posted on 2024-02-27, 01:13authored byYong Zhao, Zhen Shi, Feng Li, Chen Jia, Qian Sun, Zhen Su, Chuan Zhao
Mesoporous
metal–nitrogen-doped carbons (M–N–C)
have shown remarkable performance as catalysts for electrochemical
CO2 reduction. However, the current understanding of the
roles of mesopores in M–N–C-catalyzed CO2 reduction has been insufficient and imprecise due to the overlooked
and intertwined influences of various structural factors on mass transport
and the catalyst microenvironment. In this work, we have decoupled
the impacts of mesopores in this process by designing Fe–N–C
with solely altered pore structures. We found that the mesopore-rich
catalyst surpassed its microporous counterpart in the overall reaction
rate but unusually fell short in CO selectivity. Our experiments and
modulation uncovered that the abundance of mesopores on the catalyst
surface facilitated CO2 diffusion to active sites and thereby
improved the CO production rate; however, the increased CO2 transport buffered the local pH surrounding active sites, which
increased H2 generation and induced a relative decrease
in CO selectivity for the mesopore-rich Fe–N–C catalyst.