Calcium-mediated nitrogen reduction for electrochemical ammonia synthesis

Fu, Xianbiao; Niemann, Valerie A.; Zhou, Yuanyuan; Li, Shaofeng; Zhang, Ke; Pedersen, Jakob B.; Saccoccio, Mattia; Andersen, Suzanne Z.; Enemark-Rasmussen, Kasper; Benedek, Peter; Xu, Aoni; Deissler, Niklas H.; Mygind, Jon Bjarke Valbæk; Nielander, Adam C.; Kibsgaard, Jakob; Vesborg, Peter C. K.; Nørskov, Jens K.; Jaramillo, Thomas F.; Chorkendorff, Ib

doi:10.1038/s41563-023-01702-1

Calcium-mediated nitrogen reduction for electrochemical ammonia synthesis

Journal Article · Thu Oct 26 00:00:00 EDT 2023 · Nature Materials

DOI:https://doi.org/10.1038/s41563-023-01702-1· OSTI ID:2310365

^[1]; Niemann, Valerie A. ^[2]; ^[3]; Li, Shaofeng ^[3]; Zhang, Ke ^[3]; ^[3]; Saccoccio, Mattia ^[3]; Andersen, Suzanne Z. ^[3]; Enemark-Rasmussen, Kasper ^[3]; ^[2]; ^[3]; ^[3]; ^[3]; Nielander, Adam C. ^[4]; Kibsgaard, Jakob ^[3]; ^[3]; ^[3]; ^[2]; ^[3]

Technical University of Denmark, Lyngby (Denmark); SLAC
Stanford University, CA (United States); SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States). SUNCAT Center for Interface Science and Catalysis
Technical University of Denmark, Lyngby (Denmark)
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States). SUNCAT Center for Interface Science and Catalysis

Ammonia (NH₃) is a key commodity chemical for the agricultural, textile and pharmaceutical industries, but its production via the Haber–Bosch process is carbon-intensive and centralized. Alternatively, an electrochemical method could enable decentralized, ambient NH₃ production that can be paired with renewable energy. The first verified electrochemical method for NH₃ synthesis was a process mediated by lithium (Li) in organic electrolytes. So far, however, elements other than Li remain unexplored in this process for potential benefits in efficiency, reaction rates, device design, abundance and stability. In our demonstration of a Li-free system, we found that calcium can mediate the reduction of nitrogen for NH₃ synthesis. Here we verified the calcium-mediated process using a rigorous protocol and achieved an NH₃ Faradaic efficiency of 40 ± 2% using calcium tetrakis(hexafluoroisopropyloxy)borate (Ca[B(hfip)₄]₂) as the electrolyte. Our results offer the possibility of using abundant materials for the electrochemical production of NH₃, a critical chemical precursor and promising energy vector

View Accepted Manuscript (DOE)

Research Organization:: SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

Sponsoring Organization:: Camille and Henry Dreyfus Foundation; European Research Council (ERC); National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB); Villum Fonden

Grant/Contract Number:: AC02-76SF00515

OSTI ID:: 2310365

Journal Information:: Nature Materials, Journal Name: Nature Materials Journal Issue: 1 Vol. 23; ISSN 1476-1122

Publisher:: Springer NatureCopyright Statement

Country of Publication:: United States

Language:: English

References (49)

Stable and High‐Power Calcium‐Ion Batteries Enabled by Calcium Intercalation into Graphite Park, Jooha; Xu, Zheng‐Long; Yoon, Gabin Advanced Materials, Vol. 32, Issue 4 https://doi.org/10.1002/adma.201904411	journal	November 2019
Graphite as a Long‐Life Ca ²⁺ ‐Intercalation Anode and its Implementation for Rocking‐Chair Type Calcium‐Ion Batteries Richard Prabakar, S. J.; Ikhe, Amol Bhairuba; Park, Woon Bae Advanced Science, Vol. 6, Issue 24 https://doi.org/10.1002/advs.201902129	journal	October 2019
Optimizing Calcium Electrolytes by Solvent Manipulation for Calcium Batteries Nielson, Kevin V.; Luo, Jian; Liu, T. Leo Batteries & Supercaps, Vol. 3, Issue 8 https://doi.org/10.1002/batt.202000005	journal	April 2020
Electrochemical Performance and Mechanism of Calcium Metal‐Organic Battery Bitenc, Jan; Scafuri, Antonio; Pirnat, Klemen Batteries & Supercaps, Vol. 4, Issue 1 https://doi.org/10.1002/batt.202000197	journal	October 2020
Elektrolytische Bindung von komprimiertem Stickstoff bei gewöhnlicher Temperatur Fichter, Fr.; Girard, Pierre; Erlenmeyer, Hans Helvetica Chimica Acta, Vol. 13, Issue 6 https://doi.org/10.1002/hlca.19300130604	journal	December 1930
X-ray photoelectron spectroscopy of boron compounds Il’inchik, E. A.; Volkov, V. V.; Mazalov, L. N. Journal of Structural Chemistry, Vol. 46, Issue 3 https://doi.org/10.1007/s10947-006-0133-y	journal	May 2005
Oxygen vacancy engineering of calcium cobaltate: A nitrogen fixation electrocatalyst at ambient condition in neutral electrolyte Chen, Xinyu; Li, Ke; Yang, Xiaoxuan Nano Research, Vol. 14, Issue 2 https://doi.org/10.1007/s12274-020-3043-y	journal	September 2020
Lithium-mediated electrochemical reduction of high pressure N2 to NH3 Tsuneto, Akira; Kudo, Akihiko; Sakata, Tadayoshi Journal of Electroanalytical Chemistry, Vol. 367, Issue 1-2 https://doi.org/10.1016/0022-0728(93)03025-K	journal	March 1994
XPS spectra of Ca, Sr, Ba and their oxides Van Doveren, H.; Verhoeven, J. A. T. H. Journal of Electron Spectroscopy and Related Phenomena, Vol. 21, Issue 3 https://doi.org/10.1016/0368-2048(80)85055-9	journal	January 1980
Recent advances and challenges of electrochemical ammonia synthesis Fu, Xianbiao; Zhang, Jiahao; Kang, Yijin Chem Catalysis, Vol. 2, Issue 10 https://doi.org/10.1016/j.checat.2022.09.001	journal	October 2022
Lithium-mediated electrochemical nitrogen reduction: Mechanistic insights to enhance performance Cai, Xiyang; Fu, Cehuang; Iriawan, Haldrian iScience, Vol. 24, Issue 10 https://doi.org/10.1016/j.isci.2021.103105	journal	October 2021
Defect-meditated efficient catalytic activity toward p-nitrophenol reduction: A case study of nitrogen doped calcium niobate system Su, Yiguo; Huang, Shushu; Wang, Tingting Journal of Hazardous Materials, Vol. 295 https://doi.org/10.1016/j.jhazmat.2015.04.036	journal	September 2015
Understanding Continuous Lithium-Mediated Electrochemical Nitrogen Reduction Lazouski, Nikifar; Schiffer, Zachary J.; Williams, Kindle Joule, Vol. 3, Issue 4 https://doi.org/10.1016/j.joule.2019.02.003	journal	April 2019
Electrosynthesis of ammonia with high selectivity and high rates via engineering of the solid-electrolyte interphase Li, Shaofeng; Zhou, Yuanyuan; Li, Katja Joule, Vol. 6, Issue 9 https://doi.org/10.1016/j.joule.2022.07.009	journal	September 2022
Toggling Calcium Plating Activity and Reversibility through Modulation of Ca ²⁺ Speciation in Borohydride-Based Electrolytes Melemed, Aaron M.; Skiba, Dhyllan A.; Gallant, Betar M. The Journal of Physical Chemistry C, Vol. 126, Issue 2 https://doi.org/10.1021/acs.jpcc.1c09400	journal	January 2022
Plating and Stripping Calcium at Room Temperature in an Ionic-Liquid Electrolyte Biria, Saeid; Pathreeker, Shreyas; Genier, Francielli S. ACS Applied Energy Materials, Vol. 3, Issue 3 https://doi.org/10.1021/acsaem.9b02529	journal	February 2020
Understanding Ca Electrodeposition and Speciation Processes in Nonaqueous Electrolytes for Next-Generation Ca-Ion Batteries Ta, Kim; Zhang, Ruixian; Shin, Minjeong ACS Applied Materials & Interfaces, Vol. 11, Issue 24 https://doi.org/10.1021/acsami.9b04926	journal	May 2019
Increasing Current Density of Li-Mediated Ammonia Synthesis with High Surface Area Copper Electrodes Li, Katja; Shapel, Sarah G.; Hochfilzer, Degenhart ACS Energy Letters, Vol. 7, Issue 1 https://doi.org/10.1021/acsenergylett.1c02104	journal	November 2021
A Versatile Li_0.5FePO₄ Reference Electrode for Nonaqueous Electrochemical Conversion Technologies McShane, Eric J.; Benedek, Peter; Niemann, Valerie A. ACS Energy Letters, Vol. 8, Issue 1 https://doi.org/10.1021/acsenergylett.2c02190	journal	November 2022
Reversible Calcium Plating and Stripping at Room Temperature Using a Borate Salt Shyamsunder, Abhinandan; Blanc, Lauren E.; Assoud, Abdeljalil ACS Energy Letters, Vol. 4, Issue 9 https://doi.org/10.1021/acsenergylett.9b01550	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
How a century of ammonia synthesis changed the world Erisman, Jan Willem; Sutton, Mark A.; Galloway, James Nature Geoscience, Vol. 1, Issue 10 https://doi.org/10.1038/ngeo325	journal	September 2008
Towards a calcium-based rechargeable battery Ponrouch, A.; Frontera, C.; Bardé, F. Nature Materials, Vol. 15, Issue 2 https://doi.org/10.1038/nmat4462	journal	October 2015
Plating and stripping calcium in an organic electrolyte Wang, Da; Gao, Xiangwen; Chen, Yuhui Nature Materials, Vol. 17, Issue 1 https://doi.org/10.1038/nmat5036	journal	November 2017
Production of ammonia via a chemical looping process based on metal imides as nitrogen carriers Gao, Wenbo; Guo, Jianping; Wang, Peikun Nature Energy, Vol. 3, Issue 12 https://doi.org/10.1038/s41560-018-0268-z	journal	October 2018
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
Electroreduction of nitrogen with almost 100% current-to-ammonia efficiency Du, Hoang-Long; Chatti, Manjunath; Hodgetts, Rebecca Y. Nature, Vol. 609, Issue 7928 https://doi.org/10.1038/s41586-022-05108-y	journal	July 2022
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
Ammonia synthesis from N ₂ and H ₂ O using a lithium cycling electrification strategy at atmospheric pressure McEnaney, Joshua M.; Singh, Aayush R.; Schwalbe, Jay A. Energy & Environmental Science, Vol. 10, Issue 7 https://doi.org/10.1039/C7EE01126A	journal	January 2017
Towards stable and efficient electrolytes for room-temperature rechargeable calcium batteries Li, Zhenyou; Fuhr, Olaf; Fichtner, Maximilian Energy & Environmental Science, Vol. 12, Issue 12 https://doi.org/10.1039/C9EE01699F	journal	January 2019
Increasing stability, efficiency, and fundamental understanding of lithium-mediated electrochemical nitrogen reduction Andersen, Suzanne Z.; Statt, Michael J.; Bukas, Vanessa J. Energy & Environmental Science, Vol. 13, Issue 11 https://doi.org/10.1039/D0EE02246B	journal	January 2020
On the utilisation of the atmospheric nitrogen in the production of calcium cyanamide, and its use in agriculture and chemistry Frank, Albert R. Transactions of the Faraday Society, Vol. 4, Issue October https://doi.org/10.1039/tf9080400099	journal	January 1908
A climbing image nudged elastic band method for finding saddle points and minimum energy paths Henkelman, Graeme; Uberuaga, Blas P.; Jónsson, Hannes The Journal of Chemical Physics, Vol. 113, Issue 22, p. 9901-9904 https://doi.org/10.1063/1.1329672	journal	December 2000
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
Self-Consistent Equations Including Exchange and Correlation Effects Kohn, W.; Sham, L. J. Physical Review, Vol. 140, Issue 4A, p. A1133-A1138 https://doi.org/10.1103/PhysRev.140.A1133	journal	November 1965
Special points for Brillouin-zone integrations Monkhorst, Hendrik J.; Pack, James D. Physical Review B, Vol. 13, Issue 12, p. 5188-5192 https://doi.org/10.1103/PhysRevB.13.5188	journal	June 1976
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
Improved adsorption energetics within density-functional theory using revised Perdew-Burke-Ernzerhof functionals Hammer, B.; Hansen, L. B.; Nørskov, J. K. Physical Review B, Vol. 59, Issue 11 https://doi.org/10.1103/PhysRevB.59.7413	journal	March 1999
An object-oriented scripting interface to a legacy electronic structure code Bahn, S. R.; Jacobsen, K. W. Computing in Science & Engineering, Vol. 4, Issue 3 https://doi.org/10.1109/5992.998641	journal	January 2002
Beyond fossil fuel–driven nitrogen transformations Chen, Jingguang G.; Crooks, Richard M.; Seefeldt, Lance C. Science, Vol. 360, Issue 6391 https://doi.org/10.1126/science.aar6611	journal	May 2018
Dinitrogen complexation and reduction at low-valent calcium Rösch, B.; Gentner, T. X.; Langer, J. Science, Vol. 371, Issue 6534 https://doi.org/10.1126/science.abf2374	journal	March 2021
Nitrogen reduction to ammonia at high efficiency and rates based on a phosphonium proton shuttle Suryanto, Bryan H. R.; Matuszek, Karolina; Choi, Jaecheol Science, Vol. 372, Issue 6547 https://doi.org/10.1126/science.abg2371	journal	June 2021
Enhancement of lithium-mediated ammonia synthesis by addition of oxygen Li, Katja; Andersen, Suzanne Z.; Statt, Michael J. Science, Vol. 374, Issue 6575 https://doi.org/10.1126/science.abl4300	journal	December 2021
Continuous-flow electrosynthesis of ammonia by nitrogen reduction and hydrogen oxidation Fu, Xianbiao; Pedersen, Jakob B.; Zhou, Yuanyuan Science, Vol. 379, Issue 6633 https://doi.org/10.1126/science.adf4403	journal	February 2023
Efficient Electrochemical Reduction of N ₂ to NH ₃ Catalyzed by Lithium Tsuneto, Akira; Kudo, Akihiko; Sakata, Tadayoshi Chemistry Letters, Vol. 22, Issue 5 https://doi.org/10.1246/cl.1993.851	journal	May 1993