Emerging Copper-Based Semiconducting Materials for Photocathodic Applications in Solar Driven Water Splitting

Hydrogen production through solar-driven water splitting is a promising approach and an alternative to the conventional steam reforming of natural gas and coal gasification. The growing energy demand and environmental degradation through carbon-emitting fossil fuels urge a transition in the usage of non-renewable to renewable sources of energy. The photocathodes in a photoelectrochemical (PEC) water-splitting cell are essential for the direct evolution of hydrogen. Among the known photocathodes, Cu-based p-type semiconducting materials are the most promising photo-absorber materials owing to their low-cost, low toxicity, natural abundance, suitable bandgaps, and favorable band edges for reduction. Moreover, the chemical stability and the rate of recombination significantly limit the longevity, the PEC performance, and practical applicability of Cu-based photocathodes. To overcome these problems, it is critical to have a thorough understanding of the constraints, improvement strategies, and an assessment of current developments in order to construct and design highly stable and efficient photocathodes. Here, in this review we have summarized the development of Cu-based metal oxide and sulfide photocathodes with the significant operational challenges and strategies that have successfully been employed to enhance the PEC performance. Furthermore, the emphasis is placed on recent reports and future perspectives regarding emerging challenges

Recent trends in photoelectrochemical water splitting: the role of cocatalysts

Environmental degradation due to the carbon emissions from burning fossil fuels has triggered the need for sustainable and renewable energy. Hydrogen has the potential to meet the global energy requirement due to its high energy density; moreover, it is also clean burning. Photoelectrochemical (PEC) water splitting is a method that generates hydrogen from water by using solar radiation. Despite the advantages of PEC water splitting, its applications are limited by poor efficiency due to the recombination of charge carriers, high overpotential, and sluggish reaction kinetics. The synergistic effect of using different strategies with cocatalyst decoration is promising to enhance efficiency and stability. Transition metal-based cocatalysts are known to improve PEC efficiency by reducing the barrier to charge transfer. Recent developments in novel cocatalyst design have led to significant advances in the fundamental understanding of improved reaction kinetics and the mechanism of hydrogen evolution. To highlight key important advances in the understanding of surface reactions, this review provides a detailed outline of very recent reports on novel PEC system design engineering with cocatalysts. More importantly, the role of cocatalysts in surface passivation and photovoltage, and photocurrent enhancement are highlighted. Finally, some challenges and potential opportunities for designing efficient cocatalysts are discussed

Mn-doped ZnO microspheres prepared by solution combustion synthesis for room temperature NH3 sensing

Despite being the most favorable ammonia (NH3) gas sensors, metal oxide semiconductors fail to deliver high selectivity and room temperature (RT) sensing. Tuning the metal oxide with doping is an attractive way of overcoming these disadvantages. Herein, we report Mn-doped ZnO microspheres as promising sensors for highly sensitive and selective RT sensing of NH3. ZnO and 2 wt% Mn-doped ZnO microspheres were synthesized by a low-cost and fast solution combustion synthesis, and their structure, morphology, and gas sensing properties were investigated. Mn-doping resulted in a change in the lattice parameters, an increase in the oxygen vacancies, and surface acidity of ZnO as confirmed by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and Temperature programmed desorption (TPD), respectively. Mn-doped ZnO showed a response (Ra/Rg) of 20.2 in 100 ppm NH3, which is significantly higher than ZnO. The sensor showed high selectivity, three times higher than that of ZnO, and good stability. Improvement in the sensing performance of Mn-doped ZnO is attributed to the increase in the defects and surface acidity with Mn-doping. © 2022 The Author(s

Integrated p-n Junctions for Efficient Solar Water Splitting upon TiO2/CdS/BiSbS3 Ternary Hybrids for Improved Hydrogen Evolution and Mechanistic Insights

The development of efficient and novel p-n heterojunctions for photoelectrochemical (PEC) water splitting is still a challenging problem. We have demonstrated the complementary nature of (p-type) BiSbS3 as a sensitizer when coupled with (n-type) TiO2/CdS to improve the photocatalytic activity and solar to hydrogen conversion efficiency. The as-prepared p-n heterojunction TiO2/CdS/BiSbS3 exhibits good visible light harvesting capacity and high charge separation over the binary heterojunction, which are confirmed by photoluminescence (PL) and electrical impedance spectroscopy (EIS). The ternary heterojunction produces higher H-2 than the binary systems TiO2/CdS and TiO2/BiSbS3. This ternary heterojunction system displayed the highest photocurrent density of 5 mA center dot cm(-2) at 1.23 V vs. reversible hydrogen electrode (RHE) in neutral conditions, and STH of 3.8% at 0.52 V vs. RHE is observed. The improved photocatalytic response was due to the favorable energy band positions of CdS and BiSbS3. This study highlights the p-n junction made up of TiO2/CdS/BiSbS3, which promises efficient charge formation, separation, and suppression of charge recombination for improved PEC water splitting efficiency. Further, no appreciable loss of activity was observed for the photoanode over 2500 s. Band alignment and interfaces mechanisms have been studied as well

TiO2 Photoanodes Sensitized with Bi2Se3 Nanoflowers for Visible–Near-Infrared Photoelectrochemical Water Splitting

Semiconducting photoelectrodes emerge as an efficient platform for converting light energy into hydrogen by photoelectrochemical (PEC) water splitting. The present study reports the improvement in PEC performance using metal oxide photoelectrodes sensitized with a narrow-band-gap semiconductor Bi2Se3, which extends the light response beyond the visible region and generates and transports charge carriers. When Bi2Se3 nanoflowers (NFs) were incorporated into the TiO2 electrode, the extent of hydrogen production was found to be increased by an order of magnitude. The binary electrode TiO2/Bi2Se3 nanocomposite exhibited a decent photocurrent density of 1.76 mA cm-2 at 1.23 V, which is three times superior to that of pure Bi2Se3 NFs. Moreover, the binary TiO2/Bi2Se3 electrode delivers the highest solar-to-hydrogen conversion efficiency of 1.01% at 0.6 V and incident photon-to-current conversion efficiency of 10.5%. Furthermore, both Bi2Se3 and TiO2/Bi2Se3 electrodes show superior photostabilities for over 6 h. The enhanced PEC activity is attributable to the facile transportation of photoelectrons from Bi2Se3 to TiO2 electrodes, thereby minimizing the charge recombination

Influence of Bi–Cu microstructure on the photoelectrochemical performance of BiVO4 photoanode for efficient water splitting

To date, photoanodes containing bimetallic alloy nanoparticles (ANPs) are exposed good photoelectrochemical (PEC) performance for hydrogen production owing to their optoelectronic properties. In this work, low-cost, visible light active and environmental-friendly BiVO4/Bi–Cu nanocomposite photoanode is fabricated via organic decomposition and electrodeposition process. Transmission electron microscope images reveals that Bi–Cu ANPs are uniformly distributed on BiVO4 which can enhance the PEC performance. Typical results originate that BiVO4/Bi–Cu nanocomposite exhibits a high photocurrent density of 10.31 mA cm−2 at 1.23 V and solar-to-hydrogen conversion efficiency of 3.55%, which is higher than other electrodes. In addition, this composite shows excellent long-term stability over 5 h and low charge transfer resistance. These results suggest the introduction of Bi–Cu ANPs enhances the broadband light absorption of BiVO4 due to the excitation of localized surface plasmons at different wavelengths and also improves the charge transportation in the photoanode. Thus, BiVO4/Bi–Cu photoelectrode reports here is superior PEC performance for hydrogen generation providing an economical and feasible route to fabricate surface plasmon resonance (SPR)-enhanced composites as photocatalysts using earth-abundant Bi and Cu metals instead of noble-metals. © 2021 Elsevier B.V

Low-cost adsorbent derived from the coconut shell for the removal of hexavalent chromium from aqueous medium

A bio-adsorbent was derived from the coconut shells and surface modification of the adsorbent was done by physical activation by using carbon dioxide (CO2), ozone (O3) and steam (H2O). The consequence of physical activation on the physicochemical properties was analyzed by N2 adsorption, thermogravimetric analysis (TGA) and temperature programmed decomposition (TPD). Typical results indicated that the physical activation of carbon is an efficient approach for the removal of heavy metal Cr(VI) from the aqueous solution and the best adsorption was achieved at pH 2.0. The equilibrium studies indicated that Cr(VI) adsorption follows Langmuir adsorption isotherm and pseudo-2nd-order kinetics

Alkali-treated Carbonized Rice Husk for the Removal of Aqueous Cr(VI)

Rice husk was chemically modified for the preparation of activated carbon. Rice husk was treated with nitric acid and carbonized at 700 C. After carbonization, the resulting rice husk char was treated with NaOH at room temperature. The 5 M NaOH-treated rice husk had the highest surface area (750 m2/g). Proximate analysis of activated carbon confirmed that NaOH treatment removed silica completely. Temperature programmed decomposition (TPD) graphs showed that the total gas contents (CO and CO2) liberated by CRH and H2O-treated CRH and CRH5M were 2l5 μmol/g, 390 μmol/g, and 970 μmol/g, respectively. The adsorption studies of the activated carbon during Cr(VI) removal from the aqueous medium indicated that CRH5M showed the highest rate of adsorption. The effect of adsorbent dosage, Cr(VI) concentration, pH, and temperature were studied to determine the best removal efficiency. With a decrease in pH from 4.4 to 2, the adsorption capacity increased from 3 mg/g to 25.2 mg/g. The adsorption of Cr(VI) followed pseudo-second-order behaviour. The changes in Gibbs free energy, enthalpy, and entropy affected by thermodynamic parameters were found to be negative, which confirmed that the adsorption of Cr(VI) on CRH5M is spontaneous, exothermic, and favours low temperatures

Facile Synthesis and Photoelectrochemical Performance of a Bi2S3@rGO Nanocomposite Photoanode for Efficient Water Splitting

Visible-light-active photoelectrodes are more responsive to high-energy conversion efficiency in photoelectrochemical (PEC) water splitting. In this work, we fabricated a bismuth sulfide@reduced graphene oxide (Bi2S3@rGO) nanocomposite photoanode via facile synthetic methods. Typical results show that the Bi2S3@rGO nanocomposite exhibited a high photocurrent density of 6.06 mA cm-2 and a maximum applied bias photon-to-current efficiency (ABPE) of 4.2% at 0.32 V. Moreover, Bi2S3 nanorods have more uniform dispersion on the surface of rGO sheets in the Bi2S3@rGO composite as demonstrated in the transmission electron microscopy images. In addition, photoluminescence and impedance studies reveal the enhanced charge-transfer properties in the Bi2S3@rGO photoelectrode. The enhanced PEC performance of the composite could be attributed to the effective visible-light absorption of Bi2S3 and the good electron-transfer properties of highly conductive rGO nanosheets, facilitating the charge separation and transportation, leading to the inhibition of charge recombination