Demonstration of no catalytical activity of Fe–N–C and Nb–N–C electrocatalysts toward nitrogen reduction using in–line quantification

Sveinbjörnsson, Arnar; Gunnarsdóttir, Anna Bergljót; Creel, Erin B.; Canales, Camila Pía; Zulevi, Barr; Lyu, Xiang; Jafta, Charl J.; Skúlason, Egill; Serov, Alexey; Flosadóttir, Helga Dögg

doi:10.1002/sus2.81

Title: Demonstration of no catalytical activity of Fe–N–C and Nb–N–C electrocatalysts toward nitrogen reduction using in–line quantification

Journal Article · 31 July 2022 · SusMat (Online)

DOI: https://doi.org/10.1002/sus2.81 · OSTI ID:1881123

Sveinbjörnsson, Arnar ^[1]; Gunnarsdóttir, Anna Bergljót ^[2]; Creel, Erin B. ^[3]; Canales, Camila Pía ^[2]; Zulevi, Barr ^[4]; Lyu, Xiang ^[3];

^[3]; Skúlason, Egill ^[5];

^[3]; Flosadóttir, Helga Dögg ^[5]

Atmonia, Reykjavik (Iceland)
University of Iceland, Reykjavík (Iceland)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Pajarito Powder, LLC, Albuquerque, NM (United States)
Atmonia, Reykjavik (Iceland); University of Iceland, Reykjavík (Iceland)

Ammonia (NH₃) production via the electrochemical nitrogen reduction reaction (NRR) is a promising method for sustainable generation of this important chemical. Efforts are ongoing in finding an efficient, stable, and selective catalyst that will enable the reaction. However, progress is hindered in the field due to lack of reproducibility, most likely a consequence of reports of false-positive results due to improper measurement control and methods. In this study, we explore the NRR activity of a promising class of single atom catalysts, transition metal-nitrogen-carbon (M-N-C) electrocatalysts. Using a state-of-the-art in-line ammonia quantification methodology, with detection limit as low as 1 ppb for ammonia, we show that single atom Nb and Fe embedded in a stable carbon and nitrogen framework do not electrochemically reduce N₂ to NH₃. Critically, this demonstrates that our experimental setup with in-line sequential injection analysis successfully excludes ammonia contamination from the gas supply and atmospheric sources, allowing for thorough and high-throughput examination of potential NRR catalysts.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Fuel Cell Technologies Office; Icelandic Research Fund; Icelandic Technology Development Fund; Companhia Brasileira de Metalurgia e Mineração (CBMM)

Grant/Contract Number:: AC05-00OR22725; EE0008419

OSTI ID:: 1881123

Journal Information:: SusMat (Online), Journal Name: SusMat (Online) Journal Issue: 4 Vol. 2; ISSN 2692-4552

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

References (48)

Heterogeneous Single‐Atom Catalysts for Electrochemical CO ₂ Reduction Reaction Li, Minhan; Wang, Haifeng; Luo, Wei Advanced Materials, Vol. 32, Issue 34 https://doi.org/10.1002/adma.202001848	journal	July 2020
A Review of Electrocatalytic Reduction of Dinitrogen to Ammonia under Ambient Conditions Cui, Xiaoyang; Tang, Cheng; Zhang, Qiang Advanced Energy Materials, Vol. 8, Issue 22 https://doi.org/10.1002/aenm.201800369	journal	May 2018
Preparation of Nafion Membranes for Reproducible Ammonia Quantification in Nitrogen Reduction Reaction Experiments Hanifpour, Fatemeh; Sveinbjörnsson, Arnar; Canales, Camila Pía Angewandte Chemie, Vol. 132, Issue 51 https://doi.org/10.1002/ange.202007998	journal	October 2020
A flow injection-fluorometric method for the determination of ammonium in fresh and saline waters with a view to in situ analyses Aminot, A. Water Research, Vol. 35, Issue 7 https://doi.org/10.1016/S0043-1354(00)00429-2	journal	May 2001
Fe-N/C catalysts for oxygen reduction reaction supported on different carbonaceous materials. Performance in acidic and alkaline direct alcohol fuel cells Osmieri, Luigi; Escudero-Cid, Ricardo; Armandi, Marco Applied Catalysis B: Environmental, Vol. 205 https://doi.org/10.1016/j.apcatb.2017.01.003	journal	May 2017
Nanostructured metal-N-C electrocatalysts for CO2 reduction and hydrogen evolution reactions Roy, Aaron; Hursán, Dorottya; Artyushkova, Kateryna Applied Catalysis B: Environmental, Vol. 232 https://doi.org/10.1016/j.apcatb.2018.03.093	journal	September 2018
Hierarchically nanostructured vanadium nitride microspheres assembled with porous nanosheets fabricated by a template-free route Liu, Hong-hui; Zhang, Hong-ling; Xu, Hong-bin Ceramics International, Vol. 44, Issue 2 https://doi.org/10.1016/j.ceramint.2017.10.078	journal	February 2018
Accelerated Dinitrogen Electroreduction to Ammonia via Interfacial Polarization Triggered by Single-Atom Protrusions Li, Jie; Chen, Shang; Quan, Fengjiao Chem, Vol. 6, Issue 4 https://doi.org/10.1016/j.chempr.2020.01.013	journal	April 2020
Corrosion behavior of carbon steel in the presence of sulfate reducing bacteria and iron oxidizing bacteria cultured in oilfield produced water Liu, Hongwei; Fu, Chaoyang; Gu, Tingyue Corrosion Science, Vol. 100 https://doi.org/10.1016/j.corsci.2015.08.023	journal	November 2015
Implementing PGM-free electrocatalysts in high-temperature polymer electrolyte membrane fuel cells Gokhale, Rohan; Asset, Tristan; Qian, Guoqing Electrochemistry Communications, Vol. 93 https://doi.org/10.1016/j.elecom.2018.06.019	journal	August 2018
Novel dual templating approach for preparation of highly active Fe-N-C electrocatalyst for oxygen reduction Gokhale, Rohan; Chen, Yechuan; Serov, Alexey Electrochimica Acta, Vol. 224 https://doi.org/10.1016/j.electacta.2016.12.052	journal	January 2017
A re-evaluation of Sn(II) phthalocyanine as a catalyst for the electrosynthesis of ammonia Shipman, Michael A.; Symes, Mark D. Electrochimica Acta, Vol. 258 https://doi.org/10.1016/j.electacta.2017.11.105	journal	December 2017
Investigation into the mechanism of electrochemical nitrogen reduction reaction to ammonia using niobium oxynitride thin-film catalysts Hanifpour, Fatemeh; Canales, Camila P.; Fridriksson, Emil G. Electrochimica Acta, Vol. 403 https://doi.org/10.1016/j.electacta.2021.139551	journal	January 2022
Ammonia and related chemicals as potential indirect hydrogen storage materials Lan, Rong; Irvine, John T. S.; Tao, Shanwen International Journal of Hydrogen Energy, Vol. 37, Issue 2 https://doi.org/10.1016/j.ijhydene.2011.10.004	journal	January 2012
Electrocatalytic Nitrogen Reduction at Low Temperature Deng, Jiao; Iñiguez, Jesus A.; Liu, Chong Joule, Vol. 2, Issue 5 https://doi.org/10.1016/j.joule.2018.04.014	journal	May 2018
An Electrochemical Haber-Bosch Process Kyriakou, Vasileios; Garagounis, Ioannis; Vourros, Anastasios Joule, Vol. 4, Issue 1 https://doi.org/10.1016/j.joule.2019.10.006	journal	January 2020
Commercial platinum group metal-free cathodic electrocatalysts for highly performed direct methanol fuel cell applications Lo Vecchio, C.; Serov, A.; Romero, H. Journal of Power Sources, Vol. 437 https://doi.org/10.1016/j.jpowsour.2019.226948	journal	October 2019
Mesoporous textured Fe-N-C electrocatalysts as highly efficient cathodes for proton exchange membrane fuel cells Akula, Srinu; Mooste, Marek; Zulevi, Barr Journal of Power Sources, Vol. 520 https://doi.org/10.1016/j.jpowsour.2021.230819	journal	February 2022
Heterogeneous electrocatalysts design for nitrogen reduction reaction under ambient conditions Wan, Yuchi; Xu, Jichu; Lv, Ruitao Materials Today, Vol. 27 https://doi.org/10.1016/j.mattod.2019.03.002	journal	July 2019
Nano-structured non-platinum catalysts for automotive fuel cell application Serov, Alexey; Artyushkova, Kateryna; Niangar, Ellazar Nano Energy, Vol. 16 https://doi.org/10.1016/j.nanoen.2015.07.002	journal	September 2015
ElectroCat: DOE's approach to PGM-free catalyst and electrode R&D Thompson, Simon T.; Wilson, Adria R.; Zelenay, Piotr Solid State Ionics, Vol. 319 https://doi.org/10.1016/j.ssi.2018.01.030	journal	June 2018
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
Electrochemical Ammonia Synthesis—The Selectivity Challenge Singh, Aayush R.; Rohr, Brian A.; Schwalbe, Jay A. ACS Catalysis, Vol. 7, Issue 1 https://doi.org/10.1021/acscatal.6b03035	journal	December 2016
Suppression of Hydrogen Evolution Reaction in Electrochemical N ₂ Reduction Using Single-Atom Catalysts: A Computational Guideline Choi, Changhyeok; Back, Seoin; Kim, Na-Young ACS Catalysis, Vol. 8, Issue 8 https://doi.org/10.1021/acscatal.8b00905	journal	July 2018
The Use of Controls for Consistent and Accurate Measurements of Electrocatalytic Ammonia Synthesis from Dinitrogen Greenlee, Lauren F.; Renner, Julie N.; Foster, Shelby L. ACS Catalysis, Vol. 8, Issue 9 https://doi.org/10.1021/acscatal.8b02120	journal	July 2018
Strategies toward Selective Electrochemical Ammonia Synthesis Singh, Aayush R.; Rohr, Brian A.; Statt, Michael J. ACS Catalysis, Vol. 9, Issue 9 https://doi.org/10.1021/acscatal.9b02245	journal	July 2019
Structure Sensitivity in Single-Atom Catalysis toward CO₂ Electroreduction Gao, Dunfeng; Liu, Tianfu; Wang, Guoxiong ACS Energy Letters, Vol. 6, Issue 2 https://doi.org/10.1021/acsenergylett.0c02665	journal	January 2021
Electrochemical Nitrogen Reduction: Identification and Elimination of Contamination in Electrolyte Li, Laiquan; Tang, Cheng; Yao, Dazhi ACS Energy Letters, Vol. 4, Issue 9 https://doi.org/10.1021/acsenergylett.9b01573	journal	August 2019
The Difficulty of Proving Electrochemical Ammonia Synthesis Kibsgaard, Jakob; Nørskov, Jens K.; Chorkendorff, Ib ACS Energy Letters, Vol. 4, Issue 12 https://doi.org/10.1021/acsenergylett.9b02286	journal	October 2019
Computational Screening Single-Atom Catalysts Supported on g-CN for N₂ Reduction: High Activity and Selectivity Niu, Huan; Wang, Xiting; Shao, Chen ACS Sustainable Chemistry & Engineering, Vol. 8, Issue 36 https://doi.org/10.1021/acssuschemeng.0c04401	journal	August 2020
Cascade surface modification of colloidal quantum dot inks enables efficient bulk homojunction photovoltaics Choi, Min-Jae; García de Arquer, F. Pelayo; Proppe, Andrew H. Nature Communications, Vol. 11, Issue 1 https://doi.org/10.1038/s41467-019-13437-2	journal	January 2020
High-performing commercial Fe–N–C cathode electrocatalyst for anion-exchange membrane fuel cells Adabi, Horie; Shakouri, Abolfazl; Ul Hassan, Noor Nature Energy, Vol. 6, Issue 8 https://doi.org/10.1038/s41560-021-00878-7	journal	August 2021
A rigorous electrochemical ammonia synthesis protocol with quantitative isotope measurements Andersen, Suzanne Z.; Čolić, Viktor; Yang, Sungeun Nature, Vol. 570, Issue 7762 https://doi.org/10.1038/s41586-019-1260-x	journal	May 2019
Non-aqueous gas diffusion electrodes for rapid ammonia synthesis from nitrogen and water-splitting-derived hydrogen Lazouski, Nikifar; Chung, Minju; Williams, Kindle Nature Catalysis, Vol. 3, Issue 5 https://doi.org/10.1038/s41929-020-0455-8	journal	May 2020
Methods for nitrogen activation by reduction and oxidation Iriawan, Haldrian; Andersen, Suzanne Z.; Zhang, Xilun Nature Reviews Methods Primers, Vol. 1, Issue 1 https://doi.org/10.1038/s43586-021-00053-y	journal	August 2021
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
Challenges in reduction of dinitrogen by proton and electron transfer van der Ham, Cornelis J. M.; Koper, Marc T. M.; Hetterscheid, Dennis G. H. Chem. Soc. Rev., Vol. 43, Issue 15 https://doi.org/10.1039/C4CS00085D	journal	January 2014
Electrochemical nitrogen reduction to ammonia at ambient conditions on nitrogen and phosphorus co-doped porous carbon Song, Pengfei; Wang, Hao; Kang, Li Chemical Communications, Vol. 55, Issue 5 https://doi.org/10.1039/C8CC09256G	journal	January 2019
Electrochemical CO ₂ reduction: from nanoclusters to single atom catalysts Lü, Fang; Bao, Haihong; Mi, Yuying Sustainable Energy & Fuels, Vol. 4, Issue 3 https://doi.org/10.1039/C9SE00776H	journal	January 2020
Determination of ammonia in low concentrations with Nessler's reagent by flow injection analysis Krug, F. J.; Růžička, J.; Hansen, E. H. The Analyst, Vol. 104, Issue 1234 https://doi.org/10.1039/an9790400047	journal	January 1979
The berthelot or indophenol reaction and its use in the analytical chemistry of nitrogen. A review Searle, Phillip L. The Analyst, Vol. 109, Issue 5 https://doi.org/10.1039/an9840900549	journal	January 1984
Flow-injection analysis with fluorescence detection for the determination of trace levels of ammonium in seawater Watson, Roslyn J.; Butler, Edward C. V.; Clementson, Lesley A. Journal of Environmental Monitoring, Vol. 7, Issue 1 https://doi.org/10.1039/b405924g	journal	January 2005
Reactions of orthophthalaldehyde with ammonia and 2-aminoethanol Kulla, Eliona; Zuman, Petr Organic & Biomolecular Chemistry, Vol. 6, Issue 20 https://doi.org/10.1039/b807714m	journal	January 2008
Electrochemical Nitrogen Reduction Reaction on Noble Metal Catalysts in Proton and Hydroxide Exchange Membrane Electrolyzers Nash, Jared; Yang, Xuan; Anibal, Jacob Journal of The Electrochemical Society, Vol. 164, Issue 14 https://doi.org/10.1149/2.0071802jes	journal	January 2017
Photocatalytic and electrocatalytic approaches towards atmospheric nitrogen reduction to ammonia under ambient conditions John, Jude; Lee, Dong-Kyu; Sim, Uk Nano Convergence, Vol. 6, Issue 1 https://doi.org/10.1186/s40580-019-0182-5	journal	April 2019
On the High Structural Heterogeneity of Fe-Impregnated Graphitic-Carbon Catalysts from Fe Nitrate Precursor Arrigo, Rosa; Schuster, Manfred Catalysts, Vol. 9, Issue 4 https://doi.org/10.3390/catal9040303	journal	March 2019
Boosting Electrochemical Nitrogen Reduction Performance over Binuclear Mo Atoms on N-Doped Nanoporous Graphene: A Theoretical Investigation Guo, Ruijie; Hu, Min; Zhang, Weiqing Molecules, Vol. 24, Issue 9 https://doi.org/10.3390/molecules24091777	journal	May 2019
Structure of Active Sites of Fe-N-C Nano-Catalysts for Alkaline Exchange Membrane Fuel Cells Kishi, Hirofumi; Sakamoto, Tomokazu; Asazawa, Koichiro Nanomaterials, Vol. 8, Issue 12 https://doi.org/10.3390/nano8120965	journal	November 2018

Similar Records

Metal-organic framework-derived nitrogen-doped highly disordered carbon for electrochemical ammonia synthesis using N₂ and H₂O in alkaline electrolytes

Journal Article · 2018 · Nano Energy · OSTI ID:1440813

Mukherjee, Shreya; Cullen, David A.; Karakalos, Stavros; +7 more

Atomically Dispersed Single Ni Site Catalysts for Nitrogen Reduction toward Electrochemical Ammonia Synthesis Using N₂ and H₂O

Journal Article · 2020 · Small Methods · OSTI ID:1712715

Mukherjee, Shreya; Yang, Xiaoxuan; Shan, Weitao; +8 more

Mesoporous textured Fe-N-C electrocatalysts as highly efficient cathodes for proton exchange membrane fuel cells

Journal Article · 2021 · Journal of Power Sources · OSTI ID:1833949

Akula, Srinu; Mooste, Marek; Zulevi, Barr; +14 more

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
NRR
ammonia synthesis
electrocatalysis
nitrogen electroreduction
single atom catalyst

Title: Demonstration of no catalytical activity of Fe–N–C and Nb–N–C electrocatalysts toward nitrogen reduction using in–line quantification

Citation Formats

References (48)

Similar Records

Related Subjects