RESUMO
Reference electrodes are used in almost every electroanalytical measurement. Here, all-solid-state reference electrodes are described that employ colloid-imprinted mesoporous (CIM) carbon as solid contact and a poly(vinyl chloride) reference membrane to contact the sample. Such a reference membrane is doped with a moderately hydrophilic ionic liquid and a hydrophobic redox couple, leading to well-defined constant potentials at the interfaces of this membrane to the sample and to the solid contact, respectively. Due to the intrinsic properties of CIM carbon, reference electrodes with a CIM carbon solid contact exhibit excellent resistance to common interfering agents such as light and O2, with outstanding potential stability in continuous potentiometric measurements. The potential drift of CIM carbon-based reference electrodes without redox couple is as low as 1.7 µV/h over 110 h, making them the most stable all-solid-state reference electrodes reported so far. To demonstrate the compatibility of CIM carbon-based reference electrodes with miniaturized potentiometric systems, these reference electrodes were integrated into paper-based potentiometric sensing devices, successfully replacing the conventional reference electrode with its reference electrolyte solution. As a proof of concept, disposable paper-based Cl(-) sensing devices that contain stencil-printed Ag/AgCl-based Cl(-) selective electrodes and CIM carbon-based reference electrodes were constructed. These sensing devices are inexpensive, easy to use, and offer highly reproducible Cl(-) measurements with sample volumes as low as 10 µL.
RESUMO
Vanadium pentoxide materials prepared through sol-gel processes act as excellent intercalation hosts for lithium as well as polyvalent cations. A chemometric approach has been applied to study the X-ray absorption near-edge structure (XANES) evolution during in situ scanning of the Cu(0.1)V(2)O(5) xerogel/Li ions battery. Among the more common techniques, the fixed size windows evolving factor analysis (FSWEFA) permits the number of species involved in the experiment to be determined and the range of existence of each of them. This result, combined with the constraints of the invariance of the total concentration and non-negativity of both concentrations and spectra, enabled us to obtain the spectra of the pure components using a multivariate curve resolution refined by an alternate least squares fitting procedure. This allowed the normalized concentration profile to be understood. This data treatment evidenced the occurrence, for the first time, of three species during the battery charging. This fact finds confirmation by comparison of the pure spectra with the experimental ones. Extended X-ray absorption fine structure (EXAFS) analysis confirms the occurrence of three different chemical environments of Cu during battery charging.
RESUMO
The title compounds, poly[[[bis(2-methoxyethyl) ether]lithium(I)]-di-mu(3)-trifluoromethanesulfonato-lithium(I)], [Li(2)(CF(3)SO(3))(2)(C(6)H(14)O(3))](n), and poly[[[bis(2-methoxyethyl) ether]lithium(I)]-di-mu(3)-trifluoroacetato-dilithium(I)-mu(3)-trifluoroacetato], [Li(3)(C(2)F(3)O(2))(3)(C(6)H(14)O(3))](n), consist of one-dimensional polymer chains. Both structures contain five-coordinate Li(+) cations coordinated by a tridentate diglyme [bis(2-methoxyethyl) ether] molecule and two O atoms, each from separate anions. In both structures, the [Li(diglyme)X(2)](-) (X is CF(3)SO(3) or CF(3)CO(2)) fragments are further connected by other Li(+) cations and anions, creating one-dimensional chains. These connecting Li(+) cations are coordinated by four separate anions in both compounds. The CF(3)SO(3)(-) and CF(3)CO(2)(-) anions, however, adopt different forms of cation coordination, resulting in differences in the connectivity of the structures and solvate stoichiometries.