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Metal‐to‐Oxide Molar Volume Ratio: The Overlooked Barrier to Solid‐State Electroreduction and a “Green” Bypass through Recyclable NH 4 HCO 3
Author(s) -
Li Wei,
Jin Xianbo,
Huang Fulong,
Chen George Z.
Publication year - 2010
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.200906833
Subject(s) - oxide , metal , molar ratio , volume (thermodynamics) , porosity , porous medium , molar volume , chemistry , chemical engineering , materials science , catalysis , organic chemistry , physics , engineering , thermodynamics
Beating the barrier : The metal‐to‐oxide molar volume ratio V m / V o determines whether electroreduction of a metal oxide forms a porous metal shell that allows reduction to proceed ( V m / V o ≪1), or nonporous one that causes it to cease ( V m / V o ≥1; see picture). In the case of TiO 2 ( V m / V o ≈1), this barrier to reduction to Ti can be circumvented by recyclable use of NH 4 HCO 3 as a fugitive porogenic agent.