Development of a metal-free black phosphorus/graphitic carbon nitride heterostructure for visible-light-driven degradation of indomethacin.

The development of affordable and efficient technologies for the removal of pharmaceuticals and personal care products (PPCPs) from water has recently been the subject of extensive attention. In this study, a black phosphorus/graphitic carbon nitride (BP-g-C3N4) heterostructure is fabricated as an extremely active metal-free photocatalyst via a newly-developed exfoliation strategy. The BP-g-C3N4 shows an 11 times better decomposition rate of a representative PPCPs-type pollutant, indomethacin (IDM), compared to the widely-used P25 TiO2 under real-sunlight illumination. Also, its visible-light activity is even better than that of the best photocatalysts previously developed, but only consumes 1/10-1/4 of the catalyst. The results show that BP performs a cocatalyst-like behavior to catalyze the generation of reactive oxygen species, thus speeding up the decomposition of IDM. In addition, the BP-g-C3N4 photocatalyst also exhibits excellent IDM removal efficiency in authentic water matrices (tap water, surface water, and secondarily treated sewage effluent). Large-scale application demonstration under natural sunlight further reveals the practicality of BP-g-C3N4 for real-world water treatment operations. Our work will open up new possibilities in the development of purely metal-free photocatalysts for "green" environmental remediation applications.

Preparation of metal-free BP/CN photocatalyst with enhanced ability for photocatalytic tetracycline degradation.

The successful application of photocatalysis in practical water treatment opreations relies greatly on the development of highly efficient, stable and low-cost photocatalysts. The low-cost metal-free photocatalyst made up of black phosphorus (BP) and graphitic carbon nitride (CN) was successfully constructed and firstly used for the photocatalytic treatment of antibiotic contaminants in this work. Compared with bare CN, the BP/CN photocatalyst exhibited the enhanced photocatalytic performance for tetracycline hydrochloride (HTC) degradation, that 99% of HTC was removed by 6BP/CN (doping amount of BP was 6%) within 30 min under the simulated visible-light irradiation. The efficiency was even comparable to those of some high-efficiency photocatalysts recently-reported such as Fe0@POCN, CuInS2/Bi2MoO6 and Cu2O@HKUST-1. Under natural sunlight illumination, the determined apparent rate constant for degradation of HTC by BP/CN was 2.7 times as that by P25 TiO2. The experimental results indicated that loading BP on CN could enhance the separation of charge carriers and promote the ability of light absorption for visible-light, thus leading to a greater catalytic activity. Meanwhile, the influences of different operating variables (pH, water, ion and HTC concentration) on HTC degradation were studied in detail. Furthermore, the degradation pathway of HTC was also proposed. In addition, the photocatalytic activity of the BP/CN for production of hydrogen peroxide (H2O2) was also studied, which could reach up to 501.04 µmol g-1h-1. It is anticipated that BP/CN photocatalyst could be used for practical water treatment.