Single-Boron Catalysts for Nitrogen Reduction Reaction

Abstract

Boron has been explored as p-block catalysts for nitrogen reduction reaction (NRR) by density functional theory. Unlike transition metals, on which the active centers need empty d orbitals to accept the lone-pair electrons of the nitrogen molecule, the sp3 hybrid orbital of the boron atom can form B-to-N π-back bonding. This results in the population of the N–N π* orbital and the concomitant decrease of the N–N bond order. We demonstrate that the catalytic activity of boron is highly correlated with the degree of charge transfer between the boron atom and the substrate. Among the 21 concept-catalysts, single boron atoms supported on graphene and substituted into h-MoS2 are identified as the most promising NRR catalysts, offering excellent energy efficiency and selectivity against hydrogen evolution reaction.

Quantification of Active Sites and Elucidation of the Reaction Mechanism of the Electrochemical Nitrogen Reduction Reaction on Vanadium Nitride

“…This amount is corrected for all amounts of ammonium production discussed in this work. TheE NRR in 14 Figure 1B,C,T ables S1 and S2). Detailed calculation procedures are included in the Supporting Information.…”

“…This method allows the comparison of intrinsic activities of active sites and facilitates the identification and improvement of active-site structures for ENRR. [8][9][10][11][12][13][14][15][16][17][18] Mechanistic insights gained so far lean heavily on computational investigations, with relatively little experimental input and insufficient theory/experiment integration. [1] Despite more than acentury of optimization, the Haber-Bosch process remains energy and carbon intensive.…”

“…[8][9][10][11][12][13][14][15][16][17][18] Mechanistic insights gained so far lean heavily on computational investigations, with relatively little experimental input and insufficient theory/experiment integration. [8][9][10][11][12][13][14][15][16][17][18] Mechanistic insights gained so far lean heavily on computational investigations, with relatively little experimental input and insufficient theory/experiment integration.…”

“…N 2 on the spent VNO catalyst (after the ENRR in15 N 2 )show that % 25 %ofthe initially active surface Ns ites are able to sustain catalytic turnovers at the steady state.S pent catalysts after the ENRR in 15 N 2 at À0.1 Vf or 24 ha re collected and rinsed with deionized water;t hey are expected to have % 10 mgN H 4 + equivalent (0.56 mmol) surface14 Nr eplaced by15 Nb ased on the amount of14 NH 4 produced in the first round of the ENRR in15 N 2 .2 .5 mgo f 15 NH 4 + is produced when the spent catalyst is used to catalyze the ENRR in 14 N 2 for both 24 and 48 h. Meanwhile,2 .5 and 8.8 mgo f 14 NH 4 + is produced after 24 and 48 h, respectively (…”

Atomic Modulation, Structural Design, and Systematic Optimization for Efficient Electrochemical Nitrogen Reduction

“…Boron is another high‐profile element for doping in carbon materials . In contrast with N‐doped carbon materials, B doping leads to the polarization of the BC σ‐bond and induces a positive charge on the boron atom owing to the lower electronegativity of boron (2.04) as compared to that of carbon (2.55).…”