RESUMEN
The interfaces between heavy metals and antiferromagnetic materials have garnered significant attention due to their interesting physical properties. La0.35Sr0.65MnO3 (LSMO), as a typical manganite, exhibits an antiferromagnetic ground state that can be controlled through epitaxial strain and interfacial spin-orbit coupling. In this work, we reported the diverse magnetoresistance, influenced by the interfacial magnetic state, in Pt (3 nm)/LSMO (6-20 nm) heterostructures. The strong spin-orbit coupling of Pt and Dzyaloshinskii-Moriya interaction alter the spin structure and enhance the electron scattering at the Pt/LSMO interface, resulting in positive magnetoresistance. The interfacial angular-dependent magnetoresistance modulated by the interfacial magnetic states was also observed in the Pt/LSMO (20 nm) heterostructures. Our findings contribute to a broader understanding of interfacial properties between heavy metals and antiferromagnetic manganites.
RESUMEN
Strong metal-support interactions characteristic of the encapsulation of metal particles by oxide overlayers have been widely observed on large metal nanoparticles, but scarcely occur on small nanoclusters (<2â nm) for which the metal-support interactions remain elusive. Herein, we study the structural evolution of Pt nanoclusters (1.5â nm) supported on anatase TiO2 upon high-temperature H2 reduction. The Pt nanoclusters start to partially evolve into a CsCl-type PtTi intermetallic compound when the reduction temperature reaches 400 °C. Upon 700 °C reduction, the PtTi nanoparticles are exclusively formed and grow epitaxially along the TiO2 (101) crystal faces. The thermodynamics of the formation of PtTi via migration of reduced Ti atoms into Pt cluster is unraveled by theoretical calculations. The thermally stable PtTi intermetallic compound, with single-atom Pt isolated by Ti, exhibits enhanced catalytic activity and promoted catalytic durability for CO oxidation.
RESUMEN
The development of efficient non-noble metal catalysts for the dehydrogenation of hydrogen (H2) storage materials is highly desirable to enable the global production and storage of H2 energy. In this study, Cu x -(CoO)1-x /TiO2 catalysts with a Cu-CoO interface supported on TiO2 are shown to exhibit high catalytic efficiency for ammonia borane (NH3BH3) hydrolysis to generate H2. The best catalytic activity was observed for a catalyst with a Cu : Co molar ratio of 1 : 1. The highest dehydrogenation turnover frequency (TOF) of 104.0 molH2 molmetal -1 min-1 was observed in 0.2 M NaOH at room temperature, surpassing most of the TOFs reported for non-noble catalysts for NH3BH3 hydrolysis. Detailed characterisation of the catalysts revealed electronic interactions at the Cu-CoO heterostructured interface of the catalysts. This interface provides bifunctional synergetic sites for H2 generation, where activation and adsorption of NH3BH3 and H2O are accelerated on the surface of Cu and CoO, respectively. This study details an effective method of rationally designing non-noble metal catalysts for H2 generation via a metal and transition-metal oxide interface.
RESUMEN
Creating synergetic metal-oxide interfaces is a promising strategy to promote the catalytic performance of heterogeneous catalysts. However, this strategy has been mainly applied to monometallic catalysts, while scarcely applied to alloy catalysts. In this work, we present a comprehensive study on the synergetic alloy-oxide interfaces in the bimetallic Pt-Co/Al2O3 catalysts for CO oxidation. A series of Pt1Cox/Al2O3 catalysts with various Co/Pt molar ratios with x ranging from 0.5 to 3.8 was synthesized via a facile wet-chemistry strategy. Among them, the Pt1Co0.5/Al2O3 catalyst exhibits the best catalytic performance for CO oxidation, with the lowest CO complete conversion temperature of -10 °C and the highest mass specific rate of 2.61 (mol CO) h-1 (g Pt)-1. From in situ X-ray absorption fine structure and diffuse reflectance infrared Fourier-transform spectroscopy studies, the superior catalytic performance of Pt1Co0.5/Al2O3 originates from the optimal length of the three-dimensional alloy-oxide perimeter sites. We further extended this strategy to other bimetallic systems of Pt-Fe and Pt-Ni, which also show similar structural properties and remarkable promotional effects on the catalytic activity.
RESUMEN
Metal-oxide/hydroxide hybrid nanostructures provide an excellent platform to study the interfacial effects on tailoring the catalysis of metal catalysts. Herein, a hybrid nanostructure of Pt@Co(OH)2 supported on SiO2 was synthesized by incipient wetness impregnation of Co(OH)2 with the aid of H2O2 and successive urea-assisted deposition-precipitation of platinum nanoparticles. The Fenton-like reaction between Co2+ and H2O2 during the impregnation process facilitates the formation of active interfacial sites. This hybrid nanostructure exhibits much higher catalytic activity towards CO oxidation than Pt/SiO2 nanoparticles with a similar Pt loading and particle size. In situ diffuse reflectance infrared Fourier transform spectroscopy was used to track the CO adsorption processes and to identify the reaction intermediates during CO oxidation. It shows that the OH species at the Pt-OH-Co interfacial sites could readily react with CO adsorbed on neighboring Pt to yield CO2 by forming *COOH intermediates and oxygen vacancies. Under the CO + O2 oxidation conditions, O2 molecules are activated by the oxygen vacancy and react with the CO molecules adsorbed on Pt to generate CO2, via forming the highly active *OOH intermediates as observed by DRIFTS.
RESUMEN
The structures, compositions and chemical states of metal catalysts are prone to dynamic changes in response to reaction conditions. In this work, a combination of in situ X-ray absorption fine structure spectroscopy and diffuse reflectance infrared Fourier transform spectroscopy has been used to monitor the temperature-dependent structural dynamics in bimetallic Pt-Co(OH)2 nanocatalysts during CO oxidation. Alloying with electron-donating Co promotes the catalytic activity of metallic Pt for CO oxidation at low temperature. At elevated temperatures under an oxidation atmosphere, O2 drives the segregation of the Pt-Co alloy into cobalt oxide and platinum metal, with the extent of alloying sharply decreasing from â¼30% at 300 K to 0 at 473 K. Reduction at high temperature could recover the formation of the Pt-Co alloy with the same alloying extent. The observed structural dynamics could be well correlated with the kinetic behavior of the catalysts. This work highlights the importance of tracking the dynamic structural changes of working catalysts for a correct understanding of their catalytic behavior.