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Operando XPS studies of precisely size-selected Pd nano-catalysts for methane oxidation
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DOI：10.1039/d5fd00171d.png)
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Abstract
En 中文
The importance of cluster-size effects in heterogeneous catalysis is now well recognized. X-ray photoelectron spectroscopy (XPS) is an obvious technique to study size-dependent changes in the chemical composition and electronic structure of catalyst nanoparticles. However, as XPS is an averaging technique based on the detection of electrons, experiments require a narrow distribution of cluster size and a conducting homogeneous support in order to avoid sample charging, which would prevent accurate measurements of chemical shifts. Traditional methods of catalyst synthesis by impregnation/calcination of support powders lead to very large particle size distributions (typically +/- 50%) and insulating samples. They therefore fail both of the above criteria and make it extremely difficult to extract precise sample characterisation. Here we present an alternative approach designed to enable XPS analysis in vacuum and under reaction conditions, whereby: (i) nanoparticles are synthesized by gas condensation and passed through a mass filter, which allows size selection in the range of 1 to 10 000 atoms with typically +/- 4% accuracy; (ii) these particles are deposited onto a thin Al2O3 film grown on Al foil, which mimics the properties of conventional alumina supports while being conductive enough to avoid any charging-related artefacts in the XPS spectra. In vacuum, size-dependent Pd 3d binding-energy shifts up to 1.65 eV were recorded for supported Pd nanoparticles. Changes in the chemical composition of Pd nanoparticles were studied by near-ambient pressure (NAP)-XPS under dry and wet reaction conditions for methane oxidation (CH4 + O-2 [+H2O]) in the temperature range between 150 degrees C and 450 degrees C. Under dry reaction conditions large Pd particles appeared to oxidise almost fully to Pd(ii), whereas smaller clusters showed a mix of Pd(0) and Pd(ii) oxidation states. Under wet conditions, oxidation starts at lower temperatures and particles of all sizes were fully oxidised when the highest temperature was reached. Sintering during the temperature ramp cannot be excluded, especially for the smaller particles, and may be part of the reason for the different behaviour under wet conditions. This study clearly shows composition changes which are particle-size dependent and demonstrates the possibilities of fine-tuning catalytic activity if better size-control can be achieved in catalyst synthesis.
Keywords:
PALLADIUM NANOPARTICLES
CARBON-MONOXIDE
OXIDE CLUSTERS
LASER-ABLATION
PRESSURE
SUPPORT
COBALT
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