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noble-metal-free nitride catalyst
Every year, billions of people depend on fertilizers for the ongoing production of food, and reducing the carbon footprint and expenses in fertilizer production would reshape the impact agriculture has on emissions. The Haber-Bosch process for fertilizer production converts nitrogen and hydrogen to ammonia. To reduce energy requirements, researchers from Tokyo Tech have developed a <anchor>noble-metal-free nitride catalyst</anchor> containing a catalytically active transition metal (Ni) on a lanthanum nitride support that is stable in the presence of moisture. Since the catalyst doesn't contain ruthenium, it presents an inexpensive option for reducing the carbon footprint of ammonia production. The La-Al-N support, along with the active metals, such as nickel and cobalt (Ni, Co), produced NH3 at rates similar to conventional metal nitride catalysts. Learn more about sustainable fertilizer production in our latest article.
Approach to Chemically Durable Nickel and Cobalt Lanthanum‐Nitride‐Based Catalysts for Ammonia Synthesis - Lu - 2022 - Angewandte Chemie International Edition - Wiley Online Library
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Research Article

# Approach to Chemically Durable Nickel and Cobalt Lanthanum-Nitride-Based Catalysts for Ammonia Synthesis

Corresponding Author

Prof. Yangfan Lu

College of Materials Science and Engineering, National Engineering Research Center for Magnesium Alloys, Chongqing University, Chongqing, 400044 China

These authors contributed equally to this work.

Prof. Tian-Nan Ye

Frontiers Science Center for Transformative Molecules, School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, Shanghai, 200240 China

These authors contributed equally to this work.

Dr. Jiang Li

Materials Research Center for Element Strategy, Tokyo Institute of Technology, 4259 Nagatsuta, Midori-ku, Yokohama, 226-8503 Japan

These authors contributed equally to this work.

Zichuang Li

Frontiers Science Center for Transformative Molecules, School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, Shanghai, 200240 China

Haotian Guan

College of Materials Science and Engineering, National Engineering Research Center for Magnesium Alloys, Chongqing University, Chongqing, 400044 China

Dr. Masato Sasase

Materials Research Center for Element Strategy, Tokyo Institute of Technology, 4259 Nagatsuta, Midori-ku, Yokohama, 226-8503 Japan

Dr. Yasuhiro Niwa

Institute of Materials Structure Science, High Energy Accelerator Research Organization, Tsukuba, Ibaraki, 305-0801 Japan

Department of Materials Structure Science, School of High Energy Accelerator Science, SOKENDAI, The Graduate University for Advanced Studies, Tsukuba, Ibaraki, 305-0801 Japan

Prof. Hitoshi Abe

Institute of Materials Structure Science, High Energy Accelerator Research Organization, Tsukuba, Ibaraki, 305-0801 Japan

Department of Materials Structure Science, School of High Energy Accelerator Science, SOKENDAI, The Graduate University for Advanced Studies, Tsukuba, Ibaraki, 305-0801 Japan

Graduate School of Science and Engineering, Ibaraki University, Mito, Ibaraki, 310-8512 Japan

Prof. Qian Li

College of Materials Science and Engineering, National Engineering Research Center for Magnesium Alloys, Chongqing University, Chongqing, 400044 China

State Key Laboratory of Advanced Special Steel, Shanghai Key Laboratory of Advanced Ferro-metallurgy, School of Materials Science and Engineering, Shanghai University, Shanghai, 200444 China

Prof. Fushen Pan

College of Materials Science and Engineering, National Engineering Research Center for Magnesium Alloys, Chongqing University, Chongqing, 400044 China

Corresponding Author

Prof. Masaaki Kitano

Materials Research Center for Element Strategy, Tokyo Institute of Technology, 4259 Nagatsuta, Midori-ku, Yokohama, 226-8503 Japan

Corresponding Author

Prof. Hideo Hosono

Materials Research Center for Element Strategy, Tokyo Institute of Technology, 4259 Nagatsuta, Midori-ku, Yokohama, 226-8503 Japan

Corresponding Author

Prof. Yangfan Lu

College of Materials Science and Engineering, National Engineering Research Center for Magnesium Alloys, Chongqing University, Chongqing, 400044 China

These authors contributed equally to this work.

Prof. Tian-Nan Ye

Frontiers Science Center for Transformative Molecules, School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, Shanghai, 200240 China

These authors contributed equally to this work.

Dr. Jiang Li

Materials Research Center for Element Strategy, Tokyo Institute of Technology, 4259 Nagatsuta, Midori-ku, Yokohama, 226-8503 Japan

These authors contributed equally to this work.

Zichuang Li

Frontiers Science Center for Transformative Molecules, School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, Shanghai, 200240 China

Haotian Guan

College of Materials Science and Engineering, National Engineering Research Center for Magnesium Alloys, Chongqing University, Chongqing, 400044 China

Dr. Masato Sasase

Materials Research Center for Element Strategy, Tokyo Institute of Technology, 4259 Nagatsuta, Midori-ku, Yokohama, 226-8503 Japan

Dr. Yasuhiro Niwa

Institute of Materials Structure Science, High Energy Accelerator Research Organization, Tsukuba, Ibaraki, 305-0801 Japan

Department of Materials Structure Science, School of High Energy Accelerator Science, SOKENDAI, The Graduate University for Advanced Studies, Tsukuba, Ibaraki, 305-0801 Japan

Prof. Hitoshi Abe

Institute of Materials Structure Science, High Energy Accelerator Research Organization, Tsukuba, Ibaraki, 305-0801 Japan

Department of Materials Structure Science, School of High Energy Accelerator Science, SOKENDAI, The Graduate University for Advanced Studies, Tsukuba, Ibaraki, 305-0801 Japan

Graduate School of Science and Engineering, Ibaraki University, Mito, Ibaraki, 310-8512 Japan

Prof. Qian Li

College of Materials Science and Engineering, National Engineering Research Center for Magnesium Alloys, Chongqing University, Chongqing, 400044 China

State Key Laboratory of Advanced Special Steel, Shanghai Key Laboratory of Advanced Ferro-metallurgy, School of Materials Science and Engineering, Shanghai University, Shanghai, 200444 China

Prof. Fushen Pan

College of Materials Science and Engineering, National Engineering Research Center for Magnesium Alloys, Chongqing University, Chongqing, 400044 China

Corresponding Author

Prof. Masaaki Kitano

Materials Research Center for Element Strategy, Tokyo Institute of Technology, 4259 Nagatsuta, Midori-ku, Yokohama, 226-8503 Japan

Corresponding Author

Prof. Hideo Hosono

Materials Research Center for Element Strategy, Tokyo Institute of Technology, 4259 Nagatsuta, Midori-ku, Yokohama, 226-8503 Japan

First published: 26 September 2022

Citations: 9

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### Graphical Abstract

While the rare-earth nitride complexes enable highly efficient ammonia synthesis, they suffer from chemical sensitivity to air and moisture. Using Al-doped LaN as the model material, we show the impact of La−Al metallic bond formation on improving the catalysts’ durability under air and moisture without affecting original functionalities.

### Abstract

Metal nitride complexes have recently been proposed as an efficient noble-metal-free catalyst for ammonia synthesis utilizing a dual active site concept. However, their high sensitivity to air and moisture has restricted potential applications. We report that their chemical sensitivity can be improved by introducing Al into the LaN lattice, thereby forming La−Al metallic bonds (La−Al−N). The catalytic activity and mechanism of the resulting TM/La−Al−N ( TM =Ni, Co) are comparable to the previously reported TM/LaN catalyst. Notably, the catalytic activity did not degrade after exposure to air and moisture. Kinetic analysis and isotopic experiment showed that La−Al−N is responsible for N2 absorption and activation despite substantial Al being introduced into its lattice because the local coordination of the lattice N remained largely unchanged. These findings show the effectiveness of metallic bond formation, which can support the chemical stability of rare-earth nitrides with retention of catalytic functionality.

## Conflict of interest

The authors declare no conflict of interest.

## Open Research

# Data Availability Statement

The data that support the findings of this study are available from the corresponding author upon reasonable request.

## Supporting Information

As a service to our authors and readers, this journal provides supporting information supplied by the authors. Such materials are peer reviewed and may be re-organized for online delivery, but are not copy-edited or typeset. Technical support issues arising from supporting information (other than missing files) should be addressed to the authors.

Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.

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