Greatly Enhanced Electrocatalytic N₂ Reduction on TiO₂ via V Doping

Abstract

As a sustainable alternative technology to the Haber–Bosch process, electrochemical N2 reduction offers the hope of directly converting N2 to NH3 at ambient conditions. However, its efficiency greatly depends on screening high‐active electrocatalysts for the N2 reduction reaction (NRR). Here, the recent experimental finding that V is an effective dopant to greatly improve the NRR performances of TiO2 toward ambient N2‐to‐NH3 fixation with excellent selectivity is reported. In 0.5 m anhydrous lithium perchlorate, V‐doped TiO2 nanorods attain a high Faradic efficiency of 15.3% and a large NH3 yield of 17.73 µg h−1 mgcat.−1 at −0.40 and −0.50 V versus reversible hydrogen electrode, respectively, rivaling the performances of most reported aqueous‐based NRR electrocatalysts. Density function theory (DFT) calculations are performed to gain further insight into the catalytic mechanism.

Greatly Improving Electrochemical N2 Reduction over TiO2 Nanoparticles by Iron Doping

“…TiO 2 is highly adaptable as a semiconductor catalyst because of its long‐term thermodynamic stability, natural abundance, and nontoxicity . Recent studies have demonstrated that TiO 2 with oxygen defects has good electrocatalytic activity for the NRR, and heteroatoms (B, C, V, and Zr,) are effective dopants to enhance the NRR performances of TiO 2 catalysts. However, Ti‐based catalysts that simultaneously achieve a large NH 3 yield with a high Faradaic efficiency (FE) are not available thus far.…”

Exploration and Investigation of Periodic Elements for Electrocatalytic Nitrogen Reduction

“…Interestingly, the results were very high when NRR was carried out in 0.5 m LiClO 4 electrolyte. [32] At −0.4 V, V-TiO 2 exhibited efficiency as high as 15.3%. The excellent performance was attributed to increased defects, synergetic effects between Ti and V and change in electronic conductivity of TiO 2 caused by V doping.…”

DyF3: An Efficient Electrocatalyst for N2 Fixation to NH3 under Ambient Conditions

“…Nonetheless, the expensiveness limits its broad applications. Therefore, much attention has focused on noble‐metal‐free catalysts . Rare‐earth elements have received research attention in the past few years due to their potential applications in catalysis fields, optics, biological labeling, etc.…”