Applying electrochemical nitrate reduction reaction (NO3RR) to produce ammonia offers a sustainable alternative to the energy-intensive Haber-Bosch process, which is crucial for clean energy and agricultural applications. While 2D MXenes hold great promise as electrocatalysts for NO3RR, their application for ammonia production remains underexplored. This study combines experimental and theoretical approaches to evaluate the catalytic performance of a series of MXenes with different central metal atoms for NO3RR. Among the materials studied (Ti3C2Tx, Ti3CNTx, Ti2CTx, V2CTx, Cr2CTx, Nb2CTx, and Ta2CTx), Ti3-based MXenes exhibit superior faradaic efficiency, ammonia yield rate, and stability. Density functional theory calculations offer further insights explaining the structure-activity-based observations. This research establishes a foundation for future studies aimed at leveraging MXenes for electrochemical nitrate reduction for green synthesis of ammonia.

Czech Advanced Technology and Research Institute Regional Centre of Advanced Technologies and Materials Palacký University Olomouc Šlechtitelů 27 Olomouc 77900 Czech Republic

Department of Chemical and Biomolecular Engineering Yonsei University 50 Yonsei ro Seodaemun gu Seoul 03722 South Korea

Department of Medical Research China Medical University Hospital China Medical University No 91 Hsueh Shih Road Taichung 40402 Taiwan

Energy Research Research Techno Plaza 10 Frontier Block Level 5 50 Nanyang Drive Singapore 637553 Singapore

Future Energy and Innovation Laboratory Central European Institute of Technology Brno University of Technology Purkyňova 123 Brno 61200 Czech Republic

IT4Innovations VSB Technical University of Ostrava 17 listopadu 2172 15 Ostrava Poruba 70800 Czech Republic

Quantum Materials Laboratory 3D Printing and Innovation Hub Center for Nanorobotics and Machine Intelligence Department of Chemical and Biochemistry Mendel University Zemědělská 1 Brno 61300 Czech Republic

Zobrazit více v PubMed

Duca M., Koper M. T. M., Energy Environ. Sci. 2012, 5, 9726.

van Langevelde P. H., Katsounaros I., Koper M. T. M., Joule 2021, 5, 290.

Li L., Tang C., Yao D., Zheng Y., Qiao S. Z., ACS Energy Lett. 2019, 4, 2111.

Jiao F., Xu B., Adv. Mater. 2019, 31, 1805173. PubMed

Lan R., Irvine J. T. S., Tao S., Int. J. Hydrogen Energy 2012, 27, 1482.

Klerke A., Christensen C. H., Nørskov J. K., Vegge T., J. Mater. Chem. 2008, 18, 2304.

Chen J. G., Crooks R. M., Seefeldt L. C., Bren K. L., Morris Bullock R., Darensbourg M. Y., Holland P. L., Hoffman B., Janik M. J., Jones A. K., Kanatzidis M. G., King P., Lancaster K. M., Lymar S. V., Pfromm P., Schneider W. F., Schrock R. R., Science 2018, 360, eaar6611. PubMed PMC

Abascal E., Gómez‐Coma L., Ortiz I., Ortiz A., Sci. Total Environ. 2022, 810, 152233. PubMed

Bhatnagar A., Sillanpää M., Chem. Eng. J. 2011, 168, 493.

Gogotsi Y., Anasori B., ACS Nano 2019, 13, 8491. PubMed

Naguib M., Mashtalir O., Carle J., Presser V., Lu J., Hultman L., Gogotsi Y., Barsoum M. W., ACS Nano 2012, 6, 1322. PubMed

Naguib M., Kurtoglu M., Presser V., Lu J., Niu J., Heon M., Hultman L., Gogotsi Y., Barsoum M. W., Adv. Mater. 2011, 23, 4248. PubMed

Mohammadi A. V., Rosen J., Gogotsi Y., Science 2021, 372, eabf1581. PubMed

Pang Y., Li J., Lv K., Tang D., Li Q., New J. Chem. 2024, 48, 12477.

Hu T., Wang M., Guo C., Li C. M., J. Mater. Chem. A Mater. 2022, 10, 8923.

Zhao F., Li G., Hua Q., Cao J., Song J., Gao L., Ma T., Ren X., Liu A., Catal. Sci. Technol. 2023, 13, 5543.

Liu L., Zheng S. J., Chen H., Cai J., Zang S. Q., Angew. Chem., Int. Ed. 2024, 63, 202316910. PubMed

Zhao Z., Chen Y., Liu Y., Zhao Y., Zhang Z., Zhang K., Mo Z., Wang C., Gao S., Appl. Surf. Sci. 2023, 614, 156077.

Li L. X., Sun W. J., Zhang H. Y., Wei J. L., Wang S. X., He J. H., Li N. J., Xu Q. F., Chen D. Y., Li H., Lu J. M., J. Mater. Chem. A Mater. 2021, 9, 21771.

Tripathy D. B., R. Soc. Chem. 2024, 8, 3801.

Johnson L. R., Sridhar S., Zhang L., Fredrickson K. D., Raman A. S., Jang J., Leach C., Padmanabhan A., Price C. C., Frey N. C., Raizada A., Rajaraman V., Saiprasad S. A., Tang X., Vojvodic A., ACS Catal. 2020, 10, 253.

Li Z., Wang L., Sun D., Zhang Y., Liu B., Hu Q., Zhou A., Mater. Sci. Eng., B 2015, 191, 33.

Vijayaprabhakaran A., Kathiresan M., Mater. Adv. 2023, 4, 3593.

Liu Y., Jiang Y., Hu Z., Peng J., Lai W., Wu D., Zuo S., Zhang J., Chen B., Dai Z., Yang Y., Huang Y., Zhang W., Zhao W., Zhang W., Wang L., Chou S., Adv. Funct. Mater. 2021, 31, 2008033.

Halim J., Cook K. M., Naguib M., Eklund P., Gogotsi Y., Rosen J., Barsoum M. W., Appl. Surf. Sci. 2016, 362, 406.

Parker T., Zhang D., Bugallo D., Shevchuk K., Downes M., Valurouthu G., Inman A., Chacon B., Zhang T., Shuck C. E., Hu Y.‐J., Gogotsi Y., Chem. Mater. 2024, 36, 8437. PubMed PMC

Chen K., Yan K., Xie Q., Zhu H., Li X., Dong Z., Yuan G., Zhang J., Cong Y., Res. Chem. Intermed. 2022, 48, 4443.

Yang Z., Yang Q., Tian Y., Ren X., Li C., Zu Y., Zaheer Ud Din S., Gao L., Wu J., Chen H., Zhang H., Liu J., He J., Al‐Sehemi A. G., J. Materiomics 2023, 9, 44.

Liu F., Zhou A., Chen J., Zhang H., Cao J., Wang L., Hu Q., Adsorption 2016, 22, 915.

Zhou W., Yu B., Zhu J., Li K., J. Mater. Sci. 2022, 57, 3954.

Jin S., Hu Q., Zhou A., arXiv:2104.12930 2021.

Deng Q., Zhao X., Zhu Q., Bo M., Feng Y., J Electroceram. 2021, 46, 124.

Liu R. J., Yang L. X., Wang Y., Bu H. P., Liu H. J., Zeng C. L., J. Solid State Electrochem. 2022, 26, 831.

Akinola O., Chakraborty I., Celio H., Akinwande D., Incorvia J. A. C., J. Mater. Res. 2021, 36, 1980.

Ma S., Ye J., Liu A., Liu Y., Wang J., Pang J., J. Am. Ceram. Soc. 2016, 99, 1943.

Schmuecker S. M., Clouser D., Kraus T. J., Leonard B. M., Dalton Trans. 2017, 46, 13524. PubMed

Loubière S., Laurent C., Bonino J.‐P., Rousset A., Mater. Res. Bull. 1998, 33, 935.

Arif N., Gul S., Sohail M., Rizwan S., Iqbal M., Ceram. Int. 2021, 47, 2388.

Tiu Z. C., Tan S. J., Yusoff N., Ahmad H., Sci. Rep. 2022, 12, 6766. PubMed PMC

Liu F., Zhou A., Chen J., Jia J., Zhou W., Wang L., Hu Q., Appl. Surf. Sci. 2017, 416, 781.

Sanna M., Novčić K. A., Ng S., Černý M., Pumera M., J. Mater. Chem. A Mater. 2023, 11, 3080.

Wu Z. Y., Karamad M., Yong X., Huang Q., Cullen D. A., Zhu P., Xia C., Xiao Q., Shakouri M., Chen F. Y., Kim J. Y. (Timothy), Xia Y., Heck K., Hu Y., Wong M. S., Li Q., Gates I., Siahrostami S., Wang H., Nat. Commun. 2021, 12, 2870. PubMed PMC

Gao W., Perales‐Rondon J. V., Michalička J., Pumera M., Appl. Catal. B 2023, 330, 122632.

Kresse G., Furthmüller J., Phys. Rev. B. 1996, 54, 11169. PubMed

Kresse G., Furthmüller J., Comput. Mater. Sci. 1996, 6, 15.

Kresse G., Joubert D., Phys. Rev. B. 1999, 59, 1758.

Blochl P. E., Phys. Rev. B. 1994, 50, 17953. PubMed

Perdew J. P., Burke K., Ernzerhof M., Phys. Rev. Lett. 1996, 77, 3865. PubMed

Grimme S., Antony J., Ehrlich S., Krieg H., J. Chem. Phys. 2010, 132, 154104. PubMed

Mathew K., Sundararaman R., Letchworth‐Weaver K., Arias T. A., Hennig R. G., J. Chem. Phys. 2014, 140, 084106. PubMed

Mathew K., Sundararaman R., Letchworth‐Weaver K., Arias T. A., Hennig R. G., J. Chem. Phys. 2014, 140, 08410. PubMed

Nørskov J. K., Rossmeisl J., Logadottir A., Lindqvist L., Kitchin J. R., Bligaard T., Jónsson H., J. Phys. Chem. B 2004, 108, 17886. PubMed

Wang V., Xu N., Liu J. C., Tang G., Geng W. T., Comput. Phys. Commun. 2021, 267, 108033.

Liu J. X., Richards D., Singh N., Goldsmith B. R., ACS Catal. 2019, 9, 7052.

Gao X., Tse E. C. M., Small 2024, 20, 2306311. PubMed

Li L., Wang X., Guo H., Yao G., Yu H., Tian Z., Li B., Chen L., Small Methods 2019, 3, 1900337.