The replacement of traditional ruthenium-based photosensitizers with low-cost and abundant iron analogs is a key step for the advancement of scalable and sustainable dye-sensitized water splitting cells. In this proof-of-concept study, a pyridinium ligand coordinated pentacyanoferrate(II) chromophore is used to construct a cyanide-based CoFe extended bulk framework, in which the iron photosensitizer units are connected to cobalt water oxidation catalytic sites through cyanide linkers. The iron-sensitized photoanode exhibits exceptional stability for at least 5 h at pH 7 and features its photosensitizing ability with an incident photon-to-current conversion capacity up to 500 nm with nanosecond scale excited state lifetime. Ultrafast transient absorption and computational studies reveal that iron and cobalt sites mutually support each other for charge separation via short bridging cyanide groups and for injection to the semiconductor in our proof-of-concept photoelectrochemical device. The reorganization of the excited states due to the mixing of electronic states of metal-based orbitals subsequently tailor the electron transfer cascade during the photoelectrochemical process. This breakthrough in chromophore-catalyst assemblies will spark interest in dye-sensitization with robust bulk systems for photoconversion applications. 相似文献
Via an oxidation reaction of Cu(I) iodide with pyridine-2,6-dicarboxylic acid (H2L) in DMF three copper(II) complexes, [(CH3)2NH2]2[CuL2] (1), K2[CuL2]?H2L?H2O (2) and [Cu(L)(H2O)]n (3), were synthesized and characterized. The structures of 1–3 were determined by single crystal X-ray diffraction studies. In-situ DMF decomposition produces dimethylamine base under solvothermal conditions and a proton transfer reaction takes place for the complex formation of 1. 3-D networks are stabilized in 1 and 2 via hydrogen bonds. Complex 3 is a 1-D coordination polymer with Cu-O semi-coordination bonds. Thermal decomposition of the complexes results in the corresponding metal oxides. Also, the electrochemical behavior of 1 was determined to be a metal-centered and diffusion-controlled, one-electron reduction process. 相似文献
In this study, electrochemical degradation of microcrystalline cellulose (MCC) under hot-compressed water was investigated via application of constant voltage on reaction medium. Constant voltage ranges from 2.5 to 8.0 V was applied between anode (Titanium) and cathode (reactor wall). As an electrolyte and proton source 5–25 mM of H2SO4 was used. Reactions were carried out in a specially designed batch reactor (450 mL) made of T316 for 240 min at temperature of 200 °C.MCC decomposition products such as glucose, fructose, furfural, 5-HMF and levulinic acid were detected and quantified by High Performance Liquid Chromatography (HPLC). In the absence of electrolyte, applied voltage (2.5 and 4.0 V) decreased the total organic carbon (TOC) yield, in contrast at 8.0 V, TOC yield increased to 13%. Application of 8.0 V in hydrothermal conditions alter MCC decomposition pathway selectively to furfural (15%). Addition of electrolyte (5 mM, H2SO4) and application of 2.5 V potential increased TOC (54%) and changed the decomposition pathway in favor of 5-HMF (30%) and levulinic acid (21%). The structural changes in solid residues of electrochemically reacted MCC was analyzed by Fourier Transform Infrared Spectroscopy (FTIR) and found that MCC particles functionalized by carboxylic acid and sulfonated groups by the application of constant voltage to reaction medium. In the presence of electrolyte, under certain voltage (2.5 V), functionalization of solid particles became more obvious in FTIR spectrum results. Therefore, change in the selectivity values of degradation products were conducted with the functionalization of MCC particles due to applied voltage under sub-critical conditions. 相似文献
An asymmetric norm is a positive sublinear functional p on a real vector space X satisfying \(x=\theta _X\) whenever \(p(x)=p(-x)=0\). Since the space of all lower semi-continuous linear functionals of an asymmetric normed space is not a linear space, the theory is different in the asymmetric case. The main purpose of this study is to define bounded and continuous linear operators acting between asymmetric cone normed spaces. After examining the differences with symmetric case, we give some results related to Baire’s characterization of completeness in asymmetric cone normed spaces. 相似文献
N,N′‐diethoxy‐4,4′‐azobis(pyridinium) hexafluorophosphate (DEAP) has been synthesized by alkylation of the corresponding N‐oxide and characterized. DEAP exhibits UV induced cis–trans isomerization with absorptions at around λ = 459 and 360 nm, respectively. The ability of the DEAP ion to act as a photoinitiator for the cationic polymerization of cyclohexene oxide and N‐vinylcarbazole is demonstrated. The initiation step involves the decay of the excited state of the trans form of the salt with homolytic bond rupture of the nitrogen–oxygen bond. Its potential use as a photoinitiator for free radical polymerization is also demonstrated using methyl methacrylate monomer as the example.
We report, for the first time, a detailed crystallographic study of the supramolecular arrangement for a set of zinc(II) Schiff base complexes containing the ligand 2,6-bis((E)-((2-(dimethylamino)ethyl)imino)methyl)-4-R-phenol], where R=methyl/tert-butyl/chloro. The supramolecular study acts as a pre-screening tool for selecting the compartmental ligand R of the Schiff base for effective binding with a targeted protein, bovine serum albumin (BSA). The most stable hexagonal arrangement of the complex [Zn − Me] (R=Me) stabilises the ligand with the highest FMO energy gap (ΔE=4.22 eV) and lowest number of conformations during binding with BSA. In contrast, formation of unstable 3D columnar vertebra for [Zn − Cl] (R=Cl) tend to activate the system with lowest FMO gap (3.75 eV) with highest spontaneity factor in molecular docking. Molecular docking analyses reported in terms of 2D LigPlot+ identified site A, a cleft of domains IB, IIIA and IIIB, as the most probable protein binding site of BSA. Arg144, Glu424, Ser428, Ile455 and Lys114 form the most probable interactions irrespective of the type of compartmental ligands R of the Schiff base whereas Arg185, Glu519, His145, Ile522 act as the differentiating residues with ΔG=−7.3 kcal mol−1. 相似文献