Electrochemical conversion of NO from gaseous pollutants into ammonia using abundant and cost-effective catalyst materials holds great promise for pollutant abatement and for advancing a more closed, sustainable nitrogen cycle. However, regulating product selectivity remains challenging because NO reduction involves complex multielectron/proton pathways. Here, we report two different crystal phases of MoS2 (2H and 1T′) exhibiting prominent activity in the electrochemical NO reduction reaction (NORR), but showing different selectivities. The faradaic efficiency of ammonia reaches 86% over 2H-MoS2, outperforming 1T′-MoS2 (31%) at 2.1 V. In contrast, 1T′-MoS2 displays higher selectivity towards N2, especially at a lower cell voltage (50% at 1.7 V). Kinetic and spectroscopic analyses further suggest phase-dependent rate-control characteristics, consistent with distinct pathway preferences on 1T′ versus 2H. Overall, these results demonstrate that NORR activity and selectivity can be efficiently tuned by choosing the appropriate MoS2 phase, providing a simple strategy to tune product selectivity in complex multistep reactions. ... Read more

Single-atom catalysts, which consist of isolated metal sites immobilized on the support, have attracted significant attention in heterogeneous catalysis due to their high catalytic performance. The so-called strong electrostatic adsorption (SEA), in which a metal precursor is deposited onto an oxide support by electrostatic attraction, is widely employed to obtain single-atom catalysts in wet synthesis. In this work, we investigated the adsorption behavior of Re precursor, perrhenate, on anatase titania as an example of SEA studied by in situ attenuated total reflection infrared (ATR-IR) spectroscopy. The study confirms that the adsorption of perrhenate on titania is enhanced at a lower pH, which is consistent with a SEA model, and that the adsorption and desorption processes are reversible at pH 3.0. The ATR-IR spectroscopic kinetic analysis of the adsorption processes of perrhenate in nitric acid, assuming the Langmuir adsorption model, reveals that the kinetics of the perrhenate adsorption onto titania is influenced by the ionic strength. Furthermore, the adsorption mechanism of perrhenate changes depending on pH between 3.0 and 5.0. This study demonstrates that in situ ATR-IR spectroscopy is a powerful tool for the real-time monitoring and the kinetic study of SEA processes to design atomically engineered catalytic active sites. ... Read more