Interface Engineering of CoS₂–CeO₂/Ti Nanocatalyst for Artificial N₂ Fixation

Abstract

The development of a highly selective electrocatalytic nitrogen reduction ammonia catalyst is an attractive and challenging task. In this letter, we reported the construction of a CoS2–CeO2 load on Ti mesh (CoS2–CeO2/Ti) based on interface engineering, which can be used as a highly efficient electrocatalytic nitrogen reduction reaction (NRR) catalyst under environmental conditions. According to density functional theory (DFT) calculations, N2 can be activated by the low-coordinated Co atom of the CoS2(110) surface, and the construction of a CoS2/CeO2 interface can effectively provide the necessary H+ for NRR, realizing the improvement of catalytic activity. In 0.1 M Na2SO4, CoS2–CeO2/Ti achieved a considerable average NH3 yield rate of 3.33 × 10–10 mol s–1 cm–2 and Faraday efficiency (FE) of 2.52% at −0.5 V vs RHE. Therefore, its performance is better than that of many known NRR electrocatalysts.

Laser synthesis of amorphous CoSxnanospheres for efficient hydrogen evolution and nitrogen reduction reactions

“…S23†). As shown, increasing the N-doping level did not enhance the NH 3 yields, and the optimal NRR performance was still 12.2 μg h −1 cm cat −2 for the CoS x /CC-L sample at −0.2 V. As a consequence, the HER and NRR results for different N-doped samples indicated that N doping may affect the electrocatalytic performance, but HER and NRR activities were mainly derived from amorphous CoS x in CoS x /CC-L. For comparison, the performance of the CoS x /CC-L was better than or comparable to most of the previously reported NRR catalysts 43–54 under neutral conditions, as illustrated in Table S3 †. In addition, the synthesis of sulfide by a laser combined with a H 2 S atmosphere is a universal method.…”

Defect and interface engineering in metal sulfide catalysts for the electrocatalytic nitrogen reduction reaction: a review

“…In another study, Ti mesh supported CoS 2 –CeO 2 based on interface engineering was developed by Zhou et al for the NRR, and an NH 3 yield of 3.33 × 10 −10 mol s −1 cm −2 with a FE of 2.52% was achieved at −0.5 V in 0.1 M Na 2 SO 4 . 86 It is suggested that the low-coordination Co in CoS 2 could effectively activate N 2 and the oxygen-containing CeO 2 could adsorb H 2 O to provide H + for the NRR, thereby reducing the overpotential of the NRR.…”

Promoting the formation of oxygen vacancies in ceria multishelled hollow microspheres by doping iron for enhanced ambient ammonia electrosynthesis

“…Due to unique properties including multivalence, easily formed oxygen vacancies and high chemical stability, ceria (CeO 2 ) based catalysts have shown promising electrocatalytic performance for the NRR, such as CoS 2 –CeO 2 /Ti, Bi 4 V 2 O 11 /CeO x , Ru/CeO 2 -Vo and r-CeO 2 nanorods. 15–18 The current works have revealed that oxygen vacancy and Ce 3+ in CeO 2 are beneficial for its catalytic activity, which could serve as a surface active site for gas adsorption, electron capture and reactant activation. 19,20 However, pure CeO 2 with low oxygen defect concentration still exhibits low electrocatalytic performance for the NRR.…”