Lanthanum-Doped Graphene for Electrocatalytic Reduction of Nitrogen Monoxide

Yan, Yu; Masood, Zaheer; Wang, Bin

doi:10.1021/acs.jpcc.3c01366

Lanthanum-Doped Graphene for Electrocatalytic Reduction of Nitrogen Monoxide

Journal Article · Wed Jun 28 00:00:00 EDT 2023 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.3c01366· OSTI ID:2007442

Yan, Yu ^[1]; Masood, Zaheer ^[2]; ^[2]

University of Oklahoma, Norman, OK (United States); University of Oklahoma
University of Oklahoma, Norman, OK (United States)

Electrocatalytic conversion of nitrogen oxides is a promising approach to address nitrogen pollution in underground water. Nitrogen oxides, such as nitrate and nitrite, can be reduced to N₂ and NH₃ over an electrocatalyst, with NO as the key intermediate, subsequent reaction of which controls the overall activity and selectivity. Here, we report density functional theory calculations of NO electrocatalytic reduction (NOER) over lanthanum embedded in graphene, through which we show that the localized states in La drive the reaction favorably due to more pronounced molecular adsorption and charge transfer than transition metals such as Co. The free energy profiles are compared between the La-based single-atom catalyst (SAC) and Co-based SAC, for producing N₂ and NH₃. We find that the La-SAC intensifies the electron transfer to the adsorbed NO, promoting the first protonation step of NO, which is the potential-limiting step on the Co-SAC. Also, an intriguing effect of the water solvent is revealed on the La-SAC. In addition to stabilizing the intermediate species, water molecules that are coordinated with La participate directly in the protonation steps, enhancing the catalyst activity. Furthermore, this study reveals the unique mechanism of NOER over rare-earth-based catalysts, highlighting the potential application of atomically dispersed f-block elements for electrocatalytic reactions.

View Accepted Manuscript (DOE)

Research Organization:: University of Oklahoma, Norman, OK (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0018284

OSTI ID:: 2007442

Alternate ID(s):: OSTI ID: 2299536

Journal Information:: Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 27 Vol. 127; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (53)

Theoretical Insights into the Mechanism of Selective Nitrate‐to‐Ammonia Electroreduction on Single‐Atom Catalysts Niu, Huan; Zhang, Zhaofu; Wang, Xiting Advanced Functional Materials, Vol. 31, Issue 11 https://doi.org/10.1002/adfm.202008533	journal	December 2020
Direct Synthesis of Ammonia from Nitrate on Amorphous Graphene with Near 100% Efficiency Huang, Libei; Cheng, Le; Ma, Tinghao Advanced Materials, Vol. 35, Issue 24 https://doi.org/10.1002/adma.202211856	journal	April 2023
Lanthanum-Based Compounds: Electronic Band-Gap-Dependent Electrocatalytic Materials for Oxygen Reduction Reaction Gu, Weiwei; Song, Ye; Liu, Jingjun Chemistry - A European Journal, Vol. 23, Issue 42 https://doi.org/10.1002/chem.201701136	journal	July 2017
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set Kresse, G.; Furthmüller, J. Computational Materials Science, Vol. 6, Issue 1, p. 15-50 https://doi.org/10.1016/0927-0256(96)00008-0	journal	July 1996
Improving the catalytic nitrate reduction Prüsse, Ulf; Hähnlein, Marc; Daum, Jörg Catalysis Today, Vol. 55, Issue 1-2 https://doi.org/10.1016/S0920-5861(99)00228-X	journal	January 2000
Catalytic nitrate removal from water, past, present and future perspectives Barrabés, Noelia; Sá, Jacinto Applied Catalysis B: Environmental, Vol. 104, Issue 1-2 https://doi.org/10.1016/j.apcatb.2011.03.011	journal	April 2011
State-of-the-art and perspectives of the catalytic and electrocatalytic reduction of aqueous nitrates Martínez, Juan; Ortiz, Alfredo; Ortiz, Inmaculada Applied Catalysis B: Environmental, Vol. 207 https://doi.org/10.1016/j.apcatb.2017.02.016	journal	June 2017
Electrocatalytic reduction of nitrate: Fundamentals to full-scale water treatment applications Garcia-Segura, Sergi; Lanzarini-Lopes, Mariana; Hristovski, Kiril Applied Catalysis B: Environmental, Vol. 236 https://doi.org/10.1016/j.apcatb.2018.05.041	journal	November 2018
Recent advances in rare-earth-based materials for electrocatalysis Wang, Xuan; Tang, Yawen; Lee, Jong-Min Chem Catalysis, Vol. 2, Issue 5 https://doi.org/10.1016/j.checat.2022.02.007	journal	May 2022
Electrolysis of water on (oxidized) metal surfaces Rossmeisl, J.; Logadottir, A.; Nørskov, J. K. Chemical Physics, Vol. 319, Issue 1-3, p. 178-184 https://doi.org/10.1016/j.chemphys.2005.05.038	journal	December 2005
VASPKIT: A user-friendly interface facilitating high-throughput computing and analysis using VASP code Wang, Vei; Xu, Nan; Liu, Jin-Cheng Computer Physics Communications, Vol. 267 https://doi.org/10.1016/j.cpc.2021.108033	journal	October 2021
Adsorbed species on Pd catalyst during nitrite hydrogenation approaching complete conversion Zhao, Yingnan; Koteswara Rao, Nidadavolu; Lefferts, Leon Journal of Catalysis, Vol. 337 https://doi.org/10.1016/j.jcat.2016.02.007	journal	May 2016
Mechanism of nitrite hydrogenation over Pd/γ-Al2O3 according a rigorous kinetic study Xu, Pengyu; Agarwal, Shilpa; Lefferts, Leon Journal of Catalysis, Vol. 383 https://doi.org/10.1016/j.jcat.2020.01.003	journal	March 2020
Proton shuttling flattens the energy landscape of nitrite catalytic reduction Huang, Pengcheng; Yan, Yu; Banerjee, Aayan Journal of Catalysis, Vol. 413 https://doi.org/10.1016/j.jcat.2022.06.007	journal	September 2022
Use of rare earth elements in single-atom site catalysis: A critical review — Commemorating the 100th anniversary of the birth of Academician Guangxian Xu Zhang, Ningqiang; Yan, Han; Li, Lingcong Journal of Rare Earths, Vol. 39, Issue 3 https://doi.org/10.1016/j.jre.2020.11.013	journal	March 2021
Insight into rare earth yttrium and nitrogen co-decorated graphene as a promising material for NO detection Xiong, Huihui; Xie, Jianxin; Dong, Jianhong Physics Letters A, Vol. 384, Issue 35 https://doi.org/10.1016/j.physleta.2020.126910	journal	December 2020
Solvent effects on catalytic reactions and related phenomena at liquid-solid interfaces Li, Gengnan; Wang, Bin; Resasco, Daniel E. Surface Science Reports, Vol. 76, Issue 4 https://doi.org/10.1016/j.surfrep.2021.100541	journal	November 2021
Catalytic Converters for Water Treatment Heck, Kimberly N.; Garcia-Segura, Sergi; Westerhoff, Paul Accounts of Chemical Research, Vol. 52, Issue 4 https://doi.org/10.1021/acs.accounts.8b00642	journal	February 2019
Single-Atom Catalysts across the Periodic Table Kaiser, Selina K.; Chen, Zupeng; Faust Akl, Dario Chemical Reviews, Vol. 120, Issue 21 https://doi.org/10.1021/acs.chemrev.0c00576	journal	October 2020
Rare-Earth Doping in Nanostructured Inorganic Materials Zheng, Bingzhu; Fan, Jingyue; Chen, Bing Chemical Reviews, Vol. 122, Issue 6 https://doi.org/10.1021/acs.chemrev.1c00644	journal	January 2022
A Quantitative Scale of Oxophilicity and Thiophilicity Kepp, Kasper P. Inorganic Chemistry, Vol. 55, Issue 18 https://doi.org/10.1021/acs.inorgchem.6b01702	journal	August 2016
Cu@g-C ₃ N ₄ : An Efficient Single-Atom Electrocatalyst for NO Electrochemical Reduction with Suppressed Hydrogen Evolution Wu, Qian; Wei, Wei; Lv, Xingshuai The Journal of Physical Chemistry C, Vol. 123, Issue 51 https://doi.org/10.1021/acs.jpcc.9b08827	journal	December 2019
Single Atomic Cerium Sites with a High Coordination Number for Efficient Oxygen Reduction in Proton-Exchange Membrane Fuel Cells Zhu, Mengzhao; Zhao, Chao; Liu, Xiaokang ACS Catalysis, Vol. 11, Issue 7 https://doi.org/10.1021/acscatal.0c05503	journal	March 2021
Structure- and Coverage-Sensitive Mechanism of NO Reduction on Platinum Electrodes Katsounaros, Ioannis; Figueiredo, Marta C.; Chen, Xiaoting ACS Catalysis, Vol. 7, Issue 7 https://doi.org/10.1021/acscatal.7b01069	journal	June 2017
How Nitrogen-Doped Graphene Quantum Dots Catalyze Electroreduction of CO ₂ to Hydrocarbons and Oxygenates Zou, Xiaolong; Liu, Mingjie; Wu, Jingjie ACS Catalysis, Vol. 7, Issue 9 https://doi.org/10.1021/acscatal.7b01839	journal	August 2017
Activity and Selectivity Trends in Electrocatalytic Nitrate Reduction on Transition Metals Liu, Jin-Xun; Richards, Danielle; Singh, Nirala ACS Catalysis, Vol. 9, Issue 8 https://doi.org/10.1021/acscatal.9b02179	journal	June 2019
Water-Mediated Heterogeneously Catalyzed Reactions Li, Gengnan; Wang, Bin; Resasco, Daniel E. ACS Catalysis, Vol. 10, Issue 2 https://doi.org/10.1021/acscatal.9b04637	journal	December 2019
Electroreduction of Nitrates, Nitrites, and Gaseous Nitrogen Oxides: A Potential Source of Ammonia in Dinitrogen Reduction Studies Choi, Jaecheol; Du, Hoang-Long; Nguyen, Cuong Ky ACS Energy Letters, Vol. 5, Issue 6 https://doi.org/10.1021/acsenergylett.0c00924	journal	May 2020
Rare-Earth Single-Atom La–N Charge-Transfer Bridge on Carbon Nitride for Highly Efficient and Selective Photocatalytic CO ₂ Reduction Chen, Peng; Lei, Ben; Dong, Xing’an ACS Nano, Vol. 14, Issue 11 https://doi.org/10.1021/acsnano.0c07083	journal	November 2020
Rare Earth Single-Atom Catalysts for Nitrogen and Carbon Dioxide Reduction Liu, Jieyuan; Kong, Xue; Zheng, Lirong ACS Nano, Vol. 14, Issue 1 https://doi.org/10.1021/acsnano.9b08835	journal	January 2020
Correction to Enthalpies and Entropies of Adsorption on Well-Defined Oxide Surfaces: Experimental Results Campbell, Charles T.; Sellers, Jason R. V. Chemical Reviews, Vol. 113, Issue 8 https://doi.org/10.1021/cr4003853	journal	August 2013
Nitrogen Cycle Electrocatalysis Rosca, Victor; Duca, Matteo; de Groot, Matheus T. Chemical Reviews, Vol. 109, Issue 6 https://doi.org/10.1021/cr8003696	journal	June 2009
Nitrate in Groundwater of the United States, 1991−2003 Burow, Karen R.; Nolan, Bernard T.; Rupert, Michael G. Environmental Science & Technology, Vol. 44, Issue 13 https://doi.org/10.1021/es100546y	journal	July 2010
Origin of the Overpotential for Oxygen Reduction at a Fuel-Cell Cathode Nørskov, J. K.; Rossmeisl, J.; Logadottir, A. The Journal of Physical Chemistry B, Vol. 108, Issue 46 https://doi.org/10.1021/jp047349j	journal	November 2004
Mechanism of Electrocatalytic Reduction of Nitric Oxide on Pt(100) Rosca, Victor; Koper, Marc T. M. The Journal of Physical Chemistry B, Vol. 109, Issue 35 https://doi.org/10.1021/jp052961b	journal	August 2005
Single-atom catalysts reveal the dinuclear characteristic of active sites in NO selective reduction with NH3 Qu, Weiye; Liu, Xiaona; Chen, Junxiao Nature Communications, Vol. 11, Issue 1 https://doi.org/10.1038/s41467-020-15261-5	journal	March 2020
Electrochemical ammonia synthesis via nitrate reduction on Fe single atom catalyst Wu, Zhen-Yu; Karamad, Mohammadreza; Yong, Xue Nature Communications, Vol. 12, Issue 1 https://doi.org/10.1038/s41467-021-23115-x	journal	May 2021
Understanding potential-dependent competition between electrocatalytic dinitrogen and proton reduction reactions Choi, Changhyeok; Gu, Geun Ho; Noh, Juhwan Nature Communications, Vol. 12, Issue 1 https://doi.org/10.1038/s41467-021-24539-1	journal	July 2021
Distributed processes for biomass conversion could aid UN Sustainable Development Goals Resasco, Daniel E.; Wang, Bin; Sabatini, David Nature Catalysis, Vol. 1, Issue 10 https://doi.org/10.1038/s41929-018-0166-6	journal	October 2018
A theoretical evaluation of possible transition metal electro-catalysts for N ₂ reduction Skúlason, Egill; Bligaard, Thomas; Gudmundsdóttir, Sigrídur Phys. Chem. Chem. Phys., Vol. 14, Issue 3 https://doi.org/10.1039/C1CP22271F	journal	January 2012
A Co–N ₄ moiety embedded into graphene as an efficient single-atom-catalyst for NO electrochemical reduction: a computational study Wang, Zhongxu; Zhao, Jingxiang; Wang, Jingyang Journal of Materials Chemistry A, Vol. 6, Issue 17 https://doi.org/10.1039/C8TA00875B	journal	January 2018
Powering denitrification: the perspectives of electrocatalytic nitrate reduction Duca, Matteo; Koper, Marc T. M. Energy & Environmental Science, Vol. 5, Issue 12 https://doi.org/10.1039/c2ee23062c	journal	January 2012
A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu Grimme, Stefan; Antony, Jens; Ehrlich, Stephan The Journal of Chemical Physics, Vol. 132, Issue 15 https://doi.org/10.1063/1.3382344	journal	April 2010
Implicit solvation model for density-functional study of nanocrystal surfaces and reaction pathways Mathew, Kiran; Sundararaman, Ravishankar; Letchworth-Weaver, Kendra The Journal of Chemical Physics, Vol. 140, Issue 8 https://doi.org/10.1063/1.4865107	journal	February 2014
Implicit self-consistent electrolyte model in plane-wave density-functional theory Mathew, Kiran; Kolluru, V. S. Chaitanya; Mula, Srinidhi The Journal of Chemical Physics, Vol. 151, Issue 23 https://doi.org/10.1063/1.5132354	journal	December 2019
In situ formation of cocatalytic sites boosts single-atom catalysts for nitrogen oxide reduction Wang, Pengfei; Liu, Guoquan; Hao, Zhifei Proceedings of the National Academy of Sciences, Vol. 120, Issue 8 https://doi.org/10.1073/pnas.2216584120	journal	February 2023
A grid-based Bader analysis algorithm without lattice bias Tang, W.; Sanville, E.; Henkelman, G. Journal of Physics: Condensed Matter, Vol. 21, Issue 8 https://doi.org/10.1088/0953-8984/21/8/084204	journal	January 2009
Ab initio molecular-dynamics simulation of the liquid-metal–amorphous-semiconductor transition in germanium Kresse, G.; Hafner, J. Physical Review B, Vol. 49, Issue 20, p. 14251-14269 https://doi.org/10.1103/PhysRevB.49.14251	journal	May 1994
Projector augmented-wave method Blöchl, P. E. Physical Review B, Vol. 50, Issue 24, p. 17953-17979 https://doi.org/10.1103/PhysRevB.50.17953	journal	December 1994
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set Kresse, G.; Furthmüller, J. Physical Review B, Vol. 54, Issue 16, p. 11169-11186 https://doi.org/10.1103/PhysRevB.54.11169	journal	October 1996
From ultrasoft pseudopotentials to the projector augmented-wave method Kresse, G.; Joubert, D. Physical Review B, Vol. 59, Issue 3, p. 1758-1775 https://doi.org/10.1103/PhysRevB.59.1758	journal	January 1999
Generalized Gradient Approximation Made Simple Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868 https://doi.org/10.1103/PhysRevLett.77.3865	journal	October 1996
VESTA 3 for three-dimensional visualization of crystal, volumetric and morphology data Momma, Koichi; Izumi, Fujio Journal of Applied Crystallography, Vol. 44, Issue 6 https://doi.org/10.1107/S0021889811038970	journal	October 2011

Similar Records

Electrocatalytic Ammonia Oxidation by Pyridyl-Substituted Ferrocenes

Journal Article · Thu Feb 13 19:00:00 EST 2025 · Journal of the American Chemical Society · OSTI ID:2516777

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Adsorption
Free energy
Metals
Molecules
Reaction mechanisms

Lanthanum-Doped Graphene for Electrocatalytic Reduction of Nitrogen Monoxide

Citation Formats

References (53)

Similar Records

Related Subjects