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At least 73 records · Page 4

Characterization of CeO{sub 2} crystals synthesized with different amino acids

We investigated the relationship between the structures of the CeO{sub 2} products (particle size, morphology and their characteristics) prepared using different amino acids. Cerium hydroxide carbonate precursors were initially prepared by a hydrothermal method and were subsequently converted to CeO{sub 2} by its thermal decomposition. Various amino acids were used as structure-directing agents in the presence of cerium nitrate and urea as precursors. The results indicate morphology selectivity using different amino acids; CeO{sub 2} structures, such as quasi-prism-sphere, straw-bundle, urchin-flower like and polyhedron prisms, indeed could be produced. Raman and photoluminescence studies indicate the presence of oxygen vacancies in the CeO{sub 2} samples. Photoluminescence spectra of CeO{sub 2} with L-Valine exhibit stronger emission compared with other amino acids utilized under this study, indicating the higher degree of defects in these particles. This study clearly indicates that the degree of defects varied in the presence of different amino acids. Improved precision to control the crystal morphology is important in various material applications and our study provides a novel method to achieve this specificity. - Highlights: • We used urea hydrolysis of process for synthesis of CeO{sub 2}. • Structures have been directed using various amino acids. • We obtained straw bundle-like, quasi prism-sphere, polyhedron prisms and urchin flower-like based on amino acids. • We have found that amino acids could achieve the specificity of different degrees of defects. • This could provide the “tailor-make” of cerium crystals.

36 MATERIALS SCIENCE↗

Combustion synthesized CeO{sub 2} as an anodic material in dye sensitized solar cells

Highlights: • One-step combustion synthesis of CeO{sub 2}. • Application of synthesized material as an anodic material for DSSC. • DSSC using CeO{sub 2} displayed an efficiency of 1.84%. - Abstract: Cerium oxide (CeO{sub 2}) has received a considerable attention due to its capacity to absorb visible light, low cost, high stability and environmental friendly catalytic applications. Among the various techniques employed to synthesize CeO{sub 2}, solution combustion synthesis is a one-step, economic and effective process. In this work, we report application of combustion synthesized CeO{sub 2} as an anodic material in the dye sensitized solar cell (DSSC). The synthesized material were characterized using standard analytical techniques such as XRD, SEM, BET, UV-DRS, and TEM. DSSC was fabricated using the synthesized material and characterized for incident photon to current conversion efficiency (IPCE), current density-voltage (J-V) measurements and electrochemical impedance spectroscopy. The power conversion efficiency of solar cell was found to be 1.84%. This is the first study to report use of combustion synthesized CeO{sub 2} for DSSC application.

36 MATERIALS SCIENCE↗

H 2 Dissociation on Noble Metal Single Atom Catalysts Adsorbed on and Doped into CeO 2 (111)

In this study, we used density functional theory (DFT) calculations to investigate the dissociation of H 2 on an Ag single atom catalyst adsorbed on the pristine CeO 2 (111) surface (Ag/CeO 2 ), or substituting a surface Ce atom on the reduced (Ag:CeO 2-x ) and partially hydrogenated (Ag:H–CeO 2 ) surfaces. The initial state of the H 2 dissociation reaction in the different investigated models corresponds to distinct oxidation states, +1, +2, or +3, of the Ag atom, thus allowing us to examine the influence of the charge transfers between the noble metal, the oxide, and the hydrogen atoms on the reaction pathway and activation energy. In all investigated models, the computed barrier of H 2 dissociation is lowered by about 0.6 eV in comparison to that on metal-free CeO 2 . On Ag/CeO 2 and Ag:CeO 2-x , also the energy of H 2 dissociative adsorption is smaller than that on metal-free ceria. These results suggest that CeO 2 modified with dispersed Ag atoms is a promising anode material for proton exchange membrane fuel cells. Lastly, further comparison of our results for Ag to analogous calculations for Cu and Au single atom catalysts reveals trends in the computed barriers that can be related to the change of the metal oxidation state in the reaction.

36 MATERIALS SCIENCE↗

In Situ Elucidation of the Active State of Co–CeO x Catalysts in the Dry Reforming of Methane: The Important Role of the Reducible Oxide Support and Interactions with Cobalt

The activation of methane and its dry reforming with CO 2 was systematically studied over a series (2–30 wt %) of Co (~5 nm in size) loaded CeO 2 catalysts, with an effort to elucidate the interplay between Co and CeO 2 during the catalytic process using in situ methods. The results of in situ time-resolved X-ray diffraction (TR-XRD) show a strong interaction of methane with the CoOx–CeO 2 systems at temperatures between 200 and 350 °C. The hydrogen produced by the dissociation of C–H bonds in methane leads to a full reduction of Co oxide, Co 3 O 4 → CoO → Co, and a partial reduction of ceria with the formation of some Ce 3+ . Upon the addition of CO 2 , a catalytic cycle for dry reforming of methane (DRM) was achieved on the CoOx–CeO 2 powder catalysts at temperatures below 500 °C. A 10 wt % Co–CeO 2 catalyst was found to possess the best catalytic activity among various cobalt loading catalysts, and it exhibits a desirable stability for the DRM with a minimal effect of carbon accumulation. The phase transitions and the nature of active components in the catalyst were investigated under reaction conditions by in situ time-resolved XRD and ambient-pressure X-ray photoelectron spectroscopy (AP-XPS). These studies showed dynamic evolutions in the chemical composition of the catalysts under reaction conditions. CO 2 attenuated the reducing effects of methane. Under optimum CO- and H 2 -producing conditions, both XRD and AP-XPS indicated that the active phase involved a majority of metallic Co with a small amount of CoO, both supported on a partially reduced ceria (Ce 3+ /Ce 4+ ). Finally, we identified the importance of dispersing Co, anchoring it onto the ceria surface sites, and then utilizing the redox properties of CeO 2 for activating and then oxidatively converting methane while inhibiting coke formation. Furthermore, a synergistic effect between cobalt and ceria and likely the interfacial sitee are essential to successfully close the catalytic cycle.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Catalytic Conversion of Bamboo Sawdust over ZrO 2 –CeO 2 /γ-Al 2 O 3 to Produce Ketonic Hydrocarbon Precursors and Furans

Here, a series of metal oxides including ZrO 2 /γ-Al 2 O 3 , CeO 2 /γ-Al 2 O 3 , and ZrO 2 –CeO 2 /γ-Al 2 O 3 were synthesized and employed to conduct catalytic fast pyrolysis of bamboo sawdust via an analytical pyrolyzer/gas chromatograph/mass spectrometer (Py-GC/MS) to produce hydrocarbon precursors such as ketones and furans. Experimental results illustrated that the use of metal oxides enhanced the formation of ketones and monoaromatic hydrocarbons compared to catalyst-free trial. Among the metal oxides, ZrO 2 –CeO 2 /γ-Al 2 O 3 exhibited the most significant ketonization and aldol condensation activities yielding the highest concentration of linear and cyclic ketones. In addition, nonacidic oxygenates such as furfural, acetol, butanedial, 2,3-dihydrobenzofuran, and methyl acetate, were efficiently converted into hydrocarbon precursors over metal oxides. A dual catalytic bed system integrating ZrO 2 –CeO 2 /γ-Al 2 O 3 and HZSM-5 significantly facilitated the production of aromatic hydrocarbons compared to pure HZSM-5 catalytic run. The use of ZrO 2 –CeO 2 /γ-Al 2 O 3 mixed with HZSM-5 mode maximized the formation of xylenes, while ZrO 2 –CeO 2 /γ-Al 2 O 3 mixed with bamboo sawdust catalytic trial increased the concentration of benzene, toluene, and alkylbenzenes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Investigation of surface defect states in CeO{sub 2-y} nanocrystals by Scanning−tunneling microscopy/spectroscopy and ellipsometry

Synthesis process strongly influences the nanocrystalline CeO{sub 2-y} defective structure. The presence of surface defects, in the form of oxygen vacancies in different charge states (F centers), can change the electronic properties of ceria nanocrystals. Nanocrystalline CeO{sub 2-y} samples were synthesized using three different methods (precipitation, self-propagating room temperature, and hydrothermal synthesis). Raman spectroscopy was used to identify the presence of oxygen vacancies which presumably were formed at the nanoparticle surface. The defect concentration depended on the crystallite size of differently prepared CeO{sub 2-y} samples. Scanning tunneling microscopy/spectroscopy and ellipsometry were employed to investigate the electronic band structure of defective CeO{sub 2-y} nanocrystals. Scanning tunneling spectroscopy measurements demonstrated that inside the band gap of CeO{sub 2-y} nanocrystals, besides the filled 4 f states, appeared additional states which were related to occupied and empty F center defect states. From the ellipsometric measurements, using the critical points model, the energy positions of different F centers states and the values of the reduced band gap energies were determined. The analysis of obtained data pointed out that depending on the synthesis method, different types of F centers (F{sup +} and F{sup 0}) can be formed in the CeO{sub 2-y} nanocrystals. The formation of different F center defect states inside the ceria gap have a strong impact on the electrical, optical, and magnetic properties of ceria nanocrystals.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Growth, sintering, and chemical states of Co supported on reducible CeO 2 (111) thin films: The effects of the metal coverage and the nature of the support

The growth, sintering, and interaction of cobalt with ceria were studied under ultrahigh vacuum conditions by vapor-deposition of Co onto well-defined CeOx(111) (1.5 < x < 2) thin films grown on Ru(0001). Charge transfer from Co to ceria occurs upon deposition of Co on CeO 1.96 and partially reduced CeO 1.83 at 300 K. X-ray photoelectron spectroscopy studies show that Co is oxidized to Co 2+ species at the cost of the reduction of Ce 4+ to Ce 3+ , at a lesser extent on reduced ceria. Co 2+ is the predominant species on CeO 1.96 at low Co coverages (e.g., ≤0.20 ML). The ratio of metallic Co/Co 2+ increases with the increase in the Co coverage. However, both metallic Co and Co 2+ species are present on CeO 1.83 even at low Co coverages with metallic Co as the major species. Scanning tunneling microscopy results demonstrate that Co tends to wet the CeO 1.96 surface at very low Co coverages at room temperature forming one-atomic layer high structures of Co–O–Ce. The increase in the Co coverage can cause the particle growth into three-dimensional structures. The formation of slightly flatter Co particles was observed on reduced CeO 1.83 . In comparison with other transition metals including Ni, Rh, Pt, and Au, our studies demonstrate that Co on ceria exhibits a smaller particle size and higher thermal stability, likely arising from strong metal–support interactions. The formed particles upon Co deposition at 300 K are present on the ceria surface after heating to 1000 K. The Co–ceria interface can be tuned by varying the Co metal coverage, the annealing temperature, and the nature of the ceria surface.

36 MATERIALS SCIENCE↗

Thermal and mechanical properties of CeO 2

In this study, the thermal and mechanical properties of cerium dioxide (CeO 2 ) were assessed using a range of experimental techniques. The oxygen potential of CeO 2 was measured by the thermogravimetric technique, and a numerical fit for the oxygen potential of CeO 2 is derived based on defect chemistry. Mechanical properties of CeO 2 were obtained using sound velocity measurement, resonant ultrasound spectroscopy and nanoindentation. The obtained mechanical properties of CeO 2 are then used to evaluate the Debye temperature and Grüneisen constant. The heat capacity and thermal conductivity of CeO 2 were also calculated using the Debye temperature and the Grüneisen constant. Lastly, the thermal conductivity was calculated based upon laser flash analysis measurements performed on pellets fabricated using a range of feedstock purities to resolve discrepancies in the existing literature.

36 MATERIALS SCIENCE↗

Construction of a Pt‐CeO x Interface for the Electrocatalytic Hydrogen Evolution Reaction

Abstract The creation of metal‐metal oxide interfaces is an important approach to fine‐tuning catalyst properties through strong interfacial interactions. This article presents the work on developing interfaces between Pt and CeO x that improve Pt surface energetics for the hydrogen evolution reaction (HER) within an alkaline electrolyte. The Pt‐CeO x interfaces are formed by depositing size‐controlled Pt nanoparticles onto a carbon support already coated with ultrathin CeO x nanosheets. This interface structure facilitates substantial electron transfer from Pt to CeO x , resulting in decreased hydrogen binding energies on Pt surfaces, and water dissociation for the HER, as predicted by the density functional theory (DFT) calculations. Electrochemical testing indicates that both Pt specific activity and mass activity are improved by a factor of 2 to 3 following the formation of Pt‐CeO x interfaces. This study underscores the significance and potential of harnessing robust interfacial effects to enhance electrocatalytic reactions.

25 ENERGY STORAGE↗

Effects of CeO{sub 2} on the Microstructure and Properties of Laser Cladding 316L Coating

Laser cladding was used to distribute a CeO{sub 2}-modified 316L powder coating onto a 316L stainless steel surface. The cladding layer phase composition was evaluated through x-ray diffraction. An analysis of the microstructure was conducted using an optical microscope and scanning electron microscope, while the micro-hardness was measured using a tester. The coating corrosion behavior in response to 3.5% NaCl solution was analyzed by polarization curves and electrochemical impedance spectroscopy. Finally, the overall performance of coatings with different CeO{sub 2} concentrations, 1, 2, and 3%, was compared. Results showed that adding CeO{sub 2} significantly refined the grains, reduced the coating porosity, and effectively limited the appearance of local corrosion. Also, additive CeO{sub 2} shifted the coating’s electrode potential in a positive direction, minimizing the current density of corrosion, creating a stable passivation film, and improving the coating’s corrosion resistance. The coating performance (hardness and corrosion behavior) was optimal when 2% CeO{sub 2} was employed as the powder mass.

36 MATERIALS SCIENCE↗

Constructing efficient CuO x -CeO 2 catalyst for NO reduction by CO: New insights into the structure–activity relationship

CuO-CeO 2 based materials have been recognized as promising substitutes for precious metal catalysts in emission control field due to their superior redox property and low cost. In this work, by optimizing the deposition process of CeO 2 and CuO onto γ-Al 2 O 3 , highly dispersed CuO clusters on unique CeO 2 -Al 2 O 3 support with small CeO 2 particles (7Cu-Ce/CeAl) were successfully constructed for efficient NO reduction by CO, which exhibited much higher NO removal efficiency and N 2 selectivity than CuO catalysts supported on γ-Al 2 O 3 (7Cu/Al) and conventional CeO 2 -Al 2 O 3 support (7Cu/CeAl). Moreover, H 2 O showed limited inhibition effect on the catalytic performance of 7Cu-Ce/CeAl catalyst. With the help of Raman spectra, X-ray absorption spectroscopy, in situ diffuse reflectance infrared Fourier transform spectroscopy, etc., it was clearly revealed that the abundant Cu + /Ce 3+ paired sites with surface synergetic oxygen vacancies (SSOV) on 7Cu-Ce/CeAl catalyst could effectively facilitate the adsorption and activation of CO and NO, thus significantly enhancing the NO removal efficiency.

36 MATERIALS SCIENCE↗

Adsorption and activation of CO 2 on Pt/CeOx/TiO 2 (110): Role of the Pt-CeO x interface

The adsorption and dissociation of CO 2 on TiO 2 (110), CeO x /TiO 2 (110) and Pt/CeO x /TiO 2 (110) surfaces has been examined using Ambient Pressure X-ray Photoelectron Spectroscopy (AP-XPS). The substrates under study exhibited different degrees of complexity which were tested for the binding of the adsorbate and the cleavage of C-O bonds. The surfaces were prepared by depositing CeO x (0.1 ML) onto TiO 2 (110) to form a mixed oxide support, onto which Pt nanoparticles (0.2 ML) were deposited. This configuration yields a complex set of interfaces between metal and oxides and we have systematically titrated the active role of each component (Pt 4f, Ce 3d and Ti 2p regions) and the arising surface intermediates (C 1s and O 1s regions). CO 2 barely bonds to stoichiometric TiO 2 (110). It heals oxygen vacancies of this oxide surface (CO 2,gas → CO gas + O a ) and does not form stable carbonates. A stable carbonate was seen upon adsorption of CO 2 on CeO x /TiO 2 (110) and on this type of substrate the adsorbate also removed O vacancies leading to the oxidation of Ti 3+ and Ce 3+ sites. Pt nanoparticles dispersed on CeO x /TiO 2 (110) were highly effective for the binding and dissociation of CO 2 , with the formation of CO 3 , CO, C and CH x species on the Pt/CeO x /TiO 2 (110) system. The results of theoretical calculations based on density-functional theory (DFT) show that Pt/CeOx/TiO2(110) binds CO2 much stronger than surfaces of bulk platinum {(111), (100), (110)} or other late transition metals. On a Pt-CeO x interface, the molecule adsorbs with a bent configuration (~ 130° O-C-O bond angle) and with a substantial elongation (~ 0.1 Å) of the C-O bonds, facilitating its transformation into high value chemicals.

36 MATERIALS SCIENCE↗

Unraveling the Origin of Photocatalytic Deactivation in CeO 2 /Nb 2 O 5 Heterostructure Systems during Methanol Oxidation: Insight into the Role of Cerium Species

The study provides deep insight into the origin of photocatalytic deactivation of Nb 2 O 5 after modification with ceria. Of particular interest was to fully understand the role of ceria species in diminishing the photocatalytic performance of CeO 2 /Nb 2 O 5 heterostructures. For this purpose, ceria was loaded on niobia surfaces by wet impregnation. The as-prepared materials were characterized by powder X-ray diffraction, nitrogen physisorption, UV-visible spectroscopy, X-ray photoelectron spectroscopy, high-resolution transmission electron microscopy, and photoluminescence measurements. Photocatalytic activity of parent metal oxides (i.e., Nb 2 O 5 and CeO 2 ) and as-prepared CeO 2 / Nb 2 O 5 heterostructures with different ceria loadings were tested in methanol photooxidation, a model gas-phase reaction. Deep insight into the photocatalytic process provided by operando-IR techniques combined with results of photoluminescence studies revealed that deactivation of CeO 2 /Nb 2 O 5 heterostructures resulted from increased recombination of photo-excited electrons and holes. The main factor contributing to more efficient recombination of the charge carriers in the heterostructures was the ultrafine size of the ceria species. The presence of such highly dispersed ceria species on the niobia surface provided a strong interface between these two semiconductors, enabling efficient charge transfer from Nb 2 O 5 to CeO 2 . However, the ceria species supported on niobia exhibited a high defect site concentration, which acted as highly active recombination centers for the photo-induced charge carriers.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Hydrogenation of CO 2 to methanol on CeO x /Cu(111) and ZnO/Cu(111) catalysts: Role of the metal-oxide interface and importance of Ce 3+ sites

The role of the interface between a metal and oxide (CeO x –Cu and ZnO–Cu) is critical to the production of methanol through the hydrogenation of CO 2 (CO 2 + 3H 2 → CH 3 OH + H 2 O). The deposition of nanoparticles of CeO x or ZnO on Cu(111), θ oxi < 0.3 monolayer, produces highly active catalysts for methanol synthesis. The catalytic activity of these systems increases in the sequence: Cu(111) < ZnO/Cu(111) < CeO x /Cu(111). The apparent activation energy for the CO 2 → CH 3 OH conversion decreases from 25 kcal/mol on Cu(111) to 16 kcal/mol on ZnO/Cu(111) and 13 kcal/mol on CeO x /Cu(111). The surface chemistry of the highly active CeO x –Cu(111) interface was investigated using ambient pressure X-ray photoemission spectroscopy (AP-XPS) and infrared reflection absorption spectroscopy (AP-IRRAS). Both techniques point to the formation of formates (HCOO – ) and carboxylates (CO 2 δ– ) during the reaction. Our results show an active state of the catalyst rich in Ce 3+ sites which stabilize a CO 2 δ– species that is an essential intermediate for the production of methanol. Furthermore, the inverse oxide/metal configuration favors strong metal–oxide interactions and makes possible reaction channels not seen in conventional metal/oxide catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Enhancing Value-Added CO Production from CO 2 Hydrogenation by Tailoring the Ru-CeO 2 Interface on MgO

Catalytic CO 2 hydrogenation presents a promising route for converting CO 2 into valuable products, contributing to the mitigation of net CO 2 emissions. Supported Ru catalysts have recently gained considerable attention due to their tunability for 100% CO selectivity via the reverse water-gas shift pathway, effectively suppressing the competing methanation route. However, despite achieving full CO selectivity, the overall CO yield remains limited by low CO 2 conversion, necessitating further improvement. In this work, CeO 2 was introduced to modify a Ru/MgO single-atom catalyst for CO 2 hydrogenation. The resulting Ru-CeO 2 /MgO catalyst, featuring abundant Ru-CeO 2 interfacial sites, exhibited a favorable balance of CO 2 conversion and CO selectivity, delivering the highest CO yield (32.5% at 500 °C), which is 9.0 and 1.8 times higher than that on Ru/MgO (3.6%) and Ru/CeO 2 (18.4%), respectively. Although the CO selectivity was slightly compromised due to enhanced CO binding at Ru-CeO 2 interfacial sites, H 2 was more efficiently activated at these interfaces and readily reacted with CO 2 adsorbed on CeO 2 -MgO surfaces, thereby boosting the CO 2 hydrogenation activity and CO yield. This study underscores the critical role of Ru-metal oxide interface engineering in improving CO yield and advancing the rational design of highly efficient Ru catalysts for CO production from CO 2 hydrogenation.

36 MATERIALS SCIENCE↗

In Situ Studies of Ru-CeO 2 –TiO 2 Catalysts for Selective CO 2 Hydrogenation to Methane: Importance of Metal ↔ Oxide–Oxide Interactions

Here, this work investigates Ru-CeO 2 -TiO 2 catalysts for the CO 2 methanation reaction and compares their performance with previously studied Ru-CeO 2 systems. Despite the lower Ru loading, the TiO 2 -containing catalysts exhibit significantly higher activity. To understand this behavior, in situ X-ray absorption spectroscopy (XAS) was carried out at the Ru K-edge and Ce L 3 -edge. Unlike Ru-CeO 2 , which displays reversible redox behavior of Ru, the Ru-CeO 2 -TiO 2 catalysts show irreversible Ru reduction and a substantially higher fraction of Ce 3+ species under all tested conditions (H 2 , CO 2 , H 2 /CO 2 ). The stabilization of metallic Ru during methanation, together with the enhanced formation of Ce 3+ promoted by TiO 2 through interfacial electronic transfer, accounts for their superior performance. Complementary in situ DRIFTS measurements reveal the formation and rapid consumption of bidentate carbonates and formates. These species act as a key intermediate in methane formation. Overall, these findings highlight the crucial role of the mixed CeO 2 -TiO 2 oxide in tuning the surface chemistry of the catalysts by stabilizing metallic Ru, enhancing ceria reducibility, and promoting efficient reaction pathways for CO 2 methanation. The manipulation of metal↔oxide-oxide interactions can be a very useful tool when dealing with the valorization of CO 2 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Enhancing the inherent catalytic activity and stability of TiO 2 supported Pt single-atoms at CeO x –TiO 2 interfaces

Single-atoms (SAs) with atomically coordinated reaction centers are considered the next generation of catalysts that can exhibit exceptional catalytic efficiency. However, the general concern about thermodynamic vulnerabilities of SAs questions their practical value. Moreover, whether the inherent catalytic nature of SAs is superior compared with that of larger nanoparticles is still under debate. Here, we address two controversies by a comparative study using two catalysts: Pt/TiO 2 and Pt/CeO x –TiO 2 . Based on a hierarchical study of density functional theory, time-resolved catalysis performance test, in situ infrared spectroscopy, and operando X-ray absorption spectroscopy, we could unveil the catalytic nature of Pt-SAs and their stability. By utilizing the heterogeneous interface formed between TiO 2 supporting particles and CeO x clusters formed on the surface of TiO 2 , we preferentially synthesized Pt-SAs pinned at the CeO x –TiO 2 interfaces on CeO x –TiO 2 hybrid-oxide supports. The strong electronic coupling between the Pt-SAs and the Ce ions at the CeO x –TiO 2 interfaces enhanced the catalytic activity toward CO oxidation of Pt-SAs and improved the long-term stability under CO oxidation conditions. The CO oxidation activity of Pt-SAs stabilized at CeO x –TiO 2 was improved by 13.5 times at 200 °C compared with the Pt-SAs on TiO 2 . The results present how to easily improve the activity and stability of Pt-SAs using a simple interface control method. Moreover, we demonstrate that the catalytic activity and the stability of Pt-SAs can be monitored through the chemical state of the interfaces. Finally, our study provides comprehensive understanding about the catalytic nature as well as a novel strategy toward applications of Pt-SAs, enabling sustainable use of Pt in heterogeneous catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

High reactivity of mesoporous CeO 2 to dissociate chemical warfare agent sarin

We perform spectroscopic surface characterization on mesoporous ceria (CeO 2 ) under exposure of sarin gas, also known as GB. We find mesoporous CeO 2 displays extraordinary reactivity towards GB dissociation under high vacuum. The spectroscopic results combined with density functional theory (DFT) calculations suggest that the cleavage of the P–F and P–OR bonds are both possible pathways for GB to dissociate on the CeO 2 surfaces. The modeling reveals differences in dissociation pathways of GB on the crystallographic (111)- and (110)-surfaces of ceria. Here we also report some dissociation of GB on mesoporous CeO 2 under ambient conditions. The finding that mesoporous CeO 2 can degrade GB under mild conditions is encouraging and implies the strong potential of ceria-based materials to be applied in combating chemical warfare agents related to the GB series.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗