Environmental application of chlorine-doped graphitic carbon nitride: Continuous solar-driven photocatalytic production of hydrogen peroxide.

Solar-driven photocatalytic generation of H2O2 over metal-free catalysts is a sustainable approach for value-added chemical production. Here, we synthesized chlorine-doped graphitic carbon nitride (Cl-doped g-C3N4) through a solvothermal method to effectively produce H2O2 with a rate of 1.19 ± 0.06 µM min-1 under visible light irradiation, which was improved by 104 times compared to pristine g-C3N4. Continuous net production of H2O2 was realized at a rate of 2.78 ± 0.10 µM min-1 up to 54 h with isopropanol as the hole scavenger, whereas H2O2 production was only sustained for ~ 6 h without scavengers. Both molecular simulations and advanced spectroscopic characterizations elucidated that the Cl dopant increased the charge transfer rate, decreased the bandgap, and reduced the activation energy of the rate-limiting step of O2 reduction, all of which favored H2O2 production. This work implemented a novel metal-free photocatalyst for sustainable H2O2 production and elucidated the mechanism for promoting H2O2 production that can guide future photoreactive nanomaterial design.

3D printed photoreactor with immobilized graphitic carbon nitride: A sustainable platform for solar water purification.

Solar-energy-enabled photocatalysis is promising for sustainable water purification. However, photoreactor design, especially immobilizing nano-sized photocatalysts, remains a major barrier preventing industrial-scale application of photocatalysis. In this study, we immobilized photocatalytic graphitic carbon nitride on chitosan to produce g-C3N4/chitosan hydrogel beads (GCHBs), and evaluated GCHB photoreactivity for degrading phenol and emerging persistent micropollutants in a 3D printed compound parabolic collector (CPC) reactor. The CPC photocatalytic system showed comparable performance with slurry reactors for sulfamethoxazole and carbamazepine degradation under simulated sunlight, and it maintained the performance for contaminant removal in real water samples collected from water/wastewater treatment plants or under outdoor sunlight irradiation. Global drinking water production was estimated for the CPC system, and it holds promise for small-scale sustainable water treatment, including, but not limited to, the production of high-quality potable water for single houses, small communities, rural areas, and areas impacted by natural disasters in both developed and developing countries.

Photocatalytic degradation of trihalomethanes and haloacetonitriles on graphitic carbon nitride under visible light irradiation.

Trihalomethanes (THMs) and haloacetonitriles (HANs), most common disinfection by-products in drinking water, pose adverse environmental impacts and potential risks to human health. There is a pressing need to develop innovative, economically feasible, and environmentally benign processes to control these persistent contaminants. In this paper, visible-light-responsive graphitic carbon nitride (g-C3N4) samples were synthesized to degrade the THMs and HANs and the photocatalytic degradation mechanism was explored. The results indicated that a carbon-doped g-C3N4 with an optimum dopant content (MCB0.07) displayed the best photocatalytic activity for the total trihalomethanes (TTHM) and total haloacetonitriles (THAN), with the reaction rate constant of 11.6 and 10.4 (10-3 min-1), respectively. MCB0.07 demonstrated a high THMs and HANs removal efficiency under visible light irradiation and could be reused. According to scavenger tests of the selected reactive species and X-ray photoelectron spectroscopy, holes play a dominant role for both THMs and HANs degradation on the MCB0.07. The degradation of HANs by holes proceeded mainly through breakage of the CC bond in the CCN group. The THMs degradation was achieved through hydrogen abstraction or/and dehalogenation. The brominated-THMs/HANs were more photosensitive than their chlorinated analogous and were less stable than bromo-chloro-THMs/HANs. This study sheds light on the mechanism of the photocatalytic degradation of THMs and HANs under visible light irradiation by carbon-doped g-C3N4. Furthermore, it could provide insights for engineering applications and contaminant control in drinking water purification.

Visible-Light-Responsive Photocatalyst of Graphitic Carbon Nitride for Pathogenic Biofilm Control.

Pathogenic biofilms raise significant health and economic concerns, because these bacteria are persistent and can lead to long-term infections in vivo and surface contamination in healthcare and industrial facilities or devices. Compared with conventional antimicrobial strategies, photocatalysis holds promise for biofilm control because of its broad-spectrum effectiveness under ambient conditions, low cost, easy operation, and reduced maintenance. In this study, we investigated the performance and mechanism of Staphylococcus epidermidis biofilm control and eradication on the surface of an innovative photocatalyst, graphitic carbon nitride (g-C3N4), under visible-light irradiation, which overcame the need for ultraviolet light for many current photocatalysts (e.g., titanium dioxide (TiO2)). Optical coherence tomography and confocal laser scanning microscopy (CLSM) suggested that g-C3N4 coupons inhibited biofilm development and eradicated mature biofilms under the irradiation of white light-emitting diodes. Biofilm inactivation was observed occurring from the surface toward the center of the biofilms, suggesting that the diffusion of reactive species into the biofilms played a key role. By taking advantage of scanning electron microscopy, CLSM, and atomic force microscopy for biofilm morphology, composition, and mechanical property characterization, we demonstrated that photocatalysis destroyed the integrated and cohesive structure of biofilms and facilitated biofilm eradication by removing the extracellular polymeric substances. Moreover, reactive oxygen species generated during g-C3N4 photocatalysis were quantified via reactions with radical probes and 1O2 was believed to be responsible for biofilm control and removal. Our work highlights the promise of using g-C3N4 for a broad range of antimicrobial applications, especially for the eradication of persistent biofilms under visible-light irradiation, including photodynamic therapy, environmental remediation, food-industry applications, and self-cleaning surface development.

Visible-Light-Responsive Graphitic Carbon Nitride: Rational Design and Photocatalytic Applications for Water Treatment.

Graphitic carbon nitride (g-C3N4) has recently emerged as a promising visible-light-responsive polymeric photocatalyst; however, a molecular-level understanding of material properties and its application for water purification were underexplored. In this study, we rationally designed nonmetal doped, supramolecule-based g-C3N4 with improved surface area and charge separation. Density functional theory (DFT) simulations indicated that carbon-doped g-C3N4 showed a thermodynamically stable structure, promoted charge separation, and had suitable energy levels of conduction and valence bands for photocatalytic oxidation compared to phosphorus-doped g-C3N4. The optimized carbon-doped, supramolecule-based g-C3N4 showed a reaction rate enhancement of 2.3-10.5-fold for the degradation of phenol and persistent organic micropollutants compared to that of conventional, melamine-based g-C3N4 in a model buffer system under the irradiation of simulated visible sunlight. Carbon-doping but not phosphorus-doping improved reactivity for contaminant degradation in agreement with DFT simulation results. Selective contaminant degradation was observed on g-C3N4, likely due to differences in reactive oxygen species production and/or contaminant-photocatalyst interfacial interactions on different g-C3N4 samples. Moreover, g-C3N4 is a robust photocatalyst for contaminant degradation in raw natural water and (partially) treated water and wastewater. In summary, DFT simulations are a viable tool to predict photocatalyst properties and oxidation performance for contaminant removal, and they guide the rational design, fabrication, and implementation of visible-light-responsive g-C3N4 for efficient, robust, and sustainable water treatment.