Fe‐VS₂ Electrocatalyst with Organic Matrix‐Mediated Electron Transfer for Highly Efficient Nitrogen Fixation

Abstract

Electrochemical N 2 fixation is considered to be a promising alternative to Haber-Bosch technology. Inspired by the composition and structure of natural nitrogenase, Fe-doped VS 2 nanosheets were prepared via one-step solvothermal method. The electron transfer system mediated by organic conductive polymer (1-AAQ-PA) was constructed to promote the electron transfer between Fe-VS 2 nanosheets and the electrode in electrocatalytic N 2 reduction reaction (NRR). The obtained 1-AAQ-PAÀ Fe-VS 2 electrode converted N 2 to NH 3 with a yield of 31.6 μg h À 1 mg À 1 at À 0.35 V vs. reversible hydrogen electrode and high faradaic efficiency of 23.5 %. The introduction of Fe dopants favored N 2 adsorption and activation, while the LiÀ S bond between Fe-VS 2 and Li 2 SO 4 effectively inhibited hydrogen evolution. The highly efficient electron utilization in the electrocatalytic NRR process was realized using the 1-AAQ-PA as the electron transfer medium. Density functional theory calculations showed that N 2 was preferentially adsorbed on Fe and reduced to NH 3 via both distal and alternating mechanism.

Single-atom catalysts supported on a hybrid structure of boron nitride/graphene for efficient nitrogen fixation via synergistic interfacial interactions

“…5 Furthermore, the undesired hydrogen evolution reaction (HER) often hinders the NRR in many catalysts, resulting in unsatisfactory yield rates. [5][6][7][8] Single-atom catalysts (SACs), [9][10][11][12][13][14][15][16][17][18][19][20][21] a new type of heterogeneous catalyst, show promise as an alternative to scarce noble-based catalysts by maximizing atom utilization efficiency and inhibiting the undesired HER. Hexagonal boron nitride (BN)-based catalysts have demonstrated promising catalytic activity in the NRR while suppressing the HER.…”

“…Single-atom catalysts (SACs), 9–21 a new type of heterogeneous catalyst, show promise as an alternative to scarce noble-based catalysts by maximizing atom utilization efficiency and inhibiting the undesired HER. Hexagonal boron nitride (BN)-based catalysts have demonstrated promising catalytic activity in the NRR while suppressing the HER.…”

High‐Efficiency Electroreduction of Nitrite to Ammonia on Ni Nanoparticles Strutted 3D Honeycomb‐Like Porous Carbon Framework

“…Industrial NH 3 synthesis has predominantly relied on the ecologically unfriendly and unsustainable Haber‐Bosch method (HBP) to date, which requires high temperature (400–600 °C), high pressure (200–350 atm) and emits large amounts of CO 2 [7,8] . Recently, electrocatalytic N 2 reduction reaction has emerged as a promising alternative to HBP for NH 3 synthesis under ambient conditions in an aqueous environment, which utilizes electricity as an energy source and N 2 and water as feedstocks [9–19] . Nevertheless, the ultra‐low water solubility of N 2 , high cleavage energy of N≡N (941.0 kJ mol −1 ), and competing hydrogen evolution reaction can cause unsatisfactory NH 3 yield and Faraday efficiency (FE) [20,21] .…”

“…[7,8] Recently, electrocatalytic N 2 reduction reaction has emerged as a promising alternative to HBP for NH 3 synthesis under ambient conditions in an aqueous environment, which utilizes electricity as an energy source and N 2 and water as feedstocks. [9][10][11][12][13][14][15][16][17][18][19] Nevertheless, the ultra-low water solubility of N 2 , high cleavage energy of N�N (941.0 kJ mol À 1 ), and competing hydrogen evolution reaction can cause unsatisfactory NH 3 yield and Faraday efficiency (FE). [20,21] Nitrite (NO 2 À ), compared with N 2 , owns higher water solubility and a lower N=O cleavage energy (204.0 kJ mol À 1 ), which would offer constructive conditions for boosting the reaction kinetics of NH 3 generation.…”

Construction of Ln2O3@C Nanosheets for Electrocatalytic Nitrogen Reduction to Ammonia

“…In the realm of electrocatalytic nitrogen fixation, significant progress has been made, with various effective catalysts, including metal, nonmetal, and metal/nonmetal heterojunction catalysts, being developed for electrocatalytic ammonia synthesis. ,− Transition metals as electrocatalysts with outstanding NRR performance have attracted attention due to the stronger coupling of the empty d orbitals and the lone-pair electrons of N 2 , which can prolongate and weaken the NN bond. , As we know, the morphology of transition metals is an essential factor in electrocatalytic ammonia synthesis, which affects the exposure of catalytic active sites of samples. , However, the metal oxide obtained via traditional sedimentation presented a bulk structure with fewer activity sites …”