not only combine globally demanded renewable energy generation and environmental remediation onto a single platform but also rationalize structure-performance synergies to devise smarter materials with remarkable performance. The robust and non-interpenetrated cationic MOF exemplifies a unique bifunctional scaffold for the efficient electrochemical oxygen evolution reaction (OER) and ultrasensitive monitoring of biohazards. The microporous framework containing Brønsted acid-functionalized [Co2(µ2-OH)(CO2)2] secondary building units (SBUs) exhibits remarkable OER performance in 1 M KOH, requiring 410 mV overpotential to obtain 10 mA cm-2 anodic current density, and a low Tafel slope of 55 mV/dec with 93.1% Faradaic efficiency. Apart from the high turnover frequency and electrochemically assessable surface area, steady OER performance over 500 cycles under potentiodynamic and potentiostatic conditions result in long-term catalyst durability. The highly emissive attribute from nitrogen-rich fluorescent struts benefits the MOF in recyclable and selective fluoro-detection of three biothiols (l-cysteine, homocysteine, and glutathione) in water with a fast response time. In addition to colorimetric monitoring in the solid and solution phases, control experiments validate size-exclusive biothiol speciation through molecular-dimension-mediated pore diffusion. The role of SBUs in the OER mechanism is detailed from density functional theory-derived free energy analysis, which also validates the importance of accessible N-sites in sensing via portraying framework-analyte supramolecular interactions.
Mots clés
Texte intégral:
1
Collection:
01-internacional
Base de données:
MEDLINE
Sujet principal:
Oxygène
/
Réseaux organométalliques
Langue:
En
Journal:
ACS Appl Mater Interfaces
Sujet du journal:
BIOTECNOLOGIA
/
ENGENHARIA BIOMEDICA
Année:
2022
Type de document:
Article
Pays d'affiliation:
Inde