Synthesis and catalytic activity to Li/SOCl<Subscript>2</Subscript> battery of asymmetric and symmetric binuclear metal phthalocyanines

In our present work, the asymmetric and symmetric binuclear metal phthalocyanines (M₂(PcTN)₂ and M₂(PcTN)₂S), battery catalysts, were synthesized through microwave reaction and characterized by EA, IR and UV-vis spectroscopy. Their catalytic activity in the Li/SOCl₂ battery was evaluated by adding right amount catalysts into the electrolyte. The results indicated that the capacity of the catalyzed battery increased by 6.74–67.26% and 13.41–84.36%, and the energy increased by 9.29–65.72% and 14.77–88.15% respectively, compared with the battery without phthalocyanines.     

Investigation on the Growth Mechanism of Cu2MoS4 Nanotube,Nanoplate and its use as a Catalyst for Hydrogen Evolution in Water

Cu₂MoS₄ is a ternary transition‐metal sulfide that shows great potential in the field of energy conversion and storage, namely catalytic H₂ evolution in water and Li‐, Na‐ or Mg‐ion battery. In this work, we report on a growth mechanism of the single‐crystalline Cu₂MoS₄ nanotube from (NH₄)₂MoS₄ salt and Cu₂O nanoparticle. By probing the nature and morphology of solid products generated in function of reaction conditions we find that the crystalline Cu(NH₄)MoS₄ nanorod is first generated at ambient conditions. The nanorod is then converted into Cu₂MoS₄ nanotube under hydrothermal treatment due to the Kirkendall effect or a selective etching of the Cu₂MoS₄ core. Extending the hydrothermal treatment causes a collapse of nanotube generating Cu₂MoS₄ nanoplate. The catalytic activities of these sulfides are investigated. The Cu₂MoS₄ shows superior catalytic activity to that of Cu(NH₄)MoS₄. Catalytic performance of the former largely depends on its morphology. The nanoplate shows superior catalytic activity to the nanotube, thanks to its higher specific electrochemical surface area.     

Experimental study of the heat generations of Li/SOCl2 and Li/SO2 batteries using a phase-change measurement method

A paraffin phase-change measurement method for the heat generation of spirally wound cylindrical Li/SOCl₂ and Li/SO₂ batteries at different ambient temperatures and discharge currents is proposed. The electrical and thermal insulations of the measurement system have been greatly improved, and the accuracy of the measurement system is 4.6 % based on calibration experiments. Compared with accelerated rate calorimetry, isothermal microcalorimetry, and radiation calorimetry methods, the phase-change measurement method is simpler, but with a high accuracy. The experimental results reveal that the heat generation of the batteries during discharge is weakly dependent on the ambient temperature in the range of 38–50 °C, but strongly affected by the discharge current. As the discharge current increases, the heat generated by the Li/SOCl₂ and Li/SO₂ batteries increases as a quadratic polynomial function. The Li/SO₂ battery generates more heat than the Li/SOCl₂ battery at the same discharge current, which is demonstrated by the qualitative analysis of the internal resistance. Furthermore, the phase-change measurement method for heat generation has a strong universality, and can be applicable for heat generation measurement of various battery types.     

The synthesis of porphyrin and metalporphyrins and their improvement to the property of Li/SOCl<Subscript>2</Subscript> primary battery

5-Hydroxyphenyl-11,15,20-triphenylporphyrin H₂Pp(1), and its six corresponding metalloporphyrins MnPp(2), FePp(3), CoPp(4), NiPp(5), CuPp(6), ZnPp(7) were synthesized and characterized. Their improvements to the Li/SOCl₂ battery were tested. The results show that the discharge voltages of the battery catalyzed by 1–5 are increased by approximately 20–120 mV except 6 and 7. And the discharge time is lengthened by 26.7–157.6 s for 1, 2, 5 and 7. The maximum initial discharge voltages of battery in the presence of 1–7 are also increased. It shows that the central metal ion influences the charge transfer process during the reduction of thionyl chloride.     

Adsorption of Li by a lithium ion-sieve using a buffer system and application for the recovery of Li from a spent lithium-ion battery

A lithium ion-sieve manganese oxide (MO) derived from Li-enriched MO was prepared by the glycolic acid complexation method. The Li adsorption performance in a LiCl–NH₃·H₂O–NH₄Cl buffer solution, simulated a spent lithium-ion battery (LIB) processing solution, and actual spent LIB processing solution were studied. An adsorption capacity of 27.4 mg/g was observed in the LiCl–NH₃·H₂O–NH₄Cl buffer solution (Li concentration of 0.2 mol/L, pH?=?9), and the adsorption behavior conformed to the Langmuir adsorption isotherm equation with a linear correlation coefficient (R²) of 0.9996. An adsorption capacity of 19 mg/g was observed in the simulated buffer spent battery solution (Li concentration of 0.15 mol/L, pH?=?7), and an adsorption capacity of 17.8 mg/g was observed in the actual spent battery solution (Li concentration of 0.15 mol/L, pH?=?7). X-ray diffraction, scanning electron microscope, and infrared spectrum results revealed that the structure and morphology of MO are stable before and after adsorption, and the adsorption of MO in all of the abovementioned buffer systems conforms to the Li⁺–H⁺ ion-exchange reaction mechanism. The lithium ion-sieve MO demonstrates promise for the recovery of lithium from spent LIBs.     

Preparation of NiO/multiwalled carbon nanotube nanocomposite for use as the oxygen cathode catalyst in rechargeable Li–O2 batteries

NiO/multiwalled carbon nanotube (NiO/MWCNT) nanocomposites have been prepared and used for a Li–O₂ battery cathode catalyst. Electrochemical measurements demonstrate that the batteries with NiO/MWCNT catalyst have a discharge capacity of 2,500 mAh g^?1, a charge capacity of 2,100 mAh g^?1, and a rechargeable ability performing better than Ketjenblack (KB) and MWCNTs. KB has the largest discharge capacity (2,700 mAh g^?1) due to the highest surface area and pore volume but the worst charging behavior due to poor mass transport in the small-width pore (2.48 nm). MWCNTs have a much better charging performance owing to a larger pore width (8.93 nm) than carbon black. NiO/MWCNTs have the largest charge capacity because of the facilitated mass transport in the comparatively large pores (7.68 nm) and the increased catalytic ability produced by the NiO nanoparticles. These improvements are also responsible for the best cycle and rate performances of the nanocomposites among the three catalysts.     

Synthesis of homoallylic alcohols via palladium-catalyzed coupling of organomercurials and vinylic oxetanes

The reaction of aryl- and vinylmercurials, cupric chloride, 5% aqueous NH₄Cl, oxygen, catalytic amounts of Li2pPdCl4 and vinylic oxetanes affords an excellent route to functionally-substituted homoallylic alcohols.     

Luminescent Blooming of Dendronic Carbon Nanotubes through Ion‐Pairing Interactions with an EuIII Complex

A multiwalled carbon nanotube (MWCNT) scaffold was covalently functionalized with a second‐generation polyamidoamine (PAMAM) dendron, presenting four terminal amino groups per grafted aryl moiety. These reactive functions were alkylated to obtain a positively charged polycationic dendron/carbon nanotube system ( d‐MWCNTs?Cl ), which eventually underwent anion exchange reaction with a negatively charged and highly luminescent Eu^III complex ( [EuL₄]?NEt₄ , in which L =(2‐naphtoyltrifluoroacetonate)). This process afforded the target material d‐MWCNTs?[EuL₄] , in which MWCNTs are combined with red‐emitting Eu^III centers through electrostatic interactions with the dendronic branches. Characterization of the novel MWCNT materials was accomplished by means of TGA and TEM, whereas d‐MWCNTs?Cl and d‐MWCNTs? [EuL₄] further underwent XPS, SEM and Raman analyses. These studies demonstrate the integrity of the luminescent [EuL₄]^? center in the luminescent hybrid, the massive load of the cationic binding sites, and the virtually complete anion‐exchange into the final hybrid material. The occurrence of the ion‐pairing interaction with MWCNTs was unambiguously demonstrated through DOSY NMR diffusion studies. Photophysical investigations show that MWCNTs?[EuL₄] is a highly soluble and brightly luminescent red hybrid material in which MWCNTs act as photochemically inert scaffolds with negligible UV/Vis absorption, compared with the grafted Eu complex, and with no quenching activity. The high dispersibility of MWCNTs?[EuL₄] in a polymer matrix makes it a promising luminophore for applications in material science.     

PNPP Hydrolysis Catalyzed by Manganese(III) Complexes with Crowned Salicylaldimine Schiff Base Ligand

Four manganese(III) complexes (MnL¹Cl, MnL²Cl, MnL⁴₂Cl, MnL⁵₂Cl) with a crowned salicylaldimine Schiff base ligand have been synthesized and employed as models to mimic hydrolase in the hydrolysis of p-nitrophenyl picolinate (PNPP). The kinetics and mechanism of catalytic PNPP hydrolysis have been investigated. The kinetic mathematical model of PNPP cleavage catalyzed by these complexes has been proposed. The effects of the ligand structure and crown ether ring in complexes, and the reactive temperature on the rate of catalytic PNPP hydrolysis have been also examined. The results show that compared with the crown-free analogous MnL³Cl and MnL⁶₂Cl, the crowned Schiff base manganese(III) complexes, MnL¹Cl, MnL²Cl, MnL⁴₂Cl and MnL⁵₂Cl, exhibit more high catalytic activity, which follow the order: MnL¹Cl >MnL²Cl >MnL⁴₂Cl >MnL⁵₂Cl >MnL³Cl >MnL⁶₂Cl; the pseudo-first-order-rate (k_obs) for the PNPP hydrolysis catalyzed by the complex MnL¹Cl containing three crown ether rings is highest among six complexes and is 1.81 times that of MnL³Cl, 1.49 × 10³ times that of spontaneous hydrolysis of PNPP, respectively, at pH = 7.00, [S] = 2.0 × 10⁻⁴ mol dm⁻³.     

Studies on the Kinetics and Mechanism of Hydrolysis of p-nitrophenyl Picolinate (PNPP) by Unsymmetrical bis-Schiff Base Complexes with Aza-crown Ether or Morpholino Pendants

Two novel unsymmetrical bis-Schiff base manganese(III) and cobalt(II) complexes with benzo-10-aza-crown ether pendants (MnL¹Cl, CoL¹), and their analogoues with morpholino pendants (MnL²Cl, CoL²), have been synthesized and employed as models to mimic hydrolase in p-nitrophenyl picolinate (PNPP). The kinetics and the mechanism of PNPP hydrolysis catalyzed by these complexes were investigated. A kinetic mathematical model of PNPP cleavage catalyzed by these complexes was proposed. The effects of the complexes structure and reactive temperature on the rate of catalytic PNPP hydrolysis have been also examined. The results showed that the rate for the catalytic PNPP hydrolysis increased following the increase in pH of the buffer solution; four complexes exhibited high activity in the catalytic PNPP hydrolysis. Compared with the crown-free analogoues MnL²Cl and CoL², the crowned Schiff base complexes (MnL¹Cl, CoL¹) exhibit a higher catalytic activity; the pseudo-first-order-rate (k_obs) for the PNPP hydrolysis catalyzed by the complex MnL¹Cl containing benzo-10-aza-crown ether is 1.04 × 10³ that of spontaneous hydrolysis of PNPP at pH = 7.00, [S] = 2.0×10⁻⁴ mol dm⁻³.     

A Rechargeable Li‐CO2 Battery with a Gel Polymer Electrolyte

The utilization of CO₂ in Li‐CO₂ batteries is attracting extensive attention. However, the poor rechargeability and low applied current density have remained the Achilles’ heel of this energy device. The gel polymer electrolyte (GPE), which is composed of a polymer matrix filled with tetraglyme‐based liquid electrolyte, was used to fabricate a rechargeable Li‐CO₂ battery with a carbon nanotube‐based gas electrode. The discharge product of Li₂CO₃ formed in the GPE‐based Li‐CO₂ battery exhibits a particle‐shaped morphology with poor crystallinity, which is different from the contiguous polymer‐like and crystalline discharge product in conventional Li‐CO₂ battery using a liquid electrolyte. Accordingly, the GPE‐based battery shows much improved electrochemical performance. The achieved cycle life (60 cycles) and rate capability (maximum applied current density of 500 mA g⁻¹) are much higher than most of previous reports, which points a new way to develop high‐performance Li‐CO₂ batteries.     

PNPP Cleavage Catalyzed by Schiff Base Mn(III) Complexes Containing Polyether Side Chains in CTAB Micellar Solutions

Two Schiff base Mn(III) complexes containing polyether side chain were synthesized and characterized. The catalytic hydrolysis of p‐nitrophenyl picolinate (PNPP) by the two complexes in the buffered CTAB micellar solution in the pH range of 6.60–8.20 was investigated kinetically in this study. The influences of acidity, temperature, and structure of complex on the catalytic cleavage of PNPP were also studied. The mechanism of PNPP hydrolysis catalyzed by Schiff base manganese(III) complexes in CTAB micellar solution was proposed. The relative kinetic and thermodynamic parameters were determined. Comparied with the pseudo‐first‐order rate constant (k ₀) of PNPP spontaneous hydrolysis in water, the pseudo‐first‐order rate constants (k _obsd) of PNPP catalytic hydrolysis are 1.93×10³ fold for MnL¹ ₂Cl and 1.06×10³ fold for MnL² ₂Cl in CTAB micellar solution at pH=7.00, T=25°C, and [S]=2.0×10^?4mol · dm^?3, respectively. Furthermore, comparing the k _obsd of PNPP catalytic hydrolysis by metallomicelles with that of PNPP hydrolysis catalyzed only by metal complexes or CTAB micelle at the above‐mentioned condition, metallomicelles of MnL₂(L=L¹, L²) Cl/CTAB exhibit notable catalytic activities for promoting PNPP hydrolysis, and MnL¹ ₂Cl/CTAB system is superior in promoting cleavage of PNPP relative to MnL² ₂Cl/CTAB system under the same experimental conditions. The results indicate that the rate of PNPP catalytic cleavage is influenced by the structures of the two complexes, the acidity of reaction systems, and the solubilization of PNPP in CTAB micelles.     

Studies on <Emphasis Type="Italic">p</Emphasis>-nitrophenyl picolinate cleavage by mono-Schiff base complexes with aza-crown ether or morpholino pendants

Abstract  Mono-Schiff base manganese(III) and cobalt(II) complexes with either benzo-10-aza-crown ether pendants (MnL¹ ₂ Cl, CoL¹ ₂) or morpholino pendants (MnL² ₂Cl, CoL² ₂) have been employed as models for hydrolase enzymes by studying the kinetics of their hydrolysis reactions with p-nitrophenyl picolinate (PNPP). A kinetic model of PNPP cleavage catalyzed by these complexes is proposed. The effects of complex structures and reaction temperature on the rate of catalytic PNPP hydrolysis have been also examined. The rate increases with pH of the buffer solution; all four complexes exhibited high activity in the catalytic PNPP hydrolysis. Compared with the crown-free analogues MnL² ₂Cl and CoL² ₂, the crowned Schiff base complexes (MnL¹ ₂Cl, CoL¹ ₂) exhibit higher catalytic activity. The pseudo-first-order-rate ( k _obs ) for the PNPP hydrolysis catalyzed by the complex MnL¹ ₂Cl containing benzo-10-aza-crown ether is 1.06 × 10³ times that of spontaneous hydrolysis of PNPP at pH = 7.00, 25 °C, [S] = 2.0 × 10⁻⁴ mol dm⁻³. Graphical Abstract   Studies on p-nitrophenyl picolinate cleavage by mono-Schiff base complexes with aza-crown ether or morpholino pendants Jian-zhang Li*, Fa-mei Feng, Bin Xu,Wei-dong Jiang Key Laboratory of Green and Technology, Department of Chemistry, Sichuan University of Science & Engineering, Zigong, Sichuan, 643000, P.R. China Sheng-ying Qin Department of Chemistry, Sichuan University, Chengdu, Sichuan, 610064, P.R. China Mono-Schiff base manganese(III) and cobalt(II) complexes with either benzo-10-aza-crown ether pendants (MnL¹ ₂Cl, CoL¹ ₂) or morpholino pendants (MnL² ₂Cl, CoL² ₂) have been employed as models for hydrolase enzymes by studying the kinetics of their hydrolysis reactions with PNPP. A kinetic model of PNPP cleavage catalyzed by these complexes is proposed. Compared with the crown-free analogy MnL² ₂Cl and CoL² ₂, the crowned Schiff base complexes (MnL¹ ₂Cl, CoL¹ ₂) exhibit higher catalytic activity.      

Superior Rechargeability and Efficiency of Lithium–Oxygen Batteries: Hierarchical Air Electrode Architecture Combined with a Soluble Catalyst

The lithium–oxygen battery has the potential to deliver extremely high energy densities; however, the practical use of Li‐O₂ batteries has been restricted because of their poor cyclability and low energy efficiency. In this work, we report a novel Li‐O₂ battery with high reversibility and good energy efficiency using a soluble catalyst combined with a hierarchical nanoporous air electrode. Through the porous three‐dimensional network of the air electrode, not only lithium ions and oxygen but also soluble catalysts can be rapidly transported, enabling ultra‐efficient electrode reactions and significantly enhanced catalytic activity. The novel Li‐O₂ battery, combining an ideal air electrode and a soluble catalyst, can deliver a high reversible capacity (1000 mAh g^?1) up to 900 cycles with reduced polarization (about 0.25 V).     

Lithium Imide Synergy with 3d Transition‐Metal Nitrides Leading to Unprecedented Catalytic Activities for Ammonia Decomposition

Alkali metals have been widely employed as catalyst promoters; however, the promoting mechanism remains essentially unclear. Li, when in the imide form, is shown to synergize with 3d transition metals or their nitrides TM(N) spreading from Ti to Cu, leading to universal and unprecedentedly high catalytic activities in NH₃ decomposition, among which Li₂NH? MnN has an activity superior to that of the highly active Ru/carbon nanotube catalyst. The catalysis is fulfilled via the two‐step cycle comprising: 1) the reaction of Li₂NH and 3d TM(N) to form ternary nitride of LiTMN and H₂, and 2) the ammoniation of LiTMN to Li₂NH, TM(N) and N₂ resulting in the neat reaction of 2 NH₃?N₂+3 H₂. Li₂NH, as an NH₃ transmitting agent, favors the formation of higher N‐content intermediate (LiTMN), where Li executes inductive effect to stabilize the TM? N bonding and thus alters the reaction energetics.     

Determination of Hemin using a Parallel Catalytic Reduction Wave of its Protoporphyrin IX Ring

Abstract

Hemin, iron (III) protoporphyrin IX chloride, in NH₃‐NH₄Cl buffer solution of pH 9.5 produces an insensitive reduction wave at about ?0.70 V (vs. saturated calomel reference electrode, SCE) by using single sweep polarography. Adding oxidant K₂S₂O₈ to the solution, hemin reduction wave is catalyzed, yielding a parallel catalytic wave. The catalytic current is 20 times of hemin original reduction current. The derivative peak height is linearly proportional to the hemin concentration in the range of 7.5×10^?8 to 4.5×10^?6 mol/l, the detection limit is 5.0×10^?8 mol/l. Serum albumin, common amino acids, and metal ions have no interference with the hemin determination. The proposed method has been applied to the determination of hemin content in oral liquid samples with satisfactory results. The parallel catalytic wave is attributed to the catalytic reduction of porphyrin ring of hemin at the dropping mercury electrode. The new method could be useful in biochemical, clinical, and pharmaceutical analysis.     

Sensitive Nucleic Acid Detection at NH2‐MWCNTs Modified Glassy Carbon Electrode and its Application for Monitoring of Gemcitabine‐DNA Interaction

An electrochemical dsDNA nanobiosensor was fabricated using amino‐functionalized multi walled carbon nanotubes modified glassy carbon electrode (NH₂fMWCNTs/GCE) for the sensitive detection of DNA bases and electrochemical monitoring of drug‐DNA interaction. The influence of functional groups on MWCNT was studied by MWCNT functionalized with NH₂ (NH₂fMWCNTs) and COOH (COOHfMWCNT) groups based on the signal of DNA bases. The modified electrodes were characterized by scanning electron microscopy. One layer of calf thymus double stranded deoxyribonucleic acid (ct‐dsDNA) was immobilized onto the NH₂fMWCNTs/GCE (dsDNA/NH₂fMWCNTs/GCE). The dsDNA/NH₂fMWCNTs/GCE were used to investigate the interaction between the dsDNA and the anticancer drug gemcitabine by differential pulse voltammetry in acetate buffer of pH 4.70. For the confirmation of interaction, the lowering in intensity of the current signals of guanine and adenine was considered as an indicator. Electrochemical impedance spectroscopy studies were performed for the comparison of the modified surfaces. In order to define and visualize the interaction mechanism between gemcitabine and dsDNA/NH₂fMWCNTs/GCE at the molecular level, in silico methods including docking and molecular dynamics simulations were employed.     

Binding Characteristics of CoPc/SnO2 by In-situ Process and Photocatalytic Activity under Visible Light Irradiation

Cobalt phthalocyanine (CoPc) was synthesized and self-assembled on the surface of nanoscale tin dioxide (SnO₂) by in-situ process, marked as i, and Co-O interaction was verified to conjugate axially between macromolecule (CoPc) and SnO₂ in CoPc/SnO₂(i). The results indicated that the binding constant of CoPc/SnO₂(i) was two-order higher than that of CoPc/SnO₂(d) synthesized by dipping process, marked as d, while the numbers of binding sites were comparable in both samples. The degradation rate in the photocatalytic activity of CoPc/SnO₂(i) was 32.5% higher than that of CoPc/SnO₂(d) under visible-light irradiation for 150 min due to the effective electron separation and energy injection from LUMO of CoPc to conduction band of SnO₂ for CoPc/SnO₂(i) based on the strong interaction between CoPc and SnO₂. The degradation recyclability of CoPc/SnO₂(i) retained 48.8% in 10 times under the same circular photocatalytic process.     

氮杂冠醚或吗啉基取代的单Schiff碱配合物催化α-吡啶甲酸对硝基苯酯水解

两种含5-取代苯并-10-氮杂-15-冠-5的Schiff碱锰(III)、钴(II)配合物( , )及其吗啉基取代的类似物( , ) 用于催化α-吡啶甲酸对硝基苯酯(PNPP)水解。探讨了氮杂冠醚Schiff 碱配合物催化PNPP水解的动力学和机理;提出了配合物催化PNPP水解的动力学模型;考察了配合物结构、反应温度、缓冲溶液pH值等对PNPP水解反应的影响。结果表明,在25℃条件下随着缓冲溶液pH值的增大,催化PNPP水解速率提高;含取代苯并-10-氮杂-15-冠-5的Schiff碱配合物表现出更高的催化活性。根据阿累尼乌斯公式和不同温度下的表观一级常数求出水解反应的表观活化能。     

The electrochemical properties of Li/TEGDME/MoS2 cells using multi-wall carbon nanotubes as a conducting agent

We investigated the first charge–discharge behavior and cycling property of Li batteries using MoS₂ electrodes with multi-wall carbon nanotubes (MWNT) as a conducting agent. The MoS₂ electrode was prepared using MWNT as the conducting agent. The battery gave a high first discharge capacity of 440 mAhg^?1 with a plateau potential region at 1.1 V. The Li/MoS₂ battery using MWNT showed a higher discharge capacity compared to acetylene black. After ten cycles of the battery using MWNT, the discharge capacity decreased to 120 mAhg^?1, which corresponded to 30% of the first discharge capacity. Adding a carbon nanotube into the MoS₂ electrode improved the first discharge behavior, but did not affect the cycling property of the Li/MoS₂ cell.