Pt-CeO2-Al2O3 catalysts play an important role in diesel oxidation and three-way catalysis. In this study, the fast structural dynamics of both platinum and ceria in a 1 wt %Pt/5 wt %CeO2-Al2O3 ...catalyst prepared by flame spray pyrolysis have been systematically investigated under reducing and oxidizing conditions to elucidate the role of the Pt–CeO2 interface for CO oxidation and fast oxygen storage/release of ceria. The catalyst showed enhanced catalytic activity, particularly after application of a reducing/oxidizing conditioning step at 250 °C, with a pronounced dependence on the reducing agent (C3H6 < H2 < CO). In situ time-resolved X-ray absorption spectroscopy (XAS) at the Ce L3-edge unraveled a dependence of the reduction extent of ceria during temperature-programmed reduction on the noble metal constituent and the applied reducing agent. Dynamic reducing/oxidizing cycling (2% H2 ↔ 10% O2 or 2% CO ↔ 10% O2) at various temperatures (150, 250, and 350 °C) showed that the reducibility of ceria increased at higher temperature and by using a more strongly reducing reaction mixture. This coincides with the trend in catalytic activity. Time-resolved XAS data recorded at the Pt L3-edge and Ce L3-edge during redox cycling revealed a close relationship between the Pt oxidation state and the ceria redox response. The formation of reduced Pt particles was found to induce variations in ceria reducibility under transient conditions and was identified as a decisive prerequisite for ceria reduction at low temperatures. Variations in the extent of ceria reduction during the reducing/oxidizing cycles indicate an evolution of the Pt–ceria interface from an inactive state toward an optimal activated state due to reduction and slight sintering of the noble metal particles. Further growth of Pt particles leads to a decrease in ceria reduction rate due to the smaller Pt–CeO2 interface perimeter. A schematic model illustrating the role of Pt for ceria reducibility is developed and the optimal Pt particle size derived. The results are relevant for various applications, particularly for catalysts operated at low temperature under highly dynamic reaction conditions such as exhaust gas catalysts.
Phosphorus (P) fertilizers from secondary resources became increasingly important in the last years. However, these novel P-fertilizers can also contain toxic pollutants such as chromium in its ...hexavalent state (Cr(VI)). This hazardous form of chromium is therefore regulated with low limit values for agricultural products even though the correct determination of Cr(VI) in these fertilizers may be hampered by redox processes, leading to false results. Thus, we applied the novel diffusive gradients in thin-films (DGT) technique for Cr(VI) in fertilizers and compared the results with the standard wet chemical extraction method (German norm DIN EN 15192) and Cr K-edge X-ray absorption near-edge structure (XANES) spectroscopy. We determined an overall good correlation between the wet chemical extraction and the DGT method. DGT was very sensitive and for most tested materials selective for the analysis of Cr(VI) in P-fertilizers. However, hardly soluble Cr(VI) compounds cannot be detected with the DGT method since only mobile Cr(VI) is analyzed. Furthermore, Cr K-edge XANES spectroscopy showed that the DGT binding layer also adsorbs small amounts of mobile Cr(III) so that Cr(VI) values are overestimated. Since certain types of the P-fertilizers contain mobile Cr(III) or partly immobile Cr(VI), it is necessary to optimize the DGT binding layers to avoid aforementioned over- or underestimation. Furthermore, our investigations showed that the Cr K-edge XANES spectroscopy technique is unsuitable to determine small amounts of Cr(VI) in fertilizers (below approx. 1% of Cr(VI) in relation to total Cr).
Bifunctional Fe–Pt ammonia slip catalysts were studied by
operando
quick-scanning extended X-ray absorption fine structure spectroscopy (QEXAFS) under conditions mimicking rapid temperature ...variations that occur in an automotive exhaust gas aftertreatment system during real driving. Two catalysts, Pt/Al
2
O
3
and Fe-ZSM-5, were tested individually, as mixtures and in dual bed arrangements. Applying QEXAFS allowed to track changes of active metal state with high time resolution. It uncovered a strong dependence of the active metal state on reaction conditions and catalyst bed layout. For example, proximity to platinum stabilized iron species in their more active oxidized state and led to higher Fe-ZSM-5 activity. On the contrary, isolated iron species were more susceptible to overreduction by ammonia which led to deactivation and low selectivity. The use of transient conditions uncovered the influence of non-equilibrium phenomena on catalytic performance under industrially relevant conditions. Specifically, the effect of ammonia storage on the increase of activity was shown. This was also accompanied by elevated N
2
O production not observed during tests with gradual heating. Additionally, unusually high NO
x
selectivity was detected for Fe-ZSM-5 under these conditions. Lastly, tracking catalyst state under dynamic reaction conditions disclosed that Fe-ZSM-5 activity did not grow directly with temperature increase but rather depended on the oxidation state of Fe and surface concentration of ammonia.
Electronic metal–support interactions (EMSI) describe the electron flow between metal sites and a metal oxide support. It is generally used to follow the mechanism of redox reactions. In this study ...of CuO‐CeO2 redox, an additional flow of electrons from metallic Cu to surface carbon species is observed via a combination of operando X‐ray absorption spectroscopy, synchrotron X‐ray powder diffraction, near ambient pressure near edge X‐ray absorption fine structure spectroscopy, and diffuse reflectance infrared Fourier transform spectroscopy. An electronic metal–support–carbon interaction (EMSCI) is proposed to explain the reaction pathway of CO oxidation. The EMSCI provides a complete picture of the mass and electron flow, which will help predict and improve the catalytic performance in the selective activation of CO2, carbonate, or carbonyl species in C1 chemistry.
During the oxidation of CO over the surface of a CuO‐CeO2 catalyst, electrons are simultaneously transferred from Cu0 to lattice Ce4+ and surface carbon species deposited from CO. These “electronic metal–support–carbon interactions” (EMSCI) are thought to play an important role in the reactions involving the support and surface carbon species in C1 chemistry.
A series of Pt/TiO
2
photocatalysts was prepared by impregnation of fresh and thermal-activated titania (commercial Evonik Aeroxide P25 TiO
2
) with an aqueous solution of H
2
PtCl
6
followed by ...reduction in an aqueous solution of NaBH
4
. The thermal activation was performed by annealing in air. The photocatalytic activity of the Pt/TiO
2
catalysts was measured for the hydrogen production from a mixture of glycerol under UV radiation. It was found that the activation at 300–600 °C provides an increase in the photoreactivity of resulting Pt/TiO
2
photocatalysts in the production of hydrogen while its structural and textural properties do not change. This effect is due to formation of cationic vacancies that limits fast electron–hole recombination.
Graphic Abstract
Novel catalysts consisting of ruthenium nanoparticles encapsulated in cross‐linked matrices based on the poly(propylene imine) dendrimers of the 1st and 3rd generations have been synthesized with a ...narrow particle size distribution (3.8 and 1.0 nm, respectively). The resulting materials showed high activity for the hydrogenation of phenols in aqueous media (specific catalytic activity reached turnover frequencies of 2975 h−1 with respect to hydrogen uptake). It has been shown that the use of water as a solvent leads to a 1.5 to 50‐fold increase in the reaction rate depending upon the nature of the substrate. It has been established that unlike the traditional heterogeneous catalysts based on ruthenium, during the hydrogenation of dihydroxybenzenes, the hydrogenation rate decreases in the order: resorcinol>hydroquinone≫catechol. The maximum specific activity for resorcinol was a turnover frequency of 243150 h−1 with respect to hydrogen uptake. The catalyst based on the dendrimer of the 3rd generation containing finer particles has significantly inferior activity to the catalyst based on the dendrimer of the 1st generation by virtue of steric factors, as well as the need for prereduction of the ruthenium oxide contained on the surface. These catalysts showed resistance to metal leaching and may be reused several times without loss of activity.
Trapped in trees and water‐loving: Novel catalysts based on ruthenium nanoparticles encapsulated into cross‐linked poly(propylene imine) (PPI) dendrimer matrices are synthesized. The materials display high activity and substrate selectivity in the hydrogenation of various phenols. They are highly resistant to metal leaching and can be recycled several times without loss of activity. The use of water as a solvent is beneficial to the activity of the catalytic system.
Microporosity and structure of a set of activated carbons was studied by combination of N
2
and CO
2
adsorption, Transmission Electron Microscopy (TEM), X-ray diffraction and scattering and ...multiwavelength Raman spectroscopy. It is shown that correlations between measured parameteres may be established for a given set of activated carbons, most often obtained from a same precursor. Comparison of results of TEM images processing and of Small-angle scattering with adsorption data suggests that super-micropores (0.7–2 nm) are highly variable in shape and strongly deviate from the ideal slit pore model. These pores are likely located in between disordered continuous graphene stacks. It is shown that Small-angle scattering is mostly caused by supermicropores; contribution of other types of porosity is of secondary importance. For a set of carbons with similar structure, a reasonable correlation between Guinier radii and pore width obtained from N
2
adsorption can be found; however, the reason for the observed offset between the data sets remain uncertain. Sensitivity of the Raman scattering to atomic scale processes leads to poor or unclear correlations between the spectroscopic and structural data, although some notable exceptions are noted.
Thermal expansion of synthetic coesite was studied with synchrotron powder X-ray diffraction in the temperature range of 100–1000 K. We determined the unit cell parameters of monoclinic coesite (
a, ...b, c
, and
β
) every 50 K in this temperature range. We observed that
a
and
b
parameters increase with increasing temperature, while
c
decreases. The
β
angle also decreases with temperature and approaches 120°. As a result, the unit cell volume expands by only 0.7% in this temperature range. Our measurements provide thermal expansion coefficients of coesite as a function of temperature: it increases from 3.4 × 10
−6
K
−1
at 100 K to 9.3 × 10
−6
K
−1
at 600 K and remains nearly constant above this temperature. The Suzuki model based on the zero-pressure Mie–Grüneisen equation of state was implemented to fit the unit cell volume data. The refined parameters are
V
0
= 546.30(2) Å
3
,
Q
= 7.20(12) × 10
6
J/mol and
θ
D
= 1018(43) K, where
θ
D
is the Debye temperature and
V
0
is the unit cell volume at 0 K with an assumption that
K
′
is equal to 1.8. The obtained Debye temperature is consistent with that determined in a previous study for heat capacity measurements.
Nanocatalysts PtAg/C with different distributions of components in bimetallic PtAg nanoparticles were synthesized by the methods of simultaneous and sequential reduction of Ag+ and Pt(IV) in carbon ...suspension, prepared on the basis of ethylene glycol–water solvent. The characterization of atomic structure of as prepared PtAg nanoparticles and PtAg nanoparticles obtained after acid treatment at 90 °C was performed by Pt L3-edge extended X-ray absorption fine structure (EXAFS) using the technique for determining local structure parameters of the absorbing Pt atoms, which have the nearest surrounding consisting of Pt and Ag atoms. This technique enabled stable and unambiguous values of parameters for the local structure of Pt atoms in PtAg nanoparticles to be obtained under severe correlations between some of these parameters. The effects of averaging over the sizes and compositions of PtAg nanoparticles on the obtained values of structural parameters were studied by the method of cluster simulations. Analysis of changes in the values of parameters of Pt local structure determined from experimental EXAFS in differently prepared nanoparticles PtAg under acid treatment, supplemented with simulations of different particle architectures by the molecular dynamics (MD) method, enabled a set of evidence of the core–shell structure in these nanoparticles to be proposed. Application of the combined approach, based on the use of EXAFS data and MD simulations, enabled us to characterize the atomic structure of PtAg nanoparticles synthesized by the two methods used and to suggest the mechanism of formation of a platinum shell in nanoparticles obtained by sequential deposition of Pt and Ag atoms on the carbon support, followed by acid treatment.
The state of palladium and copper on the surface of the PdCl₂-CuCl₂/γ-Al₂O₃ nanocatalyst for the low-temperature oxidation of CO by molecular oxygen was studied by various spectroscopic techniques. ...Using X-ray absorption spectroscopy (XAS), powder X-ray diffraction (XRD), and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), freshly prepared samples of the catalyst were studied. The same samples were also evaluated after interaction with CO, O₂, and H₂O vapor in various combinations. It was shown that copper exists in the form of Cu₂Cl(OH)₃ (paratacamite) nanophase on the surface of the catalyst. No palladium-containing crystalline phases were identified. Palladium coordination initially is comprised of four chlorine atoms. It was shown by XAS that this catalyst is not capable of oxidizing CO at room temperature in the absence of H₂O and O₂ over 12 h. Copper(II) and palladium(II) are reduced to Cu(I) and Pd(I,0) species, respectively, in the presence of CO and H₂O vapor (without O₂). It was found by DRIFTS that both linear (2114 cm
, 1990 cm
) and bridging (1928 cm
) forms of coordinated CO were formed upon adsorption onto the catalyst surface. Moreover, the formation of CO₂ was detected upon the interaction of the coordinated CO with oxygen. The kinetics of CO oxidation was studied at 18-38 °C at an atmospheric pressure for CO, O₂, N₂, and H₂O (gas) mixtures in a flow reactor (steady state conditions).
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