Nitrogen Vacancy Engineering in Graphitic Carbon Nitride for Strong, Stable, and Wavelength Tunable Electrochemiluminescence Emissions

As an attractive electrochemiluminescence (ECL) emitter, graphitic carbon nitride (CN) still suffers from weak and unstable ECL signals for its poor conductivity and the occurrence of electrode passivation. In this study, a simple nitrogen vacancy (NV) engineering strategy has been developed for the improvement of ECL performances (intensity and stability) for the first time. In comparison to pristine CN (RSD = 51.98% for 10 continuous scan), ca. 60 times amplification in ECL intensity and 70 times enhancement in ECL efficiency for CN modified with NVs (CN-NVs) were obtained. In addition, more stable ECL emissions (RSD = 0.53%) were achieved for CN-NV-550 by thermal treatment of pristine CN in a N₂ atmosphere for another 2 h at 550 °C. The mechanism study for the vital role of NVs on the ECL of CN-NVs revealed that NVs can not only facilitate electron transfer to amplify the ECL intensity but also serve as the electron trap to inhibit electrode passivation. More interestingly, a series of CN-NVs exhibited a tunable ECL wavelength range from 470 to 516 nm with different NV contents. Moreover, their ECL spectra showed an obvious red-shift of the wavelength with their corresponding fluorescence spectra. These findings confirmed that the ECL emissions of CN-NVs were susceptible to the relevant surface states of NVs. Our work may open up a promising pathway for improving ECL performances of CN and create new possibilities for multitarget simultaneous detection based on ECL and construction of color tunable light-emitting devices.