ABSTRACT
This study investigated the hydrochar-based porous carbon prepared by combining the technical route of hydrothermal carbonization (HTC) + chemical activation. The hydrochar morphology was adjusted by changing the activation reaction conditions and adding metal salts. Experiments showed that the activation of KHCO3 significantly increased the specific surface area and pore size of the hydrochar. Besides, oxygen-rich groups on the surface of the activated hydrochar interacted with heavy metal ions to achieve efficient adsorption. The activated hydrothermal carbon adsorption capacity for Pb2+ and Cd2+ ions reached 289 and 186 mg/g, respectively. The adsorption mechanism study indicated that the adsorption of Pb2+ and Cd2+ was related to electrostatic attraction, ion exchange, and complexation reactions. The "HTC + chemical activation" technology was environmentally friendly and effectively implemented antibiotic residues. Carbon materials with high adsorption capacity can be prepared so that biomass resources can be utilized with excessive value, as a consequence presenting technical assistance for the comprehensive disposal of organic waste in the pharmaceutical industry and establishing a green and clean production system.
ABSTRACT
We assess a tandem photoelectrochemical cell consisting of a W:BiVO4 photoanode top absorber and a CuBi2O4 photocathode bottom absorber for overall solar water splitting. We show that the W:BiVO4 photoanode oxidizes water and produces oxygen at potentials ≥0.7 V vs RHE when CoPi is added as a cocatalyst. However, the CuBi2O4 photocathode does not produce a detectable amount of hydrogen from water reduction even when Pt or RuOx is added as a cocatalyst because the photocurrent primarily goes toward photocorrosion of CuBi2O4 rather than proton reduction. Protecting the CuBi2O4 photocathode with a CdS/TiO2 heterojunction and adding RuOx as a cocatalyst prevents photocorrosion and allows for photoelectrochemical production of hydrogen at potentials ≤0.3 V vs RHE. A tandem photoelectrochemical cell composed of a W:BiVO4/CoPi photoanode and a CuBi2O4/CdS/TiO2/RuOx photocathode produces hydrogen which can be detected under illumination at an applied bias of ≥0.4 V. Since the valence band of BiVO4 and conduction band of CuBi2O4 are adequately positioned to oxidize water and reduce protons, we hypothesize that the applied bias is required to overcome the relatively low photovoltages of the photoelectrodes, that is, the relatively low quasi-Fermi level splitting within BiVO4 and CuBi2O4. This work is the first experimental demonstration of hydrogen production from a BiVO4-CuBi2O4-based tandem cell and it provides important insights into the significance of photovoltage in tandem devices for overall water splitting, especially for cells containing CuBi2O4 photocathodes.
ABSTRACT
p-Type CuBi2O4 is considered a promising metal oxide semiconductor for large-scale, economic solar water splitting due to the optimal band structure and low-cost fabrication. The main challenge in utilizing CuBi2O4 as a photoelectrode for water splitting, is that it must be protected from photo-corrosion in aqueous solutions, an inherent problem for Cu-based metal oxide photoelectrodes. In this work, several buffer layers (CdS, BiVO4, and Ga2O3) were tested between CuBi2O4 and conformal TiO2 as the protection layer. RuO x was used as the co-catalyst for hydrogen evolution. Factors that limit the photoelectrochemical performance of the CuBi2O4/TiO2/RuO x , CuBi2O4/CdS/TiO2/RuO x , CuBi2O4/BiVO4/TiO2/RuO x and CuBi2O4/Ga2O3/TiO2/RuO x heterojunction photoelectrodes were revealed by comparing photocurrents, band offsets, and directed charge transfer measured by modulated surface photovoltage spectroscopy. For CuBi2O4/Ga2O3/TiO2/RuO x photoelectrodes, barriers for charge transfer strongly limited the performance. In CuBi2O4/CdS/TiO2/RuO x , the absence of hole traps resulted in a relatively high photocurrent density and faradaic efficiency for hydrogen evolution despite the presence of pronounced deep defect states at the CuBi2O4/CdS interface. Hole trapping limited the performance moderately in CuBi2O4/BiVO4/TiO2/RuO x and strongly in CuBi2O4/TiO2/RuO x photoelectrodes. For the first time, our results show that hole trapping is a key factor that must be addressed to optimize the performance of CuBi2O4-based heterojunction photoelectrodes.
