Structure-sensitive scaling relations among carbon-containing species and their possible impact on CO2 electroreduction

The arduous modelling of reactions at heterogeneous catalysts is greatly simplified when adsorption-energy scaling relations between intermediates exist. Generally, the offset these linear structure-independent slope unity and otherwise depends on coordination number active sites. Here we examine adsorption *C, *CH, *CH2, *CH3 *COH five different surface sites nine transition metals to establish their structure-sensitive relations. Interestingly, show that *C (valency 4) C-containing species with valency 3 (*CH, *COH) have peculiar offsets. These offsets stem from analogous bonding those sites, in spite dissimilar valency. We how this result implies reaction pathways catalysis involving *CH *COH, for instance CO2 electroreduction CH4, will usually sizable thermodynamic limits imposed optimization.