ZnCu Metal–Organic Framework Electrocatalysts for Efficient Ammonia Decomposition to Hydrogen

The electrocatalytic decomposition of ammonia represents a promising route for sustainable hydrogen production, yet current systems rely heavily on noble metal catalysts with prohibitive costs and limited durability. A critical challenge lies in developing non-noble electrocatalysts that simultaneously achieve high active site exposure, optimized electronic configurations, and robust structural stability. Addressing these requirements, this study strategically engineered Cu-doped ZIF-8 architectures via in situ growth on nickel foam (NF) substrates through a facile room-temperature hydrothermal synthesis approach. Systematic optimization of the Cu/Zn molar ratio revealed that Cu0.7Zn0.3-ZIF/NF achieved optimal performance, exhibiting a distinctive nanoflower-like architecture that substantially increased accessible active sites. The hybrid catalyst demonstrated superior electrocatalytic performance with a current density of 124 mA cm−2 at 1.6 V vs. RHE and a notably low Tafel slope of 30.94 mV dec−1, outperforming both Zn-ZIF/NF (39.45 mV dec−1) and Cu-ZIF/NF (31.39 mV dec−1). Combined XPS and EDS analyses unveiled a synergistic electronic structure modulation between Zn and Cu, which facilitated charge transfer and enhanced catalytic efficiency. A gas chromatography product analysis identified H2 and N2 as the primary gaseous products, confirming the predominant occurrence of the ammonia oxidation reaction (AOR). This study not only presents a noble metal-free electrocatalyst with exceptional efficiency and durability for ammonia decomposition but also demonstrates the significant potential of MOF-derived materials in sustainable hydrogen production technologies.