Basal Plane‐Activated Boron‐Doped MoS₂ Nanosheets for Efficient Electrochemical Ammonia Synthesis

Abstract

Under the dual pressure of energy crisis and environmental pollution, ammonia (NH3) is an indispensable chemical product in the global economy. The electrocatalytic synthesis of NH3 directly from nitrogen and water using renewable electricity has become one of the most attractive and important topics. Basal plane‐activated boron‐doped MoS2 nanosheets (B−MoS2) as a non‐noble metal catalyst with excellent performance for N2 electroreduction are synthesized by a facile one‐step hydrothermal method. In 0.1 m Na2SO4 solution, MoS2 nanosheets doped with 300 mg boric acid (B−MoS2‐300) give rise to a good ammonia yield rate of 75.77 μg h−1 mg−1cat. at −0.75 V vs. RHE, and an excellent Faradaic efficiency of 40.11 % at −0.60 V vs. RHE. In addition, the B−MoS2‐300 nanosheets show good selectivity and chemical stability, and no hydrazine (N2H4) by‐product is generated during the reaction. 15N isotopic labeling confirms that nitrogen in produced ammonia originates from N2 in the electrolyte. On the one hand, the high conductivity of MoS2 guarantees guarantees a high electron transfer rate from nitrogen to ammonia; on the other hand, the successful incorporation of heteroatom B enlarges the interlayer spacing of MoS2, and the B atom can act as an active site for basal plane activation, providing more active sites for the nitrogen reduction reaction (NRR). Density functional theory calculations show that the doping of B activates the base plane of 1T‐MoS2, which makes the adsorption of N2 on the base plane easier and promotes the NRR.

Interlinking electronic band properties in catalysts with electrochemical nitrogen reduction performance: a direct influence

“…Apart from that, the intrinsic semiconducting nature of main group elements shows sluggish electronic conductivity which further restricts HER process as it is highly dependent on surface electrons availability [109]. In this regard, Chen et al [110] demonstrated that boron doping onto the basal Boron and nitrogen were co-doped into biomass carbon leading to the generation of pyridinic-N and BC 2 O acting as active site for NRR as investigated by Tian et al [111] with the ammonia production rate of 41 µg h −1 mg −1 cat at −1 V vs RHE. XPS analysis data showed gradual shifting in the binding energy of boron and nitrogen depicting about synergism occurring between boron and nitrogen centers producing sufficient charge density for NRR process.…”

The energy storage application of core-/yolk–shell structures in sodium batteries

“…They implied suitable NASICON electrolyte design for SIBs. 272 Yildirim and co-workers also collected 1227 data points from 335 published papers and applied for random forest (for discharge capacity prediction) and decision tree (classification). 271 Chao et al describes the different carbon-based material as anode for sodium battery.…”

Synthesis and Electrocatalytic Applications of Layer‐Structured Metal Chalcogenides Composites

“…fabricated the CoS 2 /CeO 2 /Ti composites through a facile method, which showed a high NH 3 yield rate of 3.33 × 10 −10 mol s −1 cm −2 in 0.1 m Na 2 SO 4 . [ 297 ] Moreover, the FeS 2 /MoS 2 /reduced graphene oxide composites, [ 298 ] the Bi 2 S 3 /MoS 2 composites, [ 299 ] the boron doped MoS 2 composites, [ 300 ] the CoS 2 /MoS 2 composites, [ 301 ] the MoS 2 /Mo 2 C composites, [ 302 ] the Au/MoS 2 composites, [ 303 ] the S‐rich MoS 2 composites, [ 304 ] the different types of transition metal (Co, Fe, Cu, Zn, Ni) doped ReS 2 composites, [ 305 ] etc., have been developed as advanced electrocatalysts for NRR. Table 5 summary of the LMCs‐based composites for NRR.…”