Newly developed electrosynthesis of Layered Double Hydroxides: application to sensing, energy storage and conversion

Layered Double hydroxides (LDHs) have been widely studied for their plethora of fascinating features and applications. The potentiostatic electrodeposition of LDHs has been extensively applied in the literature as a fast and direct method to substitute classical chemical routes. However, it does not usually allow for a fine control of the M(II)/M(III) ratio in the synthesized material and it is not suitable for large anions intercalation. Therefore, in this work a novel protocol has been proposed with the aim to overcome all these constraints using a method based on potentiodynamic synthesis. LDHs of controlled composition were prepared using different molar ratios of the trivalent to bivalent cations in the electrolytic solution ranging from 1:1 to 1:4. Moreover, we were able to produce electrochemically LDHs intercalated with carbon nanomaterials for the first time. A one-step procedure which contemporaneously allows for the Ni/Al-LDH synthesis, the reduction of graphene oxide (GO) and its intercalation inside the structure has been developed. The synthesised materials have been applied in several fields of interest. First of all, LDHs with a ratio 3:1 were exploited, and displayed good performances as catalysts for 5-(hydroxymethyl)furfural electro-oxidation, thus suggesting to carry out further investigation for applications in the field of industrial catalysis. The same materials, but with different metals ratios, were tested as catalysts for Oxygen Evolution Reaction, obtaining results comparable to LDHs synthesised by the classical co-precipitation method and also a better activity with respect to LDHs obtained by the potentiostatic approach. The composite material based on LDH and reduced graphene oxide was employed to fabricate a cathode of a hybrid supercapacitor coupled with an activated carbon anode. We can thus conclude that, to date, the potentiodynamic method has the greatest potential for the rapid synthesis of reproducible films of Co and Ni-based LDHs with controlled composition.

Photoactive (supra)molecular devices in double layer membranes

Biological systems are complex and highly organized architectures governed by non-covalent interactions responsible for the regulation of essential tasks in all living organisms. These systems are a constant source of inspiration for supramolecular chemists aiming to design multicomponent molecular assemblies able to perform elaborated tasks, thanks to the role and action of the components that constitute them. Artificial supramolecular systems exploit non-covalent interactions to mimic naturally occurring events. In this context, stimuli-responsive supramolecular systems have attracted attention due to the possibility to control macroscopic effects through modifications at the nanoscale. This thesis is divided in three experimental chapters, characterized by a progressive increase in molecular complexity. Initially, the preparation and studies of liposomes functionalized with a photoactive guest such as azobenzene in the bilayer were tackled, in order to evaluate the effect of such photochrome on the vesicle properties. Subsequently, the synthesis and studies of thread-like molecules comprising an azobenzene functionality was reported. Such molecules were conceived to be intercalated in the bilayer membrane of liposomes with the aim to be used as components for photoresponsive transmembrane molecular pumps. Finally, a [3]rotaxane was developed and studied in solution. This system is composed of two crown ether rings interlocked with an axle containing three recognition sites for the macrocycles, i.e. two pH-switchable ammonium stations and a permanent triazolium station. Such molecule was designed to achieve a change in the ratio between the recognition sites and the crown ethers as a consequence of acid-base inputs. This leads to the formation of rotaxanes containing a number of recognition sites respectively larger, equal or lower than the number of interlocked rings and connected by a network of acid-base reactions.

A double chance to investigate populist influence: The Five Star Movement.

In the last decade, new kinds of European populist parties and movements characterized by a left wing, right wing or “eclectic” attitude have succeeded in entering in governments where they could exert a direct populist influence on their coalition partners or, conversely, become victims themselves of the influence of the institutional background. Such a scenario brought this research to formulate two questions: (i) “To what extent did populist parties succeed in influencing their government coalition partners, leading them to adopt populist rhetoric and change their policy positions?” and (ii) “Have populist parties been able to retain their populist “outside mainstream politics” identity, or have they been assimilated to mainstream parties?”. As a case study this project chose the Italian Five Star Movement. Since 2018 this eclectic populist actor has experienced three different governments first with the radical right wing populist League (2018-2019) and then with the mainstream center left Democratic Party (2019-2021). In addition to this, currently the Five Star Movement is a coalition partner of the ongoing Draghi’s government. Theoretically based on the ideological definition of populism (Mudde, 2004), on a new “revised” model of the inclusionary - exclusionary framework to classify populist parties and on a novel definition of “populist influence”,this research made use of both quantitative (bidimensional and text analysis) and qualitative methods (semi-structured interviews) and mainly focuses on the years 2017- 2020.The importance of this study is threefold. First it contributes to the study of populist influence in government in relation to the ideological attachment of the political actors involved. Second, it contributes to understand if populists in power necessarily need to tone down their anti-system character in order to survive. Third, this study introduces conceptual and methodological novelties within the study of populism and populist influence in government.

Black hole scattering from Worldline Quantum Field Theory and the Classical Double Copy of Spinning particles

This PhD thesis focuses on studying the classical scattering of massive/massless particles toward black holes, and investigating double copy relations between classical observables in gauge theories and gravity. This is done in the Post-Minkowskian approximation i.e. a perturbative expansion of observables controlled by the gravitational coupling constant κ = 32πGN, with GN being the Newtonian coupling constant. The investigation is performed by using the Worldline Quantum Field Theory (WQFT), displaying a worldline path integral describing the scattering objects and a QFT path integral in the Born approximation, describing the intermediate bosons exchanged in the scattering event by the massive/massless particles. We introduce the WQFT, by deriving a relation between the Kosower- Maybee-O’Connell (KMOC) limit of amplitudes and worldline path integrals, then, we use that to study the classical Compton amplitude and higher point amplitudes. We also present a nice application of our formulation to the case of Hard Thermal Loops (HTL), by explicitly evaluating hard thermal currents in gauge theory and gravity. Next we move to the investigation of the classical double copy (CDC), which is a powerful tool to generate integrands for classical observables related to the binary inspiralling problem in General Relativity. In order to use a Bern-Carrasco-Johansson (BCJ) like prescription, straight at the classical level, one has to identify a double copy (DC) kernel, encoding the locality structure of the classical amplitude. Such kernel is evaluated by using a theory where scalar particles interacts through bi-adjoint scalars. We show here how to push forward the classical double copy so to account for spinning particles, in the framework of the WQFT. Here the quantization procedure on the worldline allows us to fully reconstruct the quantum theory on the gravitational side. Next we investigate how to describe the scattering of massless particles off black holes in the WQFT.