Çeşitli metallerle dekore edilmiş alüminyum katkılı altıgen bor nitrür nano levhaların hidrojen depolama özelliklerinin hesaplamalı incelenmesi

Abstract

Bu çalışmada, hidrojen depolama uygulamaları açısından potansiyellerini değerlendirmek amacıyla altıgen (hekzagonal) bor nitrür (B19N18) nano levhaların alüminyum katkılı yapıları (Al-hBN); alkali (Li+, Na+, K+), toprak alkali (Mg2+, Ca2+) ve dördüncü periyot geçiş metali (Sc3+, Ti4+, V3+, Cr2+, Mn7+, Fe3+, Co3+, Ni2+, Cu+, Cu2+, Zn2+) katyonları ile tek atom dekorasyonu yoluyla modifiye edilmiştir. Yapısal kararlılık, adsorpsiyon enerjileri ve elektronik özellikleri incelemek için yoğunluk fonksiyoneli teorisi (DFT) hesaplamaları, Perdew–Burke–Ernzerhof (PBE) değiş-korelasyon fonksiyoneli ve def2-SVP baz seti kullanılarak gerçekleştirilmiştir. Termodinamik kararlılık analizleri, tüm dekorasyonlu sistemlerin negatif toplam elektronik ve termal entalpi değerleri sergileyerek termodinamik olarak kararlı yapıların oluştuğunu göstermektedir. Hidrojen adsorpsiyon özellikleri; adsorpsiyon enerjileri, bağ uzunlukları ve sınır moleküler orbital (FMO) analizi ile incelenen moleküler orbital özellikleri dikkate alınarak değerlendirilmiştir. Sc3+, Fe3+ ve Co3+ dekorasyonlu Al-hBN yüzeylerinde elde edilen adsorpsiyon enerjileri sırasıyla 0,42, 0,56 ve 0,58 eV/H2 olup, bu değerler hidrojenin oda sıcaklığında tersinir olarak adsorplanabilmesi için önerilen optimum aralık (~0,2 ila 0,6 eV/H2) içerisindedir. Buna karşın, Li+, Na+, K+, Ca2+ ve Zn2+ dekorasyonlu sistemlerde pozitif Gibbs adsorpsiyon serbest enerji değerleri, kısa adsorpsiyon mesafeleri ve geniş bant aralığı nedeniyle hidrojen adsorpsiyonunun zayıf veya termodinamik olarak elverişsiz olduğu belirlenmiştir. Bu bulgular, uygun metal dekorasyonu ile birleştirilen Al-hBN nano levhalarının, verimli, hafif ve geri dönüştürülebilir hidrojen depolama malzemeleri için umut verici adaylar olduğunu göstermektedir.

Keywords

• altıgen bor nitrür nano levhalar
• alüminyum katkılı dekorasyon
• hidrojen depolama
• DFT

Computational investigation of hydrogen storage properties of several metal decorated aluminum-doped hexagonal boron nitride nanosheets

Abstract

: In this study, aluminum-doped structures (Al-hBN) of hexagonal boron nitride (B19N18) nanosheets were modified via single-atom decoration with alkali (Li+, Na+, K+), alkaline earth (Mg2+, Ca2+), and fourth-period transition metal cations (Sc3+, Ti4+, V3+, Cr2+, Mn7+, Fe3+, Co3+, Ni2+, Cu+, Cu2+, Zn2+) in order to evaluate their potential for hydrogen storage applications. Density functional theory (DFT) calculations using the Perdew–Burke–Ernzerhof (PBE) exchange-correlation functional and def2-SVP basis set were performed to investigate structural stability, adsorption energies, and electronic properties. Thermodynamic stability analyses revealed that all decorated systems exhibit negative total electronic and thermal enthalpy values, confirming their thermodynamic feasibility. Hydrogen adsorption features were assessed considering adsorption energies, bond lengths, and molecular orbital properties examined via frontier molecular orbital (FMO) analysis. Adsorption energies obtained for Sc3+, Fe3+, and Co3+ decorated Al-hBN surfaces are 0,42, 0,56, and 0,58 eV/H₂, respectively, which fall within the suggested optimal range (~0,2 to 0,6 eV/H₂) for reversible hydrogen adsorption at room temperature. In contrast, Li+, Na+, K+, Ca2+ and Zn2+ decorated systems show weak or thermodynamically unfavorable hydrogen adsorption due to positive Gibbs adsorption free energy values, short adsorption distances, and wide energy gaps. Overall, this study suggests that Al-hBN nanosheets, when combined with appropriate transition metal decoration, can serve as promising candidates for lightweight, stable, and recyclable hydrogen storage materials.

Keywords

• hexagonal boron nitride nanosheets
• aluminum-doped decoration
• hydrogen storage
• DFT

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