Yujie Bian, Shilong Zhang, Linlin Wang, Xusheng Liu, Shijie Zhou, Xingyue Yang, Guanyi Zhang, Haisong Feng, Xin Zhang, Yusen Yang
ABSTRACT Toluene (TOL) hydrogenation to methylcyclohexane (MCH) represents a promising liquid organic hydrogen carriers (LOHC) system due to its high hydrogen storage density and favorable techno‐economic feasibility. In this study, three Pt‐TM (TM = Co, Ni, and Cu) alloy catalysts were prepared via topotactic transformation method from layered double hydroxide (LDH) precursors. Structural characterization (XRD, XPS, in situ CO‐DRIFT, etc.) shows that the alloy components are highly dispersed on the composite oxide support with electron transfer from the transition metals to Pt. In the TOL hydrogenation reaction, the PtCo catalyst exhibits excellent performance under a facile reaction condition (100°C, 2.0 MPa H 2 ), with 99.75% conversion, 100% selectivity, and a mass‐specific activity of 498.75 mmol·g cat −1 ·h −1 , surpassing most reported noble metal‐based catalysts. Mechanistic studies based on in situ IR spectroscopy and DFT calculations indicate that the introduction of transition metals effectively modulates the d ‐band center of Pt through electron transfer, which optimizes the adsorption behavior of substrate. On the surface of PtCo alloy catalyst, TOL shows the most favorable adsorption strength with the lowest reaction energy barrier of rate‐determining step (the first hydrogenation step: 1.19 eV), accounting for its excellent hydrogenation activity. This study provides new insights into the design of high‐performance TOL hydrogenation catalysts and demonstrates potential application in LOHC‐based hydrogen storage.