The hydrogenation of aromatics is a ubiquitous chemical transformation used in both the petrochemical and specialty industry and is important for the generation of clean diesel fuels. Reported herein is the discovery of a superior heterogeneous catalyst, superior in terms of catalytic activity, selectivity, and lifetime in the hydrogenation of aromatics in the solvent-free system under mild conditions (at 25 °C and 42 ± 1 psig initial H
2 pressure). Ruthe
nium(0) nanoclusters stabilized by a nanozeolite framework as a new catalytic material is reproducibly prepared from the borohydride reduction of a colloidal solution of ruthe
nium(III)-exchanged nanozeolites at room temperature and characterized by using ICP-OES, XRD, XPS, DLS, TEM, HRTEM, TEM/EDX, mid-IR, far-IR, and Raman spectroscopy. The resultant ruthe
nium(0) nanoclusters hydrogenate neat benzene to cyclohexane with 100% conversion under mild conditions (at 25 °C and 42 ± 1 psig initial H
2 pressure) with record catalytic activity (
initial TOF = 5430 h
−1) and lifetime (TTO = 177200). They provide exceptional catalytic activity not only in the hydrogenation of neat benzene but also in the solvent-free hydrogenation of methyl substituted aromatics such as toluene,
o-xylene, and mesitylene under otherwise identical conditions. Moreover, they are an isolable, bottleable, and reusable catalyst in the hydrogenation of neat aromatics. When the isolated ruthe
nium(0) nanoclusters are reused, they retain 92% of their initial catalytic activity even for the third run in the hydrogenation of neat benzene under the same conditions as those of the first run. The work reported here also includes (
i) far-infrared spectroscopic investigation of nanozeolite, ruthe
nium(III)-exchanged-nanozeolite, and ruthe
nium(0) nanoclusters stabilized by a nanozeolite framework, indica
ting that the host framework remains intact after the formation of a nanozeolite framework stabilized ruthe
nium(0) nanoclusters; (
ii) the poisoning experiments performed by using tricyclohexylphosphine (P(C
6H
11)
3) and 4-ethyl-2,6,7-trioxa-1-phosphabicyclo[2.2.2]octane PC
6H
11O
3 to examine whether the ruthe
nium(0) nanoclusters are encapsulated in the cages or supported on the external surface of nanozeolite; (
iii) a summary section detailing the main findings for the “green chemistry”; and (
iv) a review of the extensive literature of benzene hydrogenation, which is also tabulated as part of the
Supporting Information.