Unveiling the destabilization of sp3 and sp2 bonds in transition metal-modified borohydrides to improve reversible dehydrogenation and rehydrogenation

Yifan Jing; Shengming Zhou; Jiaxi Liu; Huicheng Yang; Jiaqi Liang; Leyu Peng; Ziyuan Li; Yongpeng Xia; Huangzhi Zhang; Fen Xu; Lixian Sun; Kostya S Novoselov; Pengru Huang

doi:10.1016/j.jcis.2024.01.164

Unveiling the destabilization of sp³ and sp² bonds in transition metal-modified borohydrides to improve reversible dehydrogenation and rehydrogenation

J Colloid Interface Sci. 2024 May:661:185-195. doi: 10.1016/j.jcis.2024.01.164. Epub 2024 Jan 27.

Authors

Affiliations

¹ School of Material Science and Engineering, Guilin University of Electronic Technology, Guangxi Key Laboratory of Information Materials, Guangxi Collaborative Innovation Center of Structure and Property for New Energy and Materials, Guilin 541004, China.
² School of Material Science and Engineering, Guilin University of Electronic Technology, Guangxi Key Laboratory of Information Materials, Guangxi Collaborative Innovation Center of Structure and Property for New Energy and Materials, Guilin 541004, China; School of Mechanical & Electrical Engineering, Guilin University of Electronic Technology, Guilin 541004, China.
³ School of Material Science and Engineering, Guilin University of Electronic Technology, Guangxi Key Laboratory of Information Materials, Guangxi Collaborative Innovation Center of Structure and Property for New Energy and Materials, Guilin 541004, China; School of Mechanical & Electrical Engineering, Guilin University of Electronic Technology, Guilin 541004, China. Electronic address: sunlx@guet.edu.cn.
⁴ Institute for Functional Intelligent Materials, National University of Singapore, 117544, Singapore. Electronic address: kostya@nus.edu.sg.
⁵ School of Material Science and Engineering, Guilin University of Electronic Technology, Guangxi Key Laboratory of Information Materials, Guangxi Collaborative Innovation Center of Structure and Property for New Energy and Materials, Guilin 541004, China; Institute for Functional Intelligent Materials, National University of Singapore, 117544, Singapore. Electronic address: pengruhuang@guet.edu.cn.

PMID: 38301457
DOI: 10.1016/j.jcis.2024.01.164

Abstract

Borohydrides offer promise as potential carriers for hydrogen storage due to their high hydrogen concentration. However, the strong chemical bonding within borohydrides poses challenges for efficient hydrogen release during usage and restricts the re-hydrogenation process when attempting to regenerate the material. These high thermodynamic and kinetic barriers present obstacles in achieving reversible de-hydrogenation and re-hydrogenation of borohydrides, impeding their practical application in hydrogen storage systems. Employing density functional theory calculations, we conduct a comprehensive investigation into the influence of transition metals on both the BH₄ cluster, a fundamental building block of borohydrides, and pure boron, which is formed as the end product following hydrogen release. Our research reveals correlations among the d-band center, work function, and surface energy of 3d and 4d transition metals. These correlations are directly linked to the weakening of bonding within the BH₄ cluster when adsorbed on catalyst surfaces. On the other hand, we also explore how various intrinsic properties of transition metals influence the formation of boron vacancies and the hydrogen bonding process. By establishing a comprehensive correlation between the weakening of sp³ hybridization in the BH₄ cluster and the sp² hybridization in boron, we facilitate the identification and screening of optimal candidates capable of achieving reversible de-hydrogenation and re-hydrogenation in borohydrides.

Keywords: Borohydride; De-hybridization effect; Hydrogen storage; Reversible hydrogenation; Transition metal.