There is a growing interest in sustainable and high performance supercapacitors (SCs) operating at elevated temperatures as they are highly demanded in heat-durable electronics. Here, we present a biomass-derived nonfluorinated ionic liquid (IL) [P₄₄₄₄][HFuA] and its structural analogue [P₄₄₄₄][TpA] as electrolytes for supercapacitors comprising multiwall carbon nanotubes and activated charcoal (MWCNTs/AC) mixed carbon composite electrodes. A detailed investigation of the effect of scan rate, temperature, potential window and orientation of ions on the electrodes surfaces is performed. The supercapacitors exhibited relatively lower specific capacitance for both [P₄₄₄₄][HFuA] and [P₄₄₄₄][TpA] ILs at room temperature. However, the specific capacitance has significantly increased with an increase in temperature and potential window. The equivalent serie resistances of the SCs is deceased with increasing temperatures, which is a result of improved ionic conductivities of the IL electrolytes. In CV cycling at 60 °C, the capacitor with [P₄₄₄₄][HFuA] IL-based electrolyte retained about 90% of its initial capacitance, while the capacitor with [P₄₄₄₄][TpA] IL-based electrolyte retained about 83% of its initial capacitance. Atomistic computations revealed that the aromatic [FuA]− and [TpA]− anions displayed perpendicular distribution that can effectively neutralize charges on the carbon surfaces. However, the [HFuA]− anion exhibited somewhat tilted configurations on the carbon electrode surfaces, contributing to their outstanding capacitive performance in electrochemical devices.

New structurally flexible 1-methyl- and 1,2-dimethyl-imidazolium phosphate ionic liquids (ILs) bearing oligoethers have been synthesized and thoroughly characterized. These novel ILs revealed high thermal stabilities, low glass transitions, high conductivity and wide electrochemical stability windows up to 6 V. Both anions and cations of 1-methyl-imidazolium ILs diffuse faster than the ions of 1,2-dimethyl-imidazolium ILs, as determined by pulsed field gradient nuclear magnetic resonance (PFG-NMR). The 1-methyl-imidazolium phosphate ILs showed relatively higher ionic conductivities and ion diffusivity as compare with the 1,2-dimethyl-imidazolium phosphate ILs. As expected, the diffusivity of all the anions and cations increases with an increase in the temperature. The 1-methyl-imidazolium phosphate ILs formed hydrogen bonding with the phosphate anions, the strength of which is decreased with increasing temperature, as confirmed by variable temperature 1H and 31P NMR spectroscopy. One of the representative IL, [EmDMIm][DEEP], presented a promising performance at elevated temperatures as an electrolyte in a supercapacitor composed of multiwall carbon nanotubes and activated charcoal (MWCNTs/AC) composite electrodes.

The translational as well as reorientational mobilities of fluorine-free electrolytes prepared by mixing lithium furan-2-carboxylate Li(FuA) salt with tetra(n-butyl)phosphonium furan-2-carboxylate (P₄₄₄₄)(FuA) ionic liquid are thoroughly investigated. The diffusivity of ions and T₁ relaxation of protons belonging to various chemical groups of (P₄₄₄₄)⁺ and (FuA)⁻ ions and the Li⁺ ion present in these electrolytes are measured as a function of lithium salt concentration and temperature. The temperature dependence of correlation time for reorientational mobility of various chemical groups of (P₄₄₄₄)⁺ and (FuA)⁻ ions and the Li⁺ ion are estimated and used in calculations temperature dependence of the corresponding reorientational rates. It is shown that an increase in the concentration of lithium salt leads to a decrease in both the diffusion coefficients and the reorientation rates for all the chemical groups in concerted way. Activation energy of the reorientational rates for different chemical groups of the organic ions and the Li⁺ are discussed in details.

Unlike conventional electrolytes, ionic liquid (IL)-based electrolytes offer higher thermal stability, acceptable ionic conductivity, and a higher electrochemical stability window (ESW), which are indispensable for the proper functioning of Li-ion batteries. In this study, fluorine-free electrolytes are prepared by mixing the lithium furan-2-carboxylate [Li(FuA)] salt with the tetra(n-butyl)phosphonium furan-2-carboxylate [(P₄₄₄₄)(FuA)] IL in different molar ratios. The anion of these electrolytes is produced from biomass and agricultural waste on a large scale and, therefore, this study is a step ahead toward the development of renewable electrolytes for batteries. The electrolytes are found to have T_onset higher than 568 K and acceptable ionic conductivities in a wide temperature range. The pulsed field gradient nuclear magnetic resonance (PFG-NMR) analysis has confirmed that the (FuA)⁻ anion diffuses faster than the (P₄₄₄₄)⁺ cation in the neat (P₄₄₄₄)(FuA) IL; however, the anion diffusion becomes slower than cation diffusion by doping Li salt. The Li⁺ ion interacts strongly with the carboxylate functionality in the (FuA)⁻ anion and diffuses slower than other ions over the whole studied temperature range. The interaction of the Li⁺ ion with the carboxylate group is also confirmed by ⁷Li NMR and Fourier transform infrared (FTIR) spectroscopy. The transference number of the Li⁺ ion is increased with increasing Li salt concentration. Linear sweep voltammetry (LSV) suggests lithium underpotential deposition and bulk reduction at temperatures above 313 K.

In this work, nine new mixed-ligand complexes with the general formula [CuBr(TPP)₂Tu^1–9] were synthesized. The copper(I) complexes of triphenylphosphine (TPP) and different N,N′-disubstituted thioureas (Tu) were characterized via spectroscopic techniques including Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance spectroscopy (¹H, ¹³C, and ³¹P NMR), and single-crystal X-ray diffraction (SC-XRD). The complexes were synthesized via the direct reaction of bromo(tris(triphenylphosphine)copper(I)) [BrCu(PPh₃)₃] precursor and thiourea ligand solution under ambient conditions. Complexes 1, 2 and 3 crystallized in a triclinic system with the P  space group. Each complex is mononuclear, and the copper atom is tetrahedrally attached to two TPP groups through the phosphorous atom, one thiourea molecule through the sulfur atom and one bromine atom. The synthesized compounds were docked with a DNA macromolecule to predict their binding site and it was found that all molecules showed favorable binding to the DNA minor grooves. The DNA interaction studies of the representative complexes demonstrated their efficient DNA binding affinities. Based on the docking and DNA interaction results, complex 7 was found to be the best binder with a docking affinity of 382.2 kJ mol⁻¹ and binding constant of 3.96 × 10⁴ M⁻¹. This compound tends to interact with the minor groove through the bromine atom positioning the side triphenylphosphine rings along the X-axis of the groove while keeping the 1-(2-chlorobenzyl)-3-(3-(trifluoromethyl)phenyl)thiourea ring on the outside.

Layered double hydroxides (LDH) are being used as electrocatalysts for oxygen evolution reactions (OERs). However, low current densities limit their practical applications. Herein, we report a facile and economic synthesis of an iron-copper based LDH integrated with a cobalt-based metal-organic framework (ZIF-12) to form LDH-ZIF-12 composite (1) through a co-precipitation method. The as-synthesized composite 1 requires a low overpotential of 337 mV to achieve a catalytic current density of 10 mA cm⁻² with a Tafel slope of 89 mV dec⁻¹. Tafel analysis further demonstrates that 1 exhibits a slope of 89 mV dec⁻¹ which is much lower than the slope of 284 mV dec⁻¹ for LDH and 172 mV dec⁻¹ for ZIF-12. The slope value of 1 is also lower than previously reported electrocatalysts, including Ni-Co LDH (113 mV dec⁻¹) and Zn-Co LDH nanosheets (101 mV dec⁻¹⁾, under similar conditions. Controlled potential electrolysis and stability test experiments show the potential application of 1 as a heterogeneous electrocatalyst for water oxidation.

Porous carbon (PC) is obtained by carbonizing a zinc-coordination polymer (MOF-5) at 950 °C and PtM (M = Fe, Co, Ni, Cu, Zn) nanoparticles (NPs), which are deposited on PC using the polyol method. Structural and morphological characterizations of the synthesized materials are carried out by powder X-ray diffraction (PXRD), X-ray photoelectron spectroscopy (XPS), and high-resolution transmission electron microscopy (HRTEM), and the porosity was determined using a N2 adsorption/desorption technique. The results revealed that PtM NPs are alloyed in the fcc phase and are well dispersed on the surface of PC. The electrochemical results show that PtM/PC 950 catalysts have higher methanol oxidation reaction (MOR) performances than commercial Pt/C (20%) catalysts. After 3000 s of chronoamperometry (CA) test, the MOR performances decreased in the order of Pt₁Cu₁/PC 950 > Pt₁Ni₁/PC 950 > Pt₁Fe₁/PC 950 > Pt₁Zn₁/PC 950 > Pt₁Co₁/PC 950. The high MOR activities of the synthesized catalysts are attributed to the effect of M on methanol dissociative chemisorption and improved tolerance of Pt against CO poisoning. The high specific surface area and porosity of the carbon support have an additional effect in boosting the MOR activities. Screening of the first row transition metals (d⁵⁺ⁿ, n = 1, 2, 3, 4, 5) alloyed with Pt binary catalysts for MOR shows that Pt with d⁸ (Ni) and d⁹ (Cu) transition metals, in equivalent atomic ratios, are good anode catalysts for alcohol fuel cells.

Here we focus on the thermal and variable temperature electrochemical stabilities of two ionic liquids (ILs) having a common tributyloctyl phosphonium cation [P_4,4,4,8]⁺ and two different orthoborate anions: bis(mandelato)borate [BMB]⁻ and bis(salicylato)borate [BScB]⁻. The thermo-gravimetric analysis data suggest that [P_4,4,4,8][BScB] is thermally more stable than [P_4,4,4,8][BMB] in both nitrogen atmosphere and air, while the impedance spectroscopy reveals that [P_4,4,4,8][BScB] has higher ionic conductivity than [P_4,4,4,8][BMB] over the whole studied temperature range. In contrast, the electrochemical studies confirm that [P_4,4,4,8][BMB] is more stable and exhibits a wider electrochemical stability window (ESW) on a glassy carbon electrode surface as compared to [P_4,4,4,8][BScB]. A continuous decrease in the ESWs of both ILs is observed as a function of operation temperature.

Ionic liquids (ILs) composed of tetra(n-butyl)phosphonium [P₄₄₄₄]⁺ and tetra(n-butyl)ammonium [N₄₄₄₄]⁺ cations paired with 2-furoate [FuA]⁻, tetrahydo-2-furoate [HFuA]⁻, and thiophene-2-carboxylate [TpA]⁻ anions are prepared to investigate the effects of electron delocalization in anion and the mutual interactions between cations and anions on their physical and electrochemical properties. The [P₄₄₄₄]⁺ cations-based ILs are found to be liquids, while the [N₄₄₄₄]⁺ cations-based ILs are semi-solids at room temperature. Thermogravimetric analysis revealed higher decomposition temperatures and differential scanning calorimetry analysis showed lower glass transition temperatures for phosphonium-based ILs than the ammonium-based counterparts. The ILs are arranged in the decreasing order of their ionic conductivities as [P₄₄₄₄][HFuA] (0.069 mS cm–1) > [P4444][FuA] (0.032 mS cm^–1) > [P₄₄₄₄][TpA] (0.028 mS cm^–1) at 20 °C. The oxidative limit of the ILs followed the sequence of [FuA]⁻> [TpA]⁻> [HFuA]⁻, as measured by linear sweep voltammetry. This order can be attributed to the electrons’ delocalization in [FuA]⁻ and in [TpA]⁻ aromatic anions, which has enhanced the oxidative limit potentials and the overall electrochemical stabilities.

We synthesized tetra(n-butyl)phosphonium furoate [P₄₄₄₄][FuA] ionic liquid (IL) by the reaction of tetra(n-butyl)phosphonium hydroxide and 2-furoic acid using water as a solvent at room temperature. The thermal stability and phase behavior of the IL are investigated through thermogravimetry (TGA) and differential scanning calorimetry (DSC), while the ionic conductivity measurement is carried out using impedance spectroscopy. Hybrid carbon-based material composed of multi walled carbon nanotubes (MWCNTs) and activated charcoal is fabricated and used as electrodes. The effect of potential scan rate, temperature and voltage on the electrochemical performance of the capacitor is thoroughly investigated through cyclic voltammetry (CV), galvanostatic charge-discharge (GCD) and electrochemical impedance spectroscopy (EIS). The results showed that the internal resistance and specific capacitance are highly dependent on the temperature and voltage, and a high specific capacitance of 141.4 F g⁻¹ (5 mV s⁻¹) from CV and 182 F g⁻¹ (1 A g⁻¹) from GCD at 100 °C is achieved, indicating an excellent electrochemical performance. The capacitor demonstrated 29.0 Wh kg⁻¹ energy density and 13.3 kW kg⁻¹ power density at 20 °C and 3 V potential, while 177 Wh kg⁻¹ energy density and 82 kW kg⁻¹ power density are achieved at higher temperature (100 °C). The FTIR analysis of the capacitor after electrochemical studies confirmed that no changes have occurred in the structure of the IL, indicating high electrochemical stability of the IL for supercapacitor applications in an extended temperature (−20 to 100 °C) and a wide potential range (3 V to 4.6 V).