• Energy Research

The development of tools to monitor water quality is mandatory in a scenario where clean water resources are decreasing. Here, the biosensing capability of an electroactive river sediment consortium was tested towards three model contaminants (glutaraldehyde, nickel(II) and chromium(III)). The proposed biosensor is a small membrane-less single chamber Microbial Fuel Cell (MFC), fabricated by 3D printing. Its semi-continuous mode of operation resulted in long-term current profile stability and reproducibility. A linear trend of response was obtained for glutaraldehyde in a concentration range of 5-1000 ppm. After the recovery of the electroactive consortium activity, the MFC-based biosensors were shown to be sensitive towards Ni(II) and Cr(III), at concentrations above 2 mg L-1. To effectively analyze biosensor response, a novel algorithm was proposed, offering advantages for the realization of energy-saving protocols for MFC-biosensor data transmission. Implementation of the device and method, from laboratory test to real environment, can offer a low cost in situ system for detection of water contaminants.

Abstract A novel method is proposed for studying kinetics and overall activity of water oxidation (WO) catalysts using a bubbling reactor, where oxygen concentration is measured simultaneously in the liquid and in the gaseous phase. Total oxygen evolution is obtained from direct integration. The actual rate of oxygen formation as a function of time, R O 2 ( t ) not accessible to direct measurement with batch reactors, is calculated from raw data through a simple but comprehensive mathematical model, taking into account mass transfer phenomena occurring in the system. Data concerning the activity of a nanostructured Co3O4 catalyst dispersed on a mesoporous silica (MSU-H), in the presence of tris(2,2′-bipyridyl)Ruthenium [ Ru ( bpy ) 3 ] 2 + as sensitizer and Na2S2O8 as sacrificial reactant, are used to illustrate data processing. Behaviour of the system is complicated by the occurrence, besides WO reaction, of the degradation of the sensitizer. Increase of sweeping gas flow increases R O 2 ( t ) , by decreasing diffusional limitations to the reactions in the system: conditions for minimizing those were established. Data reported show that the assumption generally made of equilibrium between gaseous and liquid phase through Henry’s law is incorrect, the more so the smaller the apparent mass transfer coefficient, kLa. An additional reason for removing oxygen from the liquid phase through bubbling is the occurrence of a parasitic reaction of molecular oxygen with the sensitizer. The method seems to yield reliable values of both kLa and the set of R O 2 ( t ) values: the former scales with the flow of sweeping gas, as expected; R O 2 ( t ) curves are in qualitative agreement with accepted reaction mechanisms. Results concerning R O 2 ( t ) lend support to our previous kinetic studies (M. Armandi et al., ACS Catal, 2013, 3, 1272) where the reaction rate was assumed as constant for the first ∼15 min. Availability of R O 2 ( t ) data not too biased by diffusional limitations opens the way to realistic studies of the kinetic features of WO heterogeneous reactions, in the present case as well as in many others.

In the present work, sedimentary microbial fuel cells (s-MFC) have been proposed as effective tools to power remote sensors in different aquatic environments, thanks to their ability to produce renewable and sustainable energy continuously and autonomously. The present work proposes the optimization of cylindrical sedimentary microbial fuel cells (s-MFC) as a compact and cost-effective system suitable to be integrated as a payload in an Autonomous Underwater Vehicle (AUV). To this purpose, a new AUV payload, named MFC-payload, is designed to host the cylindrical s-MFC and a data acquisition system to collect and store information on the voltage produced by the cell. Its overall performance was evaluated during two field measurement campaigns carried out in the Mediterranean Sea. This investigation demonstrates the power production by s-MFC during operation of the AUV in seawater and analyzes the actual influence of environmental conditions on the output power. This study demonstrates that energy production by s-MFCs integrated in AUV systems is decoupled by the navigation of the autonomous vehicle itself, showing the effectiveness of the application of MFC-based technology as a power payload for environmental analysis. All these latter results demonstrate and confirm the ability of the devices to continuously produce electricity during different AUV operation modes (i.e., depth and speed), while changing environmental conditions (i.e., pressure, temperature and oxygen content) demonstrate that cylindrical s-MFC devices are robust system that can be successfully used in underwater applications.

Abstract A new-designed transparent, conductive and porous electrode was developed for application in a compact laboratory-scale proton exchange membrane (PEM) photo-electrolyzer. The electrode is made of a thin transparent quartz sheet covered with fluorine-doped tin oxide (FTO), in which an array of holes is laser-drilled to allow water and gas permeation. The electrical, morphological, optical and electrochemical characterization of the drilled electrodes is presented in comparison with a non-drilled one. The drilled electrode exhibits, in the visible region, a good transmittance (average value of 62%), a noticeable reflectance due to the light scattering effect of the hole-drilled internal region, and a higher effective surface area than the non-drilled electrode. The proof-of-concept of the applicability of the drilled electrode was achieved by using it as a support for a traditional photocatalyst (i.e. commercial TiO 2 nanoparticles). The latter, coupled with a polymeric electrolyte membrane (i.e.Nafion 117) and a Pt counter electrode, forms a transparent membrane electrode assembly (MEA), with a good conductivity, wettability and porosity. Electrochemical impedance spectroscopy (EIS) was used as a very powerful tool to gain information on the real active surface of the new drilled electrode and the main electrochemical parameters driving the charge transfer reactions on it. This new electrode architecture is demonstrated to be an ideal support for testing new anodic and cathodic photoactive materials working in tandem configuration for solar fuels production by water photo-electrolysis.

Metal-free dye molecules for dye-sensitized solar cells application can avoid some of the typical drawbacks of common metal-based sensitizers, that are high production costs, relatively low molar extinction coefficient in the visible region, limited availability of precursors, and waste disposal issues. Recently we have proposed an innovative organic dye based on a simple hemi-squaraine molecule (CT1). In the present work, the effect of the sensitization time of the TiO2photoelectrode in the dye solution is studied with the aim of optimizing the performance of CT1-based DSCs. Moreover, the addition of the chenodeoxycholic acid (CDCA) as coadsorbent in the dye solution at different concentrations is investigated. Both CT1-sensitized mesoporous TiO2photoanodes and complete solar cells have been fully characterized in their electrical and absorption properties. We have found that the best photoconversion performances are obtained with 1 hour of impregnation time and a 1 mM CDCA concentration. The very fast kinetics in dye adsorption, with optimal sensitization steps almost 15 times faster than conventional Ru-based sensitizers, confirms the theoretical predictions and indicates a strong interaction of the semisquaric acid group with the anatase surface. This result suggests that this small molecule can be a promising sensitizer even in a continuous industrial process.

A highly efficient ZnO photoanode for dye-sensitized solar cells was successfully grown by a simple, low cost, and scalable method. A nanostructured coral-shaped Zn layer was deposited by sputtering onto fluorine-doped tin oxide/glass slices at room temperature and then thermally oxidized in ambient atmosphere. Stoichiometry, crystalline phase, quality, and morphology of the film were investigated, evidencing the formation of a highly porous branched nanostructure, with a pure wurtzite crystalline structure. ZnO-based dye-sensitized solar cells were fabricated with customized microfluidic architecture. Dye loading on the oxide surface was analyzed with ultraviolet-visible spectroscopy, and the dependence of the cell efficiency on sensitizer incubation time and film thickness was studied by current-voltage electrical characterization, incident photon-to-electron conversion efficiency, and impedance spectroscopy measurements, showing the promising properties of this material for the fabrication of dye-sensitized solar cell photoanodes with a solar conversion efficiency up to 4.58%. Copyright © 2012 John Wiley & Sons, Ltd.

A mixed microbial population naturally presents in seawater was used as active anodic biofilm of two Microbial Fuel Cells (MFCs), employing either a 2D commercial carbon felt or 3D carbon-coated Berl saddles as anode electrodes, with the aim to compare their electrochemical behavior under continuous operation. After an initial increase of the maximum power density, the felt-based cell reduced its performance at 5 months (from 7 to 4 μW cm(-2)), while the saddle-based MFC exceeds 9 μW cm(-2) (after 2 months) and maintained such performance for all the tests. Electrochemical impedance spectroscopy was used to identify the MFCs controlling losses and indicates that the mass-transport limitations at the biofilm-electrolyte interface have the main contribution (>95%) to their internal resistance. The activation resistance was one order of magnitude lower with the Berl saddles than with carbon felt, suggesting an enhanced charge-transfer in the high surface-area 3D electrode, due to an increase in bacteria population growth.