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Self-assembling of formic acid on the partially oxidized p(2 × 1) Cu(110) surface reconstruction at low coverages.

Carbon dioxide (CO2) reduction for synthetic fuel generation could be an integral part of a sustainable energy future. Copper (Cu) is the leading electrocatalyst for CO2 reduction to produce multiple C-containing products such as C1 and C2 hydrocarbons and oxygenates. Understanding the mechanisms leading to their production could help optimize these pathways further. Adsorption studies of the many possible intermediates on well-characterized surfaces are crucial to elucidating these mechanisms. In this work, we explore the adsorption configurations of formic acid (HCOOH) on the surface of the partially oxidized p(2 × 1) reconstruction of the Cu(110) surface, using low-temperature scanning tunneling and atomic force microscopy, in conjunction with density functional theory modeling. We find that HCOOH adsorbs favorably on the CuO chain comprising the reconstruction. The adsorption interactions involve dative bonding of the carbonyl O to the oxidized Cu and hydrogen bonding of the OH group to the surface O or to an adjacently adsorbed HCOOH molecule. Cooperative adsorption of the molecules occurs, forming two- to three-molecule-long oligomer chains, facilitated by intermolecular hydrogen bonding and mutual polarization of the CuO acid-base adsorption sites.