RESUMEN

The single-chamber bio-photoelectrochemical system (BPES) with a bioanode and a Bi2O3/CuO photocathode is developed for chlortetracycline (CTC) degradation under simulated solar irradiation, using phosphate buffer solution (PBS) or NaHCO3 as buffer solution. The optimized Bi2O3/CuO photocathode possesses rich vacancies, great photoresponse capability, and exhibits great photocatalytic activity toward CTC degradation due to its Z-scheme structure. Electron spin-resonance spectroscopy (ESR) and reactive species trapping experiments reveal that superoxide radicals/hydroxyl radicals are both the main radicals contributing to CTC degradation. Moreover, carbonate radical plays a more effective role toward CTC degradation, resulting in 40% improvement for CTC degradation in the BPES within 2 h. Higher current density (maximum of 137.6 A m-2) and more negative cathode potential are obtained from the illuminated BPES with NaHCO3 buffer. Possible mechanism and pathways of CTC degradation are proposed. This study contributes to the development of BPESs for antibiotics degradation.

Asunto(s)

Clortetraciclina , Bicarbonatos , Clortetraciclina/química , Cobre , Radical Hidroxilo

RESUMEN

Enhancing stability against photocorrosion and improving photocurrent response are the main challenges toward the development of cupric oxide (CuO) based photocathodes for solar-driven hydrogen production. In this paper, stable and efficient CuO-photocathodes have been developed using in situ materials engineering and through gold-palladium (Au-Pd) nanoparticles deposition on the CuO surface. The CuO photocathode exhibits a photocurrent generation of ∼3 mA/cm2 at 0 V v/s RHE. Time-of-flight secondary ion mass spectrometry (TOF-SIMS) analysis and X-ray spectroscopy (XPS) confirm the formation of oxygen-rich (O-rich) CuO film which demonstrates a highly stable photocathode with retained photocurrent of ∼90% for 20 min. The influence of chemical composition on the photocathode performance and stability has been discussed in detail. In addition, O-rich CuO photocathodes deposited with Au-Pd nanostructures have shown enhanced photoelectrochemical performance. Linear scan voltammetry characteristic shows ∼25% enhancement in photocurrent after Au-Pd deposition and reaches ∼4 mA/cm2 at "0" V v/s RHE. Hydrogen evolution rate significantly depends on the elemental composition of CuO and metal nanostructure. The present work has demonstrated a stable photocathode with high photocurrent for visible-light-driven water splitting and hydrogen production.

RESUMEN

Cupric oxide (CuO) thin film was sputtered onto fluorine-doped tin oxide (FTO) coated glass substrate and incorporated into a photoelectrochemical (PEC) cell as a photocathode. Through in situ nanocrystal engineering, sputtered CuO film shows an improvement in its stability and photocurrent generation capability. For the same CuO film thickness (150 nm), films deposited at a sputtering power of 300 W exhibit a photocurrent of ∼0.92 mAcm(-2) (0 V vs RHE), which is significantly higher than those deposited at 30 W (∼0.58 mAcm(-2)). By increasing the film thickness to 500 nm, the photocurrent is further enhanced to 2.5 mAcm(-2), which represents a photocurrent conversion efficiency of 3.1%. Systematic characterization using Raman, XRD, and HR-TEM reveals that the high sputtering power results in an improvement in CuO film crystallinity, which enhances its charge transport property and, hence, its photocurrent generation capabilities.