Surface Plasmon Enabling Nitrogen Fixation in Pure Water through a Dissociative Mechanism under Mild Conditions

Abstract

Nitrogen fixation in a simulated natural environment (i.e., near ambient pressure, room temperature, pure water, and incident light) would provide a desirable approach to future nitrogen conversion. As the NN triple bond has a thermodynamically high cleavage energy, nitrogen reduction under such mild conditions typically undergoes associative alternating or distal pathways rather than following a dissociative mechanism. Here, we report that surface plasmon can supply sufficient energy to activate N 2 through a dissociative mechanism in the presence of water and incident light, as evidenced by in situ synchrotron radiationbased infrared spectroscopy and near ambient pressure X-ray photoelectron spectroscopy. Theoretical simulation indicates that the electric field enhanced by surface plasmon, together with plasmonic hot electrons and interfacial hybridization, may play a critical role in NN dissociation. Specifically, AuRu coreantenna nanostructures with broadened light adsorption cross section and active sites achieve an ammonia production rate of 101.4 μmol g −1 h −1 without any sacrificial agent at room temperature and 2 atm pressure. This work highlights the significance of surface plasmon to activation of inert molecules, serving as a promising platform for developing novel catalytic systems.

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

“…Moreover, the preparation of hydrogen via the reforming of natural gas is accompanied by the emission of huge amounts of greenhouse gas . Thus, using water as a hydrogen source to prepare ammonia through electrocatalytic and photo(electro)catalytic nitrogen reduction has attracted increasing attention . However, the breaking of the N≡N triple bond (941 kJ mol −1 ) in nitrogen gas is challenging and the competitive hydrogen evolution reaction hampers the Faraday efficiency .…”

“…[14] Thus, using water as a hydrogen source to prepare ammonia through electrocatalytic and photo(electro)catalytic nitrogen reduction has attracted increasing attention. [15][16][17][18][19][20] However, the breaking of the N N triple bond (941 kJ mol À1 ) in nitrogen gas is challenging and the competitive hydrogen evolution reaction hampers the Faraday efficiency. [21][22][23] Simultaneously, vast amounts of nitrate (NO 3 À ) are discharged into the surface water and underground aquifer, threatening human health.…”

Operando Oxygen Vacancies for Enhanced Activity and Stability toward Nitrogen Photofixation

“…To begin with, nanoporous W was synthesized via etching commercial WCo powders with the size of 5-40 µm using sulfuric acid at 150 °C for 4 h (Figure 1a; Figures S1-S3, Supporting Information). After etching, the ratio of residual Co element in nanoporous W was determined to be ≈0.1 wt% by inductively 3 -600. The pictures of e) WO 3 /W-400 and f) WO 3 -600. g) O 1s XPS spectra, h) XANES spectra, and i) Fourier-transformed EXAFS spectra in R space for WO 3 /W-400, WO 3 -600, WO 3 -800, and WO 3 -NPs (W foil was used as the reference).…”

New Aspects of Platinum Group Metal‐Based Solid‐Solution Alloy Nanoparticles: Binary to High‐Entropy Alloys

“…Au or Ru is fcc or hcp in bulk, respectively. Several interesting architectures such as Au‐Ru heterostructures, branched Au‐Ru, and Au‐Ru core–antenna have been recently reported to show superior catalytic properties such as the H evolution reaction (HER), OER, and photo N 2 fixation. Consequently, Au‐Ru solid‐solution alloys are also expected to show superior or novel properties.…”