Production of hydrogen peroxide in an intra-meander hyporheic zone at East River, Colorado

The traditionally held assumption that photo-dependent processes are the predominant source of H2O2 in natural waters has been recently questioned by an increrasing body of evidence showing the ubiquitiousness of H2O2 in dark water bodies and in groundwater. In this study, we conducted field measurement of H2O2 in an intra-meander hyporheic zone and in surface water at East River, CO. On-site detection using a sensitive chemiluminescence method suggests H2O2 concentrations in groundwater ranging from 6 nM (at the most reduced region) to ~ 80 nM (in a locally oxygen-rich area) along the intra-meander transect with a maxima of 186 nM detected in the surface water in an early afternoon, lagging the maximum solar irradiance by ∼ 1.5 h. Our results suggest that the dark profile of H2O2 in the hyporheic zone is closely correlated to local redox gradients, indicating that interactions between various redox sensitive elements could play an essential role. Due to its transient nature, the widespread presence of H2O2 in the hyporheic zone indicates the existence of a sustained balance between H2O2 production and consumption, which potentially involves a relatively rapid succession of various biogeochemically important processes (such as organic matter turnover, metal cycling and contaminant mobilization). More importantly, this study confirmed the occurrence of reactive oxygen species at a subsurface redox transition zone and further support our understanding of redox boundaries on reactive oxygen species generation and as key locations of biogeochemical activity.

Methionine Restriction Prevents Lipopolysaccharide-Induced Acute Lung Injury via Modulating CSE/H2S Pathway

Acute lung injury (ALI) and acute respiratory distress syndrome (ARDS) result in high mortality, whereas effective treatments are limited. Methionine restriction (MR) has been reported to offer various benefits against multiple pathological processes of organ injuries. However, it remains unknown whether MR has any potential therapeutic value for ALI/ARDS. The current study was set to investigate the therapeutic potential of MR on lipopolysaccharide (LPS)-induced ALI and its underlying mechanisms. We found that MR attenuated LPS-induced pulmonary edema, hemorrhage, atelectasis, and alveolar epithelial cell injuries in mice. MR upregulated cystathionine-gamma-lyase (CSE) expression and enhanced the production of hydrogen sulfide (H2S). MR also inhibited the activation of Toll-like receptors 4 (TLR4)/NF-κB/NOD-like receptor protein 3 (NLRP3), then reduced IL-1β, IL-6, and TNF-α release and immune cell infiltration. Moreover, the protective effects of MR on LPS-induced ALI were abrogated by inhibiting CSE, whereas exogenous H2S treatment alone mimicked the protective effects of MR in Cse−/− mice after LPS administration. In conclusion, our findings showed that MR attenuated LPS-induced lung injury through CSE and H2S modulation. This work suggests that developing MR towards clinical use for ALI/ARDS patients may be a valuable strategy.

Photocatalytic overall water splitting under visible light enabled by a particulate conjugated polymer loaded with iridium

The production of hydrogen from water via solar water splitting is a potential method to overcome the intermittency of the Sun’s energy by storing it as a chemical fuel. Inorganic semiconductors have been studied extensively as photocatalysts for overall water splitting, but polymer photocatalysts are also receiving growing attention. So far, most studies involving organic polymers report hydrogen production with sacrificial electron donors, which is unsuitable for large-scale hydrogen energy production. Here we show that a linear conjugated polymer photocatalyst can be used for overall water splitting to produce stoichiometric amounts of H2 and O2. We studied a range of different metal co-catalysts in conjunction with the linear polymer photocatalyst, the homopolymer of dibenzo[b,d]thiophene sulfone (P10). Photocatalytic activity was observed for palladium/iridium oxide-loaded P10, while other co-catalysts resulted in materials that showed no activity for overall water splitting. The reaction conditions were further optimized and the overall water splitting using the IrO2-loaded P10 was found to proceed steadily for an extended period (>60 hours) after the system stabilized. These results demonstrate that conjugated polymers can act as single component photocatalytic systems for overall water splitting when loaded with suitable co-catalysts, albeit currently with low activities. Significantly, though, organic polymers can be designed to absorb a large fraction of the visible spectrum, which can be challenging with inorganic catalysts. Transient spectroscopy shows that the IrO2 co-catalyst plays an important role in the generation of the charge separated state required for water splitting, with evidence for fast hole transfer to the co-catalyst. This solid-state approach should be transferable to other polymer photocatalysts, allowing this field to move away from sacrificial hydrogen production towards overall water splitting.

Remarkable Enhancement of Catalytic Activity of Cu-Complexes in the Electrochemical Hydrogen Evolution Reaction (HER) by Using Triply-Fused Porphyrin

Developing efficient molecular catalysts for the electrocatalytic hydrogen evolution reaction (HER) is a highly important goal in contemporary science. We report here on a bimetallic triply fused copper porphyrin complex (1) comprising two monomeric porphyrin units linked through β–β, meso–meso, β′–β′ triple covalent linkages, that exhibits remarkable enhancement of catalytic activity for the electrochemical HER in comparison to the analogous monomeric copper porphyrin complex (2). Spectroscopic characterization, in association with magnetic measurements, clearly establish the ground state structures of both the bimetallic and monometallic complexes as containing two and one copper (II) centers, respectively. The fused metalloporphyrin complex is found to undergo electrochemical reduction at a lower negative applied potential compared to the metalloporphyrin monomer, as evident from the significant anodic shift (~800mV) in the potential of the first reduction process. Electrochemical investigations in the presence of a proton source (trifluoroacetic acid) confirm that the catalytic activity of the fused metalloporphyrin occurs at a significantly lower onset potential, (overpotential decreased by ~320 mV), compared to the non-fused monomer. Controlled potential electrolysis combined with the kinetic analysis of catalysts 1 and 2 confirm the production of hydrogen, with 96% and 71% faradaic efficiencies and turnover numbers of 102 and 18, respectively. Kinetic investigations further reveal an observed rate constant of around 107 (s-1), implying high efficiency of the bimetallic catalyst towards hydrogen evolution reaction. Mechanistic insights are presented by using a combination of UV-vis-NIR and EPR spectroscopy and electrochemistry. Our results thus firmly establish the triply fused porphyrin ligands as candidates for generating highly efficient molecular electrocatalysts in combination with transition metal centers.

The Role of Strontium in CeNiO3 Nano-Crystalline Perovskites for Greenhouse Gas Mitigation to Produce Syngas

The transition metal-based catalysts for the elimination of greenhouse gases via methane reforming using carbon dioxide are directly or indirectly associated with their distinguishing characteristics such as well-dispersed metal nanoparticles, a higher number of reducible species, suitable metal–support interaction, and high specific surface area. This work presents the insight into catalytic performance as well as catalyst stability of CexSr1−xNiO3 (x = 0.6–1) nanocrystalline perovskites for the production of hydrogen via methane reforming using carbon dioxide. Strontium incorporation enhances specific surface area, the number of reducible species, and nickel dispersion. The catalytic performance results show that CeNiO3 demonstrated higher initial CH4 (54.3%) and CO2 (64.8%) conversions, which dropped down to 13.1 and 19.2% (CH4 conversions) and 26.3 and 32.5% (CO2 conversions) for Ce0.8Sr0.2NiO3 and Ce0.6Sr0.4NiO3, respectively. This drop in catalytic conversions post strontium addition is concomitant with strontium carbonate covering nickel active sites. Moreover, from the durability results, it is obvious that CeNiO3 exhibited deactivation, whereas no deactivation was observed for Ce0.8Sr0.2NiO3 and Ce0.6Sr0.4NiO3. Carbon deposition during the reaction is mainly responsible for catalyst deactivation, and this is further established by characterizing spent catalysts.

Kinetic Study on the Effect of Substrate and Micronutrient Inhibition during Anaerobic Fermentation of Biohydrogen

There are several factors that influence the production of biohydrogen by dark fermentation including inoculum seeds, type and concentration of substrate, pH, temperature, presence of micronutrient and reactor configuration. Previous research has proven that the concentration of substrate and the presence of micronutrient will influence the yield and productivity of biohydrogen production. However, improvement of yield and productivity of the process can only be achieved once the system is under the optimum amount of substrate and micronutrient. Therefore, the best way to determine the effect of substrate concentration and presence of micronutrient is through kinetic study that was done using Monod model along with Andrews model. Besides that, the substrate inhibition effect also will be evaluated to determine the maximum substrate that needs to be supplied for maximum hydrogen production, and thus supplied the information for economic feasibility for fermentation process. In the meantime, the inhibition effect of adding the iron nanoparticles also had been evaluated in order to understand the interaction effect between iron nanoparticles and bacteria in term of catabolism reaction. It was found that increasing the substrate concentration more than 10 g/l will cause the inhibition to the system, in which it will slow down the reaction process and reduced the production of hydrogen. While the presence of iron NPs more than its optimum value (200 mg/l) will inhibit the bacterial growth and hence, affect the hydrogen production. For both cases, when the inhibition occurred at the respective concentration, it was found that the metabolic pathway was shifted to produce more hydrogen-consuming metabolite such as propionate acid, and thus, dropped the hydrogen production.