First principles study on the catalytic reduction mechanism of CO2 to formic acid on Cu(110)crystal surface
Copper-based catalysts are efficient green catalysts for the reduction of CO2 to formic acid.Under-standing the reduction mechanisms on different crystal surfaces is of significant importance for the design and development of catalysts.However,the catalytic mechanism on the Cu(110)crystal surface remains unclear.In this study,we employed first-principles methods based on density functional theory to investigate the reduction mechanism on the Cu(110)surface.We systematically studied the adsorption properties of various intermediate products and explored the corresponding adsorption mechanisms.The adsorption energy results indicate that CO2 cannot chemically adsorb on the Cu(110)surface.Instead,the most stable adsorption sites for*COOH,*HCOO,HCOOH molecules,and H atoms are the long-bridge site,short-bridge site,top site,and HCP site,respectively.Population analysis results show that*HCOO and HCOOH molecules form ionic bonds with Cu atoms on the Cu(110)surface during the adsorption process,while there is a hydrogen bond interaction between H atoms and Cu atoms.In the case of*COOH molecules,a covalent bond forms between the C and Cu atoms.Additionally,electronic density of states results indicate the formation of O-Cu bonds between*HCOO groups and Cu atoms,C-Cu bonds between C and Cu atoms in*COOH molecules,and O-Cu bonds between O and Cu atoms in HCOOH molecules.Furthermore,compared to the*COOH/Cu(110)system,the*HCOO/Cu(110)adsorption system exhibits stronger charge density,charge transfer,and bonding capability.This suggests that the intermediate*HCOO is more stable during the CO2 reduction process on Cu(110),indi-cating a more efficient synthesis pathway:CO2→*HCOO→HCOOH.
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