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Synergistic Effect Between Ca 4 V 4 O 14 and Vanadium‐Substituted Hydroxyapatite in the Oxidative Dehydrogenation of Propane
Author(s) -
Petit Sarah,
Thomas Cyril,
Millot Yannick,
Averseng Frederic,
Brouri Dalil,
Krafft JeanMarc,
Dzwigaj Stanislaw,
Rousse Gwenaelle,
LabertyRobert Christel,
Costentin Guylène
Publication year - 2021
Publication title -
chemcatchem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.497
H-Index - 106
eISSN - 1867-3899
pISSN - 1867-3880
DOI - 10.1002/cctc.202100807
Subject(s) - dehydrogenation , vanadium , propane , catalysis , propene , nanorod , electron paramagnetic resonance , chemistry , phase (matter) , redox , inorganic chemistry , materials science , crystallography , nanotechnology , organic chemistry , physics , nuclear magnetic resonance
The present work reports on a new type of V‐based catalysts, namely V‐substituted hydroxyapatites, and the influence of the synthesis conditions on their catalytic performance in the oxidative dehydrogenation of propane (ODHP) reaction. V x ‐substituted hydroxyapatite materials prepared with the periodic addition of ammonia during the maturation step (V x ‐HAp‐pH‐per) were shown to exhibit a Ca 4 V 4 O 14 phase in addition to the V‐substituted hydroxyapatite phase for x greater than or equal to 3.5. TEM characterization of the biphasic samples allowed us to demonstrate that the Ca 4 V 4 O 14 phase was grown epitaxially on the V x ‐HAp nanorods. The close intimacy between the two phases was confirmed by NMR suggesting the involvement of V 4+ species. Consistently EPR data of the fresh and spent samples showed that V 4+ species may be stabilized at the boundaries of these two phases. The strong promotion of the oxidative dehydrogenation reaction to propene observed from 723 K for the V 4 ‐HAp‐pH‐per composition is attributed to a synergistic effect between the V x ‐HAp nanorods that enable the activation of propane and the Ca 4 V 4 O 14 phase that helps the redox exchanges. This synergy may be attributed to an easier electron delocalization on the V 4 O 14 units located at the phases’ boundaries.