Mechanistic Investigation of NH3 Decomposition Reaction on Iridium-Doped Graphene Surface: Density Functional Theory Approach

Abstract

Ammonia (NH3) decomposition reaction is of great importance owing to its potential use in COx-emission-free H2 production. Although many different catalysts are used in the NH3 decomposition reaction, metal-embedded graphene systems can be synthesized experimentally and are much cheaper than single-atom crystal surfaces due to the use of only a few metal atoms. In this study, NH3 decomposition reaction on Iridium (Ir) doped graphene surface was investigated using density functional theory (DFT). Grime D2 correction was used for Van der Waals interactions that can be induced by interactions between adsorbed structures and the surface. Metal-embedded graphene systems can be synthesized experimentally and are much cheaper than single-atom crystal surfaces due to the use of only a few metal atoms. First of all, bader charge analysis was performed on the Ir doped graphene surface and the obtained charge density regions were shown with electron density difference. The adsorption of NHx (x = 0 → 3) species on the ir doped graphene surface and their fragmented NHx + yH (x + y = 3) double bonding nature were investigated. Finally, the reaction mechanism for NH3 decomposition on the Ir doped graphene surface is proposed and the energy barriers required for each reaction step are calculated by the CINEB method. The results obtained showed that the Ir doped graphene exhibits high catalytic activity for the NH3 decomposition reaction. In addition, the NH → N + H step was determined to be the rate determining step of the overall reaction. In the light of this information obtained, it is concluded that different strategies and technologies can be used on the Ir doped graphene materials for NH3 decomposition.

Keywords

• Iridium Doped Graphene
• Binding Energy
• NH3 Decomposition
• Single Atom Catalyst
• Density Functional Theory

İridyum Katkılı Grafen Yüzey Üzerinde NH3 Ayrışma Reaksiyonu Mekanistik İncelemesi: Yoğunluk Fonksiyonel Teori Yaklaşımı

Öz

Amonyak (NH3) ayrışma reaksiyonu, COx emisyonu içermeyen H2 üretmedeki potansiyel kullanımı nedeniyle önemlidir. NH3 ayrışma reaksiyonunda pek çok farklı katalizör kullanılmasına rağmen, metal gömülü grafen sistemler, deneysel olarak sentezlenebilir ve sadece birkaç metal atomu kullanılmasından dolayı tek atom kristal yüzeylere göre çok daha ucuzdur. Bu çalışmada, İridyum (Ir) katkılı grafen yüzey üzerinde gerçekleşen NH3 ayrışma reaksiyon mekanizması yoğunluk fonksiyonel teorisi (YFT) kullanılarak incelenmiştir. Grime D2 düzeltmesi, adsorbe edilmiş yapılar ve yüzey arasındaki etkileşimlerle indüklenebilecek Van der Waals etkileşimleri için kullanılmıştır. Öncelikle, Ir katkılı grafen yüzey üzerinde Bader yük analizi yapılmış ve elde edilen yük yoğunluğu bölgeleri elektron yoğunluk farklı ile gösterilmiştir. Ir katklı grafen yüzey üzerinde NHx (x= 0→3) türlerinin adsorpsiyonu ve onların parçalanmış NHx + yH (x+y=3) ikili bağlanma doğası araştırılmıştır. Son olarak, Ir katklı grafen yüzey üzerinde NH3 ayrışması için reaksiyon mekanması önerilmiş ve her bir reaksiyon adımı için ihtiyaç duyulan enerji bariyerleri CINEB metodu yoluyla hesaplanmıştır. Elde edilen sonuçlar, Ir katkılı grafenin, NH3 ayrışma reaksiyonu için yüksek katalitik aktivite sergilediğini göstermiştir. Ayrıca NH → N+H adımı, genel reaksiyonun hız belirleyici adımı olduğu belirlenmiştir. Elde edilen bu bilgiler ışığında, NH3 ayrışması için, Ir katklı grafen malzemeler üzerinde farklı stratejilerin ve teknolojilerin geliştirilmesinde kullanılabileceği sonucuna varılmıştır.

Anahtar Kelimeler

• Iridyum Katkılı Grafen
• Bağlanma Enerjisi
• NH3 Ayrışması
• Tek-Atom Katalizör
• Yoğunluk Fonksiyonel Teorisi

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