Hydrogen is well established as a renewable and clean alternative to conventional fossil fuels and is a potential solution to the global energy crisis. With the ever-rising demand for hydrogen in numerous industries worldwide, there is a clear need for more efficient hydrogen storage
methods. In this dissertation, ab-initio density functional theory calculations were performed to extensively investigate both well-ordered and amorphous carbon-based materials for hydrogen adsorption and further metal decoration for possible enhancement in their performance. It was observed that although pristine graphene does not favour spontaneous dissociation and adsorption of hydrogen atoms due to a stable sp2 hybridized structure, local distortions due to defects can cause a change in hybridization to dissociate and adsorb hydrogen spontaneously on certain two-fold coordinated carbon sites. Similarly, the presence of different bonding environments in amorphous carbon structures play an active role in hydrogen adsorption. Hydrogen interacts stronger with two-fold coordinated carbon atoms as compared to three- and four-fold coordinated carbon. High migration barriers for hydrogen atoms on
carbon supports make them unlikely to spontaneously spread over the surfaces. To achieve further enhancement, the interaction of metal clusters (Pt and Ni) with these surfaces were considered. It was observed that hydrogen adsorption strength on the carbon atoms of graphene
and amorphous carbon increases due to the presence of metal clusters. In addition, the metal support interaction is found to increase with the presence of vacancy defects in the vicinity, which leads to lower energy barriers for hydrogen migration from the metal cluster to the surface. Hydrogen adsorption in a dissociative form on all these surfaces shows a higher saturation limit in the case of Pt clusters as compared to Ni. Overall, metal clusters adsorbed on the carbon supports was proven beneficial for hydrogen adsorption and is crucial to designing efficient materials for H-storage.

Abstract 8
1Introduction 9
1.1 Hydrogen and its applications 9
1.2 Hydrogen: overview of generation and storage 11
1.3 Carbon-based materials for hydrogen adsorption 15
1.4 Efficient use of metal catalyst and spillover phenomenon 21
1.5 Motivation 23
2Methods 25
2.1 Introduction 25
2.2 The many-body problem 26
2.3 Born-Oppenheimer Approximation 27
2.4 Density Functional Theory 28
2.5 The Pseudopotential method 33
2.5.1 Projector Augmented Wave (PAW) method 34
2.6 DFT-D3 Dispersion correction 37
2.7 Ab-initio Molecular dynamics (AIMD) 39
2.8 Bader charge 42
2.9 Nudged Elastic band (NEB) method 45
3Hydrogen dissociation, adsorption, and migration on pristine and defective graphene surfaces
48
3.1 Introduction 48
3.2 Computational details 50
3.3 Result and discussions 52
3.3.1 Pristine and defective (Single and di-vacancy) graphene surfaces 52
3.3.2 Atomic hydrogen adsorption on single and di-vacancy graphene 54
3.3.3 Molecular and dissociative hydrogen adsorption on single and di-vacancy graphene 58
3.3.4 Multiple hydrogen adsorption on single vacancy graphene 63
3.3.5 Hydrogen migration on single and di-vacancy graphene 64
3.4 Conclusions 65
4Hydrogen dissociation and adsorption on amorphous carbon surfaces 67
4.1 Introduction 67
4.2 Computational details 68
4.3 Results and discussions 70
4.3.1 Amorphous carbon structure 70
4.3.2 H2 adsorption on the amorphous carbon surface 72
4.3.3 Single H atom adsorption on the amorphous carbon surface 76
4.3.4 Multiple H2 dissociative adsorptions on the amorphous carbon surface 82
4.4 Conclusions 85
5Hydrogen dissociation, adsorption, and spillover on Pt4 and Ni4 adsorbed on graphene
surfaces 87
5.1 Introduction 87
5.2 Computational details 88
5.3 Results and discussion 90
5.3.1 Pt4 and Ni4 adsorption on the graphene surface 90
5.3.2 Multiple H2 dissociative adsorptions on isolated atoms and clusters 94
5.3.3 Hydrogen adsorption on Pt4/graphene and Ni4/graphene surfaces 100
5.3.4 H spillover phenomenon 103
5.4 Conclusions 109
6Hydrogen dissociation, adsorption, and spillover on Pt4 adsorbed defective graphene surfaces
111
6.1 Introduction 111
6.2 Computational details 112
6.3 Results and discussion 113
6.3.1 Pt4 adsorption on single and di-vacancy graphene 113
6.3.2 Atomic hydrogen adsorption on Pt4/defective graphene 116
6.3.3 Atomic hydrogen adsorption on graphene surface of Pt4/defective graphene 117
6.3.4 Hydrogen spillover 119
6.4 Conclusion 127
7Hydrogen dissociation, adsorption, and spillover on Pt and Ni adsorbed amorphous carbon
surfaces 129
7.1 Introduction 129
7.2 Computational details 130
7.3 Results and discussion 131
7.3.1 Nin and Ptn adsorption on the amorphous carbon surface 131
7.3.2 Hydrogen adsorption on Ni and Pt for Nin/a-C and Ptn/a-C surfaces 135
7.3.3 Hydrogen adsorption on amorphous carbon for Ni4/a-C and Pt4/a-C surfaces 139
7.3.4 H spillover phenomenon 140
7.4 Conclusion 144
8Concluding remarks and outlook 146
8.1 Conclusion 146
8.2 Scope for future work 149
9Bibliography 151
10Appendix 160
11List of publications 184
12Acknowledgements 185

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