The effects of crystallite size on the physicochemical properties and surface defects of pure monoclinic ZrO 2 catalysts for isobutene synthesis were studied. We prepared a series of monoclinic ZrO 2 catalysts with different crystallite size by changing calcination temperature and evaluated their catalytic performance for isobutene synthesis from syngas. ZrO 2 with small crystalline size showed higher CO conversion and isobutene selectivity, while samples with large crystalline size preferred to form dimethyl ether (DME) instead of hydrocarbons, much less to isobutene. Oxygen defects (O Defects ) analyzed by X-ray photoelectron spectroscopy (XPS) provided evidence that more O Defects occupied on the surface of ZrO 2 catalysts with smaller crystalline size. Electron paramagnetic resonance (EPR) and ultraviolet–visible diffuse reflectance (UV–vis DRS) confirmed the presence of high concentration of surface defects and Zr 3+ on m -ZrO 2 -5.9 sample, respectively. In situ diffuse reflectance infrared Fourier transform spectroscopy ( in situ DRIFTS) analysis indicated that the adsorption strength of formed formate species on catalyst reduced as the crystalline size decreased. These results suggested that surface defects were responsible for CO activation and further influenced the adsorption strength of surface species, and thus the products distribution changed. This study provides an in-depth insight for active sites regulation of ZrO 2 catalyst in CO hydrogenation reaction.
The surface protonic conductivity of porous monoclinic ZrO2 sintered at temperatures in the range 700–1100 °C yielding relative densities of around 60% and grain sizes of approximately 160 nm has been studied using impedance spectroscopy as a function of temperature well below the sintering temperature in wet atmospheres (pH2O = 0.03 bar). The sum of two high-frequency impedance responses is argued to represent surface conductance according to a new model of impedance over curved surfaces. A simple brick layer model is applied to compare the measured macroscopic conductivities with predicted surface conductances. The well-faceted samples sintered at the highest temperatures exhibited activation enthalpies up to 58 kJ mol−1 of surface protonic conduction in wet atmospheres at temperatures above 300 °C. We attribute this to the mobility of dissociated protons over surface oxide ions, and the high preexponential is in good agreement with a model comprising relatively strong dissociative chemisorption. With decreasing sintering temperature, the particles appear more rounded, with less developed facets, and we obtain activation enthalpies of surface protonic conduction in the chemisorbed layer down to around 30 kJ mol−1, with correspondingly smaller preexponentials and an observed dependency. Supported by the thermogravimetry of adsorption, we attribute this to weaker and more molecular chemisorption on the more randomly terminated less faceted surfaces, providing water layers with fewer dissociated charge carrying protons, but also smaller activation enthalpies of mobility. Below 200 °C, all samples exhibit a strongly inverse temperature dependency characteristic of conduction in the 1st physisorbed layer with increasing coverage. The preexponentials correspond well to the models of physisorption, with dissociation to and proton migration between physisorbed water molecules. The enthalpies fit well to physisorption and with enthalpies of dissociation and proton mobility close to those of liquid water. We have by this introduced models for proton conduction in chemisorbed and physisorbed water on ZrO2, applicable to other oxides as well, and shown that preexponentials are quantitatively assessable in the order-of-magnitude level to discriminate models via a simple brick layer model based topographical analysis of the ceramic microstructure.
Au supported on monoclinic ZrO2 (Au/m-ZrO2) prepared by deposition–precipitation method showed excellent catalytic performance in the aerobic oxidation of amino alcohols to amino acids, i.e., glycine, alanine, serine, β-alanine, and 2-aminobutyric acid. The Au particle size and valence distribution of the gold species were adjusted by calcination temperature, as demonstrated by XRD, TEM, UV–vis DRS, XPS, and H2-TPR, which significantly influenced the catalytic activity but not the selectivity of amino acids. Metallic gold atoms on the surface were shown to be the active sites by the correlation between reaction rate per mole of metallic Au and Au particle size. The kinetics of oxidation of monoethanolamine (MEA) was studied in detail, and the results indicated that MEA oxidation is a first-order reaction with an activation energy of 52.8 kJ·mol–1.
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