CeO2-supported copper species have been reported as an active catalyst for the hydrogenation of carbon–oxygen bonds (CO, CO2, furfural, esters, etc.). However, the identification of active sites remains challenging. Herein, we prepared a series of rod-shaped ceria-supported copper catalysts with different copper sizes (single-atom, 1.4 nm nanoclusters, 3.0 nm and 6.8 nm nanoparticles) and applied them for methyl acetate (MA) hydrogenation. The structure and chemical environment of copper species were detected, and the surface Cu0 and Cuσ+ species and defects (oxygen vacancy and M–[O x ]–Ce solid solution) were quantitatively measured. To identify the active sites for MA hydrogenation, we also prepared contrast samples with increased surface defects or with reduced Cu0–Cuσ+ species. It is demonstrated that the Cu0–Cuσ+ species rather than oxygen vacancies or M–[O x ]–Ce solid solution are the primary active sites for MA hydrogenation. From the results of in situ experiments and various chemisorption and density functional theory calculations, the Cu0–Cuσ+ interface located at the surface Cu deposits is evidenced to play the key role in enhancing the adsorption and activation of MA. The turnover frequency of Cu/CeO2 catalysts for MA hydrogenation is linearly increased with the increase of the Cu0–Cuσ+ interfacial perimeter. This insight into active sites for carbon–oxygen bond hydrogenation may provide guidance for high-performance catalyst design.
Organic spintronic devices have been appealing because of the long spin lifetime of the charge carriers in the organic materials and their low cost, flexibility and chemical diversity. In previous studies, the control of resistance of organic spin valves is generally achieved by the alignment of the magnetization directions of the two ferromagnetic electrodes, generating magnetoresistance. Here we employ a new knob to tune the resistance of organic spin valves by adding a thin ferroelectric interfacial layer between the ferromagnetic electrode and the organic spacer: the magnetoresistance of the spin valve depends strongly on the history of the bias voltage, which is correlated with the polarization of the ferroelectric layer; the magnetoresistance even changes sign when the electric polarization of the ferroelectric layer is reversed. These findings enable active control of resistance using both electric and magnetic fields, opening up possibility for multi-state organic spin valves.
By loading microemulsion containing both sensitizer and emitter into the treated eco-friendly hydrogel, a new solid-state material of triplet−triplet annihilation based upconversion (TTA-UC) material was first reported. This UC hydrogel has shown an excellent stable emission of the green-to-blue luminescence, owing to the honeycomb-like nanoporous structure of the hydrogel. Moreover, this emission of UC hydrogel was strongly dependent on the temperature. The UC fluorescence intensity is close to the linear growth from 30 to 60 °C. This thermoresponsive upconversion hydrogel, which could be easily molded into various shapes, has provided a new perspective in manufacturing a novel temperature indicator and as well other applications in stabilizing air-sensitive species in aerated systems.
Tailoring molecular spinterface between novel magnetic materials and organic semiconductors offers promise to achieve high spin injection efficiency. Yet it has been challenging to achieve simultaneously a high and nonvolatile control of magnetoresistance effect in organic spintronic devices. To date, the largest magnetoresistance (~300% at T = 10 K) has been reached in tris-(8-hydroxyquinoline) aluminum (Alq 3 )-based organic spin valves (OSVs) using La 0.67 Sr 0.33 MnO 3 as a magnetic electrode. Here we demonstrate that one type of perovskite manganites, i.e., a (La 2/3 Pr 1/3 ) 5/8 Ca 3/8 MnO 3 thin film with pronounced electronic phase separation (EPS), can be used in Alq 3 -based OSVs to achieve a large magnetoresistance (MR) up to 440% at T = 10 K and a typical electrical Hanle effect as the Hallmark of the spin injection. The contactless magnetic field-controlled EPS enables us to achieve a nonvolatile tunable MR response persisting up to 120 K. Our study suggests a new route to design high performance multifunctional OSV devices using electronic phase separated manganites.
Electronic phase separation in complex oxides is the inhomogeneous spatial distribution of electronic phases, involving length scales much larger than those of structural defects or nonuniform distribution of chemical dopants. While experimental efforts focused on phase separation and established its correlation with nonlinear responses under external stimuli, it remains controversial whether phase separation requires quenched disorder for its realization. Early theory predicted that if perfectly “clean” samples could be grown, both phase separation and nonlinearities would be replaced by a bicritical-like phase diagram. Here, using a layer-by-layer superlattice growth technique we fabricate a fully chemically ordered “tricolor” manganite superlattice, and compare its properties with those of isovalent alloyed manganite films. Remarkably, the fully ordered manganite does not exhibit phase separation, while its presence is pronounced in the alloy. This suggests that chemical-doping-induced disorder is crucial to stabilize the potentially useful nonlinear responses of manganites, as theory predicted.
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