Jing-Wen HsuehLai-Hsiang KuoPo-Han ChenWan-Hsin ChenChi-Yao ChuangChia-Nung KuoChin-Shan LueHung-Wei ShiuBo-Hong LiuChia-Hsin WangYao-Jane HsuChun-Liang LinJyh-Pin ChouMeng-Fan Luo2025-05-062025-05-062025-04-1114639076https://www.scopus.com/record/display.uri?eid=2-s2.0-105003094356&origin=resultslisthttps://scholars.lib.ntu.edu.tw/handle/123456789/728897The reactivity of layered PdTe2 toward methanol (CH3OH) decomposition was promoted by surface under-coordinated Pd (denoted as Pduc) generated by removing surface Te with controlled Ar ion bombardment. Methanol on the Pduc sites at surface Te vacancies decomposed through competing dehydrogenation and C-O bond cleavage processes; approximately 26% of methanol was converted to CHx* and 17% to CHxO* (* denotes adspecies; x = 2 and 3) as major intermediates at 180 K, leading to a reaction probability of >40% and an ultimate gaseous production of molecular hydrogen, formaldehyde, methane and water. The characteristic reactivity arose from both geometric and electronic effects—the hexagonal-lattice positioning and partial oxidation of the Pduc; its comparison with that of PtTe2 surface emphasized the critical role of electronic structures in determining the reactivity and selectivity. Notably, these reaction processes produced scarce C* as the intermediate CHx* was preferentially hydrogenated. Our results suggest that a PdTe2 surface with Pduc at surface Te vacancies can serve as an efficient catalyst toward methanol decomposition and against carbon poisoning. © 2025 The Royal Society of Chemistry.enfalsejournal article10.1039/d5cp00130g2-s2.0-105003094356