Tailoring the Band Gap of ZIF-8 via Cobalt Doping for Enhanced Visible-Light Photocatalysis and Hydrogen Evolution

Abstract

Metal–organic frameworks (MOFs), particularly Zeolitic Imidazolate Framework-8 (ZIF-8), are promising photocatalysts; however, their practical application is limited by a wide band gap (~3.85 eV), which restricts light absorption mainly to the ultraviolet region. This limitation was addressed by synthesizing a series of cobalt-doped ZIF-8 materials, Co(x)ZIF-8 (x = 0, 2.5, 5, 7.5, and 10 wt%), using a cost-effective aqueous synthesis route. Structural and compositional analyses using X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR), and energy-dispersive X-ray spectroscopy (EDS) confirmed the formation of phase-pure ZIF-8 topology, with no significant change in nanoparticle morphology upon the partial substitution of Zn2+ by Co2+ ions within the framework. UV–Vis diffuse reflectance and Tauc plot analysis revealed a systematic and substantial reduction in the optical band gap (Eg) with increasing Co content, indicating enhanced visible-light absorption capability. All Co(x)ZIF-8 samples exhibited superior photocatalytic activity compared to pristine ZIF-8 under light irradiation. Among them, Co(2.5)ZIF-8 displayed the highest apparent reaction rate constant for pollutant degradation, while Co(5)ZIF-8 achieved the highest overall degradation efficiency (~87%) after 40 min. The enhanced photocatalytic performance is attributed to the synergistic effects of band-gap narrowing and the presence of Co2+ ions, which act as effective charge-trapping centers and suppress electron–hole recombination. Electrochemical measurements further demonstrated that Co(5)ZIF-8 exhibits the highest current density (most negative J) at large negative potentials (e.g., J ≈ −0.105 A cm−2 at E = −2.0 V), indicating superior intrinsic catalytic activity. These findings highlight cobalt-doped ZIF-8 as a highly tunable and efficient photocatalyst with strong potential for environmental remediation applications.