AbstractIn this work the hydrogen absorption behaviour of two types of Pd-clusters, different in structure but similar in size (3.1 nm), will be presented. First, icosahedral Pd clusters stabilised in surfactants; second, cubic Pd clusters stabilised in a Teflon-AF matrix. The phase transition in these samples was monitored by in-situ X-ray diffraction. It will be shown that the hydrogen uptake ability depends strongly on the lattice structure, which is affected by the type of stabiliser. Teflon AF stabilised clusters (cubic clusters) show the phase transition which is common for bulk Pd, whereas the surfactant stabilised clusters (icosahedral clusters) show only weak lattice dilatation upon hydrogen absorption. Pressure–lattice parameter isotherms show that the cubic clusters absorb large amounts of hydrogen in comparison to the icosahedral clusters. The measured lattice expansion is 0.130 Å at 105 Pa and 300 K, which is about 320% the amount measured for icosahedral clusters (0.04 Å). This suggests that surface sites are available for hydrogen in the Pd–Teflon-AF samples which are not accessible for Pd–surfactant-clusters, and that the icosahedral lattice absorbs less hydrogen for similar external pressures.