ABSTRACT
Due to the limited exploitation and utilization of fossil energy resources in recent years, it is imperative to explore and develop new energy materials. As an electrode material for batteries, MnCO3 has the advantages of safety, non-toxicity, and wide availability of raw materials. But it also has some disadvantages, such as short cycle period and low conductivity. In order to improve these deficiencies, we designed a MnCO3@Mn3O4 heterostructure material by a simple solvothermal method, which possessed a microstructure of "butterfly-tie". Owing to the introduction of Mn3O4 and the layered structure of "butterfly-tie", MnCO3@Mn3O4 possessed a discharge capacity of 165 mAh/g when the current density was 0.2 A/g and exhibited satisfactory rate performance. The MnCO3@Mn3O4 heterostructure was optimized by density functional theory (DFT), and the deformation charge density was calculated. It was found that the MnCO3@Mn3O4 heterostructure is stable owing to the molecular interaction between the O atoms from MnCO3 and the Mn atoms from Mn3O4 at the interface of heterojunction. Therefore, the MnCO3@Mn3O4 heterostructure material has promising applications as safe and efficient cathode material for energy batteries.
ABSTRACT
Zinc is a vital metal element with extensive applications in various fields such as industry, metallurgy, agriculture, food, and healthcare. For living organisms, zinc ions are indispensable, and their deficiency can lead to physiological and metabolic abnormalities that cause multiple diseases. Hence, there is a significant need for selective recognition and effective detection of free zinc ions. As a probe method with high sensitivity, high selectivity, real-time monitoring, safety, harmlessness and ease of operation, fluorescent probes have been widely used in metal ion identification studies, and many convenient, low-cost and easy-to-operate fluorescent probes for Zn2+ detection have been developed. This article reviews the latest research advances in fluorescent chemosensors for Zn2+ detection from 2019 to 2023. In particular, sensors working through photo-induced electron transfer (PET), excited state intramolecular proton transfer (ESIPT), intramolecular charge transfer (ICT), fluorescence resonance energy transfer (FRET), chelation-enhanced fluorescence (CHEF), and aggregation-induced emission (AIE) mechanisms are described. We discuss the use of various recognition mechanisms in detecting zinc ions through specific cases, some of which have been validated through theoretical calculations.
ABSTRACT
Polyhedral oligomeric silsesquioxane (POSS) has a nanoscale silicon core and eight organic functional groups on the surface, with sizes from 0.7 to 1.5 nm. The three-dimensional nanostructures of POSS can be used to build all types of hybrid materials with specific performance and controllable nanostructures. The applications of POSS-based fluorescent materials have spread across various fields. In particular, the employment of POSS-based fluorescent materials in sensing application can achieve high sensitivity, selectivity, and stability. As a result, POSS-based fluorescent materials are attracting increasing attention due to their fascinating vistas, including unique structural features, easy fabrication, and tunable optical properties by molecular design. Here, we summarize the current available POSS-based fluorescent materials from design to sensing applications. In the design section, we introduce synthetic strategies and structures of the functionalized POSS-based fluorescent materials, as well as photophysical properties. In the application section, the typical POSS-based fluorescent materials used for the detection of various target objects are summarized with selected examples to elaborate on their wide applications.
Subject(s)
Nanostructures , Organosilicon Compounds , Coloring Agents , Nanostructures/chemistry , Organosilicon Compounds/chemistryABSTRACT
In the current work, we studied the sensing process of the sensor (E)-2-((quinolin-8ylimino) methyl) phenol (QP) for fluoride anion (F-) with a "turn on" fluorescent response by density functional theory (DFT) and time-dependent density functional theory (TDDFT) calculations. The proton transfer process and the twisted intramolecular charge transfer (TICT) process of QP have been explored by using potential energy curves as functions of the distance of N-H and dihedral angle C-N=C-C both in the ground and the excited states. According to the calculated results, the fluorescence quenching mechanism of QP and the fluorescent response for F- have been fully explored. These results indicate that the current calculations completely reproduce the experimental results and provide compelling evidence for the sensing mechanism of QP for F-.
Subject(s)
Fluorides , Schiff Bases , Anions , Models, Molecular , ProtonsABSTRACT
In recent years, aqueous zinc ion batteries (ZIBs) have attracted much attention due to their high safety, low cost, and environmental friendliness. Owing to the unique layered structure and more desirable layer spacing, transition metal dichalcogenide (TMD) materials are considered as the comparatively ideal cathode material of ZIBs which facilitate the intercalation/ deintercalation of hydrated Zn2+ between layers. However, some disadvantages limit their widespread application, such as low conductivity, low reversible capacity, and rapid capacity decline. In order to improve the electrochemical properties of TMDs, the corresponding modification methods for each TMDs material can be designed from the following modification strategies: defect engineering, intercalation engineering, hybrid engineering, phase engineering, and in-situ electrochemical oxidation. This paper summarizes the research progress of TMDs as cathode materials for ZIBs in recent years, discusses and compares the electrochemical properties of TMD materials, and classifies and introduces the modification methods of MoS2 and VS2. Meanwhile, the corresponding modification scheme is proposed to solve the problem of rapid capacity fading of WS2. Finally, the research prospect of other TMDs as cathodes for ZIBs is put forward.
ABSTRACT
The interaction of 1-Phenyl-3-(pyren-1-yl) urea (LH) and fluoride anion (F-) with a unique ON1-OFF-ON2 fluorescent response has been investigated by the density functional theory (DFT) and time-dependent density functional theory (TDDFT) calculations. The hydrogen-bonding dynamics and photophysical properties of the complex LH-F, as well as its isolated receptor LH and anion form L-H1, have been studied in detail. We demonstrate that the intermolecular hydrogen bond (N-H F) of the complex LH-F is greatly enhanced in the electronically excited state. The nonradiative deactivation via electron transfer and internal conversion rather than excited-state intramolecular proton transfer (ESIPT) can be facilitated by the excited state hydrogen bond strengthening. The results have been cross-validated by molecular structure, electronic spectra, frontier molecular orbitals, and infrared spectra as well as hydrogen bond binding energy. These results indicate that the current calculations completely reproduce the experimental results and provide compelling evidence for the sensing mechanism of LH for F-.
ABSTRACT
The effects of substituent on excited-state intramolecular proton transfer (ESIPT) and hydrogen bonding of N-(8-Quinolyl) salicylaldimine (QS) have been studied by theoretical calculation with DFT and TDDFT. The representative electron-withdrawing nitryl and electron-donating methoxyl were selected to analyze the effects on geometries, intramolecular hydrogen bond interaction, absorption/fluorescence spectra, and the ESIPT process. The configurations of the three molecules (QS, QS-OMe and QS-NO2) were optimized in the ground and excited states. The structure parameters, infrared spectra, hydrogen bond interactions, frontier molecular orbitals, absorption/fluorescence spectra, and potential curves have cross-validated the current results. The results show that the introduction of substituent results in a bathochromic-shift of the absorption and fluorescence spectra with large Stokes shift, and is more beneficial to the ESIPT process. The current work will be beneficial to the improvement of ESIPT properties and deepen understanding of the mechanism of ESIPT process.
ABSTRACT
DFT and TDDFT calculations are adopted to study the sensing mechanism of a turn-on-type cysteine fluorescent probe (2-(1-phenyl-imidazo[1,5-α]pyridine-3-yl)phenyl acrylate, denoted as MZC-AC). The photoinduced electron transfer (PET) process of MZC-AC and the excited state intramolecular proton transfer (ESIPT) process of MZC have been investigated in detail. We demonstrate that the fluorescence quenching of MZC-AC is ascribed to the PET mechanism and the large Stokes shift fluorescence emission of MZC is the result of the ESIPT mechanism. The results have been cross-validated by geometries, frontier molecular orbital analysis, and potential energy curve scanning. As a result, our calculations completely reproduce the experimental results and give powerful evidence for the sensing mechanism of MZC-AC for cysteine.
ABSTRACT
A density functional theory (DFT) and time-dependent density functional theory (TDDFT) calculations have been used to study the sensing mechanism of an ON1-OFF-ON2 type fluoride anion fluorescent chemosensor (Bis[[7-(diethylamino)-2-oxo-2H-chromene]methyl-ene]carbonothioic dihydrazide (CTC). The current theoretical calculation presents a different sensing mechanism from the experimentally proposed one (Sensor and Actuators B 2016, 222, 823-828). Instead of the combination of CTC deprotonation and poorly emissive excited state tautomer or ICT mechanism, the theoretical results predict the sensing mechanism based on dissociation reaction and excited-state proton transfer (ESPT). The calculated vertical excitation energies both in the ground states and first excited states of different forms of CTC, as well as the potential-energy curves, have completely reproduced the experimental results, providing powerful evidence for our proposed CTC sensing mechanism for fluoride anion.
ABSTRACT
Metastable hexagonal h-MoO(3) nanorods were synthesized by a simple sonochemical method, and then were transformed into thermodynamically stable a-MoO(3) microbelts by calcination. The obtained samples were characterized by X-ray diffraction (XRD), differential thermal analysis (DTA), field-emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM). It was found that the as-prepared h-MoO(3) nanorods were of 0.2-1.2 µm in width and 1-6 µm in length. A possible formation and growth mechanism of hexagonal MoO(3) nanorods is proposed, in which ultrasound plays a crucial role and cannot be ignored. Moreover, the effect of temperature on the transformation process by calcination is investigated and a possible growth process of microbelts is also discussed.
