Fast and Sensitive Detection of Ammonia from Electrochemical Nitrogen Reduction Reactions by 1H NMR with Radiation Damping

Abstract

A facile NMR method is reported for analysis of ammonia from the electrochemical reduction of nitrogen, which compares a calibrated colorimetric method, a calibrated 1H NMR method and two 1H NMR direct measurements using external reference materials. Unlike spectrophotometric methods, 1H NMR requires less bench time and does not require separation of ammonia from the electrolyte. A novel approach to the problem of radiation damping in NMR measurements considered the specific role of hardware tuning. Radiation damping is suppressed improving signal-to-noise ratio and detection limit (1.5 µg L−1). The method is demonstrated to be effective for the analysis of ammonia from direct electrochemical nitrogen reduction in KOH, and from lithium-mediated nitrogen reduction in a non-aqueous solution. An uncertainty budget is prepared for the measurement of ammonia.