22 research outputs found
Characterization of AlPO<sub>4</sub>(110) Surface in Adsorption of Rh Dimer and Its Comparison with γ‑Al<sub>2</sub>O<sub>3</sub>(100) Surface: A Theoretical Study
Adsorption
of Rh dimer on AlPO<sub>4</sub>(110) and γ-Al<sub>2</sub>O<sub>3</sub>(100) surfaces was theoretically investigated
by periodic DFT calculation with a slab model to elucidate characteristic
features of the AlPO<sub>4</sub> surface in comparison with the γ-Al<sub>2</sub>O<sub>3</sub> surface. The adsorption at the PO site is the
most favorable in both nonhydrated and hydrated AlPO<sub>4</sub> surfaces,
which is consistent with the experimental finding. The adsorption
at the AlO site is the least favorable. The adsorption energy at the
PO site of the AlPO<sub>4</sub> surface is considerably larger than
that at the γ-Al<sub>2</sub>O<sub>3</sub> surface. One important
reason is that the deformation energy of the γ-Al<sub>2</sub>O<sub>3</sub> surface is much larger than that of the AlPO<sub>4</sub> surface. Bader charge analysis, difference electron density map,
and projected density of states (p-DOS) clearly disclose that the
charge transfer (CT) occurs from the Rh dimer to the AlPO<sub>4</sub> surface. This CT is stronger than in the adsorption on the γ-Al<sub>2</sub>O<sub>3</sub> surface. The lowest unoccupied band (LU band
in conduction band) plays a crucial role as an electron-acceptor orbital
in this CT interaction. The LU band of the AlPO<sub>4</sub> exists
at a lower energy than that of γ-Al<sub>2</sub>O<sub>3</sub>. Therefore, the CT from the Rh dimer to the AlPO<sub>4</sub> surface
is considerably larger than that to the γ-Al<sub>2</sub>O<sub>3</sub> surface. These results show that the presence of the isolated
LU band at a low energy and the flexible AlPO<sub>4</sub> structure
are important factors for the anchoring effect, which achieves outstanding
thermal stability of the supported Rh nanoparticles on the AlPO<sub>4</sub> surface and therefore enables a reduction in quantity of
Rh in the three-way catalyst using AlPO<sub>4</sub>
The Role of CeO<sub>2</sub> as a Gateway for Oxygen Storage over CeO<sub>2</sub>‑Grafted Fe<sub>2</sub>O<sub>3</sub> Composite Materials
The surface grafting of CeO<sub>2</sub> onto Fe<sub>2</sub>O<sub>3</sub> with a 1:5 molar ratio produced
a thermally stable composite
material with greater and faster oxygen storage/release than its separate
constituents. In the composite, CeO<sub>2</sub> and Fe<sub>2</sub>O<sub>3</sub> were intimately contacted by interfacial Ce–O–Fe
bonding, and no solid solutions or mixed Ce and Fe oxides were formed
after heating at 900 °C. The oxygen storage capacity and initial
rate of oxygen release/storage were both increased in the composite
structure by virtue of the Fe<sub>2</sub>O<sub>3</sub> and CeO<sub>2</sub>, respectively. The reduction–oxidation cycles in which
Fe<sub>2</sub>O<sub>3</sub> is reduced via Fe<sub>3</sub>O<sub>4</sub> to Fe metal by CO or H<sub>2</sub> and then reoxidized by O<sub>2</sub> were stabilized by surface-grafting Fe<sub>2</sub>O<sub>3</sub> with CeO<sub>2</sub>. In situ Raman spectra demonstrated that the
surface-grafted CeO<sub>2</sub> acts as an oxygen gateway, activating
the dissociation of O<sub>2</sub> into oxide ions or the recombination
of oxide ions into O<sub>2</sub> and transferring oxide ions to/from
Fe<sub>2</sub>O<sub>3</sub>. Meanwhile, Fe<sub>2</sub>O<sub>3</sub> acts as an oxygen reservoir that expands the O<sub>2</sub> storage
capacity. The composite material was tested in a simulated exhaust
gas stream with lean/rich perturbations (which occur in automotive
three-way catalysts). The synergistic effect of the surface grafting
effectively buffered the system against air-to-fuel ratio fluctuations
Role of Oxygen Vacancies in Catalytic SO<sub>3</sub> Decomposition over Cu<sub>2</sub>V<sub>2</sub>O<sub>7</sub> in Solar Thermochemical Water Splitting Cycles
We
report the structure–activity relationship of copper
pyrovanadate (Cu<sub>2</sub>V<sub>2</sub>O<sub>7</sub>) as an efficient
catalyst for SO<sub>3</sub> decomposition in solar thermochemical
water splitting cycles. Of the α, β, and γ polymorphs
of Cu<sub>2</sub>V<sub>2</sub>O<sub>7</sub>, the α-phase, which
has a blossite-type structure, was stable under the catalytic reaction
conditions. Spontaneous oxygen desorption accompanied by charge compensation
through the reduction of Cu<sup>2+</sup> to Cu<sup>+</sup> produced
an oxygen deficiency corresponding to Cu<sub>16</sub>V<sub>16</sub>O<sub>55</sub> at 600 °C. Density functional theory calculations
based on these results showed that oxygen vacancy formation is more
favorable on the Cu–O–V bridging sites than on the V–O–V
site in the pyrovanadate unit. The oxygen vacancy formation energy
of the (100) surface is considerably less than that of bulk Cu<sub>16</sub>V<sub>16</sub>O<sub>56</sub>. The reaction, Cu<sub>16</sub>V<sub>16</sub>O<sub>55</sub> + SO<sub>3</sub> → Cu<sub>16</sub>V<sub>16</sub>O<sub>56</sub> + SO<sub>2</sub>, is exothermic, suggesting
that oxygen vacancies play a key role in catalytic SO<sub>3</sub> decomposition
over a Cu<sub>2</sub>V<sub>2</sub>O<sub>7</sub> catalyst
Surface Properties of Rh/AlPO<sub>4</sub> Catalyst Providing High Resistance to Sulfur and Phosphorus Poisoning
A rhodium catalyst supported on AlPO<sub>4</sub> exhibited a much
higher resistance to sulfur and phosphorus poisoning compared with
a reference catalyst (Rh/Al<sub>2</sub>O<sub>3</sub>). The acidic
surface of AlPO<sub>4</sub> was effective in preventing the adsorption
of sulfur oxides (SO<sub>2</sub>), whereas Lewis acid/base sites on
Al<sub>2</sub>O<sub>3</sub> favored SO<sub>2</sub> adsorption followed
by the formation of sulfite, leading to deterioration of the activity
of Rh/Al<sub>2</sub>O<sub>3</sub> for the model NO–CO–C<sub>3</sub>H<sub>6</sub>–O<sub>2</sub> reaction. Similarly, the
AlPO<sub>4</sub> support suppressed the extent of phosphorus poisoning
caused by dimethylphosphite (DMP) (CH<sub>3</sub>O)<sub>2</sub>POH,
which was used as a model phosphorus source. A greater amount of inactive
phosphate overlayers were deposited from the gas feed containing DMP
and O<sub>2</sub> on Rh/Al<sub>2</sub>O<sub>3</sub> than Rh/AlPO<sub>4</sub> because of the reaction between P<sub>2</sub>O<sub>5</sub> vapors and Al<sub>2</sub>O<sub>3</sub>. Consequently, the active
Rh surface was covered to a greater extent for Rh/Al<sub>2</sub>O<sub>3</sub> than Rh/AlPO<sub>4</sub>
Stability of Molten-Phase Cs–V–O Catalysts for SO<sub>3</sub> Decomposition in Solar Thermochemical Water Splitting
Supported molten
cesium vanadate catalysts (Cs–V–O/SiO<sub>2</sub>) showed
activities comparable to that of a reference Pt catalyst (1 wt % Pt/TiO<sub>2</sub>) for SO<sub>3</sub> decomposition at moderate temperatures
(∼600 °C), which is essential as an O<sub>2</sub> evolution
reaction in solar thermochemical water splitting cycles. Stability
testing of the catalyst over a 1000 h continuous reaction at 600 °C
resulted in deactivation by ∼20% of the initial activity. Kinetic
analysis of the activity versus time-on-stream indicated that the
observed deactivation behavior can be divided into an induction period
(≤100 h) and an acceleration period (>100 h). The deactivation
is mainly caused by the vaporization loss of active components (Cs
and V) from the molten phase. At the earliest stage, most vapor is
generated in the upstream section of the catalyst bed and then redeposits
therebelow. Upon repeating these vaporization and deposition cycles,
Cs and V move gradually downstream. During this induction period,
the deactivation is not obvious because the total Cs and V content
of the catalyst bed remains almost unchanged. After this period, however,
detachment of Cs and V from the downstream end of the catalyst bed
induces accelerated deactivation. The vaporization loss was found
to be significantly suppressed by inverting the catalyst bed every
100 h during the stability test. Consequently, this operation reduced
the extent of catalyst deactivation from 20% to less than 10% of the
initial activity
Selective Formation of Cu Active Sites with Different Coordination States on Pseudospinel CuAl<sub>2</sub>O<sub>4</sub> and Their NO Reduction Catalysis
In the spinel framework,
copper (Cu) in two distinct
coordination
states exhibits catalytic activity for NO reduction through different
mechanisms. However, detailed exploration of their respective catalytic
properties, such as the redox behavior of Cu and substrate molecule
adsorption, has been challenging due to difficulties in their separate
formation. In this study, we present the controlled formation of pseudospinel
CuAl2O4, containing exclusively tetrahedrally
or octahedrally coordinated Cu, achieved by manipulating aging temperature
and O2 concentration. Through these materials, we observed
that in the CO–NO reaction, the step primarily determining
the rate differs: NO reduction dominates with octahedrally coordinated
Cu, whereas carbon monoxide (CO) oxidation is prominent with tetrahedrally
coordinated Cu. The lower coordination number of Cu significantly
benefits NO reduction but negatively impacts the CO–NO reaction,
albeit positively influencing NO reduction in three-way catalytic
reactions
Catalytic SO<sub>3</sub> Decomposition Activity and Stability of Pt Supported on Anatase TiO<sub>2</sub> for Solar Thermochemical Water-Splitting Cycles
Pt-loaded anatase
TiO<sub>2</sub> (Pt/TiO<sub>2</sub>-A) was found
to be a highly active and stable catalyst for SO<sub>3</sub> decomposition
at moderate temperatures (∼600 °C), which will prove to
be the key for solar thermochemical water-splitting processes used
to produce H<sub>2</sub>. The catalytic activity of Pt/TiO<sub>2</sub>-A was found to be markedly superior to that of a Pt catalyst supported
on rutile TiO<sub>2</sub> (Pt/TiO<sub>2</sub>-R), which has been extensively
studied at a higher reaction temperature range (≥800 °C);
this superior activity was found despite the two being tested with
similar surface areas and metal dispersions after the catalytic reactions.
The higher activity of Pt on anatase is in accordance with the abundance
of metallic Pt (Pt<sup>0</sup>) found for this catalyst, which favors
the dissociative adsorption of SO<sub>3</sub> and the fast removal
of the products (SO<sub>2</sub> and O<sub>2</sub>) from the surface.
Conversely, Pt was easily oxidized to the much less active PtO<sub>2</sub> (Pt<sup>4+</sup>), with the strong interactions between the
oxide and rutile TiO<sub>2</sub> forming a fully coherent interface
that limited the active sites. A long-term stability test of Pt/TiO<sub>2</sub>-A conducted for 1000 h at 600 °C demonstrated that there
was no indication of noticeable deactivation (activity loss ≤
4%) over the time period; this was because the phase transformation
from anatase to rutile was completely prevented. The small amount
of deactivation that occurred was due to the sintering of Pt and TiO<sub>2</sub> and the loss of Pt under the harsh reaction atmosphere
Macroporous Supported Cu–V Oxide as a Promising Substitute of the Pt Catalyst for Sulfuric Acid Decomposition in Solar Thermochemical Hydrogen Production
The macroporous supported Cu–V oxide prepared
by a novel
dissolution–reprecipitation process was found to be the first
example of a promising substitute of Pt catalysts for sulfuric acid
decomposition at moderate temperatures (∼600 °C), which
is required in solar thermochemical hydrogen production. Stepwise
impregnation of CuÂ(NO<sub>3</sub>)<sub>2</sub> and NH<sub>4</sub>VO<sub>3</sub> onto 3-D ordered mesoporous SiO<sub>2</sub>, and subsequent
heating at 650 °C yielded the deposition of copper pyrovanadate
(Cu<sub>2</sub>V<sub>2</sub>O<sub>7</sub>, melting point: 780 °C)
not only in mesopores but also on the external surface. Thermal aging
at 800 °C caused the congruent melting of Cu<sub>2</sub>V<sub>2</sub>O<sub>7</sub> followed by smooth penetration of the melt into
mesopores and homogeneous covering of cavity walls. Because of the
solubility of SiO<sub>2</sub> into the molten vanadate, dissolution–reprecipitation
should be equilibrated to allow substantial structural conversion
from mesoporous to macroporous SiO<sub>2</sub> frameworks. The resulting
macroporous catalyst consisting of highly dispersed thin layers of
active Cu<sub>2</sub>V<sub>2</sub>O<sub>7</sub> is considered efficient
for catalytic reactions and the mass transfer of reactants and products
in the presence of high-concentration vapors
Catalytic SO<sub>3</sub> Decomposition Activity and Stability of A–V–O/SiO<sub>2</sub> (A = Na, K, Rb, and Cs) for Solar Thermochemical Water-Splitting Cycles
SiO<sub>2</sub>-supported molten
alkaline metal oxides (A–V–O/SiO<sub>2</sub>) were studied
as SO<sub>3</sub> decomposition catalysts for
solar thermochemical water splitting. Their catalytic activities at
moderate temperatures (≤600 °C), which were superior to
those of Cu–V–O/SiO<sub>2</sub> catalysts, were dependent
on A, exhibiting the following sequence: Cs > Rb > K > Na.
These activities
increased with the A/V ratio. This result is in accordance with the
basicity, which favors the adsorption of SO<sub>3</sub> to form sulfate.
Another important effect of A is to form molten liquid phases, which
dissolve the sulfate and facilitate its decomposition to SO<sub>2</sub>/O<sub>2</sub>. However, the molten phase with high A/V ratios led
to the collapse of the porous SiO<sub>2</sub> structure by a corrosion
effect. Consequently, the highest catalytic activity was achieved
at a composition of A/V ≈ 1.0 for A = K and Cs. The long-term
stability test of K–V–O/SiO<sub>2</sub> at 550 °C
demonstrated no indication of noticeable deactivation during the first
100 h, whereas 20% deactivation occurred during the following 400
h. The deactivation mechanism involves the vaporization loss of active
components from the molten phase, which is accelerated in the presence
of SO<sub>3</sub>
Platinum Supported on Ta<sub>2</sub>O<sub>5</sub> as a Stable SO<sub>3</sub> Decomposition Catalyst for Solar Thermochemical Water Splitting Cycles
Platinum
supported on Ta<sub>2</sub>O<sub>5</sub> was found to be a very active
and stable catalyst for SO<sub>3</sub> decomposition, which is a key
reaction in solar thermochemical water splitting processes. During
continuous reaction testing at 600 °C for 1,800 h, the Pt/Ta<sub>2</sub>O<sub>5</sub> catalyst showed no noticeable deactivation (activity
loss ≤ 1.5% per 1,000 h). This observed stability is superior
to that of the Pt catalyst supported on anatase TiO<sub>2</sub> developed
in our previous study and to those of Pt catalysts supported on other
SO<sub>3</sub>-resistant metal oxides Nb<sub>2</sub>O<sub>5</sub> and
WO<sub>3</sub>. The higher stability of Pt/Ta<sub>2</sub>O<sub>5</sub> is due to the abundance of metallic Pt (Pt<sup>0</sup>), which favors
the dissociative adsorption of SO<sub>3</sub> and the smooth desorption
of the products (SO<sub>2</sub> and O<sub>2</sub>). This feature is
in accordance with a lower activation energy and a less negative partial
order with respect to O<sub>2</sub>. Pt sintering under the harsh
reaction environment was also suppressed to a significant extent compared
to that observed with the use of other support materials. Although
a small fraction of the Pt particles were observed to have grown to
more than several tens of nanometers in size, nanoparticles smaller
than 5 nm were largely preserved and were found to play a key role
in stable SO<sub>3</sub> decomposition