Spontaneous Deposition of Single Platinum Atoms on Anatase TiO2 for Photocatalytic H2 Evolution.

Single-atom (SA) decoration has emerged as a frontier in catalysis due to its unique characteristics. Recently, decorated Pt single atoms on titania have shown promise in photocatalytic hydrogen evolution. In this work, we demonstrate that Pt SAs can spontaneously deposit on the surface, driven by electrostatic forces; the key is to determine the golden pH and surface potential. We conducted a comprehensive investigation into the influence of the pH of the deposition precursor on the spontaneous adsorption of Pt SAs onto TiO2 nanosheets (TiNSs). We introduced a straightforward pH-dependent and charge-dependent strategy for the solid electrostatic anchoring of Pt SAs on TiO2. Furthermore, we established that the level of Pt loading can be controlled by adjusting the precursor pH. X-ray photoelectron spectroscopy (XPS) and high-angle annular dark-field imaging scanning transmission electron microscopy (HAADF-STEM) were used to evaluate the Pt SA-decorated samples. Photocatalytic hydrogen production activity was assessed under ultraviolet (UV) (365 nm) irradiation. Notably, we found that at a pH of 8, slightly below the measured point of zero charge (PZC), a unique mixture of Pt clusters and single atoms was deposited on the surface of TiNSs. This unique composition significantly improved hydrogen production, resulting in ∼3.7 mL of hydrogen generated after 8 h of UV exposure by only 10 mg of the Pt-decorated TiNS (with Pt loadings of 0.12 at. %), which is ∼300 times higher than the undecorated TiNS.

Thermal Reduction of MoO3 Particles and Formation of MoO2 Nanosheets Monitored by In Situ Transmission Electron Microscopy.

Nanoscale forms of molybdenum trioxide have found widespread use in optoelectronic, sensing, and battery applications. Here, we investigate the thermal evolution of micrometer-sized molybdenum trioxide particles during in situ heating in vacuum using transmission electron microscopy and observed drastic structural and chemical changes that are strongly dependent on the heating rate. Rapid heating (flash heating) of MoO3 particles to a temperature of 600 °C resulted in large-scale formation of MoO2(001) nanosheets that were formed in a wide area around the reducing MoO3 particles, within a few minutes of time frame. In contrast, when heated more gently, the initially single-crystal MoO3 particles were reduced into hollow nanostructures with polycrystalline MoO2 shells. Using density functional theory calculations employing the DFT-D3 functional, the surface energy of MoO3(010) was calculated to be 0.187 J m-2, and the activation energy for exfoliation of the van der Waals bonded MoO3 (010) layers was calculated to be 0.478 J m-2. Ab initio molecular dynamics simulations show strong fluctuations in the distance between the (010) layers, where thermal vibrations lead to additional separations of up to 1.8 Å at 600 °C. This study shows efficient pathways for the generation of either MoO2 nanosheets or hollow MoO2 nanostructures with very high effective surface areas beneficial for applications.

Effect of a glyphosate-based herbicide in Cyprinus carpio: assessment of acetylcholinesterase activity, hematological responses and serum biochemical parameters.

The objective of this study was to investigate the toxicity effects of acute and sublethal of Roundup® as a glyphosate-based herbicide on acetylcholinesterase (AChE) activity and several hematological and biochemical parameters of Cyprinus carpio. The LC50-96 h of Roundup® to C. carpio was found to be 22.19 ppm. Common carp was subjected to Roundup® at 0 (control), 3.5, 7 and 14 ppm for 16 days, and the AChE activity is verified in tissues of gill, muscle, brain and liver. After 5 days, a significant decrease was observed in the AChE activity of muscle, brain and liver tissues. Besides, a time- and dose-dependent increase in mean cell hemoglobin (MCH) and mean cell volume (MCV) was observed. In contrast, a significant decrease was found in the quantities of hemoglobin (Hb), hematocrit (HCT) and, red (RBC) and white (WBC) blood cell count. Also, the activities of aspartate aminotransferase (AST), alanine aminotransferase (ALT) and lactate dehydrogenase (LDH) in Roundup® treated groups were significantly higher than the controlled group at experimental periods. However, the level of alkaline phosphatase (ALP) had a significant reduction behavior during the sampling days. It seems that the changes in hematological and biochemical parameters as well as AChE activity could be used as efficient biomarkers in order to determine Roundup® toxicity in aquatic environment.

Optimization of recovery patterns in common carp exposed to roundup using response surface methodology: evaluation of neurotoxicity and genotoxicity effects and biochemical parameters.

The present study is the first report on optimization of recovery conditions of fishes exposed to pesticides using response surface methodology-central composite rotatable design (RSM-CCRD). The sub-lethal toxicity bioassay of Roundup® (2 ppm ~10 percent LC50, 96 h) in common carp (1, 4, 9, 16, 25, 35 and 40 day) was investigated. After exposure for 16 days to Roundup®, some the fishes were introduced to herbicide-free water. The effects of four recovery parameters including time (5-25 d), temperature (18-26 °C), water exchange rate (WER, 10-30), and salinity (0-8 ppt) on the levels of biomarkers of genotoxicity (DNA damage), neurotoxicity (acetylcholinesterase activity (AChE)), and the serum alanine (ALT) and aspartate (AST) aminotransferase in plasma were studied. The polynomial equations were significantly fitted for all response variables with high R² values (>0.95), which revealed no indication of lack of fit. The optimum conditions for the maximum AChE activity (37.14 nmol/min/mg protein) and the minimum levels of DNA damage (8.00 percent tail DNA), ALT (27.0 IU/L) and AST (91.0 IU/L) were time of 20 d, temperature of 20 °C, WER of 25 and water salinity of 6 ppt. Thus, a promising improvement for the recovery trend of fishes exposed to Roundup® stress was obtained under the optimized conditions using RSM-CCRD.