Nitrogen Fixation Reaction Derived from Nanostructured Catalytic Materials

Abstract

An efficient nitrogen fixation reaction is highly desirable for obtaining the essential chemicals and energy carriers but remains a challenge due to the strong nonpolar bonding and considerable activation barrier of the NN triple bond (bond energy 940.95 kJ mol−1). Using an appropriate nanostructured catalyst that strongly interacts with nitrogen could promote adsorption and activation, lowering the energy barrier of nitrogen fixation and thus resulting in a relatively mild reaction. In this article, the review of the recent progress in nanostructured catalytic materials for nitrogen fixation is presented, including a comprehensive introduction and discussion on the pathway and mechanism of nitrogen fixation reaction, the recent achievements of a variety of nanostructured catalysts, and the kinds of catalytic nitrogen fixation reactions they are used in. In addition, the challenges faced by the reaction, strategies of catalyst design, and outlooks for further improving the performance of nitrogen fixation are also highlighted.

Unveiling the Activity Origin of a Copper‐based Electrocatalyst for Selective Nitrate Reduction to Ammonia

“…In particular, ammonia (NH 3 ) is one of the most common industrial chemicals. It not only plays a significant role in agriculture, textile industries, plastics, and the pharmaceutical industry, but also shows promise as a next‐generation energy carrier owing to its high energy density (4.3 kWh kg −1 ) and clean emissions . NH 3 has been synthesized through the reaction of hydrogen and nitrogen under high temperature and high pressure, namely the Haber–Bosch method .…”

Electrochemical Synthesis of Ammonia Based on a Perovskite LaCrO3 Catalyst

“…The catalyst plays an essential role for the cost and efficiency of the NRR and replacing the noble metal catalyst systems with high performance and inexpensive electrocatalysts is significant for large‐scale industrial applications . To design a catalyst with the optimal nanostructure is believed to be the most promising solution . Possible transition metals have been theoretically evaluated for ammonia production with the coincidental HER reaction.…”

Overcoming Chemical Inertness under Ambient Conditions: A Critical View on Recent Developments in Ammonia Synthesis via Electrochemical N2 Reduction by Asking Five Questions

“…The change of the electron density and electron density distribution in a N 2 molecule during adsorption on a catalyst surface leads to its activation. Considering the extremely strong N≡N bond with high bond energy of 962 kJ mol −1 and high first bond cleavage energy of 410 kJ mol −1 , it is not surprising that N 2 molecules usually show chemical inertness . The first protonation of N 2 is endothermic.…”

“…Designing catalysts with desirable composition and structure can further modulate the secondary local environment, which has recently become a key research area. Over the past few decades, researchers have been devoted to design different catalysts based on both experimental and theoretical studies, including bio‐inspired catalysts, homogeneous catalysts and heterogeneous catalysts . Different catalytically active sites for activation of N 2 have been reported and the catalyst is presumably the most crucial part of the NRR process.…”

“…They can be mainly classified into metals and their alloys, metal oxides, metal nitrides, metal carbides and many others . In general, most transition metals or some p‐electron metals with incompletely filled orbitals can donate or accept electrons, which makes them candidates for N 2 activation . For nanostructured metals it should always be considered that their surface exhibits different facets and that the energetics of N 2 adsorption and activation (as also the energetics of ammonia binding) will differ on these different facets.…”