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Second-generation biodiesel is the dominant biomass-derived liquid fuel produced from nonedible natural or waste oils and fatty acids through selective oxygen removal. Here, we developed a highly selective sulfur-free NiMo/TiO2 catalyst by disentangling electronic and geometric effects to produce second-generation biodiesel via the hydrodeoxygenation of palmitic acid-one of the most common fatty acids in these feedstocks. An unprecedented hexadecane yield of 96.0% (on a mole basis) was achieved over the Ni1Mo1/TiO2 catalyst (with a Ni:Mo ratio of similar to 1:1) at 300 degrees C and 3 MPa H2. Kinetic studies reveal that the competition between hydrodeoxygenation (C-O scission) and decarbonylation (C-C scission) of the intermediate hexadecanol is key to optimizing selectivity. Furthermore, Mo incorporation markedly lowers the apparent activation energy of hydrodeoxygenation-especially in the Ni1Mo1/TiO2 catalyst, which has the lowest Ni-Ni coordination number. Combined with catalyst characterization, these findings elucidate a Mo-induced "Ni coordination environment"-directed reaction pathway: the superb hydrodeoxygenation activity and selectivity of Ni1Mo1/TiO2 stem from its abundant NiMo interfacial sites, where Mo-induced oxygen vacancies synergize with adjacent Ni sites to facilitate the adsorption of O-containing groups and subsequent C-O bond cleavage.
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INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
ISSN: 0888-5885
Year: 2025
Issue: 11
Volume: 64
Page: 5962-5972
3 . 8 0 0
JCR@2023
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SCOPUS Cited Count:
ESI Highly Cited Papers on the List: 0 Unfold All
WanFang Cited Count:
Chinese Cited Count:
30 Days PV: 2
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