A new process for the low-cost synthesis of 2,6-DMN, the high-efficiency transalkylation of C-10, aromatics (C(10)A) with 2-MN in H-2 atmosphere was developed depending on a multifunctional SiO2(II)-3.0%Mo-HBeta catalyst with three kinds of active sites located only inside its 12-ring channels. Firstly, the high-efficient synergistic catalysis from metal-Mo monomer and Lewis & Bronsted acid-sites significantly improved transalkylation, attributed to a surface behavior (involving hydrogen spillover) may producing the active hydrogen-species which markedly enhance the proton-transfer efficiency in this proton-acid catalytic reaction. Secondly, the hydrogenation & subsequent ring-opening etc. side-reactions of naphthalene series and the formation of multi-alkylnaphthalene byproducts were almost completely suppressed due to both the passivation of the external surface of catalyst and the transition-state shape-selectivity & the diffusion-constraint effect inside pores. Besides, both the reasonable catalytic hydrogenation (from metal-Mo monomer) immediately converting light olefins (from dealkylation) into alkanes and the transition-state shape-selectivity suppressing the formation of larger-molecular multi-alkylnaphthalenes in channels, effectively prevented from the coking-deactivation of catalyst. As a result, the 2-MN conversion of above 75.3% and the 2,6-DMN yield of above 9.7% were obtained during the 50 h on-stream reaction. Our work may provide a promising model for rationally designing the elegant catalyst for a complicated conversion reaction. (C) 2019 Elsevier Inc. All rights reserved.