N2 reduction to NH3 on surfaces of Co-Al18P18, Ni-Al21N21, Fe-B24N24, Mn-B27P27, Ti-C60 and Cu-Si72 catalysts

Chou-Yi Hsu; Mohammed Ahmed Mustafa; Anupam Yadav; Khalid Mujasam Batoo; Mandeep Kaur; Sajjad Hussain; Salim B Alsaadi; Ahmed Read Al-Tameemi; Zahraa F Hassan; Eftikhaar Hasan Kadhum; Laith H Alzubaidi; Liguan Nai

doi:10.1007/s00894-024-05862-y

N₂ reduction to NH₃ on surfaces of Co-Al₁₈P₁₈, Ni-Al₂₁N₂₁, Fe-B₂₄N₂₄, Mn-B₂₇P₂₇, Ti-C₆₀ and Cu-Si₇₂ catalysts

J Mol Model. 2024 Feb 7;30(3):62. doi: 10.1007/s00894-024-05862-y.

Authors

Chou-Yi Hsu¹, Mohammed Ahmed Mustafa², Anupam Yadav³, Khalid Mujasam Batoo⁴, Mandeep Kaur^{5

6}, Sajjad Hussain^{7

8}, Salim B Alsaadi⁹, Ahmed Read Al-Tameemi¹⁰, Zahraa F Hassan¹¹, Eftikhaar Hasan Kadhum¹², Laith H Alzubaidi^{13

14

15}, Liguan Nai¹⁶

Affiliations

¹ Department of Pharmacy, Chia Nan University of Pharmacy and Science, Tainan City, 71710, Taiwan.
² Department of Medical Laboratory Technology, University of Imam Jaafar AL-Sadiq, Al-Muthanna, Iraq.
³ Department of Computer engineering and Application, GLA University Mathura-281406, Mathura, India.
⁴ King Abdullah Institute For Nanotechnology, King Saud University, P.O. Box-2455, Riyadh-11451, Saudi Arabia. Khalid.mujasam@gmail.com.
⁵ Department of Chemistry, School of Sciences, Jain (Deemed-to-be) University, Bengaluru, Karnataka, 560069, India.
⁶ Department of Sciences, Vivekananda Global University, Jaipur, Rajasthan-303012, India.
⁷ Hybrid Materials Center (HMC), Sejong University, Seoul-05006, Republic of Korea.
⁸ Department of Nanotechnology and Advanced Materials Engineering, Sejong University, Seoul-05006, Republic of Korea.
⁹ Department of pharmacy, Al-Hadi University College, Baghdad, 10011, Iraq.
¹⁰ Department of pharmacy, AL-Nisour University College, Baghdad, Iraq.
¹¹ College of Dentistry, Al-Ayen University, Thi-Qar, Iraq.
¹² College of pharmacy, National University of Science and Technology, Dhi Qar, Iraq.
¹³ College of technical engineering, the Islamic University, Najaf, Iraq.
¹⁴ College of technical engineering, the Islamic University of Al Diwaniyah, Al Diwaniyah, Iraq.
¹⁵ College of technical engineering, the Islamic University of Babylon, Babylon, Iraq.
¹⁶ Science Department, ChiFeng University, ChiFeng, China. LijuanMa1203@chmail.ir.

PMID: 38321301
DOI: 10.1007/s00894-024-05862-y

Abstract

Context: The abilities of Co-Al₁₈P₁₈, Ni-Al₂₁N₂₁, Fe-B₂₄N₂₄, Mn-B₂₇P₂₇, Ti-C₆₀ and Cu-Si₇₂ as catalysts for N₂-RR to create the NH₃ are investigated by theoretical levels. The ∆E_adoption and ∆E_formation of Co-Al₁₈P₁₈, Ni-Al₂₁N₂₁, Fe-B₂₄N₂₄, Mn-B₂₇P₂₇, Ti-C₆₀ and Cu-Si₇₂ are investigated. The ∆E_adsorption of N₂-RR intermediates and ΔG_reaction of reaction steps of N₂-RR on Co-Al₁₈P₁₈, Ni-Al₂₁N₂₁, Fe-B₂₄N₂₄, Mn-B₂₇P₂₇, Ti-C₆₀ and Cu-Si₇₂ are examined. In acceptable mechanisms, the *NN → *NNH step is potential limiting step and *NN → *NNH step in enzymatic mechanism is endothermic reaction. The ∆G_reaction of *NHNH2 → *NH₂NH₂ step on Co-Al₁₈P₁₈, Ni-Al₂₁N₂₁, Fe-B₂₄N₂₄, Mn-B₂₇P₂₇, Ti-C₆₀ and Cu-Si₇₂ are -0.904, -0.928, -0.860, -0.882, -0.817 and -0.838 eV, respectively. The Co-Al₁₈P₁₈ and Ni-Al₂₁N₂₁ have the highest ∆G_reaction values for reaction steps of N₂-RR. Finally, it can be concluded that the Co-Al₁₈P₁₈, Ni-Al₂₁N₂₁, Fe-B₂₄N₂₄ and Mn-B₂₇P₂ have acceptable potential for N₂-RR by acceptable pathways.

Methods: The structures of Co-Al₁₈P₁₈, Ni-Al₂₁N₂₁, Fe-B₂₄N₂₄, Mn-B₂₇P₂₇, Ti-C₆₀ and Cu-Si₇₂ and N₂-RR intermediates are optimized by PW91PW91/6-311+G (2d, 2p) and M06-2X/cc-pVQZ as theoretical levels in GAMESS software. The convergence for force set displacement of Co-Al₁₈P₁₈, Ni-Al₂₁N₂₁, Fe-B₂₄N₂₄, Mn-B₂₇P₂₇, Ti-C₆₀ and Cu-Si₇₂ and N₂-RR intermediates are 1.5 × 10⁵ Hartree/Bohr and 6.0 × 10^-5 Angstrom. The Opt = Tight and MaxStep = 30 are considered to optimize Co-Al₁₈P₁₈, Ni-Al₂₁N₂₁, Fe-B₂₄N₂₄, Mn-B₂₇P₂₇, Ti-C₆₀ and Cu-Si₇₂ and N₂-RR intermediates. The frequencies of Co-Al₁₈P₁₈, Ni-Al₂₁N₂₁, Fe-B₂₄N₂₄, Mn-B₂₇P₂₇, Ti-C₆₀ and Cu-Si₇₂ and N₂-RR intermediates are calculated.

Keywords: Catalyst; Mechanism; Metal adoption; N2 reduction reaction; NH3; Theoretical chemistry.