A major challenge in the face of increasing global energy demand is the development of alternative environmentally friendly and renewable energy resources. Hydrogen is an excellent energy carrier, but has drawbacks in storage density and is dangerous to handle. An alternative approach involves controlled release of hydrogen from suitable materials, and an excellent candidate for this is formic acid. Because hydrogen production from formic acid is more convenient in acidic aqueous solutions, development of direct carbon dioxide hydrogenation has to be carried out under the same acidic conditions that provides a direct reversible hydrogen storage system. As current sources of formic acid are derived from fossil fuels, emphasis must be placed on conversion of renewable carbon sources to this materials. This thesis examines the direct hydrogenation of carbon dioxide to formic acid using homogeneous catalysts. Importantly, this reaction was achieved in base and additive-free conditions. Direct formic acid synthesis, without any additives has several advantages, including simpler isolation of the product. In addition, formic acid can also be used as a feedstock chemical and thus contributing to decrease the released CO2 to the atmosphere and consequently to the possible reduction of the greenhouse effect. A homogeneous catalytic system based on a [RuCl2(PTA)4] pre-catalyst active for carbon dioxide hydrogenation without the need for additives was developed. While unprecedented conversions were achieved in aqueous mixtures, a remarkable solvent effect was discovered for dimethyl sulfoxide. Furthermore, both catalytic systems are air stable and highly robust allowing for multiple recycling runs. Studies on the activity of the ruthenium pre-catalyst in the reverse reaction of hydrogen delivery in dimethyl sulfoxide have been undertaken and revealed promising results to achieve a CO2 neutral catalytic cycles. Mechanistic studies were carried out using NMR spectroscopy and provide valuable insights into the reasons for the high activities for the catalyst. After a general introduction on current hydrogen storage technologies, the research undertaken in this thesis will be presented in three main parts: (1) Optimization of the high pressure sapphire NMR techniques used for the study of systems under pressure; (2) Development of homogeneous ruthenium catalytic systems for the direct hydrogenation of carbon dioxide to formic acid; (3) Mechanistic studies on the direct carbon dioxide hydrogenation using the [RuCl2(PTA)4] pre-catalyst