Ni-based alloy catalysts for cost-effective hydrogen production from ammonia decomposition

Due to its high hydrogen storage capacity and established infrastructure, ammonia (NH3) decomposition has been extensively investigated as a clean hydrogen production process. However, hydrogen production via ammonia decomposition faces various challenges. Although ruthenium (Ru) catalysts exhibit t...

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Main Authors: Yeongjun Yoon, Yunseo Choi, Yonggyun Bae, Jongsup Hong, Kyeounghak Kim
Format: Article
Language:English
Published: Elsevier 2025-06-01
Series:Applied Surface Science Advances
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Online Access:http://www.sciencedirect.com/science/article/pii/S2666523925000674
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author Yeongjun Yoon
Yunseo Choi
Yonggyun Bae
Jongsup Hong
Kyeounghak Kim
author_facet Yeongjun Yoon
Yunseo Choi
Yonggyun Bae
Jongsup Hong
Kyeounghak Kim
author_sort Yeongjun Yoon
collection DOAJ
description Due to its high hydrogen storage capacity and established infrastructure, ammonia (NH3) decomposition has been extensively investigated as a clean hydrogen production process. However, hydrogen production via ammonia decomposition faces various challenges. Although ruthenium (Ru) catalysts exhibit the highest activity for ammonia decomposition, their scarcity and high cost hinder commercial application. Consequently, nickel (Ni) catalysts have emerged as a potential alternative, owing to their cost-effectiveness and high activity. To further optimize Ni catalysts, developing Ni-based alloy catalysts with other metals is a promising solution. Herein, density functional theory (DFT) calculations are performed to elucidate the catalytic activity of 3d transition metals (Ni, Co, Cu, and Fe) and their promising alloys. The key reaction steps of overall ammonia decomposition are NHx‒H bond scission (NHx*→NHx-1*+H*) and N + N recombination (N*+N*→N2*). In particular, nitrogen adsorption energy (Ead(N)) serves as a descriptor for predicting the activation energies of key elementary steps, revealing a volcano-like relationship between experimental catalytic activity and DFT-calculated Ead(N). Additionally, we discover a strong correlation between d-band filling (fd) and Ead(N), establishing fd as an effective descriptor that not only predicts Ead(N) but also the catalytic activity of NH3 decomposition. Our descriptor-based design principle identifies Ni0.64Fe0.36 as a potentially effective and cost-efficient candidate for hydrogen production from ammonia, with experimental data demonstrating its superior performance compared to pure Ni. These findings offer valuable insights into the development of efficient, economically viable transition metal-based catalysts for hydrogen production through ammonia decomposition.
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spelling doaj-art-74f809cb33014ec1af1864bffe2812592025-08-20T02:30:56ZengElsevierApplied Surface Science Advances2666-52392025-06-012710075910.1016/j.apsadv.2025.100759Ni-based alloy catalysts for cost-effective hydrogen production from ammonia decompositionYeongjun Yoon0Yunseo Choi1Yonggyun Bae2Jongsup Hong3Kyeounghak Kim4Department of Chemical Engineering and Clean-Energy Research Institute, Hanyang University, 222 Wangsimni-ro, Seongdong-gu, Seoul 04763, South KoreaSchool of Mechanical Engineering, Yonsei University, 50 Yonsei-ro, Seodaemun-gu, Seoul 03722, South KoreaSchool of Mechanical Engineering, Yonsei University, 50 Yonsei-ro, Seodaemun-gu, Seoul 03722, South Korea; Department of Zero-carbon Fuel & Power Generation, Korea Institute of Machinery & Materials, Daejeon, Republic of KoreaSchool of Mechanical Engineering, Yonsei University, 50 Yonsei-ro, Seodaemun-gu, Seoul 03722, South Korea; Corresponding authors.Department of Chemical Engineering and Clean-Energy Research Institute, Hanyang University, 222 Wangsimni-ro, Seongdong-gu, Seoul 04763, South Korea; Corresponding authors.Due to its high hydrogen storage capacity and established infrastructure, ammonia (NH3) decomposition has been extensively investigated as a clean hydrogen production process. However, hydrogen production via ammonia decomposition faces various challenges. Although ruthenium (Ru) catalysts exhibit the highest activity for ammonia decomposition, their scarcity and high cost hinder commercial application. Consequently, nickel (Ni) catalysts have emerged as a potential alternative, owing to their cost-effectiveness and high activity. To further optimize Ni catalysts, developing Ni-based alloy catalysts with other metals is a promising solution. Herein, density functional theory (DFT) calculations are performed to elucidate the catalytic activity of 3d transition metals (Ni, Co, Cu, and Fe) and their promising alloys. The key reaction steps of overall ammonia decomposition are NHx‒H bond scission (NHx*→NHx-1*+H*) and N + N recombination (N*+N*→N2*). In particular, nitrogen adsorption energy (Ead(N)) serves as a descriptor for predicting the activation energies of key elementary steps, revealing a volcano-like relationship between experimental catalytic activity and DFT-calculated Ead(N). Additionally, we discover a strong correlation between d-band filling (fd) and Ead(N), establishing fd as an effective descriptor that not only predicts Ead(N) but also the catalytic activity of NH3 decomposition. Our descriptor-based design principle identifies Ni0.64Fe0.36 as a potentially effective and cost-efficient candidate for hydrogen production from ammonia, with experimental data demonstrating its superior performance compared to pure Ni. These findings offer valuable insights into the development of efficient, economically viable transition metal-based catalysts for hydrogen production through ammonia decomposition.http://www.sciencedirect.com/science/article/pii/S2666523925000674NH3 decompositionH2 productionBimetallic alloy catalystDFTCost efficientCatalytic descriptor
spellingShingle Yeongjun Yoon
Yunseo Choi
Yonggyun Bae
Jongsup Hong
Kyeounghak Kim
Ni-based alloy catalysts for cost-effective hydrogen production from ammonia decomposition
Applied Surface Science Advances
NH3 decomposition
H2 production
Bimetallic alloy catalyst
DFT
Cost efficient
Catalytic descriptor
title Ni-based alloy catalysts for cost-effective hydrogen production from ammonia decomposition
title_full Ni-based alloy catalysts for cost-effective hydrogen production from ammonia decomposition
title_fullStr Ni-based alloy catalysts for cost-effective hydrogen production from ammonia decomposition
title_full_unstemmed Ni-based alloy catalysts for cost-effective hydrogen production from ammonia decomposition
title_short Ni-based alloy catalysts for cost-effective hydrogen production from ammonia decomposition
title_sort ni based alloy catalysts for cost effective hydrogen production from ammonia decomposition
topic NH3 decomposition
H2 production
Bimetallic alloy catalyst
DFT
Cost efficient
Catalytic descriptor
url http://www.sciencedirect.com/science/article/pii/S2666523925000674
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