Density functional study of hydrogen spillover on direct Pd-doped metal-organic frameworks IRMOF-1

The direct doping of small Pd cluster on IRMOF-1 and its influence on H2 adsorption were investigated using periodic density functional methods. Our calculations indicate that the Pd cluster prefers to be deposited on the linker. The doped Pd cluster can not only play the important role for dissociating H2 molecules, but also enhance the H interaction with IRMOF-1 by altering its electronic structures. As a result, hydrogen spillover in IRMOF-1 by directly doping Pd catalysts is thermodynamically feasible and the odd numbered H bottlenecks on undoped IRMOF-1 are eliminated. In addition, we discuss a working mechanism for releasing H2 from the chemisorbed states.