Figures of Merit for Photocatalysis: Comparison of NiO/La-NaTaO3 and Synechocystis sp. PCC 6803 as a Semiconductor and a Bio-Photocatalyst for Water Splitting

While photocatalysis is considered a promising sustainable technology in the field of heterogeneous catalysis as well as biocatalysis, figures of merit (FOM) for comparing catalytic performance, especially between disciplines, are not well established. Here, photocatalytic water splitting was conducted using a semiconductor (NiO/La-NaTaO3) and a bio-photocatalyst (Synechocystis sp. PCC 6803) in the same setup under similar reaction conditions, eliminating the often ill-defined influence of the setup on the FOMs obtained. Comparing the results enables the critical evaluation of existing FOMs and a quantitative comparison of both photocatalytic systems. A single FOM is insufficient to compare the photocatalysts, instead a combination of multiple FOMs (reaction rate, photocatalytic space time yield and a redefined apparent quantum yield) is superior for assessing a variety of photocatalytic systems.

Noble-Metal-Free NixSy-C3N5 Hybrid Nanosheet with Highly Efficient Photocatalytic Performance

The construction of highly efficient, low-cost and noble-metal-free photocatalysts depends on photocatalytic technology. Recently, N-rich C3N5 has been explored as a novel carbon nitride material with a much narrower band gap (~2.2 eV) than that of traditional C3N4 (~2.7 eV). Planting noble-metal-free active sites on C3N5 to improve its photocatalytic activity is of great significance. Herein, 2D NixSy nanosheet is facially loaded on 2D C3N5 using a hydrothermal procedure under a low temperature. Due to the quick separation of photogenerated carries between C3N5 and NixSy, this inexpensive noble-metal-free NixSy-C3N5 hybrid nanosheet is highly efficient and stable as a multifunctional catalyst in various applications, including photocatalytic H2 production from water and NO removal. Impressively, the apparent quantum yield (AQY) value for H2 production reaches 37.0% (at 420 nm) on optimal NixSy-C3N5 hybrids, which is much higher than that of Pt-C3N5 material. This work opens an avenue to the fabrication of low-cost and noble-metal-free catalysts for multifunctional photocatalytic applications.

Interfacial chemical bond and internal electric field modulated Z-scheme Sv-ZnIn2S4/MoSe2 photocatalyst for efficient hydrogen evolution

Construction of Z-scheme heterostructure is of great significance for realizing efficient photocatalytic water splitting. However, the conscious modulation of Z-scheme charge transfer is still a great challenge. Herein, interfacial Mo-S bond and internal electric field modulated Z-scheme heterostructure composed by sulfur vacancies-rich ZnIn2S4 and MoSe2 was rationally fabricated for efficient photocatalytic hydrogen evolution. Systematic investigations reveal that Mo-S bond and internal electric field induce the Z-scheme charge transfer mechanism as confirmed by the surface photovoltage spectra, DMPO spin-trapping electron paramagnetic resonance spectra and density functional theory calculations. Under the intense synergy among the Mo-S bond, internal electric field and S-vacancies, the optimized photocatalyst exhibits high hydrogen evolution rate of 63.21 mmol∙g−1·h−1 with an apparent quantum yield of 76.48% at 420 nm monochromatic light, which is about 18.8-fold of the pristine ZIS. This work affords a useful inspiration on consciously modulating Z-scheme charge transfer by atomic-level interface control and internal electric field to signally promote the photocatalytic performance.

Mechanistic analysis of multiple processes controlling solar-driven H2O2 synthesis using engineered polymeric carbon nitride

Solar-driven hydrogen peroxide (H2O2) production presents unique merits of sustainability and environmental friendliness. Herein, efficient solar-driven H2O2 production through dioxygen reduction is achieved by employing polymeric carbon nitride framework with sodium cyanaminate moiety, affording a H2O2 production rate of 18.7 μmol h −1 mg−1 and an apparent quantum yield of 27.6% at 380 nm. The overall photocatalytic transformation process is systematically analyzed, and some previously unknown structural features and interactions are substantiated via experimental and theoretical methods. The structural features of cyanamino group and pyridinic nitrogen-coordinated soidum in the framework promote photon absorption, alter the energy landscape of the framework and improve charge separation efficiency, enhance surface adsorption of dioxygen, and create selective 2e− oxygen reduction reaction surface-active sites. Particularly, an electronic coupling interaction between O2 and surface, which boosts the population and prolongs the lifetime of the active shallow-trapped electrons, is experimentally substantiated.

Yield, Physiological Performance, and Phytochemistry of Basil (Ocimum basilicum L.) under Temperature Stress and Elevated CO2 Concentrations

Early season sowing is one of the methods for avoiding yield loss for basil due to high temperatures. However, basil could be exposed to sub-optimal temperatures by planting it earlier in the season. Thus, an experiment was conducted that examines how temperature changes and carbon dioxide (CO2) levels affect basil growth, development, and phytonutrient concentrations in a controlled environment. The experiment simulated temperature stress, low (20/12 °C), and high (38/30 °C), under ambient (420 ppm) and elevated (720 ppm) CO2 concentrations. Low-temperature stress prompted the rapid closure of stomata resulting in a 21% decline in net photosynthesis. Chlorophylls and carotenoids decreased when elevated CO2 interacted with low-temperature stress. Basil exhibited an increase in stomatal conductance, intercellular CO2 concentration, apparent quantum yield, maximum photosystem II efficiency, and maximum net photosynthesis rate when subjected to high-temperature stress. Under elevated CO2, increasing the growth temperature from 30/22 °C to 38/30 °C markedly increased the antioxidants content of basil. Taken together, the evidence from this research recommends that varying the growth temperature of basil plants can significantly affect the growth and development rates compared to increasing the CO2 concentrations, which mitigates the adverse effects of temperature stress.

Oxygen Evolution Activity of LaNbN2O-Based Photocatalysts Obtained from Nitridation of a Precursor Oxide Structurally Modified by Incorporating Volatile Elements

The perovskite-type oxynitride LaNbN2O is a photocatalyst that can evolve oxygen from aqueous solutions in response to long-wavelength visible light. However, it is challenging to obtain active LaNbN2O because of the facile reduction of Nb5+ during the nitridation of the precursor materials. The present study attempted to synthesize a perovskite-type oxide La0.6Na0.4Zn0.4Nb0.6O3, containing equimolar amounts of La3+ and Nb5+ in addition to volatile Na+ and Zn2+, followed by the nitridation of this oxide to generate LaNbN2O. The obtained oxide was not the intended single-phase material but rather comprised a cuboid perovskite-type oxide similar to La0.5Na0.5Zn0.33Nb0.67O3 along with spherical LaNbO4 particles and other impurities. A brief nitridation was found to form a LaNbN2O-like shell structure having a light absorption onset of approximately 700 nm on the cuboid perovskite-type oxide particles. This LaNbN2O-based photocatalyst, when loaded with a CoOx cocatalyst, exhibited an apparent quantum yield of 1.7% at 420 nm during oxygen evolution reaction from an aqueous AgNO3 solution. This was more than double the values obtained from the nitridation products of LaNbO4 and LaKNaNbO5. The present work demonstrates a new approach to the design of precursor oxides that yield highly active LaNbN2O and suggests opportunities for developing efficient Nb-based perovskite oxynitride photocatalysts.

Interfacial Chemical Bond and Internal Electric Field Modulated Z-Scheme Vs-ZnIn2S4/MoSe2 Photocatalyst for Efficient Hydrogen Evolution

Construction of Z-scheme heterostructure is of momentous significance for realizing efficient photocatalytic water splitting. However, the consciously modulate of Z-scheme charge transfer is still a great challenge. Herein, interfacial Mo-S bond and internal electric field modulated Z-Scheme heterostructure composed by sulfur vacancies-rich ZnIn2S4 (Vs-ZIS) and MoSe2 was rationally fabricated for efficient photocatalytic hydrogen evolution. Systematic investigations reveal that Mo-S bond and internal electric field induce the Z-scheme charge transfer mechanism as confirmed by the SPS and DMPO spin-trapping EPR spectra. Under the intense synergy among the Mo-S bond, internal electric field and S-vacancies, the optimized photocatalyst exhibits ultrahigh hydrogen evolution rate of 63.21 mmol∙g-1·h-1 with an apparent quantum yield of 76.48% at 420 nm monochromatic light, which is about 18.8-fold of the pristine ZIS. This work affords a new inspiration on consciously modulating Z-scheme charge transfer by atomic-level interface control and internal electric field to signally promote the photocatalytic performance.

Sequential cocatalyst decoration on BaTaO2N towards highly-active Z-scheme water splitting

Oxynitride photocatalysts hold promise for renewable solar hydrogen production via water splitting owing to their intense visible light absorption. Cocatalyst loading is essential for activation of such oxynitride photocatalysts. However, cocatalyst nanoparticles form aggregates and exhibit weak interaction with photocatalysts, which prevents eliciting their intrinsic photocatalytic performance. Here, we demonstrate efficient utilization of photoexcited electrons in a single-crystalline particulate BaTaO2N photocatalyst prepared with the assistance of RbCl flux for H2 evolution reactions via sequential decoration of Pt cocatalyst by impregnation-reduction followed by site-selective photodeposition. The Pt-loaded BaTaO2N photocatalyst evolves H2 over 100 times more efficiently than before, with an apparent quantum yield of 6.8% at the wavelength of 420 nm, from a methanol aqueous solution, and a solar-to-hydrogen energy conversion efficiency of 0.24% in Z-scheme water splitting. Enabling uniform dispersion and intimate contact of cocatalyst nanoparticles on single-crystalline narrow-bandgap particulate photocatalysts is a key to efficient solar-to-chemical energy conversion.

Co3C as a promising cocatalyst for superior photocatalytic H2 production based on swift electron transfer processes

The inexpensive Co3C proved itself as highly efficient cocatalyst to generate economical H2. An apparent quantum yield of 19% was achieved which is among the best reported carbide-based cocatalysts.

Polyoxometalate Template-Based Synthetic Strategy to Prepare Ni, Mo Co-Doped CdS for Efficient Photocatalytic Hydrogen Evolution from Water Splitting

In this work, a novel polyoxometalate template-based strategy was applied to construct the bi-metal-doped CdS photocatalysts. NiMo6 polyoxometalate template precursor was applied for the preparation of Ni, Mo co-doped CdS photocatalysts (NiMo-CdS). The structures of the materials were explored by XRD, SEM, HRTEM, HAADF, element mapping, XPS, Raman spectrum and UV-vis DRS. Moreover, the results of the UV-vis spectrum showed that NiMo-CdS exhibited an enhanced performance on light absorption. The results of photocatalytic hydrogen evolution from water splitting demonstrated that the NiMo-CdS showed higher efficiency on hydrogen evolution than noble-metal Pt-doped CdS. The reason could be ascribed to the enhanced light absorption ability and charge separation after Ni and Mo were introduced, which could also act as co-catalysts. The apparent quantum yield (AQY) efficiency could reach 42% at 365 nm. This work proposed a novel and inexpensive method to synthesize the bi-metal (Ni, Mo) decorated CdS photocatalysts for efficient hydrogen evolution from water splitting.