Based on quantum properties, electron spin sensors have high sensitivity and can be widely used to probe various physicochemical properties, such as electric field, magnetic field, molecular or protein dynamics, and nuclear or other particles. These unique advantages and potential application scenarios make spin-based sensors a hot research direction at present. Sc3C2@C80 has a highly stable electron spin protected by a carbon cage, which is suitable for gas adsorption detection within porous materials. Py-COF is a recently emerged porous organic framework material with unique adsorption properties, which was prepared using a self-condensing building block with a formyl group and an amino group. prepared with a theoretical pore size of 1.38 nm. Thus, a metallofullerene Sc3C2@C80 unit (~0.8 nm in size) can enter one of the nanopores of Py-COF.
A nanospin sensor based on metal fullerene was developed by Taishan Wang, a researcher at the Institute of Chemistry, Chinese Academy of Sciences, for detecting gas adsorption within a porous organic framework. The paramagnetic metal fullerene, Sc3C2@C80, was embedded in the nanopores of a pyrene-based covalent organic framework (Py-COF). The adsorbed N2、CO、CH4、CO2、C3H6 and C3H8 within the Py-COF embedded with the Sc3C2@C80 spin probe were recorded using the EPR technique ( CIQTEK EPR200-Plus).It was shown that the EPR signals of the embedded Sc3C2@C80 regularly correlated with the gas adsorption properties of the Py-COF. The results of the study were published in Nature Communications under the title "Embedded nano spin sensor for in situ probing of gas adsorption inside porous organic frameworks".
Probing gas adsorption properties of Py-COF using molecular spin of Sc3C2@C8
In the study, the authors used a metallofullerene with paramagnetic properties, Sc3C2@C80 (~0.8 nm in size), as a spin probe embedded into one nanopore of pyrene-based COF (Py-COF) to detect gas adsorption within Py-COF. Then, the adsorption properties of Py-COF for N2、CO、CH4、CO2、C3H6 and C3H8 gases were investigated by recording the embedded Sc3C2@C80 EPR signals. It is shown that the EPR signals of Sc3C2@C80 regularly follow the gas adsorption properties of Py-COF. And unlike conventional adsorption isotherm measurements, this implantable nanospin sensor can detect gas adsorption and desorption by in situ real-time monitoring. The proposed nanospin sensor was also used to probe the gas adsorption properties of metal-organic framework (MOF-177), demonstrating its versatility.
Relationship between gas adsorption properties and EPR signals
Effect of gas pressure on EPR signal
EPR signal line width analysis
Spin-based sensors have attracted considerable attention owing to their high sensitivities. Herein, we developed a metallofullerene-based nano spin sensor to probe gas adsorption within porous organic frameworks. For this, spin-active metallofullerene, Sc3C2@C80, was selected and embedded into a nanopore of a pyrene-based covalent organic framework (Py-COF). Electron paramagnetic resonance (EPR) spectroscopy recorded the EPR signals of Sc3C2@C80 within Py-COF after adsorbing N2, CO, CH4, CO2, C3H6, and C3H8. Results indicated that the regularly changing EPR signals of embedded Sc3C2@C80 were associated with the gas adsorption performance of Py-COF. In contrast to traditional adsorption isotherm measurements, this implantable nano spin sensor could probe gas adsorption and desorption with in situ, real-time monitoring. The proposed nano spin sensor was also employed to probe the gas adsorption performance of a metal–organic framework (MOF-177), demonstrating its versatility. The nano spin sensor is thus applicable for quantum sensing and precision measurements.