Durable multifunctional electrocatalysts with zero emission and high catalytic activity are desirable for environmentally benign clean energy technologies such as water-splitting devices, fuel cells, and rechargeable metal−air batteries. Herein, we investigate a new antisite disordered polycrystalline double-perovskite oxide Ca 2 FeRuO 6 (CFR) material for catalytic activity. This makes it a remarkable electrocatalyst with excellent stability in a highly alkaline (1 M KOH) medium for oxygen reduction reaction (ORR), oxygen evolution reaction (OER), and hydrogen evolution reaction (HER). The bulk perovskite exhibits significant onset potentials of 0.9 V for ORR and 1.57 V vs the reversible hydrogen electrode (RHE) for OER, creating a superior bifunctional electrocatalyst. The novelty enhances for trifunctionality as it shows a moderate onset potential of −0.19 V vs RHE for HER. Substantially, the present material efficiently accelerates visible-light-driven water splitting for OER at neutral pH with excellent recyclability. The photo-/electroactive perovskite is an exceptional example of a heterogeneous catalyst for multifunctional activity. A plausible mechanistic pathway for the synergistic effects of e g orbit-filling in perovskite oxides for OER, ORR, and HER activities is proposed by density functional theory (DFT) calculations.
A fluorescent probe for the monitoring of H 2 S levels in living cells and organisms is highly desirable. In this regard, nearinfrared (NIR) fluorescent probes have emerged as a promising tool. NIR-I and NIR-II probes have many significant advantages; for instance, NIR light penetrates deeper into tissue than light at visible wavelengths, and it causes less photodamage during biosample analysis and less autofluorescence, enabling higher signal-to-background ratios. Therefore, it is expected that fluorescent probes having emission in the NIR region are more suitable for in vivo imaging. Consequently, a considerable increase in reports of new H 2 Sresponsive NIR fluorescent probes appeared in the literature. This review highlights the advances made in developing new NIR fluorescent probes aimed at the sensitive and selective detection of H 2 S in biological samples. Their applications in real-time monitoring of H 2 S in cells and in vivo for bioimaging of living cells/animals are emphasized. The selection of suitable dyes for designing NIR fluorescent probes, along with the principles and mechanisms involved for the sensing of H 2 S in the NIR region, are described. The discussions are focused on small-molecule and nanomaterialsbased NIR probes.
Colorimetric sensors based on Sudan-III (1) and Alizarin red S (2) have been developed for the detection of a trace amount of water in organic solvents such as THF, acetone, acetonitrile, and DMSO. The deprotonated (anionic) forms of 1 and 2 namely 1.F and 2.F are reprotonated by using a trace amount of water. Deprotonation of 1 and 2 was obtained by using fluoride anion. Test papers of 1.F and 2.F in organic solvents with and without moisture showed dramatic changes in color. Receptor 1.F exhibits high sensitivity for water in acetone and THF with the detection limit as low as 0.0042 and 0.0058 wt %. Remarkably, probes 1.F and 2.F are reversible in nature both in solution and in test strips. 1.F and 2.F are reversible and reusable for sensing moisture in the organic solvents with high selectivity, high sensitivity, and fast response. The reversible moisture sensor 1.F has also been used for application in inkless writing.
A new approach for the detection of hydrogen sulfide (HS) was constructed within vesicles comprising phospholipids and amphiphilic copper complex as receptor. 1,2-Distearoyl- sn-glycero-3-phosphocholine (DSPC) vesicles with embedded metal complex receptor (1.Cu) sites have been prepared. The vesicles selectively respond to HS in a buffered solution and show colorimetric as well as spectral transformation. Other analytes such as reactive sulfur species, reactive nitrogen species, biological phosphates, and other anions failed to induce changes. The HS detection is established through a metal indicator displacement (MIDA) process, where Eosin-Y (EY) was employed as an indicator. Fluorescence, UV-vis spectroscopy, and the naked eye as the signal readout studies confirm the high selectivity, sensitivity, and lower detection limit of the vesicular receptor. The application of vesicular receptors for real sample analysis was also confirmed by fluorescence live cell imaging.
Heteroleptic ruthenium (II) complexes featuring donor functionalized phenyl‐terpyridine (ph‐tpy) and a monocarboxylic‐(ph‐tpy)/(tpy) are synthesized and characterized. Reactions of ruthenium (II) precursors at 80 °C favored heteroleptic complexes formation over the homoleptic side products. Visible light excitation of these complexes resulted in the metal‐to‐ligand charge transfer (MLCT) transitions. The inter‐planar torsional angle between the atoms of donor functionalized phenyl ring and the central pyridine (py) of the tpy core strongly influences visible light absorption and photovoltaic properties. The lower inter‐ring py‐ph torsion in the acceptor end of the MLCT structures and its increase in the oxidized doublets could prevent the back electron transfer. The ruthenium atom and the acceptor functionalized tpy host the triplet‐MLCT spin density. Ambient temperature excited‐state decay followed the energy gap law and occurred in the order of a few nanoseconds. Herein, we evaluate the photosensitizing ability of these complexes via a combined experimental and computational approach.
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