An official website of the United States government
Abstract Direct electrochemical production of dissolved ozone could potentially provide economic wastewater treatment and sanitation or a valuable chemical oxidant. Although Ni‐Sb‐SnO2electrocatalysts have the highest known faradaic efficiencies for electrochemical ozone production, the activity and selectivity are not yet sufficient for commercial implementation. This work finds that co‐doping Ni and Gd increases the ozone selectivity by a factor of three over Ni alone. These findings are the first demonstration of an active dopant other than Ni in SnO2. Electrochemical and physical characterization show that trends in ozone activity are caused by chemical catalysis, not morphology effects, and that conduction band alignment is not a catalytic descriptor for the system. Selective radical quenching experiments and quantum chemistry calculations of thermodynamic energies suggest that the kinetic barriers to form solution‐phase intermediates are important for understanding the role of dopants in electrochemical ozone production.
more »
« less
S-Nitrosothiols: chemistry and reactions
The formation of S -nitrosothiols (SNO) in protein cysteine residues is an important post-translational modification elicited by nitric oxide (NO). This process is involved in virtually every class of cell signaling and has attracted considerable attention in redox biology. On the other hand, their unique structural characters make SNO potentially useful synthons. In this review, we summarized the fundamental chemical/physical properties of SNO. We also highlighted the reported chemical reactions of SNO, including the reactions with phosphine reagents, sulfinic acids, various nucleophiles, SNO-mediated radical additions, and the reactions of acyl SNO species.
more »
« less
- Award ID(s):
- 1738305
- PAR ID:
- 10057355
- Date Published:
- Journal Name:
- Chem. Commun.
- Volume:
- 53
- Issue:
- 82
- ISSN:
- 1359-7345
- Page Range / eLocation ID:
- 11266 to 11277
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
Atomic layer deposition (ALD) is a technologically important method to grow thin films with high conformality and excellent thickness control from vapor phase precursors. The development of new thermal ALD processes can be limited by precursor reactivity and stability: reaction temperature and precursor design are among the few variables available to achieve higher reactivity, unlike in solution synthesis where the use of solvent and/or a catalyst can promote a desired reaction. To bridge this synthesis gap between vapor and solution, we demonstrate the use of an ultrathin coating layer of a vapor-phase compatible solvent—an ionic liquid (IL)— onto our growth substrate to perform ALD of SnO. Successful SnO deposition is achieved using tin acetylacetonate and water, a process that otherwise would require a stronger counter-reactant such as ozone. The layer of IL allows a solvent-mediated reaction mechanism to take place on the growth substrate. We report a growth per cycle of 0.67 Å/cycle at a deposition temperature of 100 °C in an IL comprised of 1-ethyl-3-methylimidazolium hydrogen sulfate. Characterization of the ALD films confirms the SnO film composition, and 1H and 13C NMR are used to probe the solvent-mediated ALD reaction, suggesting a solvent-mediated addition-elimination type mechanism forming acetone and acetate. Density functional theory calculations show that the ionic liquid solvent is beneficial to the proposed solvent-mediated mechanism by lowering the C-C bond cleavage energetics of acetylacetonate compared to the vapor phase. A general class of ligand-modification reactions for thermal ALD is thus introduced in this work.more » « less
-
Multi-component materials are a new trend in catalyst development for electrochemical CO 2 reduction. Understanding and managing the chemical interactions within a complex catalyst structure may unlock new or improved reactivity, but is scientifically challenging. We report the first example of capping ligand-dependent metal–oxide interactions in Au/SnO 2 structures for electrocatalytic CO 2 reduction. Cetyltrimethylammonium bromide capping on the Au nanoparticles enables bifunctional CO 2 reduction where CO is produced at more positive potentials and HCOO − at more negative potentials. With citrate capping or no capping, the Au–SnO 2 interactions steer the selectivity toward H 2 evolution at all potentials. Using electrochemical CO oxidation as a probe reaction, we further confirm that the metal–oxide interactions are strongly influenced by the capping ligand.more » « less
-
The stabilization of the B-site oxidation state in ABO 3 perovskites using wet-chemical methods is a synthetic challenge, which is of fundamental and practical interest for energy storage and conversion devices. In this work, defect-controlled (Sr-deficiency and oxygen vacancies) strontium niobium( iv ) oxide (Sr 1−x NbO 3−δ , SNO) metal oxide nanoparticles (NPs) were synthesized for the first time using a low-pressure wet-chemistry synthesis. The experiments were performed under reduced oxygen partial pressure to prevent by-product formation and with varying Sr/Nb molar ratio to favor the formation of Nb 4+ pervoskites. At a critical Sr to Nb ratio (Sr/Nb = 1.3), a phase transition is observed forming an oxygen-deficient SrNbO 3 phase. Structural refinement on the resultant diffraction pattern shows that the SNO NPs consists of a near equal mixture of SrNbO 3 and Sr 0.7 NbO 3−δ crystal phases. A combination of Rietveld refinement and X-ray photoelectron spectroscopy (XPS) confirmed the stabilization of the +4 oxidation state and the formation of oxygen vacancies. The Nb local site symmetry was extracted through Raman spectroscopy and modeled using DFT. As further confirmation, the particles demonstrate the expected absorption highlighting their restored optoelectronic properties. This low-pressure wet-chemical approach for stabilizing the oxidation state of a transition metal has the potential to be extended to other oxygen sensitive, low dimensional perovskite oxides with unique properties.more » « less
-
Abstract BackgroundProtein S-nitrosylation (SNO) plays a key role in transferring nitric oxide-mediated signals in both animals and plants and has emerged as an important mechanism for regulating protein functions and cell signaling of all main classes of protein. It is involved in several biological processes including immune response, protein stability, transcription regulation, post translational regulation, DNA damage repair, redox regulation, and is an emerging paradigm of redox signaling for protection against oxidative stress. The development of robust computational tools to predict protein SNO sites would contribute to further interpretation of the pathological and physiological mechanisms of SNO. ResultsUsing an intermediate fusion-based stacked generalization approach, we integrated embeddings from supervised embedding layer and contextualized protein language model (ProtT5) and developed a tool called pLMSNOSite (protein language model-based SNO site predictor). On an independent test set of experimentally identified SNO sites, pLMSNOSite achieved values of 0.340, 0.735 and 0.773 for MCC, sensitivity and specificity respectively. These results show that pLMSNOSite performs better than the compared approaches for the prediction of S-nitrosylation sites. ConclusionTogether, the experimental results suggest that pLMSNOSite achieves significant improvement in the prediction performance of S-nitrosylation sites and represents a robust computational approach for predicting protein S-nitrosylation sites. pLMSNOSite could be a useful resource for further elucidation of SNO and is publicly available athttps://github.com/KCLabMTU/pLMSNOSite.more » « less
- Free Publicly Accessible Full Text
-
Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/c7cc06574d
