Martin Siron1,2,Oxana Andriuc1,2,Kristin Persson1,2
University of California, Berkeley1,Lawrence Berkeley National Laboratory2
Martin Siron1,2,Oxana Andriuc1,2,Kristin Persson1,2
University of California, Berkeley1,Lawrence Berkeley National Laboratory2
Photocatalytic CO<sub>2</sub> reduction is a promising method for reducing greenhouse gas emissions, which has resulted in climate change. Finding an efficient, stable, highly active, and selective material for photocatalytic CO<sub>2</sub> reduction reaction (CO<sub>2</sub>RR) is an ongoing challenge. While much theoretical groundwork has been established on transitional metal catalysts to elucidate their interaction with adsorbates of interest, semiconductor photocatalysts lack basic understanding of surface-adsorbate interactions with molecules of importance to CO<sub>2</sub>RR.<br/>Recently, computational screenings have led to materials, which have yet to be explored computationally or experimentally for photocatalytic CO<sub>2</sub>RR. Tellurium-containing semiconductors emerged as an important class of materials. Even more recently, some of these materials have started to be explored for CO<sub>2</sub>RR experimentally. Yet many of the remaining materials remain unexplored for photocatalysis. These tellurium-containing semiconductors fit broadly in a class of materials exhibiting high carrier mobility, tunability, stability, and varied electronic properties, compositions, and structures, which could make them interesting candidates for this application.<br/>Previously, we developed a high-throughput computational workflow, leveraging Density Functional Theory, to calculate the adsorption enthalpy of various molecules adsorbed to semiconducting surfaces. We utilized this workflow on various chalcogenides of interest including ZnTe, YbTe, RbTeAu, GaTe, GaTeCl, InTeBr, BiTeBr, and Ga<sub>2</sub>TeSe<sub>2</sub>, Zn(GaTe<sub>2</sub>)<sub>2</sub>, testing the adsorption energy of CO, H, and CHO. As part of the workflow, we employ the DDEC6 charge partitioning scheme to quantify the charge transfer as well as LOBSTER to perform a Crystal Orbital Hamiltonian Population analysis to further understand the adsorbate-surface interaction on these materials.<br/>From these explorations, we deduce that on most materials, CO has a narrow, weakly favorable, range of adsorption energy from 0 to -0.5eV. Meanwhile, H can vary significantly, anywhere from -2 to 2eV. Thus, hydrogen’s adsorption energy dictates its competition with CO. We will also showcase other important material trends gathered from these high-throughput calculations that help elucidate potential competition with the Hydrogen Evolution Reaction (HER), a design rule for charge transfer into key adsorbates and explain bonding strength by trends in molecular orbital interactions.<br/>These trends help to elucidate how key adsorbates interact with semiconductor surfaces and provide insight for surface interaction during the photocatalytic CO<sub>2</sub>RR process. This class of materials is vastly unexplored in photocatalytic research and uncovering these trends will guide us towards the rational design of more efficient, and selective photocatalysts for CO<sub>2</sub> reduction.