Graphdiyne coordinated transition metals as single-atom catalysts for nitrogen fixation

• Published in: Physical chemistry chemical physics : PCCP 2020-05, Vol.22 (17), p.9216-9224
• Main Authors: Feng, Zhen, Tang, Yanan, Chen, Weiguang, Li, Yi, Li, Renyi, Ma, Yaqiang, Dai, Xianqi
• Format: Article
• Language: English
• Subjects: Adsorption; Ammonia; Cadmium; Chemical reduction; Constraining; First principles; Iron; Monolayers; Nitrogen; Nitrogenation; Single atom catalysts; Titanium; Transition metals; Yttrium; Zinc; Zirconium
• ISSN: 1463-9076; 1463-9084
• DOI: 10.1039/d0cp00722f

The reduction of N 2 molecules to NH 3 is a very challenging task in chemistry. The electrocatalytic nitrogen reduction reaction (NRR) is a promising technology for NH 3 synthesis. By using first-principles calculation, a new class of single-atom catalysts (SACs), graphdiyne coordinated single transition metal atoms (TM@GDY, TM = Sc-Zn, Y-Cd, and La-Hg) were designed, and the NRR catalytic character of TM@GDY was systematically investigated. The results demonstrated that some TM@GDY (TM = Ti, V, Fe, Co, Zr, Rh, and Hf) monolayers exhibit better NRR activities than a Ru(0001) stepped surface. There is an obvious linear correlation between the limiting potential and the atomic N adsorption energy, which confirms that the N adsorption energy may be a descriptor for evaluation of the NRR catalytic performance. The V@GDY monolayer possesses the best NRR catalytic character with the lowest limiting potential of −0.67 V and the potential-limiting step (PLS) of *N 2 → *NNH for both alternating and distal mechanisms. Our results highlight a new family of efficient and stable TM@GDY catalysts and provide useful guidelines for SAC development and practical applications. 2D graphdiyne is a superior candidate for dispersing single transition metal atoms, which can be used as SACs for nitrogen fixation.