yyufbed Yüzüncü Yıl Üniversitesi Fen Bilimleri Enstitüsü Dergisi 1300-5413 2667-467X Van Yüzüncü Yıl Üniversitesi 10.53433/yyufbed.1781393 Chemical Reaction Kimyasal Reaksiyon Ni–Co–V Alaşım Yapılarının NaBH₄’ün Teorik Hidrolizindeki Elektronik ve Katalitik Etkilerinin DFT ile İncelenmesi DFT Investigation of the Electronic and Catalytic Effects of Ni–Co–V Alloy Structures on the Theoretical Hydrolysis of NaBH₄ https://orcid.org/0000-0003-2550-550X Akkuş Meryem Sena ANKARA YILDIRIM BEYAZIT ÜNİVERSİTESİ 04 29 2026 31 84 94 09 10 2025 02 26 2026 Copyright © 1995, Yüzüncü Yıl Üniversitesi Fen Bilimleri Enstitüsü Dergisi 1995 Yüzüncü Yıl Üniversitesi Fen Bilimleri Enstitüsü Dergisi

Bu çalışma, hidrojen üretimi için sodyum borhidrürün (NaBH₄) hidrolizine yönelik Ni–V, Co–V ve Ni–Co–V alaşım kümelerinin (Ni₇V₂, Co₈V₂, Ni₆Co₄V₃ ve Ni₄Co₄V₄) yoğunluk fonksiyonel teorisi (DFT) ile incelenmesini sunmaktadır. Katalitik davranış, saf kümeler ve bunların NaBH₄ + H₂O adsorbe edilmiş reaksiyon kompleksleri karşılaştırılarak analiz edilmiştir. Yapısal optimizasyonlar, özellikle Ni açısından zengin yüzeylerde, adsorpsiyon üzerine belirgin B–H bağ uzaması ve metal-metal bağ esnekliğini ortaya koymaktadır. Elektronik yapı analizleri, NaBH₄ adsorpsiyonunu takiben HOMO–LUMO enerji aralığında sistematik bir azalma olduğunu ve yüzey reaktivitesinin arttığını doğrulamaktadır. Löwdin popülasyon analizleri, hidrit karakterinin kaybı ve hidrojen atomlarının etkili aktivasyonu eşliğinde, borhidritten metal iskelete önemli bir yük transferi olduğunu göstermektedir. Termodinamik hesaplamalar, tüm reaksiyon komplekslerinin sulu ortamda oldukça kararlı olduğunu, güçlü negatif entalpi ve Gibbs serbest enerji değerlerine sahip olduğunu ve bunun da kendiliğinden ve ekzotermik kompleks oluşumunu gösterdiğini ortaya koymaktadır. Genel olarak, Ni açısından zengin ve sinerjik Ni–Co–V kümeleri, üstün elektronik uyarlanabilirlik ve yapısal kararlılık sergileyerek, verimli NaBH₄ hidrolizi için umut vadeden adaylar haline gelmektedir.

This study presents a density functional theory (DFT) investigation of Ni–V, Co–V, and Ni–Co–V alloy clusters (Ni₇V₂, Co₈V₂, Ni₆Co₄V₃, and Ni₄Co₄V₄) toward sodium borohydride (NaBH₄) hydrolysis for hydrogen generation. The catalytic behavior was analyzed by comparing bare clusters and their NaBH₄ + H₂O adsorbed reaction complexes. Structural optimizations reveal pronounced B–H bond elongation and metal–metal bond flexibility upon adsorption, particularly on Ni-rich surfaces. Electronic structure analyses indicate a systematic reduction in the HOMO–LUMO energy gap following NaBH₄ adsorption, confirming enhanced surface reactivity. Löwdin population analyses show significant charge transfer from borohydride to the metal framework, accompanied by a loss of hydride character and effective activation of hydrogen atoms. Thermodynamic calculations demonstrate that all reaction complexes are highly stable in aqueous media, with strongly negative enthalpy and Gibbs free energy values, indicating spontaneous and exergonic complex formation. Overall, Ni-rich and synergistic Ni–Co–V clusters exhibit superior electronic adaptability and structural stability, making them promising candidates for efficient NaBH₄ hydrolysis.

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