Development of innovative materials used in electrochemical devices for the renewable production of hydrogen and electricity

One of the most important challenges for our society is providing powerful devices for renewable energy production. Many technologies based on renewable energy sources have been developed, which represent a clean energy sources that have a much lower environmental impact than conventional energy technologies. Nowadays, many researches focus their attention on the development of renewable energy from solar, water, organic matter and biomass, which represent abundant and renewable energy sources. This research is mainly focused on the development of promising electrode materials and their potential application on emerging technologies such as artificial photosynthesis and microbial fuel cell (MFC). According to desired proprieties of functional materials, this research was focused on two main materials: (1) TiO2 for the development of electrodes for the water splitting reaction due to its demonstrated application potential as photocatalyst material and (2) carbon-based materials for the development of electrodes for MFC. In the first part of the investigation, different TiO2 nanostructures have been studied including: synthesis, characterization and test of TiO2-based materials with the aim of improving the limiting factors of the photocatalytic reaction: charge recombination and separation/migration processes. The photo-catalytic properties of different TiO2 nanostructures were evaluated including: TiO2 nanoparticles (NPs) film, TiO2 nanotubes (NTs) and ZnO@TiO2 core-shell structures. Photo-electrochemical activity measurements and electrochemical impedance spectroscopy analysis showed an improvement in charge collection efficiency of 1D-nanostructures, related to a more efficient electron transport in the materials. The efficient application of both the TiO2 NTs and the ZnO@TiO2 core-shell photoanodes opens important perspectives, not only in the water splitting application field, but also for other photo-catalytic applications (e.g. photovoltaic cells, degradation of organic substances), due to their chemical stability, easiness of preparation and improved transport properties. Additionally, in order to improve the photo-catalytic activity of TiO2 NPs, PANI/TiO2 composite film was synthesized. PANI/TiO2 composite film was successfully applied as anode material for the PEC water splitting reaction showing a significant increase in the photocatalytic activity of TiO2 NPs composite film essentially attributed to the efficient separation of the generated electron and hole pairs. To date, no cost-effective materials system satisfies all of the technical requirements for practical hydrogen production under zero-bias conditions. For this propose, to promote the sustainability of the process, the bias require to conduct PEC water splitting reaction could be powered by MFC systems in which many efforts have been done to improve power and electricity generation as is explained below. In this work, different strategies were also applied in order to improve the performance of anode materials for MFCs. The investigation of commercial carbon-based materials demonstrated that these materials, normally used for other ends are suitable electrodes for MFC and their use could reduce MFC costs and improve the energy sustainability of the process. In addition, to enhance power generation in MFC by using low-cost and commercial carbon-based materials, nitric acid activation (C-HNO3) and PANI deposition (C-PANI) were performed on commercial carbon felt (C-FELT) in order to increase the performance of MFC. Electrochemical determinations performed in batch-mode MFC reveled a strong reduction of the activation losses contribution and an important decrease of the internal resistance of the cell using C-HNO3 and C-PANI of about 2.3 and 4.4 times, respectively, with respect to C-FELT. Additionally, with the aim of solvent different MFC operational problems such as: biofouling, low surface area and large-scale MFC, an innovative three-dimensional material effectively developed and used as anode electrode. The conductive carbon-coated Berl saddles (C-SADDLES) were successfully used as anode electrode in batch-mode MFC. Electrochemical results suggested that C-SADDLES offer a low-cost solution to satisfy either electrical or bioreactor requirements, increasing the reliability of the MFC processes, and seems to be a valid candidate for scaled-up systems and for continuous mode application of MFC technology. In addition, the electrochemical performance and continuous energy production of the most promising materials obtained during this work were evaluated under continuous operation MFC in a long-term evaluation test. Remarkable results were obtained for continuous MFCs systems operated with three different anode materials: C-FELT, C-PANI and C-SADDLES. From polarization curves, the maximum power generation was obtained using C-SADDLES (102 mW•m-2) with respect to C-FELT (93 mW•m-2) and C-PANI (65 mW•m-2) after three months of operation. The highest amount of electrical energy was produced by C-PANI (1803 J) with respect to C-FELT (1664 J) and C-SADDLES (1674 J). However, it is worth to note that PANI activity was reduced during time by the operating conditions inside the anode chamber. In order to demonstrate the wide application potential MFC, this work reports on merging heterogeneous contributions and combining the advantages from three separate fields in a system which enables the ultra-low-power monitoring of a microbial fuel cell voltage status and enables pressure monitoring features of the internal conditions of a cell. The solution is conceived to provide an efficient energy source, harvesting wastewater, integrating energy management and health monitoring capabilities to sensor nodes which are not connected to the energy grid. Finally, this work presented a general concept of the integration of both devices into a hybrid device by interfacing PEC and MFC devices (denoted as PEC-MFC), which is proposed to generate electricity and hydrogen using as external bias the potential produce by microbial fuel cell