4 research outputs found
Modes of Interaction of Simazine with the Surface of Amorphous Silica in Water. Part II: Adsorption at Temperatures Higher than Ambient
The conclusions of a previous study
(S. Esposito et al. <i>J. Phys. Chem. C</i> <b>2013</b>, <i>117</i>, 11203ā11210) concerning room temperature
adsorption of simazine
(Sim) on amorphous silica in water have been checked against a set
of experiments in the range 40Ā° to 60 Ā°C, where equilibrium
conditions are more likely to be attained. Adsorbed amount as a function
of pH has a complex behavior with temperature, confirming the presence
of two types of protonated adsorbed species, respectively monomeric
(SimH<sup>+</sup>) and dimeric (Sim<sub>2</sub>H<sup>+</sup>), the
latter prevailing both at high temperatures and loadings. A simple
model for adsorption involving proton transfer from the solid indicates
that the pH value at which the uptake is maximum (pH*) is the half
sum of the p<i>K</i><sub>a</sub>ās of both the active
silanol species and the protonated entity given rise, pH* = [p<i>K</i><sub>a</sub>(1) + p<i>K</i><sub>a</sub>(2)]/2.
From this, it results that (i) the dimer Sim<sub>2</sub> is more basic
than the monomer Sim by 2 units of p<i>K</i><sub>a</sub>; (ii) adsorbed simazine is more basic then the molecule in solution
also by ca. 2 units in p<i>K</i><sub>a</sub>; and (iii)
the p<i>K</i><sub>a</sub> of the silanol species involved
is probably not ca. 4 as recently proposed, but more likely ca. 7,
in agreement with old classical views. From the qualitative energetic
point of view, the reaction SimĀ(aq) + SiOH ā SiO<sup>ā</sup>Ā·Ā·Ā·SimH<sup>+</sup> is exothermic, the formation of
the dimer from the monomer is endothermic (reaction SiO<sup>ā</sup>Ā·Ā·Ā·SimH<sup>+</sup> + SimĀ(aq) ā SiO<sup>ā</sup>Ā·Ā·Ā·Sim<sub>2</sub>H<sup>+</sup>), whereas the reaction SimĀ(aq) + SiOH ā SiO<sup>ā</sup>Ā·Ā·Ā·Sim<sub>2</sub>H<sup>+</sup> is slightly exothermic. At 25 Ā°C, the adsorbed
monomer is irreversibly held, and the dimer only partially. The isotherm
at 40Ā° shows that adsorption of the dimer occurs almost reversibly,
whereas equilibrium in the formation of the monomer is not completely
reached. The isotherm at 60 Ā°C shows instead that both species
are formed under near-equilibrium conditions
Visible-Light Driven Oxidation of Water as Catalyzed by Co-APOā5 in the Presence of Ru Sensitizer
Cobalt aluminum phosphate with AFI
zeolitic structure (Co-APO-5) catalyzes light-driven water oxidation
(WO) when both the ruthenium complex [RuĀ(bpy)<sub>3</sub>]<sup>2+</sup>, as photosensitizer, and persulfate species S<sub>2</sub>O<sub>8</sub><sup>2ā</sup>, as sacrificial electron acceptor, are present.
Measurements have been run in a flow reactor, allowing the amount
of oxygen evolved to be evaluated and, in particular, the initial
rate of WO reaction to be measured. The latter has been studied as
a function of chemical composition, and some kinetic features have
been established. Competitive reactions occur extensively, causing
the oxidation of the Ru complex to the detriment of oxygen production.
The initial rate of WO increases with the amount of catalyst until
turbidity of the suspension sets in. A reaction order close to ā1
with respect to persulfate was found, which indicates the occurrence
of surface processes involving Co centers at the outer layer of Co-APO-5
particles (accessed by the bulky [RuĀ(bpy)<sub>3</sub>]<sup>2+</sup> species, at variance with Co species in the core), for the adsorption
onto which competition takes place between the Ru complex and persulfate
species. A less pronounced negative order (ca. ā0.4) for the
sensitizer was also observed, for which an interpretation is proposed
Hematite Nanoparticles Larger than 90 nm Show No Sign of Toxicity in Terms of Lactate Dehydrogenase Release, Nitric Oxide Generation, Apoptosis, and Comet Assay in Murine Alveolar Macrophages and Human Lung Epithelial Cells
Three hematite samples were synthesized by precipitation
from a
FeCl<sub>3</sub> solution under controlled pH and temperature conditions
in different morphology and dimensions: (i) microsized (average diameter
1.2 Ī¼m); (ii) submicrosized (250 nm); and (iii) nanosized (90
nm). To gain insight into reactions potentially occurring <i>in vivo</i> at the particleālung interface following
dust inhalation, several physicochemical features relevant to pathogenicity
were measured (free radical generation in cell-free tests, metal release,
and antioxidant depletion), and cellular toxicity assays on human
lung epithelial cells (A549) and murine alveolar macrophages (MH-S)
were carried out (LDH release, apoptosis detection, DNA damage, and
nitric oxide synthesis). The decrease in particles size, from 1.2
Ī¼m to 90 nm, only caused a slight increase in structural defects
(disorder of the hematite phase and the presence of surface ferrous
ions) without enhancing surface reactivity or cellular responses in
the concentration range between 20 and 100 Ī¼g cm<sup>ā2</sup>
Mixed 1Tā2H Phase MoS<sub>2</sub>/Reduced Graphene Oxide as Active Electrode for Enhanced Supercapacitive Performance
A hybrid
aerogel, composed of MoS<sub>2</sub> sheets of 1T (distorted octahedral)
and 2H (trigonal prismatic) phases, finely mixed with few layers of
reduced graphene oxide (rGO) and obtained by means of a facile environment-friendly
hydrothermal cosynthesis, is proposed as electrode material for supercapacitors.
By electrochemical characterizations in three- and two-electrode configurations
and symmetric planar devices, unique results have been obtained, with
specific capacitance values up to 416 F g<sup>ā1</sup> and
a highly stable capacitance behavior over 50000 chargeādischarge
cycles. The in-depth morphological and structural characterizations
through field emission scanning electron microscopy, Raman, X-ray
photoelectron spectroscopy, X-ray diffraction, BrunauerāEmmettāTeller,
and transmission electron microscopy analysis provides the proofs
of the unique assembly of such 3D structured matrix. The unpacked
MoS<sub>2</sub> structure exhibits an excellent distribution of 1T
and 2H phase sheets that are highly exposed to interaction with the
electrolyte, and so available for surface/near-surface redox reactions,
notwithstanding the quite low overall content of MoS<sub>2</sub> embedded
in the reduced graphene oxide (rGO) matrix. A comparison with other
āmore conventionalā hybrid rGO-MoX<sub>2</sub> electrochemically
active materials, synthesized in the same conditions, is provided
to support the outstanding behavior of the cosynthesized rGO-MoS<sub>2</sub>