Two electrodeposition strategies for the morphology-controlled synthesis of cobalt nanostructures

In this contribution, two different strategies are discussed to synthesize cobalt nanostructures: direct cobalt electrodeposition on a planar aluminum electrode and cobalt electrodeposition into nanoporous alumina templates generated by aluminum anodization (template electrodeposition). In the direct electrodeposition of cobalt on aluminum, cobalt nanoparticles are formed during the early stage of electrodeposition, which causes the depletion of cobalt ions near the electrode. Water reduction then takes place catalyzed by electrodeposited cobalt nanoparticles, which increases the pH near the electrode and can induce cobalt hydroxide precipitation. By varying the electrode potential and the cobalt ion concentration, the interplay between electrochemical growth of cobalt and water reduction could be controlled to induce transition from cobalt hexagonal nano-platelets to nanostructured films composed of cobalt nanoparticles and cobalt hydroxide nano-flakes. Cobalt nanowires can be synthesized by electrodeposition into nanoporous alumina templates generated by aluminum anodization. This approach typically involves the application of alumina templates produced by a two-step anodization procedure: the alumina nanoporous layer generated by a first anodization is dissolved in a chromic acid solution while a very ordered alumina nanoporous layer is produced by a second anodization stage. In accordance with previous studies, this procedure is fundamental to achieve uniform filling of the nanopores in the subsequent electrodeposition stage. In the present study, uniform filling of the nanoporous alumina generated by one-step anodization could be achieved by the electrodeposition of cobalt nanowires. This result was made possible by the application of a novel pulsed electrodeposition strategy

Photovoltaic panel recycling: from type-selective processes to flexible apparatus for simultaneous treatment of different types.

Photovoltaic (PV) technology for renewable energy utilization is constantly growing throughout the world. This widespread application is going to determine the disposal of large amounts of wastes (as end of life panels): only in Europe about 500,000 ton/year are expected in the next 20 years. European Union issued the Guideline 2012/19/EU in order to fix rules about end of life photovoltaic panel’s treatment establishing both collecting rates and minimum recovery targets. Currently the dominant PV technology uses crystalline silicon (monocrystalline and polycrystalline) as semiconductor, but the thin film photovoltaic modules using cadmium telluride (CdTe), amorphous silicon, Copper Indium Gallium Selenide (CIGS) and Copper Indium Selenide (CIS) are recently getting much more importance. Wastes of PV installations are secondary raw materials which could be treated in order to recover glass and Al, but also other metals such as Cu, Ti, Ag, Te, In, Se, Ga, along with plastic and metallic components of electronic equipment. Many recent efforts were devoted to the treatment of end of life panels, but only two full scale processes were developed for crystalline silicon modules (Deutsche Solar) and CdTe panels (First Solar). Furthermore, recent developments concerned with new technologies designed for treating together more kinds of photovoltaic panels by automated processes. In this work a picture of the PV world in terms of market, typology, waste dynamics and recoverable materials will be given. A description of full scale processes will be reported evidencing products and yields of recovery. A case study of process development for the simultaneous treatment of different kinds of PV panels will be presented. In particular experimental results in lab and pilot scale will be described regarding the development and optimization of a process including both physical pre-treatment and hydrometallurgical recovery of target metal concentrates. The process will be validated in pilot scale within the activities of the Photolife project (LIFE13 ENV/IT/001033) financed by European Community in the LIFE+ program

Synthesis of cobalt nanoparticles by electrodeposition onto aluminium foils

In this contribution a study of electrochemical deposition of cobalt nanoparticles onto aluminium foils is presented. The study is aimed at deriving information required for design and control of cobalt nanoparticles electrodeposition onto aluminium foams employed as catalysts support in ethanol reforming. A thorough experimental analysis was in this perspective conducted to determine the influence of applied potential and amount of electric charge passing thorough the cell (amount of charge), on number density and size of the synthesized nanoparticles. Chronoamperometric tests were for this purpose performed in a three electrode cell to determine the current responses to variations in the selected operating parameters. Mathematical models accounting for charge transfer and diffusion limitations were implemented to attain fitting of the derived data, leading to an estimation of the number density of active sites. Scanning electron microscopy of cathode aluminium foils was performed to validate the predictions of the employed mathematical models and characterize the influence of the considered operating parameters on the size and number density of the electrodeposited nanoparticles

Hydrogen photo-production by mixotrophic cultivation of chlamydomonas reinhardtii: Interaction between organic carbon and nitrogen

Hydrogen photo-production by a wild type and two engineered strains of Chlamydomonas reinhardtii was investigated. Growth rate values and hydrogen yields attained as the concentration of acetate and nitrogen vary were compared. In the analysis of microalgal growth, the interaction between organic carbon (acetate) and nitrogen (nitrate) was investigated by recourse to an experimental factorial design. This analysis evidenced the existence of a statistically significant interaction between organic carbon and nitrate. Hydrogen production was attained by cultivating microalgae previously grown in mixotrophic regime with sulphur deprived medium. The influence of varying the photobioreactor headspace on hydrogen production was investigated. This analysis revealed an increase in the hydrogen produced per unit volume of culture of about one order of magnitude when the headspace volume is modified from 100 to 350 mL. This result provides valuable indications on how to design and operate photobioreactors for hydrogen production optimization and was thoroughly discussed in terms of the metabolic pathways activated by sulphur depletion. ©2014, AIDIC Servizi S.r.l

Lanthanum biosorption by different Saccharomyces cerevisiae strains

Biosorption can be a promising technology in rare earth metal separation and recovery due to the low costs of waste biomasses (used as biosorbents) and the high selectivity exploiting specific interaction between metals and biological active sites. In this work, Saccharomyces cerevisiae biomass was used to recover lanthanum. Biosorption properties of two S. cerevisiae strains, wild type and rim20. mutant, have been tested. Potentiometric titrations were carried out for rim20. mutant strain and compared with wild type. Nature of the main active sites and their concentration were determined by implementing mechanistic models. Carboxylic, amino and phosphoric sites are the main groups present. Higher concentration of negatively charged sites was found in rim20. (0.0024 mol/g) than in wild type (0.0022 mol/g). The rate of lanthanum biosorption process is very fast requiring only 10-20 minutes to reach equilibrium condition for both strains. Then biosorption equilibrium tests were done for both biomasses by testing two equilibrium pH (4.0 and 6.0). Maximum uptake capacities (qmax) were: 70 mg/g and 40 mg/g at pH 4.0 for rim20. and wild type, respectively, and 67 mg/g and 80 mg/g at pH 6.0 for wild type and rim20., respectively. These data evidenced that: rim20. mutant had a higher maximum biosorption capacity with respect to wild type counterpart, and that pH had a relevant effect on lanthanum removal. S. cerevisiae yeast denoted good lanthanum biosorption properties and, between tested strains, rim20. was found to be the most promising for such aim

Two stage process of microalgae cultivation for starch and carotenoid production

Biotechnological processes based on microalgae cultivation are promising for several industrial applications. Microalgae are photoautotrophic microorganisms and can thus grow by using renewable and inexpensive resources as sunlight, inorganic salts, water and CO2. They can store high amounts of neutral lipids (bioil), carbohydrates (mainly starch), carotenoids (such as lutein, astaxanthin, beta-carotene), proteins and other molecules. Productions of lipids and carbohydrates have recently received an increasing interest for biofuel production, while proteins, carotenoids and other minor products are usable as feed additives and nutraceutical compounds. Biofuel production from microalgae is not yet economically sustainable, while there are different industrial plants in the world for the production of high values chemicals as carotenoids. Starch production from microalgae has been investigated mainly for the production of biofuels (e.g. bioethanol) by successive fermentation. However, purified starch can be used for other aims such as the production of bioplastics. Superior plants as corn, potato and wheat are currently used for this purpose. However, there are different environmental and economic issues related to the use of fertile lands and edible plants for these kinds of productions. Microalgae can solve these social and ethical issues because they can grow on nonfertile lands and also reach starch productivity per hectare higher than plants. In this work, the production of starch and carotenoids from Scenedesmus sp. microalgal strain is reported. A two-stage process has been developed in order to reduce operative and investment costs. In the first stage, microalgae are cultivated in photoautotrophic conditions and then, when biomass concentration rises and light becomes a limiting factor for growth, microalgae are transferred to a heterotrophic reactor. In this reactor, microalgae are cultivated by using wastewaters as source of nutrients (mainly organic carbon). Microalgae use organic carbon to synthesize starch and simultaneously reduce the content of pollutants in the wastewater (codepuration). Biomass separated by the culture medium is treated for the extraction of lipids containing different antioxidant carotenoids (such as astaxanthin and lutein) and starch granules as raw material for biopolymers

Effect of lipids and carbohydrates extraction on astaxanthin stability in scenedesmus sp

Elevated costs of biomass downstream processing represent a severe limit to the industrial development of microalgal production systems. Biorefinery solutions allowing simultaneously deriving biofuels and extracting high value compounds must be explored to enhance economic feasibility. In this work, the possibility to extract carbohydrates, lipids and astaxanthin from a strain of Scenedesmus sp. is investigated. The analysis is mainly focused on analyzing the effect of consolidated procedures of extraction of carbohydrates and lipids on the degradation and recovery of astaxanthin. Microalgae were cultivated till achieving stationary phase and maintained in this phase to enhance lipids and astaxanthin accumulation. The fractions of total lipids, carbohydrates and astaxanthin of the produced biomass were 17 %, 33 % and 0.02 % respectively. No statistically significant difference in the astaxanthin content determined following Soxhlet extraction and a more gentle extraction method (Yuan et al. 2002) was found. The effect of transesterification conditions was also evaluated revealing a scarce degradation of astaxanthin in response to the achievement of elevated temperature, NaOH and dissolved oxygen concentrations. Reductions in astaxanthin content were in contrast obtained in response to the addition of H2SO4. These reductions were proportional to acid sample concentration. However a regeneration of astaxanthin was obtained by NaOH addition indicating reversibility of the degradation process. In accordance with these results, the possibility to perform biomass saccharification for carbohydrate extraction at progressively lower acid concentrations was investigated. Copyright © 2015, AIDIC Servizi S.r.l

Full recycling of spent lithium ion batteries with production of core-shell nanowires//exfoliated graphite asymmetric supercapacitor

A novel process is reported which produces an asymmetric supercapacitor through the complete recycling of end-of-life lithium ion batteries. The electrodic powder recovered by industrial scale mechanical treatment of spent batteries was leached and the dissolved metals were precipitated as mixed metals carbonates. Nanowires battery-type positive electrodes were produced by electrodeposition into nanoporous alumina templates from the electrolytic baths prepared by dissolution of the precipitated carbonates. The impact of the different metals contained in the electrodic powder was evaluated by benchmarking the electrochemical performances of the recovered nanowires-based electrodes against electrodes produced by using high-purity salts. Presence of inactive Cu in the nanowires lowered the final capacitance of the electrodes while Ni showed a synergistic effect with cobalt providing a higher capacitance with respect to synthetic Co electrodes. The carbonaceous solid recovered after leaching was in-depth characterized and tested as negative electrode. Both the chemical and electrochemical characterization indicate that the recovered graphite is characterized by the presence of oxygen functionalities introduced by the leaching treatment. This has led to the obtainment of a recovered graphite characterized by an XPS C/O ratio, Raman spectrum and morphology close to literature reports for reduced graphene oxide. The asymmetric supercapacitor assembled using the recovered nanowires-based positive electrodes and graphite as negative electrodes has shown a specific capacitance of 42 Fg-1, computed including the whole weight of the positive electrode and recovered graphite, providing a maximum energy density of ∼9 Whkg−1 and a power density of 416 Wkg−1 at 2.5 mA cm-

Ti/TiO2/Cu2O electrodes for photocatalytic applications: synthesis and characterization

Energy from renewables (solar, photovoltaic, geothermal), is a major challenge for researchers' efforts in reason of the intermittent nature of these energy sources. Systems like photoelectrochemical (PEC) cells are promising devices that allow the direct conversion of solar energy into electric power and/or chemical fuels. The direct conversion of solar energy in fuels can be achieved using photocatalysts, based on semiconductors like TiO2. In this work TiO2 nanotubes were achieved through “one-step” anodization of titanium, a low cost and accurate method which allowed to control dimensions and morphology of the nanostructured Ti/TiO2 electrodes. Central limit for TiO2 photoconversion efficiency is its wide bandgap (i.e. a3.2eV), which limits light absorption to the ultraviolet region (3-5% of the solar radiation). Composite Cu2O/TiO2 systems have attracted much attention: Cu2O is a promising semiconductor material (bandgap 2.0-2.6eV), suitable to absorb visible light. Traditionally, Cu2O deposition techniques include the impregnation of TiO2 with a copper salt and subsequent calcination, but offers little control on sizes, shape and deposit's composition. In this work we developed an electrodeposition method in order to control Cu2O morphology and sizes in the composed Ti/TiO2/Cu2O electrodes

Microalgae cultivation for lipids and carbohydrates production

Microalgae are photoautotrophic microorganisms that can produce energy both by using sunlight, water and CO2 (phototrophic metabolism) and by using organic sources such as glucose (heterotrophic metabolism). Heterotrophic growth is a key factor in microalgae research, due to its increased productivity and the lower capital and operative costs compared to photoautotrophic growth in photobioreactors. Carbohydrate production from microalgae is usually investigated for the production of biofuels (e.g. bioethanol) by successive fermentation, but also other applications can be envisaged in biopolymers. In this work an increment in carbohydrate purity after lipid extraction was found. Protein hydrolysis for different microalgae strains (Scenedesmus sp. and Chlorella sp.) was investigated. Microalgae were cultivated under photoautotrophic or heterotrophic conditions, collecting biomass at the end of the growth. Biomass samples were dried or freeze dried and used for carbohydrate and lipid extraction tests. Lipid extraction was achieved using different organic solvents (methanol-chloroform and hexane-2propanol). Basic protein hydrolysis has been carried out testing different temperatures and NaOH concentrations values. Lipids were spectrophotometrically quantified, while residual biomass was saccharificated and the total amount of sugars was measured. Significant differences about the purity of extracted carbohydrates were found comparing dried with freeze dried biomass. However, not a very promising purification of carbohydrates was achieved after protein hydrolysis, asking for further analysis. © Copyright 2017, AIDIC Servizi S.r.l