Oxygen Vacancies on NH4 V4 O10 Accelerate Ion and Charge Transfer in Aqueous Zinc-Ion Batteries.

Vanadium-based compounds are identified as promising cathode materials for aqueous zinc ion batteries due to their high specific capacity. However, the low intrinsic conductivity and sluggish Zn2+ diffusion kinetics seriously impede their further practical application. Here, oxygen vacancies on NH4 V4 O10 is reported as a high-performing cathode material for aqueous zinc ion batteries via a facile hydrothermal strategy. The introduction of oxygen vacancy accelerates the ion and charge transfer kinetics, reduces the diffusion barrier of zinc ions, and establishes a stable crystal structure during zinc ion (de-intercalation). As a result, the oxygen vacancy enriched NH4 V4 O10 exhibits a high specific capacity of ≈499 mA h g-1 at 0.2 A g-1 , an excellent rate capability of 296 mA h g-1 at 10 A g-1 and the specific capacity cycling stability with 95.1% retention at 5 A g-1 for 4000 cycles, superior to the NVO sample (186.4 mAh g-1 at 5 A g-1 , 66% capacity retention).

Photoelectrochemical thrombin biosensor based on perylene-3,4,9,10-tetracarboxylic acid and Au co-functionalized ZnO nanorods with signal-off quenching effect of Ag@Ag2S.

In this work, a thrombin photoelectrochemical aptasensor was reported based on a photoanode of perylene-3,4,9,10-tetracarboxylic acid (PTCA), Au nanoparticle co-functionalized ZnO nanorods (ZnO NRs) and the "signal-off" amplification effect of Ag@Ag2S. The photocurrent response of the ZnO NRs was improved greatly due to the excellent visible-light photoelectric performance of PTCA and the surface plasmon resonance (SPR) effect of Au nanoparticles. Due to the specific recognition between thrombin and aptamers, the non-conductive complex with a steric hindrance structure blocked the diffusion path of the electron donating ascorbic acid (AA) and then the "signal-off" Ag@Ag2S quencher was captured. The quencher blocked the irradiation light toward the ZnO NRs/PTCA/Au electrode and competitively consumed the electron donor AA that could have been involved in the oxidation reaction with photogenerated holes of PTCA, resulting in the further decrease of the photocurrent. Based on the evident photocurrent response of the photoanode and the superior quenching strategies, the detection limit of thrombin is as low as 33 fM with a wide linear detection range from 0.0001 nM to 50 nM. The prepared biosensor also exhibited good specificity, reproducibility and stability, suggesting potential application in thrombin specific detection.

Hg2+ Significantly Enhancing the Peroxidase-Like Activity of H2TCPP/ZnS/CoS Nanoperoxidases by Inducing the Formation of Surface-Cation Defects and Application for the Sensitive and Selective Detection of Hg2+ in the Environment.

Exploring excellent peroxidase mimics with enhanced peroxidase-like activity is important to the construction of a fast, low-cost, and convenient colorimetric sensing platform for heavy ions. In this work, 5,10,15,20-tetrakis(4-carboxyphenyl)porphyrin (H2TCPP) was first used to modify ZnS/CoS and make it show better peroxidase-like activity. The metal-cation vacancies generated by Hg2+ contacting H2TCPP/ZnS/CoS further stimulate the catalytic activity. It is reported that the addition of Hg2+ usually causes a decrease of the peroxidase-like activity of metal sulfides. Oppositely, in our work, Hg2+ can trigger the colorimetric signal amplification because of lots of metal-cation vacancies generated on the surface of the nanocomposites (bimetallic sulfides). The peroxidase-like activity of ZnS/CoS was evaluated by virtue of the chromogenic substrate 3,3,5,5-tetramethylbenzidine (TMB) from colorless to blue in 3 min. The enhanced catalytic activity of H2TCPP/ZnS/CoS was attributed to lots of active sites from the metal-cation defects on the surface of H2TCPP/ZnS/CoS as well as the synergistic effect of porphyrin molecules and ZnS/CoS. The adsorption behavior of H2O2 on the H2TCPP/ZnS/CoS surface with defects was studied by density functional theory calculation. Thus, a colorimetric sensing platform based on Hg2+ trigger signal amplification has been successfully constructed, which can be used to sensitively and selectively determine Hg2+ in environmental samples.

Hydroquinone colorimetric sensing based on platinum deposited on CdS nanorods as peroxidase mimics.

Pt deposited on CdS nanorods (Pt/CdS) have been prepared via the UV light photoreduction method. The Pt/CdS nanocomposites possess highly significant peroxidase-like activity with the assistance of the colorless substrate 3,3,5,5-tetramethylbenzidine (TMB). In the presence of peroxidase mimic Pt/CdS, TMB is quickly oxidized into a typical blue product (oxTMB, which has an obvious absorption at 652 nm) by H2O2 only in 3 min, which is easily detected visually. The catalytic activity of Pt/CdS originates from the accelerated electron transfer between the reactants. Combining the peroxidase-like activity of Pt/CdS with the blue change of TMB, a fast colorimetric sensing platform for detection of H2O2 has been constructed with a linear range 0.10-1.00 mM and a detection limit of 45.5 µM. The platform developed is further used to detect hydroquinone (HQ) in the range1.0-10 µM with a lower detection limit of 0.165 µM. The colorimetric platform has a potential to detect HQ residue in real water samples with recoveries ranging from 83.56 to 91.76%. Graphical abstract.

Porphyrin functionalized Co(OH)2/GO nanocomposites as an excellent peroxidase mimic for colorimetric biosensing.

5,10,15,20-Tetrakis(4-carboxyl phenyl)porphyrin (Por) modified Co(OH)2 deposited on the surface of GO nanocomposites (Por/Co(OH)2/GO) were prepared and characterized by transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and XRD. For the first time, H2TCPP/Co(OH)2/GO is found to have enhanced peroxidase-like activity and catalyze the oxidation of the substrate 3,3,5,5-tetramethylbenzidine (TMB) by hydrogen peroxide (H2O2). Notably, the colorless TMB rapidly transformed into blue oxTMB in just 60 s, which was easily observed visually. The catalytic kinetics of H2TCPP/Co(OH)2/GO is in accord with the Michaelis-Menten equation. The catalytic mechanism of H2TCPP/Co(OH)2/GO nanocomposites is attributed to hydroxyl radicals (˙OH), due to decomposition of H2O2, which is verified by using terephthalic acid as a fluorescent probe. What's more, H2O2 can be detected in a wide linear detection range from 5 to 35 mM with a detection limit of 0.385 mM. Furthermore, based on the excellent peroxidase-like activity of H2TCPP/Co(OH)2/GO, a colorimetric sensor is established to sensitively detect glutathione (GSH) in a linear range from 10 to 300 µM with a low detection limit of 9.5 µM.

Rapid colorimetric determination of dopamine based on the inhibition of the peroxidase mimicking activity of platinum loaded CoSn(OH)6 nanocubes.

Platinum nanoparticles were loaded on CoSn(OH)6 nanocubes via a co-precipitation method. The material (NCs) is shown to be a viable peroxidase mimic that catalyzes the oxidation of 3,3',5,5'-tetramethylbenzidine (TMB) by hydrogen peroxide (H2O2) to generate oxidized TMB (oxTMB) with absorption at 652 nm. The formation of the blue color can be observed in <30 s. Thus, a visual and colorimetric assay was worked out for H2O2. It has a detection limit as low as 4.4 µM and works in the 5 to 200 µM concentration range. The method was also used to detect dopamine (DA) which is found to inhibit the enzyme mimicking activity of the NCs. Hence, less blue color is formed in its presence. The respective DA assay has a linear response in the 5.0 to 60 µM concentration range and a 0.76 µM detection limit. Graphical abstractSchematic diagram of a visual colorimetric method for determination of H2O2 and dopamine (DA) with the aid of color change of 3,3',5,5'-tetramethylbenzidine (oxTMB), based on the peroxidase-like activity of Pt/CoSn(OH)6 nanocubes.

An amorphous MgF2 anti-reflective thin film for enhanced performance of inverted organic-inorganic perovskite solar cells.

The effective control of light plays an important role in optoelectronic devices. However, the effect of anti-reflection thin film (ARTF) in inverted perovskite solar cells (PSCs) (p-i-n) has so far remained elusive. Herein, MgF2 ARTF with different thicknesses (approximately 100, 330, and 560 nm) were deposited on the glass side of FTO conductive glass substrates by vacuum thermal evaporation. The results of reflectance and transmittance spectroscopy show that approximately 330 nm MgF2 ARTF can reduce reflectivity and increase transmittance on FTO conductive glass substrates. The results of SEM, XRD, and AFM show that the surface of amorphous MgF2 ARTF possesses a lot of nanoscale pits. The effect of the MgF2 ARTF on the performance of inverted perovskite solar cells (PSCs) (p-i-n) was investigated. The power conversion efficiencies (PCE) of inverted PSCs without and with MgF2 ARTF are 18.20 and 21.28%, respectively. The significant improvement in PCE of the devices with MgF2 ARTF is caused by the improvement in short-circuit current density. The stability results of the devices show that the PCE remains above 70% of the initial PCE after 300 h illumination.

All-catecholate-stabilized black titanium-oxo clusters for efficient photothermal conversion.

The controlled synthesis of titanium-oxo clusters (TOCs) completely stabilized by organic dye ligands with high stability and superior light absorption remains a significant challenge. In this study, we report the syntheses of three atomically precise catechol (Cat)-functionalized TOCs, [Ti2(Cat)2(OEgO)2(OEgOH)2] (Ti2), [Ti8O5(Cat)9(iPrO)4(iPrOH)2] (Ti8), and [Ti16O8(OH)8(Cat)20]·H2O·PhMe (Ti16), using a solvent-induced strategy (HOEgOH = ethylene glycol; iPrOH = isopropanol; PhMe = toluene). Interestingly, the TiO core of Ti16 is almost entirely enveloped by catechol ligands, making it the first all-catechol-protected high-nuclearity TOC. In contrast, Ti2 and Ti8 have four weakly coordinated ethylene glycol ligands and six weakly coordinated iPrOH ligands, respectively, in addition to the catechol ligands. Ti16 is visually evident in its distinctively black appearance, which belongs to black TOCs (B-TOCs) and exhibits an ultralow optical band gap. Furthermore, Ti16 displays exceptional stability in various media/environments, including exposure to air, solvents, and both acidic and alkaline aqueous solutions due to its comprehensive protection by catechol ligands and rich intra-cluster supramolecular interactions. Ti16 has superior photoelectric response qualities and photothermal conversion capabilities compared to Ti2 and Ti8 due to its ultralow optical band gap and remarkable stability. This discovery not only represents a huge step forward in the creation of all-catecholate-protected B-TOCs with ultralow optical band gaps and outstanding stability, but it also gives key valuable mechanistic insights into their photothermal/electric applications.

Electrochemically Induced Phase Transformation in Vanadium Oxide Boosts Zn-Ion Intercalation.

Vanadium oxides are excellent cathode materials with large storage capacities for aqueous zinc-ion batteries, but their further development has been hampered by their low electronic conductivity and slow Zn2+ diffusion. Here, an electrochemically induced phase transformation strategy is proposed to mitigate and overcome these barriers. In situ X-ray diffraction analysis confirms the complete transformation of tunnel-like structural V6O13 into layered V5O12·6H2O during the initial electrochemical charging process. Theoretical calculations reveal that the phase transformation is crucial to reducing the Zn2+ migration energy barrier and facilitating fast charge storage kinetics. The calculated band structures indicate that the bandgap of V5O12·6H2O (0.0006 eV) is lower than that of V6O13 (0.5010 eV), which enhanced the excitation of charge carriers to the conduction band, favoring electron transfer in redox reactions. As a result, the transformed V5O12·6H2O delivers a high capacity of 609 mA h g-1 at 0.1 A g-1, superior rate performance (300 mA h g-1 at 20 A g-1), fast-charging capability (<7 min charging for 465 mA h g-1), and excellent cycling stability with a reversible capacity of 346 mA h g-1 at 5 A g-1 after 5000 cycles.

Self-Seeding Synthesis of Hierarchically Branched Rutile TiO2 for High-Efficiency Dye-Sensitized Solar Cells.

This study presents a unique and straightforward room temperature-based wet-chemical technique for the self-seeding preparation of three-dimensional (3D) hierarchically branched rutile TiO2, abbreviated HTs, employing titanate nanotubes as the precursor. In the course of the synthesis, spindle-like rutile TiO2 and the intermediate anatase phase were first obtained through a dissolution/precipitation/recrystallization process, with the former serving as the substrates and the latter as the nucleation precursor to growing the branches, which finally gave birth to the production of 3D HTs nanostructures. When the specifically created hierarchical TiO2 was used as the photoanode in dye-sensitized solar cells (DSCs), a significantly improved power conversion efficiency (PCE) of 8.32% was achieved, outperforming a typical TiO2 (P25) nanoparticle-based reference cell (η = 5.97%) under the same film thickness. The effective combination of robust light scattering, substantial dye loading, and fast electron transport for the HTs nanostructures is responsible for the remarkable performance.

Ultrasmall nitrogen-doped Cu0·92Co2·08O4 nanocrystal-decorated cerium dioxide nanoparticles for fast and complete degradation of ranitidine via permonosulfate activation.

A simple and efficient coagulation method was used for the rapid preparation of nitrogen-doped copper-cobalt oxide (N-Cu0.92Co2·08O4) supported on cerium dioxide (CeO2), that is, N-Cu0.92Co2·08O4@CeO2. A low concentration of N-Cu0.92Co2·08O4@CeO2 (0.15 g L-1) was shown to rapidly activate permonosulfate (PMS) (0.15 g L-1) to achieve 100% degradation of ranitidine within 10 min. A 100% degradation of ranitidine enabled by the catalyst was achieved over a wide range of pH (5.5-9.0), which could be completed within 8 min in the presence of anionic H2PO4-. Moreover, the N-Cu0.92Co2·08O4@CeO2 catalyst enabled more than 90% degradation of various typical antibiotics within 30 min, including tetracycline, sulfaixoxazole, and chloramphenicol, with degradation rates of 100%, 93.51%, and 90.01%, respectively. Even after four catalytic cycles, N-Cu0.92Co2·08O4@CeO2 could be regenerated to achieve 100% degradation of ranitidine. Electrochemical analysis demonstrated that the combination of N-Cu0.92Co2·08O4@CeO2 and PMS immediately produced a strong current density, thereby rapidly producing reactive oxygen species (ROS) with high performance for the degradation of the target pollutant. Combined ion quenching and electron paramagnetic resonance analyses indicated that the main ROS was the non-free radical 1O2. Finally, a plausible ranitidine degradation pathway was deduced based on liquid chromatography-mass spectrometry (LC-MS) analysis, wherein the toxic substance N-nitrosodimethylamine was not produced during the degradation process. In short, this study provides a new perspective for preparing ternary metal catalysts for advanced oxidation processes with practical application significance.

Facile Synthesis of a Multifunctional SnO2 Nanoparticles/Nanosheets Composite for Dye-Sensitized Solar Cells.

Synthesizing SnO2 composite nanostructures via a facile one-step method has been proven to be a great challenge. By adjusting operating variables, such as the reaction solution's pH and solvent type, several SnO2 nanostructures, in particular, a function-matching SnO2 hybrid structure composed of irregular zero-dimensional nanoparticles (NPs) and two-dimensional nanosheets (NSs), could be created. The as-prepared SnO2 composites were then characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscope (SEM), and diffuse reflectance spectroscopy (DRS) to determine their physical properties. Dye-sensitized solar cells (DSCs) constructed with the resultant multifunctional SnO2 NPs/NSs composite exhibited the highest overall power conversion efficiency (PCE) of 5.16% among all products with a corresponding short-circuit current density of 18.6 mA/cm2 and an open-circuit voltage of 0.626 V. The improved performance can be attributed to the combined effects of each component in the composite, i.e., the intentionally introduced nanosheets provide desired electron transport and enhanced light scattering capability, while the nanoparticles retain their large surface area for efficient dye absorption.

Growth, structural, optical and electronic transport properties of tetragonal CH3NH3SnBr3 perovskite single crystals.

The structural and electronic transport properties of tetragonal CH3NH3SnBr3 single crystals (T-MASnBr3 SCs) are rarely reported. In this study, we synthesized T-MASnBr3 single crystals by volatilizing DMF solvent at room temperature. The crystal system and space group of the T-MASnBr3 SC are tetragonal and P4/mmm, respectively. In addition, the nitrogen atom in the methylamine group exhibits position disorder. The band gap of the T-MASnBr3 SC was determined to be 2.07 eV using the Tauc plot. Six fluorescence peaks and a lifetime up to 10 microseconds were observed in the steady-state fluorescence spectra and time-resolved fluorescence spectra of the T-MASnBr3 SC, respectively. The carrier mobility (electron) of T-MASnBr3 was 321 cm2 V-1 s-1. The curve of ln(square resistance) against T-1 was a straight line. The value of the activation energy (Ea) was 5421 J mol-1. The stability of the T-MASnBr3 SC was good before 473 K. The results indicate that T-MASnBr3 SCs have promising applications in the field of temperature sensors.

Cyclometalated iridium(III) complexes based on phenyl-imidazole ligand.

Phenyl-imidazole-based ligands with various substitution patterns have been used as the main ligand for heteroleptic bis-cyclometalated iridium complexes. Two series of complexes have been prepared and their photophysical and electrochemical properties were studied. The phosphorescence emission maxima range from about 490 to 590 nm, that is, from greenish-blue to orange. The first series is of the form Ir(L)2(acac) (L: a phenyl-imidazole based ligand; acac: acetylacetonate). In the first complex, 1a, L is 1,4,5-trimethyl-2-phenyl-1H-imidazole. Then, methyl groups are replaced with phenyl groups and chlorines are grafted on the cyclometalated phenyl ring. The second series is of the form Ir(4,5-dimethyl-1,2-diphenyl-1H-imidazole)2(La) (La: ancillary ligand being acetylacetonate, acac, N,N-dimethylamino-picolinate, NPic, picolinate, Pic, or 2-(diphenylphosphino)acetic acid, P). These series show that modifying the substitution pattern on the ligands can alter the photophysical and electrochemical properties of the complexes. Overall, we show that compared to complexes containing phenyl-pyridine ligands, highest occupied molecular orbitals (HOMOs) and lowest unoccupied molecular orbitals (LUMOs) are more delocalized over the entire main ligand in complexes containing phenyl-imidazole. Contrary to expectations, when chlorine atoms are used as strong acceptor substituents on the orthometalated phenyl, a red shift of the emission is observed. This behavior has been rationalized using theoretical calculations on the excited state of the chloro-substituted complex 3a compared to the model 1a.

Synthesis, structure, mobility and memristor properties of tetragonal CH3NH3PbBr3 perovskite single crystals.

The structure, mobility and memristor properties of tetragonal CH3NH3PbBr3 single crystals (T-MAPbBr3 SC) are rarely reported. In this study, we synthesized T-MAPbBr3 SC with the P4/mmm (123) space group by the growing, dropping and growing (GDG) crystal seed method. A CH3NH3+ cation is a disordered state in T-MAPbBr3 SC. The mobility values of T-MAPbBr3 SC under light and dark conditions are 464.28 and -1685.3 cm2 V-1 s-1, respectively. The carrier types under light and dark conditions are holes and electrons, respectively. The memristor based on T-MAPbBr3 SC has a wide and low operating voltage window (0-0.9 V). The high and low resistances of the memristor based on T-MAPbBr3 SC achieve values of 41 and 0.35 GΩ, respectively. The values of high and low resistances are relatively stable for 100 cycles. Thus, the memristor device based on T-MAPbBr3 SC has good applications in the field of memristors.

Theoretical screening of -NH2-, -OH-, -CH3-, -F-, and -SH-substituted porphyrins as sensitizer candidates for dye-sensitized solar cells.

Following former studies, the donor-acceptor combinations of -NH(2)-substituted porphyrin donor and the acceptors C, D, E, F, H and G, those of -OH-, -CH(3)- and -Ph-substituted porphyrins as well as porphine donors and the acceptors E, G, and H, and those of -F- and -SH-substituted porphyrin donors and the acceptor G as novel sensitizer candidates have been designed and calculated at the density functional B3LYP level. The result shows that -NH(2)-, -OH- and -CH(3)-substituted porphyrins as donors combined with the acceptor G are very promising to provide good performances as sensitizers because of their smaller HOMO-LUMO gaps, much red-shifted absorption bands, and good frontier molecular orbital spatial distributions. They are all promising to challenge the current photon-to-current conversion efficiency record 7.1% of porphyrin-sensitized solar cells in which the -NH(2)-substituted porphyrins as donors combined with the acceptor G are the best systems.

Tris(2,2'-bipyridine)-cobalt(II) µ(6)-oxido-dodeca-µ(2)-oxido-hexa-oxidohexa-molydate(VI).

In the title compound, [Co(C(10)H(8)N(2))(3)][Mo(6)O(19)], the Co(2+) cation is surrounded in a distorted octa-hedral coordination by six N atoms from three 2,2'-bipyridine ligands. The distribution of Mo-O bond lengths in the Lindqvist isopolyanion is consistent with other structures containing the same unit. In the crystal, the cations and anions are linked by C-H⋯O inter-actions.

Dibutyl 5-[(4-ethoxycarbonylphenyl)diazenyl]benzene-1,3-dicarboxylate.

In the title compound, C(25)H(30)N(2)O(6), the dihedral angle between the aromatic rings is 3.79 (1) Šand the N=N bond shows a trans conformation. Both butyl side chains show evidence of disorder.

Organic-Inorganic Composite Nanorods as an Excellent Mimicking Peroxidases for Colorimetric Detection and Evaluation of Antioxidant.

N,N'-Dicarboxy methyl perylene diimide-coated CeO2 nanorods (PDI/CeO2 NR) were synthesized via an ultrasonic-assisted method. PDI/CeO2 exhibits the superb mimic peroxidase functions confirmed by the catalyzed oxidation of TMB by hydrogen peroxide in less than 60 s along with color transformation from colorless to blue. The catalytic mechanism was confirmed to be an electronic transfer mechanism by fluorescence experiment. Thus, a visual colorimetric sensor was constructed for hydrogen peroxide detection with a low detection limit (LOD = 2.23 µM). Comparing the inhibition effects of l-cysteine (Cys), ascorbic acid (AA) and glutathione (GSH) on the catalytic oxidation of TMB, it can be found that they possessed different types of inhibition on the oxidation of TMB by H2O2 using PDI/CeO2, and AA has better antioxidant effect, followed by Cys and GSH. On the basis of the excellent antioxidant effect of AA, a low-cost colorimetric sensor was also used to detect AA, and a lower LOD value (0.68 µM) was obtained in the linear range of 5.0-30 µM.

Effects of Carbon Content and Current Density on the Li+ Storage Performance for MnO@C Nanocomposite Derived from Mn-Based Complexes.

In this study, a simple method was adopted for the synthesis of MnO@C nanocomposites by combining in-situ reduction and carbonization of the Mn3O4 precursor. The carbon content, which was controlled by altering the annealing time in the C2H2/Ar atmosphere, was proved to have great influences on the electrochemical performances of the samples. The relationships between the carbon contents and electrochemical performances of the samples were systematically investigated using the cyclic voltammetry (CV) as well as the electrochemical impedance spectroscopy (EIS) method. The results clearly indicated that the carbon content could influence the electrochemical performances of the samples by altering the Li+ diffusion rate, electrical conductivity, polarization, and the electrochemical mechanism. When being used as the anode materials in lithium-ion batteries, the capacity retention rate of the resulting MnO@C after 300 cycles could reach 94% (593 mAh g-1, the specific energy of 182 mWh g-1) under a current density of 1.0 A g-1 (1.32 C charge/discharge rate). Meanwhile, this method could be easily scaled up, making the rational design and large-scale application of MnO@C possible.