Unveiling Valence State-Dependent Photocatalytic Water Splitting Activity and Photocathodic Behavior in Visible Light-Active Iridium-Doped BaTiO3.

Despite having favorable energetics and tunable optoelectronic properties, utilization of BaTiO3 (BTO) for photocatalytic reactions is limited by its absorption only in the ultraviolet region. To address this challenge, BTO is doped with iridium (Ir) to induce visible light absorption. The visible light-induced photocatalytic H2 generation efficiency is enhanced by 2 orders of magnitude on selective conversion of the Ir valence state from Ir4+ to Ir3+. To understand such intriguing behavior, valence state-dependent changes in the optoelectronic, structural, and surface properties and electronic band structure are comprehensively investigated. The effect of electron occupancy change between Ir4+ (t2g5 eg0) and Ir3+ (t2g6 eg0) and their energetic positions within the band gap is found to significantly influence H2 generation. Besides this, converting Ir4+ to Ir3+ enhanced the photocathodic current and lowered the onset potential. Results aid in designing photocatalysts to efficiently use low-energy photons for enhancing solar H2 production in these emerging BTO-based photocatalysts. Collectively, the observations made in this work highlight the promising application of Ir3+:BTO in z-scheme photocatalysis.

Biomass-derived versatile activated carbon removes both heavy metals and dye molecules from wastewater with near-unity efficiency: Mechanism and kinetics.

Due to the ever-increasing industrialization, it is critical to protect the environment and conserve water resources by developing efficient wastewater treatment methods. Traditional methods that simultaneously remove heavy metal ions and complex dyes are too expensive and tedious to commercialize. This work demonstrates the versatility, effectiveness, and potential of a biomass-derived adsorbent (from a mangrove fruit of Rhizophora mucronata) synthesized using a simple route for rapid adsorption of complex dyes and heavy metals with an efficiency of near unity. The cartridges were prepared using activated carbon that removes both dye molecules and heavy metal ions simultaneously from wastewater, corroborating its applicability/feasibility to treat wastewater. Owing to the high surface area (1061.5 m2g-1) and the pore volume (0.5325 cm3g-1), the adsorbent showed >99% removal efficiency in just 12 min of exposure to wastewater. The cartridge exhibits >90% removal efficiency of both dyes and heavy metals from its mixed feed solution. The Langmuir and Freundlich models successfully explained the adsorption kinetics. These developed cartridges are versatile, rapid, efficient, and promising candidates for environmental remediation.

Utilizing 2D materials to enhance H2 generation efficiency via photocatalytic reforming industrial and solid waste.

Sustainable valorization of industrial and solid wastes by utilizing them as feedstock to generate H2 via the photocatalytic reforming (PR) process holds great promise. It can also be an effective method to treat solid waste that otherwise would require tedious and expensive processes. This approach has the potential to offer energy solutions and form value-added chemicals. In this direction, developing photocatalysts and tuning their properties play an essential role in advancing the H2 generation efficiency. This Review article explores the application of 2D photocatalysts to generate H2 via PR of industrial waste (H2S) and solid waste, such as plastic and biomass. Despite having favorable optoelectronic properties, 2D photocatalysts are not widely employed for the PR process. The latest progress in employing 2D photocatalysts to realize efficient H2 evolution from biomass, plastic, and industrial waste such as H2S is detailed in this Review. A correlation between the properties of 2D photocatalysts with H2 evolution rate is discussed. We also emphasize understanding the mechanism involved in the PR process and the importance of 2D photocatalysts design. Such rational insight aids in further enhancing the H2 generation efficiency by effectively using solid/industrial waste as a feedstock.

Origin of the overall water splitting activity of Ta3N5 revealed by ultrafast transient absorption spectroscopy.

Tantalum nitride (Ta3N5) is one of the few visible light absorbing photocatalysts capable of overall water splitting (OWS), by which the evolution of both H2 and O2 is possible. Despite favourable energetics, realizing the OWS or efficient H2 evolution in Ta3N5 prepared by the nitridation of tantalum oxide (Ta2O5) or Ta foil remains a challenge even after 15 years of intensive research. Recently our group demonstrated OWS in Ta3N5 when prepared by the short time nitridation of potassium tantalate (KTaO3). To obtain a mechanistic insight on the role of Ta precursor and nitridation time in realizing OWS, ultrafast dynamics of electrons (3435 nm probe) and holes (545 nm probe) is investigated using transient absorption spectroscopy. Electrons decay majorly by trapping in Ta3N5 prepared by the nitridation of Ta2O5, which do not show OWS. However, OWS activity in Ta3N5 prepared by 0.25 hour nitridation of KTaO3 is particularly favoured by the virtually absent electron and hole trapping. On further increasing the nitridation time of KTaO3 from 0.25 to 10 hour, trapping of both electron and hole is enhanced which concurrently results in a reduction of the OWS activity. Insights from correlating the synthesis conditions-structural defects-carrier dynamics-photocatalytic activity is of importance in designing novel photocatalysts to enhance solar fuel production.

Enhancement of Charge Separation and Hydrogen Evolution on Particulate La5Ti2CuS5O7 Photocathodes by Surface Modification.

Particulate La5Ti2CuS5O7 (LTC) photocathodes prepared by particle transfer show a positive onset potential of 0.9 V vs RHE for the photocathodic current in photoelectrochemical (PEC) H2 evolution. However, the low photocathodic current imposes a ceiling on the solar-to-hydrogen energy conversion efficiency of PEC cells based on LTC photocathodes. To improve the photocurrent, in this work, the surface of Mg-doped LTC photocathodes was modified with TiO2, Nb2O5, and Ta2O5 by radio frequency reactive magnetron sputtering. The photocurrent of the modified Mg-doped LTC photocathodes was doubled because these oxides formed type-II heterojunctions and extended the lifetimes of photogenerated charge carriers. The enhanced photocathodic current was attributed to hydrogen evolution at a positive potential of +0.7 V vs RHE. This work opens up possibilities for improving PEC hydrogen evolution on particulate photocathodes based on surface oxide modifications and also highlights the importance of the band gap alignment.

Contactless photoconductance study on undoped and doped nanocrystalline diamond films.

Hydrogen and oxygen surface-terminated nanocrystalline diamond (NCD) films are studied by the contactless time-resolved microwave conductivity (TRMC) technique and X-ray photoelectron spectroscopy (XPS). The optoelectronic properties of undoped NCD films are strongly affected by the type of surface termination. Upon changing the surface termination from oxygen to hydrogen, the TRMC signal rises dramatically. For an estimated quantum yield of 1 for sub-bandgap optical excitation the hole mobility of the hydrogen-terminated undoped NCD was found to be ∼0.27 cm(2)/(V s) with a lifetime exceeding 1 µs. Assuming a similar mobility for the oxygen-terminated undoped NCD a lifetime of ∼100 ps was derived. Analysis of the valence band spectra obtained by XPS suggests that upon oxidation of undoped NCD the surface Fermi level shifts (toward an increased work function). This shift originates from the size and direction of the electronic dipole moment of the surface atoms, and leads to different types of band bending at the diamond/air interface in the presence of a water film. In the case of boron-doped NCD no shift of the work function is observed, which can be rationalized by pinning of the Fermi level. This is confirmed by TRMC results of boron-doped NCD, which show no dependency on the surface termination. We suggest that photoexcited electrons in boron-doped NCD occupy nonionized boron dopants, leaving relatively long-lived mobile holes in the valence band.