(Invited) New Approaches to Photoelectrochemical Cascade Reactions and Protection of Photoelectrodes

Abstract

A half-century of research has positioned direct photoelectrochemical (PEC) fuel generation as a promising technology that still requires substantial development. Work on the hydrogen evolution reaction (HER) has provided a strong basis for realizing the generation of more complex fuels through the carbon dioxide reduction reaction (CO2RR), but multiple challenges remain. The CO2RR requires larger driving forces and integration of multiple catalysts in order to selectively generate multi-carbonproducts, while still presenting many unsolved issues from HER, such stabilizing photoelectrodes under operation. In this talk I will discuss advances in the integration of multiple catalytic microenvironments in a single photoelectrochemical device, and progress toward the stabilization of photoelectrodes for fuel generation.First, I will highlight the adaptation of three-terminal tandem (3TT) photovoltaic technology to photoelectrochemical applications. In our 3TT devices, a two-junction III-V solar cell device has an additional contact, enabling two unique catalyst sites operating at different voltages under the same illumination. Idealized circuit modeling shows the promise of these 3TT devices compared to traditional two-terminal, two-junction devices, particularly with respect to spectral tolerance. We have adapted the structure of 3TT photovoltaics to function as PEC devices and developed multiple catalysts for integration into the two solution contact sites. We demonstrate progress toward light-driven cascade catalysis for multi-carbon CO2RR products.Second, I will highlight our approaches to protective schemes for photoelectrodes: one which is independent of semiconductor chemistry, and one which is driven by that chemistry. In the first approach, transparent conductive encapsulants (TCEs) are demonstrated as photoabsorber-agnostic protective layers. Unlike many protection schemes, these TCEs can be applied to semiconductors post-processing and without substantial modification, providing facile and robust protection. We have characterized the electrochemical performance of TCEs and demonstrate their integration with multiple semiconductors for the reduction of methyl viologen as a proxy for PEC fuel formation. In the second approach, we use the knowledge generated over fifty years of photoelectrode research to develop a new material, ZnTiN2, which can be directly integrated with established semiconductors and which will degrade under PEC conditions. We leverage this degradation to create protective layers which may be self-healing, and demonstrate rapid refinement of ZnTiN2 optoelectronic properties enabling integration with other semiconductors in tandem configurations.