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Highly Dispersed Molybdenum Oxycarbide Clusters Supported on Multilayer Graphene for the Selective Reduction of Carbon Dioxide
Author(s) -
Wakizaka Masanori,
Imaoka Takane,
Yamamoto Kimihisa
Publication year - 2021
Publication title -
small
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 3.785
H-Index - 236
eISSN - 1613-6829
pISSN - 1613-6810
DOI - 10.1002/smll.202008127
Subject(s) - graphene , materials science , catalysis , molybdenum , adsorption , carbothermic reaction , chemical engineering , nanomaterials , carbon fibers , nanotechnology , inorganic chemistry , composite number , chemistry , organic chemistry , composite material , metallurgy , carbide , engineering
Molybdenum oxycarbide clusters are novel nanomaterials that exhibit attractive catalytic activity; however, the methods for their production are currently very restrictive. This work represents a new strategy for the creation of near‐subnanometer size molybdenum oxycarbide clusters on multilayer graphene. To adsorb Mo‐based polyoxometalates of the type [PMo 12 O 40 ] 3− as a precursor for Mo oxycarbide clusters, the novel tripodal‐phenyl cation N , N , N ‐tri(4‐phenylbutyl)‐ N ‐methylammonium ([TPBMA] + ) is synthesized. [TPBMA] + exhibits superior adsorption on multilayer graphene compared to commercially available cations such as tetrabutylammonium ([ n Bu 4 N] + ) and tetraphenylphosphonium ([PPh 4 ] + ). Using [TPBMA] + as an anchor, highly dispersed precursor clusters (diameter: 1.0 ± 0.2 nm) supported on multilayer graphene are obtained, as confirmed by high‐resolution scanning transmission electron microscopy. Remarkably, this new material achieves the catalytic reduction of CO 2 to selectively produce CO (≈99.9%) via the reverse water‐gas‐shift reaction, by applying carbothermal hydrogen reduction to generate Mo oxycarbide clusters in situ.