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Theoretical exploration of bare and oxygen-functionalized Ti3C2 clusters for catalytic NH3 production

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Abstract

In this work, we performed high-level quantum chemical calculations to understand the comparative efficiency of Ti3C2 and oxygen-functionalized Ti3C2 (Ti3C2O2) clusters for the catalytic conversion of N2 to NH3. The global minima structures of N2-free and N2-adsorbed cluster were predicted using the ABC algorithm. Accordingly, N2 can be adsorbed on Ti atoms in a side-on fashion. Binding energy, Wiberg bond index, and Bader charge analyses suggest that the N2-binding ability of the Ti3C2O2 cluster is far better than that of the Ti3C2 cluster. Relative free energy diagrams indicate that cluster-catalyzed NH3 synthesis prefers to follow the distal pathway. The calculation of the energetic span model concludes that catalytic conversion of N2 to NH3 on Ti3C2O2 possesses a lower effective activation barrier than that on the Ti3C2 cluster, which implies that the Ti3C2O2 is a more efficient catalyst than Ti3C2 for the synthesis of NH3. Moreover, from the comparison with other metal clusters like V3C2O2 and Nb3C2O2, we find that although the latter cluster possesses comparatively less energy span N2-philicity of Ti3C2O2 is found to be far higher than that of Nb3C2O2 cluster. Thus, the present study will provide a molecular-level understanding of improved N2 reduction efficiency of the Ti3C2 cluster through O-functionalization.

Graphical Abstract

Herein, we have performed quantum chemical calculations to understand the comparative efficiency of Ti3C2 and oxygen-functionalized Ti3C2 (Ti3C2O2) clusters for the catalytic conversion of N2 to NH3. We found that oxygen functionalization can dramatically enhance the N2 reduction efficiency of the Ti3C2 cluster.

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Acknowledgments

The authors sincerely acknowledge the financial support from the National Post-Doctoral Fellowship [Sanction PDF/2021/000107], the UGC Midcareer Award Grant [Sanction F.19-257/2021(BSR)], and CSIR (HRDG) [Sanction no. 01(3086)/21/EMR-II], Government of India.

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Correspondence to Pranab Sarkar.

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This paper is dedicated to Professor S. P. Bhattacharyya on the happy occasion of his 75th birth anniversary.

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Saha, S., Ghoshal, S. & Sarkar, P. Theoretical exploration of bare and oxygen-functionalized Ti3C2 clusters for catalytic NH3 production. J Chem Sci 135, 48 (2023). https://doi.org/10.1007/s12039-023-02169-y

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