High-pressure NMR spectroscopic and calorimetric studies on formic acid dehydrogenation and carbon dioxide hydrogenation

Our current energy production is convenient and simple, but it is not sustainable. The negative impacts on our environment are omnipresent in the form of smog, extinction of species, and global warming. A major challenge of our generation is the transition to new, responsible methods of energy production. The maxim is renewable energy. Hydrogen could serve as an intermediary energy carrier. However, problems arise with the storage of hydrogen due to safety concerns and low volumetric energy density. The reduction of carbon dioxide (CO2) to formic acid (FA) is an elegant process to âcompressâ hydrogen by transforming it into a chemical which is easier and safer to handle. In this dissertation, catalytic FA dehydrogenation, CO2 reduction and calorimetric studies of the involved thermodynamics are described.

The first chapter provides a global overview, beginning with general considerations about energy economy, then crossing over to hydrogen storage and infrastructure for a future hydrogen economy, before discussing FA as a hydrogen storage medium and summarizing the developments of FA dehydrogenation and CO2 hydrogenation.

Chapter two describes different compounds we have studied as potential catalysts for FA dehydrogenation and CO2 hydrogenation. The focus is on complexes of Ir, Rh, and Ru regarding metals, and on Cp* and an ethylene-spaced diamine as ligands. Other motifs were also explored including Ru-phosphine complexes which afforded unexpected results. The most promising candidates are examined more closely.

The third chapter summarizes our findings of formic acid dehydrogenation with homogeneous catalysts, presented in three parts. Each subchapter highlights a different structural feature or metal center. The first one focuses on Ir and Rh metal centers, equipped with Cp* and diamines. In the second section, we explore the catalytic performance of a RAPTA-type precatalyst, and the last one addresses our achievements with a rhodium catalyst containing Cp* and di(1-pyrazolyl)methane ligands. The catalysts were evaluated towards core properties such as stability (TON), activity (TOF) and recycling.

Chapter four elucidates the interactions of FA with different solvents and additives, which influence the kinetics and thermodynamics of FA dehydrogenation and CO2 hydrogenation. NMR and FT-IR spectroscopy, conductometry, calorimetric measurements and computational methods were used to analyze the systems thoroughly.

In chapter five, high-pressure calorimetric measurements are employed to quantify the actual energy balance during the endothermic process of FA dehydrogenation. For this purpose, we modified an off-the-shelf high-pressure reactor to suit our needs and constructed a thermo-controlled environment.

Chapter six describes our research into catalytic CO2 hydrogenation to FA with two ruthenium-based phosphine pre-catalysts. One has three 1,4,7-triaza-9-phosphatricyclotridecane (CAP) ligands coordinated, which is a just recently described phosphine compound. The other complex is prepared via a straightforward synthesis route with an inexpensive, simple ligand. Both are stable in aqueous FA over weeks, making them potential catalysts for large-scale application.

Decreasing the Stability of Borohydride with Ionic Liquids for Hydrogen Storage and Carbon Dioxide Conversion

Loris Giovanni Lombardo

The world needs to move from a fossil fuel to a renewable energy based society. With the increasing electricity production from wind and PV, short and long term energy storage are becoming one of challenge of the 21st century. While batteries are the preferred method for short term storage, another technology is required for seasonal storage. Hydrogen is a valuable energy carrier owning its high energy density (122 kJ/g). However, compact and safe storage of H2 is challenging. The current solution is to compress hydrogen up to 700 bar for mobile application (fuel cell cars), and metal hydrides for stationary application. Material-based H2 storage avoids using high-pressure cylinder. Complex hydrides are especially attractive for solid-state H2 storage due to their high gravimetric and volumetric hydrogen density. Sodium borohydride (NaBH4) contains 10.6 mass% of H2, but high temperatures are needed to release H2 (505 Â°C) and the reaction is not reversible under moderate conditions. To apply complex hydrides in real applications, they must be modified to improve the kinetics and thermodynamics of H2 desorption. Several possibilities exist such as confinement into scaffolds, catalyst addition, or combination of several hydrides to modify the dehydrogenation pathway. The stability of complex hydrides is determined by the localization of the charge on the central atom of the complex. Therefore, in this thesis the interaction of highly polar or ionic compounds with complex hydrides were investigated. We combine NaBH4 with a special class of organic salts: ionic liquids (IL). Considering their chemical and thermal stability, IL are attractive additive. Using organic additives instead of expensive metal catalysts is another advantage. Two different techniques were employed to combine the IL and NaBH4. The first one consists of mechanochemically milling them to create an interaction between BH4- and IL. The second one is to directly synthesized IL borohydrides ([IL][BH4]) by metathesis reaction. Different ILs, such as vinylbenzyltrimethylammonium chloride ([VBTMA][Cl]), 1-butyl-3-methylimidazolium chloride ([bmim][Cl]), and 1-ethyl-1-methylpyrrolidinium bromide ([EMPY][Br]) were tested. [bmim][BH4] was able to release H2 below 100 Â°C. The hydrogen content ranges between 2.4 mass% and 2.9 mass%. The second challenge of this century is the CO2 problematic. Atmospheric CO2 concentration linearly increases, leading to greenhouse effect. Carbon capture and sequestration (CCS) and utilization (CCU) are primordial research topic to stabilize the CO2 emission. Hydrides are primary reducing agents, thus reduction of CO2 can be accomplished with them. Direct CO2 reduction at ambient conditions is challenging for classical borohydrides. With our [IL][BH4], gaseous CO2 can be captured and reduced under ambient conditions (1 bar, RT). Three CO2 bounds with boron to give triformatoborohydride ([HB(OCHO)3]â. Dilute CO2 (6 vol%) can be used as well. The reaction was followed in real time with a magnetic suspended balance (MSB). Further, CO2 reduction happened when air is used as a carbon dioxide source. Formic acid can be obtained by adding HCl. Thus, ionic liquid borohydrides have great potential as a CO2 absorber and reducer to alternative fuels. In short, we applied ionic liquid to destabilized borohydrides. The resulting materials exhibited potential for solid-state hydrogen storage, as well as CO2 capture and transformation.

EPFL2021

Direct Carbon Dioxide Hydrogenation into Formic Acid in Acidic Media

Séverine Joëlle Moret

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

EPFL2014

Kinetics and Mechanism of Formic Acid Decomposition in Aqueous Solution using Ruthenium Pre-catalysts with Hydrophilic Phosphine Ligands

Weijia Gan

Hydrogen holds the potential to be an alternative to replace fossil fuels in the future. The tremendous research effort dedicated to the issue of hydrogen storage has led to considerable advancements in the development of both adsorption materials and chemical storage. Still, for many of these systems the gap between current state of research and industrial application is considerable. When it comes to systems for the reversible storage of hydrogen, the HCOOH/CO2 cycle currently shows the most promises. Its physical-chemical properties make formic acid an ideal system for hydrogen storage. Herein, a series of homogeneous catalytic systems have been developed for hydrogen generation from formic acid in aqueous solution. These catalysts are formed from commercially available RuCl3 with a variety of water-soluble phosphine ligands. These ligands vary in the type, number and position of their hydrophilic substituents. Most of them allow the efficient decomposition of formic acid under mild conditions for a large number of catalytic cycles. Especially a new series of cationic phosphine ligands provide the catalytic systems with high activity. Due to the observed high initial reaction rate of many catalytic systems, mechanistic studies have also been undertaken with important intermediates and a catalytic cycle being proposed. Accordingly, the heterogeneous catalysts have also been developed based on the immobilization of homogeneous ruthenium complexes. The immobilized catalysts also afford hydrogen with high purity and allow easy catalyst separation, overcoming the previous limitations in the use of homogeneous catalysts, particularly for mobile/portable applications. The research undertaken in this thesis is presented in three main parts: (i) the development and optimization of homogeneous catalytic systems; (ii) the development and optimization of heterogeneous/immobilized catalytic systems; (iii) the mechanistic studies on the initial fast catalytic cycle of homogeneous catalysts.

EPFL2012