BCN-Encapsulated Nano-nickel Synergistically Promotes Ambient Electrochemical Dinitrogen Reduction

Abstract

The electricity provided by solar or wind power can drive nitrogen in the atmosphere, combining with ubiquitous water to form ammonia, and distributed production methods can alleviate the irreversible damage to the environment caused by the energy-intensive Haber−Bosch process. Here, we have designed a novel Ni-doped BCN heterojunction (S/ M-BOPs-1) as a catalyst for the electrochemical nitrogen reduction reaction (NRR). The ammonia yield rate and Faraday efficiency in NRR driven by S/ M-BOPs-1 reach up to 16.72 μg −1 h −1 cm −2 and 13.06%, respectively. Moreover, S/M-BOPs-1 still maintains high NRR activity and excellent stability after recycling for eight times and long-time operation of 12 h. Using density functional theory calculations, we reveal a possible NRR path for N 2 to NH 3 on Ni, BCN, and the S/M-BOPs-1 composite surfaces. The interaction between the BCN matrix and Ni nanoparticles promotes a synergetic effect for the electrochemical NRR efficiency due to the partial electron transfer from the Ni particles to BCN that inhibits hydrogen evolution reaction and decreases the rate-determining step on Ni surfaces toward NRR by ∼1.5 times. Therefore, efficient NRR performance can be achieved by tuning the electronic properties of non-noble metals via the formation of a heterointerface.

Strategies to activate inert nitrogen molecules for efficient ammonia electrosynthesis: current status, challenges, and perspectives

“…As for carbon-based supports, Zhang et al designed a catalyst of Ni nanoparticles supported on a boron–carbon–nitrogen (BCN) matrix for the electrocatalytic NRR and attained an NH 3 yield rate of 16.72 μg h −1 cm −2 and an FE of 13.06%. 124 Using DFT calculations, the authors revealed that the BCN support can accelerate the electron delocalization of the Ni particles and induce the distribution of positive charge on the Ni particles. The positively charged Ni particles are closely related to the N 2 activation process, thereby promoting the NRR performance.…”

Activity and selectivity of N2 fixation on B doped g-C9N10: a density functional theory study

“…16 Several experimental and theoretical works on boron doped CN x materials and boron-based clusters proved that boron materials are beneficial for the N 2 RR activity. [17][18][19][20][21] Zhao et al 17 reported that the BCN matrix and Ni nanoparticles promote a synergetic effect on the electrochemical N 2 RR efficiency. Li et al 22 proved that the doped B-N pairs in the carbon matrix can efficiently improve N 2 RR activity.…”

Rational Synthesis and Regulation of Hollow Structural Materials for Electrocatalytic Nitrogen Reduction Reaction

“…Currently, researchers have made enormous efforts in designing catalysts, including noble metal catalysts, non‐noble metal catalysts, and nonmetal catalysts. [ 17 , 18 , 19 ] In addition, many effective strategies have been developed to regulate the physical and chemical properties of catalysts to enhance their catalytic activity. For example, the structure and morphology of these materials (2D flakes, porous structure, hollow structure, etc.)…”