Interstitial carbon atoms enhance both selectivity and activity of rhodium catalysts toward C-C cleavage in direct ethanol fuel cells

Selective breaking of the C-C bond in ethanol holds the key to many industrial processes, including the operation of direct ethanol fuel cells and steam reforming. Interstitial C atoms in the subsurface region of noble-metal catalysts have major impacts on the selectivity and activity, but an understanding of the mechanistic details is still elusive due to their nature of in situ formation and metastability. Herein, we develop a method to obtain stable RhCx (x & AP; 0.5) by introducing C atoms into the interstitial sites of well-defined Rh nanosheets of 8-10 at. layers in thickness, and further elucidate the electronic and geometric effects of the interstitial C atoms on the cleavage of C-C bond. With the introduction of C atoms into half of the octahedral sites, the Rh lattice changes from a cubic to an orthorhombic structure. The lattice expansion induced by the insertion of C atoms, together with the electron transfer between C and Rh atoms, effectively suppresses the coupling reaction between OH* and CH3CO* to form acetic acid while making the cleavage of C-C bond more exothermic. As such, we obtain a selectivity of ethanol to CO2 as high as 18.1 %, much higher than those of the Rh counterpart (10.0 %), together with 3.1-fold improvement in kinetics. Guided by these findings, a new method is also developed to directly introduce C atoms into the subsurface of a commercial Rh black to enhance its selectivity and activity by 2.5- and 1.6- folds, respectively.