Tailoring Electron-Riched Boron Sites in BCN for Nitrogen Fixation via Alternate Mechanism

Yang, Yutong1,2; Wang, Yin1; Wang, Xia1; Chen, Shaoqing2; Duan, Limei1; Zhang, Wei3; Li, Wanfei4; Liu, Jinghai1,4

2022

10.1002/admi.202101842

Advanced Materials Interfaces   影响因子和分区

2196-7350

The electrochemical nitrogen reduction reaction (eNRR) is promising for achieving sustainable ammonia (NH3) production under mild conditions. However, it is still challenged by nitrogen activation and strong competition with the hydrogen evolution reaction. Here, it is revealed that fine-tuning the local electron density of boron (B) sites at the boron carbon nitride (BCN) solid catalysts has significant effects on the eNRR activity and selectivity. The concentration of electron-rich B sites at BCN catalysts are mediated by solid-state reaction, where their electronic structures are confirmed by electron energy-loss spectroscopy (EELS) and electron paramagnetic resonance (EPR). Over the density functional theory (DFT) calculations, the nitrogen (N-2) activation and reduction at an electron-riched B site is through an alternate pathway with the determining-step energy of only 0.92 eV. The optimized BCN5 catalyst with the highest ratio of electron-riched B sites achieves an outstanding NH3 production rate of 29.3 mu g h(-1) mg(cat)(-1) and the highest Faradaic efficiency of 39%.

electrochemical nitrogen reduction reaction (eNRR) electron-riched boron site Faradaic efficiency nitrogen activation

SCI ; EI

英语

通讯

Natural Science Foundation of China[21961024,21961025,22161036] ; Natural Science Foundation of Inner Mongolia["2018JQ05","2019BS02007"] ; Inner Mongolia Autonomous Region Funding Project for Science & Technology Achievement Transformation[CGZH2018156] ; Inner Mongolia Autonomous Region Science & Technology Planning Project for Applied Technology Research and Development[2019GG261] ; Doctoral Scientific Research Foundation of Inner Mongolia University for the Nationalities[BS437] ; Department of Science and Technology of Guangdong Province[2017ZT07Z479]

Chemistry ; Materials Science

Chemistry, Multidisciplinary ; Materials Science, Multidisciplinary

WOS:000740661200001

WILEY

20220311462275

Ammonia ; Chemical activation ; Density functional theory ; Electrocatalysts ; Electron energy levels ; Electron energy loss spectroscopy ; Electron scattering ; Electron spin resonance spectroscopy ; Electronic structure ; Energy dissipation ; Nitrogen fixation ; Paramagnetic resonance

Energy Losses (industrial and residential):525.4 ; Magnetism: Basic Concepts and Phenomena:701.2 ; Chemistry:801 ; Chemical Reactions:802.2 ; Chemical Agents and Basic Industrial Chemicals:803 ; Chemical Products Generally:804 ; Inorganic Compounds:804.2 ; Probability Theory:922.1 ; Atomic and Molecular Physics:931.3 ; Quantum Theory; Quantum Mechanics:931.4

Web of Science

1.Inner Mongolia MinZu Univ, Nano Innovat Inst NII, Inner Mongolia Key Lab Carbon Nanomat, Coll Chem & Mat Sci, Tongliao 028000, Peoples R China
2.Southern Univ Sci & Technol, Dept Mat Sci & Engn, Shenzhen 518055, Peoples R China
3.Jilin Univ, Coll Mat Sci, Key Lab Mobile Mat MOE, State Key Lab Automot Simulat & Control, Changchun 130012, Peoples R China
4.Suzhou Univ Sci & Technol, Sch Mat Sci & Engn, Res Ctr Nanophoton & Nanoelect Mat, Suzhou 215009, Peoples R China

Yang, Yutong,Wang, Yin,Wang, Xia,et al. Tailoring Electron-Riched Boron Sites in BCN for Nitrogen Fixation via Alternate Mechanism[J]. Advanced Materials Interfaces,2022,9.

Yang, Yutong.,Wang, Yin.,Wang, Xia.,Chen, Shaoqing.,Duan, Limei.,...&Liu, Jinghai.(2022).Tailoring Electron-Riched Boron Sites in BCN for Nitrogen Fixation via Alternate Mechanism.Advanced Materials Interfaces,9.

Yang, Yutong,et al."Tailoring Electron-Riched Boron Sites in BCN for Nitrogen Fixation via Alternate Mechanism".Advanced Materials Interfaces 9(2022).