Crystalline Modulation Engineering of Ru Nanoclusters for Boosting Ammonia Electrosynthesis from Dinitrogen or Nitrate.

Developing highly efficient nitrogen reduction reaction (NRR) and nitrate reduction reaction (NITRR) electrocatalysts is an ongoing challenge. Herein, we report the in situ growth of ultrafine amorphous Ru nanoclusters with a uniform diameter of ∼1.2 nm on carbon nanotubes as a highly efficient electrocatalyst for both the NRR and the NITRR. The amorphous Ru nanoclusters were prepared via a convenient ambient chelated co-reduction method, in which trisodium citrate as a chelating agent played a key role to form amorphous Ru instead of crystalline Ru. The strong d-π interaction between Ru metal and carbon nanotubes led to the homogeneous distribution and good long-term stability of ultrafine Ru nanoclusters. Compared with crystalline Ru, amorphous Ru nanoclusters with abundant low-coordinate atoms can provide more catalytic sites. The amorphous Ru nanoclusters exhibited an NH yield of 10.49 μg·h·mg and a FE of 17.48% at -0.2 V vs reversible hydrogen electrode (RHE) for NRR. For the NITRR, an NH yield of 145.1 μg·h·mg and a FE of 80.62% were also achieved at -0.2 V vs RHE. This work provides new insights into crystalline modulation engineering of metal nanoclusters for electrocatalytic ammonia synthesis.