Atomic‐Scale CuTe/PdTe Intermetallic Heterointerface Enhances Electrochemical Glycerol Oxidation

ABSTRACT Intermetallic materials have shown great potential for electrocatalytic molecular valorization, benefiting from their abundant intrinsic active sites. However, synthesizing intermetallic electrocatalysts with unique atomic‐scale interfacial structures remains a significant challenge. Herein, we report the synthesis of a previously unknown ternary intermetallic nanowire with exquisite atomic‐scale interfaces, achieved through optimal crystal facets mediated selective phase alloying. At the phase interface, the PdTe <100> {001} plane is parallel to the CuTe <0−11> {100} plane, achieving quasi‐epitaxial bonding. This orientation relationship demonstrates high structural coherence at the PdTe‐CuTe interface and minimizes interfacial strain. The novel structure is rich in interfacial active sites, facilitating the overcoming of the slow catalytic oxidation kinetics. The glycerol oxidation selectivity of the as‐prepared interface‐enriched catalysts is highly enhanced with an ultra‐high Faradaic efficiency of 96.5% toward formate at 1.425 V. In situ spectra and theoretical calculations demonstrate that the enriched Pd‐Cu‐Te ternary interfaces can optimize the adsorption configuration of glycerol, accelerating the subsequent O‐H cleavage of *COOHCOCH 2 OH and C–C cleavage. This approach paves the way to rationally designed intermetallic catalysts with modified interfaces for biomass electrooxidation.