Chemisorption Manipulation by Adjusting the Carrier Concentration of the Adsorbent and Its Application to Adsorbate Identification

Abstract

Progress in techniques for manipulating chemisorption has substantially advanced various applications. Herein, we present a widely applicable method to manipulate chemisorption by adjusting the carrier concentration of the adsorbent. We demonstrate that in both n- and p-type adsorbents, an increase in the electron concentration of the adsorbent enhances the chemisorption of oxidizing adsorbates. In contrast, a decrease in electron concentration promotes the chemisorption of reducing adsorbates. These findings are verified using first-principles calculations based on density functional theory. We demonstrate that the adsorption energy of the adsorbate and the energy difference between the adsorbate states and the Fermi energy can be manipulated by the proposed method. The manipulation method yields different effects for each adsorbate. Therefore, the degree of manipulation can be utilized as a unique fingerprint for adsorbate identification. The proposed method allows for repeatable manipulations and is compatible with existing techniques.