Water dissociation and H migration on metal decorated B40: A density functional theory (DFT) study

doi:10.1016/j.molliq.2020.113759

Journal of Molecular Liquids

Volume 315, 1 October 2020, 113759

https://doi.org/10.1016/j.molliq.2020.113759 Get rights and content

Highlights

•
The binding energy between the metal atom and B₄₀ are much large due to the existence of heptagonal holes.
•
The adsorption energies of H₂O on metal-decorated M&B₄₀ are significantly larger than those of metal surface.
•
The reaction energies and barriers for H₂O dissociation and H migration on M&B₄₀ were obtained.
•
The metal-decorated B₄₀ can be applied as nanocatalyst for H₂O splitting.

Abstract

The doping of the metal atoms in B₄₀ can efficiently extend the applications of borospherene. The dissociation of H₂O and H migration on metal-decorated exohedral M&B₄₀ (M = Be, Mg, Fe, Ru, and Pd) were investigated with density functional theory (DFT). The binding energy between the metal atom and B₄₀ are much large due to the existing of heptagonal holes. The adsorption energies of H₂O on metal-decorated M&B₄₀ are significantly larger than those of metal surfaces, which results in an effective activation of H₂O. The reaction energies and barriers for H₂O dissociation and H migration on this series of metal-decorated M&B₄₀ clusters were obtained. Our results provide fundamental insights into the mechanisms of water dissociation and H migration on borospherene and suggest that metal-decorated B₄₀ could be utilized as a potential nanocatalyst for water splitting.

Introduction

The generation of clean and energy is one of the most sought being pursued world-wide intensely and actively. Hydrogen is a green energy carrier, which is regarded as a promising solution for the energy crisis. The water dissociation reaction H₂O → H₂ + 1/2O₂ is a great promise for hydrogen production due to its nonpolluting reactivity nature. However, the direct thermal splitting of water requires temperatures above 2500 °C, making its practical implementation very challenging [1].

Carbon-based nanomaterials were extensively investigated as potential catalysts for water-based reactions. For example, the doping of Al atom into graphene can facilitate the dissociative adsorption of H₂O molecules. The dissociative energy barrier is reduced from 3.609 eV on pristine graphene to 0.456 eV on Al-doped graphene [2]. The splitting of a water molecule on Ru doped Stone-Wales graphene only needs a small activation energy of 0.43 eV [3]. Liu et al. [4] found that TiN₄-graphene membrane can remarkably decrease the dissociation energy barrier of H from H₂O. Ti-doped carbon nanotubes [5] show extremely low barrier (0.12 eV) for splitting the second H₂O. The activation barrier for water dissociation is as low as 0.19 eV when one molecule dissociated over Ti single bond C₆₀ [6], and the increased coverage of Ti on C₆₀ does not change the catalytic ability [7]. Recently, the all-boron fullerene (B₄₀) was discovered in an experiment [8], and results in the flourishing growth of borospherene chemistry. The finding of B₄₀ was followed immediately by the studies of endohedral metalloborospherene. Bai et al. [9] performed structural searches with density functional theory (DFT) for some metalloborospherene, and they found that Ca or Sr atom was located at the center, corresponding to endohedral structures (Ca@B₄₀ and Sr@B₄₀), on the other hand, Be&B₄₀ and Mg&B₄₀ favor exohedral geometries. Fa et al. [10] proposed that the comparable atomic size with the cage size along with the specific interaction between the dopant and B atoms can together affect the stability of endohedral versus exohedral configuration. The doping of the metal atoms in B₄₀ can efficiently extend the applications of borospherene. The metal decorated B₄₀ [[11], [12], [13]] was predicted as a promising hydrogen storage material. The Li and Ba doped B₄₀ [14] were studied as gas sensors, and the doping can enhance the adsorption strength and electric conductivity response for acetone adsorption. However, there is none study for dissociative of H₂O relevant to metal decorated borospherene.

In the present work, we performed the DFT calculations to investigate the elementary step (H₂O → OH + H) of the water dissociation reaction on the metal-decorated M&B₄₀ (M = Be, Mg, Fe, Ru, Pd) surface to reveal the possibility of using borospherene-based nanostructures as catalysts for water dissociation. This paper is organized as follows, the calculational details are introduced in Section 1. The results and associated discussions are presented in Section 3. Section 4 gives the conclusions.

Section snippets

Computational details

The geometries of all the reactants, intermediates, transition states, and products were fully relaxed without any constrains using the hybrid HF/DFT functional B3LYP, which consists of the Lee-Yang-Parr nonlocal correlation functional [15] and three-parameter hybrid exchange functional proposed by Becke [16]. The 6-31G (d, p) split-valence basis set was used to describe the light atoms, H, Be, B, O, and Mg, and the Stuttgart relativistic effective core pseudopotential (RECP) [17,18] and

Results and discussions

The exohedral and endohedral structures were considered in the geometry optimizations of M-doped B₄₀ (M = Be, Mg, Fe, Ru, Pd). All the species studied favor exohedral structures with a η⁷ face-capping metal atom as shown in Fig. 1. The exohedral structures with metal atom decorated on the 6-ring face come next in energy (see Fig. S1 in the supporting information). On the other hand, the endohedral structures possess the lowest stability among all optimized isomers, and the highest relative

Conclusions

DFT calculations were performed to investigate the reaction of H₂O with metal-decorated M&B₄₀ (M = Be, Mg, Fe, Ru, Pd) to discuss the possibility of using borospherene-based nanostructures as catalysts for water dissociation. All the species studied favor exohedral structures with a η⁷ face-capping metal atom, which provides a potential active site for adsorption and dissociation of H₂O. The binding energy between the metal atom and B₄₀ are much large due to the existing of heptagonal holes.

CRediT authorship contribution statement

Xiyuan Sun: Methodology, Formal analysis, Writing - original draft. Jiguang Du: Conceptualization, Writing - review & editing. Liang Zhao: Visualization, Investigation. Gang Jiang: Writing - review & editing.

Declaration of competing interest

The authors declare no conflict of interest.

Acknowledgment

We acknowledge the computational resources of the High-Performance Computing Center at the Physics Discipline of Sichuan University. This work is supported by the Project of Education Department in Sichuan Province (No. 15ZB0006).

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Water dissociation and H migration on metal decorated B40: A density functional theory (DFT) study

Highlights

Abstract

Introduction

Section snippets

Computational details

Results and discussions

Conclusions

CRediT authorship contribution statement

Declaration of competing interest

Acknowledgment

Int. J. Hydrog. Energy

Carbon

Angew. Chem. Int. Ed.

Int. J. Hydrogen Storage

Int. J. Hydrogen Storage

J. Mol. Liq.

Appl. Surf. Sci.

Surf. Sci. Rep.

Sustainable hydrogen production

Science

First principles study on the hydrophilic and conductive graphene doped with Al atoms

Phys. Chem. Chem. Phys.

Initial interactions between water molecules and Ti-adsorbed carbon nanotubes

Appl. Phys. Lett.

Dissociation of water over Ti-decorated C60

J. Chem. Phys.

Initial interactions between water molecules and Ti-adsorbed carbon nanotubes

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Water dissociation and H migration on metal decorated B₄₀: A density functional theory (DFT) study

Dissociation of water over Ti-decorated C₆₀