In situ X-ray absorption fine structure analysis of redox reactions of nickel species with variable particle sizes supported on silica

Abstract

The chemical states of Ni species were systematically investigated using an in situ XAFS technique for a series of SiO2-supported Ni catalysts with different Ni particle sizes. The Ni particles were refined by varying the Ni loading in the range between 0.10 and 5wt% and by adding citric acid into the precursor solution. An in situ observation cell for fluorescence-yield XAFS measurements was developed for the dilute Ni catalysts. The chemical state of the supported Ni species converted between Ni(0) and NiO, and no other stable species were formed during the temperature-programmed oxidation and reduction processes. Refinement of the Ni particles resulted in decreasing the oxidation temperature and increasing the reduction temperature. These shifts were explained by the affinity of NiO to SiO2, and more effective stabilization was thus anticipated for flattened small NiO particles with an increased contact area. In addition, the inhomogeneous distribution of small Ni particles observed for dilute catalysts was explained in terms of the precursor solution volume when nuclei of the precursor compound precipitated on SiO2 during the drying process.