Synergistic Effect of Diatomic Mo-B Site Confined in Graphene-Like C2N Enables Electrocatalytic Nitrogen Reduction via Novel Mechanism
Abstract
Structural modulation of active site with atomic-level precision is of great importance to meet the activity and selectivity challenges that electrocatalysts are commonly facing. In this work, we have designed a metal (M) - nonmetal (NM) diatomic site embedded in graphene-like C2N (denoted as Mo-B@C2N), where electrocatalytic N2 reduction reaction (eNRR) was thoroughly explored using density functional theory combined with computational hydrogen electrode method. Compared to M-M diatomic sites, Mo-B site can generate pronounced synergistic effect that led to eNRR proceeding via a novel quasi-dissociative reaction mechanism that has not been reported relative to the conventional enzymatic, consecutive, distal, and alternating associative mechanism. This newly uncovered mechanism in which N-N bond scission takes place immediately after the first proton-coupled electron transfer (PCET) step (i.e., *NH-*N + H+ + e– ® *NH2*N) has demonstrated much advantage in PCET process over the four conventional mechanism in terms of thermodynamic barrier, except that the adsorption of side-on *N2 seemed thermodynamically unfavorable (DGads = 0.61eV). Our results have revealed that the activation of inert NºN triple bond is dominated by π*-backdonation mechanism as a consequence of charge transfers from both B and Mo site, and unexpectedly, from the substrate C2N itself as well. Moreover,more »
- Publication Date:
- Research Org.:
- Brookhaven National Laboratory (BNL), Upton, NY (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC)
- OSTI Identifier:
- 1897685
- Grant/Contract Number:
- SC0012704
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Chemical Physics
- Additional Journal Information:
- Journal Volume: 157; Journal Issue: 21; Journal ID: ISSN 0021-9606
- Publisher:
- American Institute of Physics (AIP)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 77 NANOSCIENCE AND NANOTECHNOLOGY; Electrocatalysis; N2 reduction; Dual-atom catalyst; Synergistic effect; DFT.
Citation Formats
Li, Yang, and An, Wei. Synergistic Effect of Diatomic Mo-B Site Confined in Graphene-Like C2N Enables Electrocatalytic Nitrogen Reduction via Novel Mechanism. United States: N. p., 2022.
Web. doi:10.1063/5.0112520.
Li, Yang, & An, Wei. Synergistic Effect of Diatomic Mo-B Site Confined in Graphene-Like C2N Enables Electrocatalytic Nitrogen Reduction via Novel Mechanism. United States. https://doi.org/10.1063/5.0112520
Li, Yang, and An, Wei. Thu .
"Synergistic Effect of Diatomic Mo-B Site Confined in Graphene-Like C2N Enables Electrocatalytic Nitrogen Reduction via Novel Mechanism". United States. https://doi.org/10.1063/5.0112520. https://www.osti.gov/servlets/purl/1897685.
@article{osti_1897685,
title = {Synergistic Effect of Diatomic Mo-B Site Confined in Graphene-Like C2N Enables Electrocatalytic Nitrogen Reduction via Novel Mechanism},
author = {Li, Yang and An, Wei},
abstractNote = {Structural modulation of active site with atomic-level precision is of great importance to meet the activity and selectivity challenges that electrocatalysts are commonly facing. In this work, we have designed a metal (M) - nonmetal (NM) diatomic site embedded in graphene-like C2N (denoted as Mo-B@C2N), where electrocatalytic N2 reduction reaction (eNRR) was thoroughly explored using density functional theory combined with computational hydrogen electrode method. Compared to M-M diatomic sites, Mo-B site can generate pronounced synergistic effect that led to eNRR proceeding via a novel quasi-dissociative reaction mechanism that has not been reported relative to the conventional enzymatic, consecutive, distal, and alternating associative mechanism. This newly uncovered mechanism in which N-N bond scission takes place immediately after the first proton-coupled electron transfer (PCET) step (i.e., *NH-*N + H+ + e– ® *NH2*N) has demonstrated much advantage in PCET process over the four conventional mechanism in terms of thermodynamic barrier, except that the adsorption of side-on *N2 seemed thermodynamically unfavorable (DGads = 0.61eV). Our results have revealed that the activation of inert NºN triple bond is dominated by π*-backdonation mechanism as a consequence of charge transfers from both B and Mo site, and unexpectedly, from the substrate C2N itself as well. Moreover, the hybrid Mo-B diatomic site demonstrated superior performance over either Mo-Mo or B-B site for driving eNRR. Furthermore, our study could provide insight into the delicate relationships among atomic site, substrate and electrocatalytic performance.},
doi = {10.1063/5.0112520},
journal = {Journal of Chemical Physics},
number = 21,
volume = 157,
place = {United States},
year = {Thu Nov 10 00:00:00 EST 2022},
month = {Thu Nov 10 00:00:00 EST 2022}
}
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Works referenced in this record:
Synergistic Effect of Active Sites of Double‐Atom Catalysts for Nitrogen Reduction Reaction
journal, September 2021
- Sun, Chang Ning; Wang, Zhi Li; Lang, Xing‐You
- ChemSusChem, Vol. 14, Issue 20
Enhanced Activity of C 2 N-Supported Single Co Atom Catalyst by Single Atom Promoter
journal, October 2019
- Zhong, Wenhui; Zhang, Guozhen; Zhang, Yachao
- The Journal of Physical Chemistry Letters, Vol. 10, Issue 22
Double-atom catalysts: transition metal dimer-anchored C 2 N monolayers as N 2 fixation electrocatalysts
journal, January 2018
- Zhang, Xu; Chen, An; Zhang, Zihe
- Journal of Materials Chemistry A, Vol. 6, Issue 38
Computational Screening Single-Atom Catalysts Supported on g-CN for N2 Reduction: High Activity and Selectivity
journal, August 2020
- Niu, Huan; Wang, Xiting; Shao, Chen
- ACS Sustainable Chemistry & Engineering, Vol. 8, Issue 36
Hybrid functionals based on a screened Coulomb potential
journal, May 2003
- Heyd, Jochen; Scuseria, Gustavo E.; Ernzerhof, Matthias
- The Journal of Chemical Physics, Vol. 118, Issue 18
Single-, double-, and triple-atom catalysts on graphene-like C2N enable electrocatalytic nitrogen reduction: insight from first principles
journal, January 2022
- Zhang, Jin; An, Wei
- Catalysis Science & Technology, Vol. 12, Issue 8
A theoretical evaluation of possible transition metal electro-catalysts for N 2 reduction
journal, January 2012
- Skúlason, Egill; Bligaard, Thomas; Gudmundsdóttir, Sigrídur
- Phys. Chem. Chem. Phys., Vol. 14, Issue 3
VASPKIT: A user-friendly interface facilitating high-throughput computing and analysis using VASP code
journal, October 2021
- Wang, Vei; Xu, Nan; Liu, Jin-Cheng
- Computer Physics Communications, Vol. 267
Advances in electrocatalytic ammonia synthesis under mild conditions
journal, November 2020
- Duan, Guoyi; Chen, Yongmei; Tang, Yang
- Progress in Energy and Combustion Science, Vol. 81
Promoting the oxygen reduction reaction with gold at step/edge sites of Ni@AuPt core–shell nanoparticles
journal, January 2017
- Wang, Hao; An, Wei
- Catalysis Science & Technology, Vol. 7, Issue 3
Emerging Dual‐Atomic‐Site Catalysts for Efficient Energy Catalysis
journal, July 2021
- Zhang, Weiyu; Chao, Yuguang; Zhang, Wenshu
- Advanced Materials, Vol. 33, Issue 36
Adsorption of Monocyclic Aromatics on Transition Metal Surfaces: Insight into Variation of Binding Strength from First-Principles
journal, August 2018
- Jia, Xin; An, Wei
- The Journal of Physical Chemistry C, Vol. 122, Issue 38
Single-metal-atom site with high-spin state embedded in defective BN nanosheet promotes electrocatalytic nitrogen reduction
journal, March 2021
- Fang, Cong; An, Wei
- Nano Research, Vol. 14, Issue 11
A fast and robust algorithm for Bader decomposition of charge density
journal, June 2006
- Henkelman, Graeme; Arnaldsson, Andri; Jónsson, Hannes
- Computational Materials Science, Vol. 36, Issue 3
Review on photocatalytic and electrocatalytic artificial nitrogen fixation for ammonia synthesis at mild conditions: Advances, challenges and perspectives
journal, May 2019
- Xue, Xiaolan; Chen, Renpeng; Yan, Changzeng
- Nano Research, Vol. 12, Issue 6
Challenges and prospects in the catalysis of electroreduction of nitrogen to ammonia
journal, March 2019
- Suryanto, Bryan H. R.; Du, Hoang-Long; Wang, Dabin
- Nature Catalysis, Vol. 2, Issue 4
Tackling the Activity and Selectivity Challenges of Electrocatalysts toward the Nitrogen Reduction Reaction via Atomically Dispersed Biatom Catalysts
journal, February 2020
- Guo, Xiangyu; Gu, Jinxing; Lin, Shiru
- Journal of the American Chemical Society, Vol. 142, Issue 12
Tuning the catalytic activity of a single Mo atom supported on graphene for nitrogen reduction via Se atom doping
journal, January 2019
- Zhou, Hong Yu; Li, Jian Chen; Wen, Zi
- Physical Chemistry Chemical Physics, Vol. 21, Issue 27
Double boron atom-doped graphdiynes as efficient metal-free electrocatalysts for nitrogen reduction into ammonia: a first-principles study
journal, January 2021
- Fu, Cheng; Li, Yafei; Wei, Haiyan
- Physical Chemistry Chemical Physics, Vol. 23, Issue 32
Electrochemical CO 2 Reduction Reaction on M@Cu(211) Bimetallic Single-Atom Surface Alloys: Mechanism, Kinetics, and Catalyst Screening
journal, November 2019
- Feng, Yonghao; An, Wei; Wang, Zeming
- ACS Sustainable Chemistry & Engineering, Vol. 8, Issue 1
Dual-atom active sites embedded in two-dimensional C2N for efficient CO2 electroreduction: A computational study
journal, October 2021
- Liu, Haimei; Huang, Qingliang; An, Wei
- Journal of Energy Chemistry, Vol. 61
A Pedestrian Approach to the Aromaticity of Graphene and Nanographene: Significance of Huckel’s (4n+2)π Electron Rule
journal, July 2015
- Zdetsis, Aristides D.; Economou, E. N.
- The Journal of Physical Chemistry C, Vol. 119, Issue 29
C
2
N: A Class of Covalent Frameworks with Unique Properties
journal, November 2020
- Tian, Zhihong; López‐Salas, Nieves; Liu, Chuntai
- Advanced Science, Vol. 7, Issue 24
Beyond fossil fuel–driven nitrogen transformations
journal, May 2018
- Chen, Jingguang G.; Crooks, Richard M.; Seefeldt, Lance C.
- Science, Vol. 360, Issue 6391
CRC Handbook of Chemistry and Physics
book, June 2016
- Haynes, W. M.; Lide, David R.; Bruno, Thomas J.
- CRC press
A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu
journal, April 2010
- Grimme, Stefan; Antony, Jens; Ehrlich, Stephan
- The Journal of Chemical Physics, Vol. 132, Issue 15
Recent Advances and Challenges of Electrocatalytic N 2 Reduction to Ammonia
journal, May 2020
- Qing, Geletu; Ghazfar, Reza; Jackowski, Shane T.
- Chemical Reviews, Vol. 120, Issue 12
Interaction of Ammonia with Nafion and Electrolyte in Electrocatalytic Nitrogen Reduction Study
journal, July 2021
- Cai, Xiyang; Iriawan, Haldrian; Yang, Fan
- The Journal of Physical Chemistry Letters, Vol. 12, Issue 29
Classification of chemical bonds based on topological analysis of electron localization functions
journal, October 1994
- Silvi, B.; Savin, A.
- Nature, Vol. 371, Issue 6499
Emerging Two-Dimensional Nanomaterials for Electrocatalysis
journal, March 2018
- Jin, Huanyu; Guo, Chunxian; Liu, Xin
- Chemical Reviews, Vol. 118, Issue 13
Nitrogen reduction on crystalline carbon nitride supported by homonuclear bimetallic atoms
journal, September 2022
- Le, Yaqian; Wei, Changgeng; Xue, Weichao
- The Journal of Chemical Physics, Vol. 157, Issue 11
Superiority of Dual‐Atom Catalysts in Electrocatalysis: One Step Further Than Single‐Atom Catalysts
journal, January 2022
- Li, Runze; Wang, Dingsheng
- Advanced Energy Materials, Vol. 12, Issue 9
Effect of Doped Metals on Hydrodeoxygenation of Phenol over Pt-Based Bimetallic Alloys: C aryl –OH Versus C aliphatic H–OH Bond Scission
journal, June 2019
- Jia, Xin; An, Wei; Wang, Zeming
- The Journal of Physical Chemistry C, Vol. 123, Issue 27
Electrochemical hydrogenation of dinitrogen to ammonia on a polyaniline electrode
journal, February 2006
- Köleli, Fatih; Röpke, Thorsten
- Applied Catalysis B: Environmental, Vol. 62, Issue 3-4
Single atom catalyst towards ammonia synthesis at mild conditions
journal, June 2018
- Fang, Zhiwei; Yu, Guihua
- Science China Chemistry, Vol. 61, Issue 9
Nitrogen fixation and reduction at boron
journal, February 2018
- Légaré, Marc-André; Bélanger-Chabot, Guillaume; Dewhurst, Rian D.
- Science, Vol. 359, Issue 6378
Tetrahedral W4 cluster confined in graphene-like C2N enables electrocatalytic nitrogen reduction from theoretical perspective
journal, March 2022
- Zhang, Jin; Fang, Cong; Li, Yang
- Nanotechnology, Vol. 33, Issue 24
A simple measure of electron localization in atomic and molecular systems
journal, May 1990
- Becke, A. D.; Edgecombe, K. E.
- The Journal of Chemical Physics, Vol. 92, Issue 9
Single and double boron atoms doped nanoporous C 2 N– h 2D electrocatalysts for highly efficient N 2 reduction reaction: a density functional theory study
journal, May 2019
- Cao, Yongyong; Deng, Shengwei; Fang, Qiaojun
- Nanotechnology, Vol. 30, Issue 33
Tuning the Catalytic Preference of Ruthenium Catalysts for Nitrogen Reduction by Atomic Dispersion
journal, November 2019
- Yu, Bing; Li, Hao; White, Jai
- Advanced Functional Materials, Vol. 30, Issue 6
A first-principles study of the effects of atom impurities, defects, strain, electric field and layer thickness on the electronic and magnetic properties of the C2N nanosheet
journal, February 2020
- Bafekry, Asadollah; Stampfl, Catherine; Ghergherehchi, Mitra
- Carbon, Vol. 157
Characterization of a Sample of Single-Walled Carbon Nanotube Array by Nitrogen Adsorption Isotherm and Density Functional Theory
journal, July 2003
- Zhang, Xianren; Wang, Wenchuan; Chen, Jianfeng
- Langmuir, Vol. 19, Issue 15
The Challenge of Electrochemical Ammonia Synthesis: A New Perspective on the Role of Nitrogen Scaling Relations
journal, June 2015
- Montoya, Joseph H.; Tsai, Charlie; Vojvodic, Aleksandra
- ChemSusChem, Vol. 8, Issue 13
Rationalization of Au Concentration and Distribution in AuNi@Pt Core–Shell Nanoparticles for Oxygen Reduction Reaction
journal, September 2015
- An, Wei; Liu, Ping
- ACS Catalysis, Vol. 5, Issue 11
A General Two‐Step Strategy–Based High‐Throughput Screening of Single Atom Catalysts for Nitrogen Fixation
journal, December 2018
- Ling, Chongyi; Ouyang, Yixin; Li, Qiang
- Small Methods, Vol. 3, Issue 9
Computational evaluation of FeMo heteroatom coeffect induced high electroreduction activity of N2-to-NH3
journal, March 2022
- Han, Xing-Qi; Lang, Zhong-Ling; Zhang, Feng-Yi
- Applied Surface Science, Vol. 579
Defect Engineering Strategies for Nitrogen Reduction Reactions under Ambient Conditions
journal, October 2018
- Yan, Dafeng; Li, Hao; Chen, Chen
- Small Methods, Vol. 3, Issue 6
Synergy of a Metallic NiCo Dimer Anchored on a C 2 N–Graphene Matrix Promotes the Electrochemical CO 2 Reduction Reaction
journal, November 2019
- Huang, Qingliang; Liu, Haimei; An, Wei
- ACS Sustainable Chemistry & Engineering, Vol. 7, Issue 23
Atomically embedded asymmetrical dual-metal dimers on N-doped graphene for ultra-efficient nitrogen reduction reaction
journal, August 2020
- He, Tianwei; Puente Santiago, Alain R.; Du, Aijun
- Journal of Catalysis, Vol. 388
How a century of ammonia synthesis changed the world
journal, September 2008
- Erisman, Jan Willem; Sutton, Mark A.; Galloway, James
- Nature Geoscience, Vol. 1, Issue 10
High-throughput identification of high activity and selectivity transition metal single-atom catalysts for nitrogen reduction
journal, February 2021
- Xue, Zhe; Zhang, Xinyu; Qin, Jiaqian
- Nano Energy, Vol. 80
Hybrid Metal–Boron Diatomic Site Embedded in C
2
N Monolayer Promotes C–C Coupling in CO
2
Electroreduction
journal, September 2021
- He, Miaomiao; An, Wei; Wang, Yuanqiang
- Small, Vol. 17, Issue 42
Origin of the Overpotential for Oxygen Reduction at a Fuel-Cell Cathode
journal, November 2004
- Nørskov, J. K.; Rossmeisl, J.; Logadottir, A.
- The Journal of Physical Chemistry B, Vol. 108, Issue 46
Electrochemical Ammonia Synthesis—The Selectivity Challenge
journal, December 2016
- Singh, Aayush R.; Rohr, Brian A.; Schwalbe, Jay A.
- ACS Catalysis, Vol. 7, Issue 1
Stepped M@Pt(211) (M = Co, Fe, Mo) single-atom alloys promote the deoxygenation of lignin-derived phenolics: mechanism, kinetics, and descriptors
journal, January 2021
- Liu, Ranran; An, Wei
- Catalysis Science & Technology, Vol. 11, Issue 21
Combining theory and experiment in electrocatalysis: Insights into materials design
journal, January 2017
- Seh, Zhi Wei; Kibsgaard, Jakob; Dickens, Colin F.
- Science, Vol. 355, Issue 6321
Unravelling the role of oxophilic metal in promoting the deoxygenation of catechol on Ni-based alloy catalysts
journal, January 2020
- Zhou, Jingwen; An, Wei
- Catalysis Science & Technology, Vol. 10, Issue 20
A Review of Electrocatalytic Reduction of Dinitrogen to Ammonia under Ambient Conditions
journal, May 2018
- Cui, Xiaoyang; Tang, Cheng; Zhang, Qiang
- Advanced Energy Materials, Vol. 8, Issue 22
High-Throughput Screening of Synergistic Transition Metal Dual-Atom Catalysts for Efficient Nitrogen Fixation
journal, February 2021
- Lv, Xingshuai; Wei, Wei; Huang, Baibiao
- Nano Letters, Vol. 21, Issue 4
First-principles computational electrochemistry: Achievements and challenges
journal, December 2012
- Calle-Vallejo, Federico; Koper, Marc T. M.
- Electrochimica Acta, Vol. 84
Bimetallic Pd-Based surface alloys promote electrochemical oxidation of formic acid: Mechanism, kinetics and descriptor
journal, March 2020
- Sui, Lijun; An, Wei; Feng, Yonghao
- Journal of Power Sources, Vol. 451
Unveiling the underlying mechanism of nitrogen fixation by a new class of electrocatalysts two-dimensional TM@g-C4N3 monosheets
journal, February 2022
- Wang, Xiaolin; Yang, Li-Ming
- Applied Surface Science, Vol. 576