Storage of Renewable Energy by Reduction of CO2 with Hydrogen

The main difference between the past energy economy during the industrialization period which was mainly based on mining of fossil fuels, e.g. coal, oil and methane and the future energy economy based on renewable energy is the requirement for storage of the energy fluxes. Renewable energy, except biomass, appears in time- and location-dependent energy fluxes as heat or electricity upon conversion. Storage and transport of energy requires a high energy density and has to be realized in a closed materials cycle. The hydrogen cycle, i.e. production of hydrogen from water by renewable energy, storage and use of hydrogen in fuel cells, combustion engines or turbines, is a closed cycle. However, the hydrogen density in a storage system is limited to 20 mass% and 150 kg/m(3) which limits the energy density to about half of the energy density in fossil fuels. Introducing CO, into the cycle and storing hydrogen by the reduction of CO, to hydrocarbons allows renewable energy to be converted into synthetic fuels with the same energy density as fossil fuels. The resulting cycle is a closed cycle (CO2 neutral) if CO, is extracted from the atmosphere. Today's technology allows CO, to be reduced either by the Sabatier reaction to methane, by the reversed water gas shift reaction to CO and further reduction of CO by the Fischer Tropsch synthesis (FTS) to hydrocarbons or over methanol to gasoline. The overall process can only be realized on a very large scale, because the large number of by-products of FTS requires the use of a refinery. Therefore, a well-controlled reaction to a specific product is required for the efficient conversion of renewable energy (electricity) into an easy to store liquid hydrocarbon (fuel). In order to realize a closed hydrocarbon cycle the two major challenges are to extract CO, from the atmosphere close to the thermodynamic limit and to reduce CO2 with hydrogen in a controlled reaction to a specific hydrocarbon. Nanomaterials with nanopores and the unique surface structures of metallic clusters offer new opportunities for the production of synthetic fuels.

Storing Renewable Energy in the Hydrogen Cycle

Elsa Callini, Shunsuke Kato

An energy economy based on renewable energy requires massive energy storage, approx. half of the annual energy consumption. Therefore, the production of a synthetic energy carrier, e.g. hydrogen, is necessary. The hydrogen cycle, i.e. production of hydrogen from water by renewable energy, storage and use of hydrogen in fuel cells, combustion engines or turbines is a closed cycle. Electrolysis splits water into hydrogen and oxygen and represents a mature technology in the power range up to 100 kW. However, the major technological challenge is to build electrolyzers in the power range of several MW producing high purity hydrogen with a high efficiency. After the production of hydrogen, large scale and safe hydrogen storage is required. Hydrogen is stored either as a molecule or as an atom in the case of hydrides. The maximum volumetric hydrogen density of a molecular hydrogen storage is limited to the density of liquid hydrogen. In a complex hydride the hydrogen density is limited to 20 mass% and 150 kg/m(3) which corresponds to twice the density of liquid hydrogen. Current research focuses on the investigation of new storage materials based on combinations of complex hydrides with amides and the understanding of the hydrogen sorption mechanism in order to better control the reaction for the hydrogen storage applications.

Swiss Chemical Soc2015

Coupling of electrocatalysts to photoabsorbers for solar fuels production

Carlos Gilberto Morales Guio

The direct transformation of sunlight into fuels and chemicals has attracted considerable attention for the potential impact on the storage of solar energies at large scales and the reduction of CO2 emissions. More than 80% of our current global energy consumption comes from the burning of non-renewable fossil fuels which produces enormous quantities of CO2 and contributes to global warming. We believe today that the key to reduce our dependence on exhaustible natural resources and limit the emission of greenhouse gases is the transition to CO2-free renewable energy sources. However, harvesting of energy from renewable sources (i.e. solar, wind, tidal) is intermittent and the deployment of devices for their transformation into useful forms of energy (i.e. electricity, chemicals, fuels, biomass) in a global scale is conditioned upon the improvement in efficiency of the energy storage mechanisms. A promising approach to store energy is the use of sunlight to drive the production of hydrogen fuel from water. Hydrogen produced from water and sunlight can be transformed back to electricity on demand or be used to generate mechanical energy in cars to power the transportation industry. The oxidation of hydrogen generates useable energy and at the same time exhaust clean, carbon-free water as the only product. Therefore, the production of hydrogen using a renewable energy source in an efficient and inexpensive device has the potential to discourage the continued use of fossil fuels and improve our environment. The viability of any mechanism for the storage of sunlight as fuel will depend on the reduction of energy penalties during the transformation process. Electrocatalysts are advanced materials that bring into one active site electrons and molecules in the appropriate orientation to lower activation energy barriers, accelerate rate of transformations and improve overall efficiencies for chemical reactions. The best catalysts for water splitting are precious metals such as Pt, Ir and Ru, which show superior rates of reaction at low overpotentials. However, these noble metals are too expensive and scarce for large scale applications. This thesis summarizes our recent research in the preparation, characterization, and application of Earth-abundant electrocatalysts for solar water splitting. Although in the last decade a great number of efficient and inexpensive electrocatalysts have been reported, methods for the deposition of these materials on the surface of photoabsorbers are rarely reported. This work shows various simple and scalable techniques for the deposition of hydrogen and oxygen evolving electrocatalysts on the surface of photocathodes and photoanodes, respectively. Surface-protected photocahodes were activated for solar hydrogen production in alkaline conditions with MoS2+x, Ni-Mo and Mo2C. A novel method for the deposition of an optically transparent amorphous iron nickel oxide oxygen evolution electrocatalyst is also reported. The catalyst was deposited on both thin film and high-aspect ratio nanostructured hematite photoanodes. The low catalyst loading combined with its high activity at low overpotential results in significant improvement on the onset potential for photoelectrochemical water oxidation. This transparent catalyst further enables the preparation of a stable hematite/perovskite solar cell tandem device, which performs unassisted water splitting.

EPFL2016

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.