Atomically Engineered Active Sites in Metal Trichalcogenides via Dual Sublattice Modulation for Electrocatalysis Applications

Quaternary alloying of nanostructured metal chalcogenides offers an exciting pathway for developing materials with unique and highly tunable properties, unlocking potential applications across a range of advanced technologies. In this study, we present the synthesis and characterization of quaternary alloys based on monoclinic TiS3 and triclinic NbS3 frameworks, achieved through the deliberate substitution of both the cation and anion sublattices. Our synthesized compounds, Ti0.75Nb0.25S2.9Se0.1 and Nb0.88Ti0.12S2.9Se0.1, exhibit notable variations in their structural and electronic properties compared to their binary counterparts, underscoring the transformative impact of compositional modulation. Building on these structural and electronic insights, we investigated the catalytic potential of these alloys using nonaqueous CO2 electroreduction as the probe reaction, which is a viable pathway for carbon capture and utilization. The activity presented herein of Nb0.88Ti0.12S2.9Se0.1 underscores the potential of quaternary metal chalcogenide alloys to advance the field of CO2 electroreduction by enabling tailored electronic properties and active sites. These findings open new avenues for enhancing reaction selectivity and efficiency, paving the way for innovative approaches to establish material design principles that support advancements in electrocatalysis, mitigate CO2 emissions, and promote sustainable chemical transformations.