Rational Modulation of Pt d Electrons to Significantly Enhance the Catalytic Dehydrogenation Performance of Liquid Organic Hydrogen Carriers

Engineering ›› DOI: 10.1016/j.eng.2025.07.045

review-article

Chao Sun ^a^,^b^,^d
, Tianzuo Wang ^a^,^b^,^d
, Ruijie Gao ^a^,^b^,^c^,^d
, Xiaoyang Liu ^d
, Kang Xue ^a^,^b^,^c^,^d
, Chengxiang Shi ^a^,^b^,^d
, Xiangwen Zhang ^a^,^b^,^c^,^d
, Lun Pan ^a^,^b^,^c^,^d^,^*
, Ji-Jun Zou ^a^,^b^,^c^,^d^,^*

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Abstract

Understanding the intrinsic features of dehydrogenation reactions of liquid organic hydrogen carriers (LOHCs) is a formidable challenge due to the combined impact of electronic and geometric effects. Herein, we constructed a series of Pt/MO_x catalysts (CeO₂, MgO, ZrO₂, TiO₂, Al₂O₃, or SiO₂) with similar sizes of Pt (∼1.7 nm) to investigate the effects of Pt electron structures (tuned by electronic metal‒support interactions) on the catalytic dehydrogenation of LOHCs. The results revealed a volcano-shaped correlation between Pt d electrons on different supports and the turnover frequency of catalytic dehydrogenation. Importantly, the Pt/MgO catalyst exhibited the highest dehydrogenation activity. With decreasing d electron content, Pt/MgO increases the bonding orbital dominance of Pt‒C bonds and leads to stable adsorption of H6-monobenzyltoluene (MBT), which facilitates subsequent C‒H bond scission. This study offers insight for the strategic development of high-efficiency dehydrogenation catalysts via d electron density modulation of Pt sites.

Keywords

Pt nanoparticles / Liquid organic hydrogen carriers / Dehydrogenation reaction / d electron

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Chao Sun, Tianzuo Wang, Ruijie Gao, Xiaoyang Liu, Kang Xue, Chengxiang Shi, Xiangwen Zhang, Lun Pan, Ji-Jun Zou. Rational Modulation of Pt d Electrons to Significantly Enhance the Catalytic Dehydrogenation Performance of Liquid Organic Hydrogen Carriers. Engineering DOI:10.1016/j.eng.2025.07.045

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