Tailoring local electron density and molecular oxygen activation behavior via potassium/halogen co-tuned graphitic carbon nitride for enhanced photocatalytic activity.

Graphite carbon nitride (g-C3N4) is a promising photocatalyst,but its inadequate reactive sites, weak visible light responsiveness, and sluggish separation of photogenerated carriers hamperthe improvement of photodegradation efficiency. In this work, potassium (K) and halogen atoms co-modified g-C3N4 photocatalysts (CN-KX, X = F, Cl, Br, I) were constructed to adjust the electrical and band structure for enhanced generation of reactive oxygen species. Through an integration of theoretical calculation and experimental exploration, the doping sites of halogen atoms as well as the evolution of crystal, band, and electronic structures were investigated. The results show that a covalent bond is formed between the F atom and the C atom, substitution of the N atom occurs with a Cl atom, and doping of Br, I, or K atoms takes place at the interstitial site. CN-KX photocatalysts exhibits lower band gap, faster photogenerated electron migration, and enhanced photocatalytic activity. Specifically, the CN-KI photocatalyst exhibits the highest photodegradation efficiency because of its smaller interplanar spacing, formation of the midgap state, and adjustable local electron density. Equally, the doping of I atom not only provides a stable adsorption site for oxygen (O2) but also facilitates electron transfer, promoting the production of superoxide radicals (O2-) and contributing to the process of photodegradation.

Ag-Modified g-C3N4 Prepared by a One-Step Calcination Method for Enhanced Catalytic Efficiency and Stability.

Ag-decorated g-C3N4 (denoted as Ag/CN-x) was prepared by a one-step calcination method, and the influences of calcination time on structure, morphology, surface composition, photocatalytic performance, and catalytic reduction activity of the prepared Ag/CN-x samples were investigated. The tests showed that the Ag/CN-8 prepared through by calcination for 8 h exhibited the best photocatalytic degradation efficiency of methyl orange (98.7% within 2 h) and the best catalytic reduction property of 4-nitrophenol (100% within 70 s). Meanwhile, these Ag/CN-x samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Brunauer-Emmett-Teller (BET), X-ray photoelectron spectroscopy (XPS), UV-vis diffuse reflectance spectra (DRS), photoluminescence (PL), photocurrent response, and electrochemical impedance spectroscopy (EIS) Nyquist plots. It was found that the Ag/CN-8 prepared through calcination for 8 h had a higher specific surface area, higher dispersibility of silver nanoparticles (Ag NPs), the widest range of visible light response, and the lowest photogenerated electron-hole recombination rate. The results of the trapping experiments indicated that a superoxide radical plays a major role. Moreover, a possible mechanism of photocatalytic degradation in methyl orange and catalytic reduction 4-nitrophenol was proposed.