Screen-printed NiO electrodes were sensitized with 11 different dyes and the respective electroch... more Screen-printed NiO electrodes were sensitized with 11 different dyes and the respective electrochemical properties were analyzed in a three-electrode cell with the techniques of cyclic voltammetry and electrochemical impedance spectroscopy. The dye sensitizers of NiO were organic molecules of different types (e.g., squaraines, coumarins, and derivatives of triphenyl-amines and erythrosine B), which were previously employed as sensitizers of the same oxide in dye-sensitized solar cells of p-type (p-DSCs). Depending on the nature of the sensitizer, diverse types of interactions occurred between the immobilized sensitizer and the screen-printed NiO electrode at rest and under polarization. The impedance data recorded at open circuit potential were interpreted in terms of two different equivalent circuits, depending on the eventual presence of the dye sensitizer on the mesoporous electrode. The fitting parameter of the charge transfer resistance through the electrode/electrolyte interface varied in accordance to the differences of the passivation action exerted by the various dyes against the electrochemical oxidation of NiO. Moreover, it has been observed that the resistive term R CT associated with the process of dark electron transfer between the dye and NiO substrate is strictly correlated to the overall efficiency of the photoconversion (η) of the corresponding p-DSC, which employs the same dye-sensitized electrode as photocathode.
Deep Eutectic Solvent (DES)-like mixtures, based on glycerol and different halide organic and ino... more Deep Eutectic Solvent (DES)-like mixtures, based on glycerol and different halide organic and inorganic salts, are successfully exploited as new media in copper-free halodediazoniation of arenediazonium salts. The reactions are carried out in absence of metal-based catalysts, at room temperature and in a short time. Pure target products are obtained without the need for chromatographic separation. The solvents are fully characterized, and a computational study is presented aiming to understand the reaction mechanism.
Before taking this position, she worked at Xi'an Jiaotong-Liverpool University (XJTLU, Suzhou, Ch... more Before taking this position, she worked at Xi'an Jiaotong-Liverpool University (XJTLU, Suzhou, China), at the Chemistry Department as Inorganic Chemistry Lecturer and prior to XJTLU, was senior researcher at WMG (Warwick Manufacturing Group), University of Warwick (UK), at the battery scale-up facility. Her current research aims to develop advanced functional materials covering the design, synthesis, characterization of novel compounds, with potential applications for electrochemical energy storage. Presently, her group's research focuses on electrospinning of nanofibers and nanocomposite materials.
Abstract Four novel diketopyrrolopyrrole (DPP) derivatives have been synthesized and characterize... more Abstract Four novel diketopyrrolopyrrole (DPP) derivatives have been synthesized and characterized: the dyes are based on a DPP electron acceptor core symmetrically functionalized with donor bi-furyl moieties and end capped with four different auxiliary electron-acceptor groups. Because of the alternation along the molecular backbone of electron acceptor and donor groups, all the dyes are characterized by optical absorption maxima approaching or exceeding 700 nm. In the solid state, this optical behavior determines for all the dyes a very low optical bandgap ranging from 1.57 eV to 1.29 eV, while electrochemical characterization shows a clear dependence of the LUMO energies on the strength of the auxiliary electron-acceptor groups. All the dyes are characterized by stable LUMO energies suitable for their application as n-type semiconductors. Organic field-effect transistors based on the reported compounds display actually n-type behavior and, in three cases, a very interesting and balanced ambipolar charge transport behavior was moreover observed.
The commercialization of perovskite solar cells (PSCs) has seen an important limitation in the in... more The commercialization of perovskite solar cells (PSCs) has seen an important limitation in the instability that afflicts the hole-transporting layer (HTL), namely, spiro-OMeTAD, used in high-efficiency devices. The latter is, in turn, relatively expensive, undermining the sustainability of the device. Its replacement with polymeric scaffolds, such as poly(3hexylthiophene) (P3HT), will solve these issues. In this work, we adopted various sustainable synthetic methods to obtain four different homemade P3HTs with different molecular weights (MWs) and regioregularities (RRs), leading to different structural properties. They are implemented as HTLs in PSCs, and the effect of their properties on the efficiency and thermal stability of devices is thoroughly discussed. The highest efficiency is obtained with the highest MW and low-RR polymer (17.6%) owing to the more sustainable approach, but a very promising value is also reached with a lower-MW but fully regioregular polymer (15%). Finally, large-area devices with an efficiency of 16.7%, fabricated with a high-MW P3HT, show more than 1000 h (T80 = 1108 h) of stability under accelerated thermal stress tests (85°C) out of glovebox while keeping over 85% of the initial efficiency of an unencapsulated device after more than 3000 min under continuous light soaking (AM 1.5G).
Since the introduction of Perovskite Solar Cells, their photovoltaic efficiencies have grown impr... more Since the introduction of Perovskite Solar Cells, their photovoltaic efficiencies have grown impressively, reaching over 25%. Besides the exceptional efficiencies, those solar cells need to be improved to overcome some concerns, such as their intrinsic instability when exposed to humidity. In this respect, the development of new and stable Hole Transporting Materials (HTMs) rose as a new hot topic. Since the doping agents for common HTM are hygroscopic, they bring water in contact with the perovskite layer, thus deteriorating it. In the last years, the research focused on “dopant-free” HTMs, which are inherently conductive without any addition of dopants. Dopant-free HTMs, being small molecules or polymers, have still been a relatively small set of compounds until now. This review collects almost all the relevant organic dopant-free small-molecule HTMs known so far. A general classification of HTMs is proposed, and structure analysis is used to identify structure–property relationsh...
Perovskite solar cells are a hot topic of photovoltaic research, reaching, in few years, an impre... more Perovskite solar cells are a hot topic of photovoltaic research, reaching, in few years, an impressive efficiency (25.5%), but their long-term stability still needs to be addressed for industrial production. One of the most sizeable reasons for instability is the doping of the Hole Transporting Material (HTM), being the salt commonly employed as a vector bringing moisture in contact with perovskite film and destroying it. With this respect, the research focused on new and stable “dopant-free” HTMs, which are inherently conductive, being able to effectively work without any addition of dopants. Notwithstanding, they show impressive efficiency and stability results. The dopant-free polymers, often made of alternated donor and acceptor cores, have properties, namely the filming ability, the molecular weight tunability, the stacking and packing peculiarities, and high hole mobility in absence of any dopant, that make them very attractive and a real innovation in the field. In this revie...
Abstract Despite the growing use of Deep Eutectic Solvents (DESs) as green reaction media in a nu... more Abstract Despite the growing use of Deep Eutectic Solvents (DESs) as green reaction media in a number of organic syntheses, no significant reactions of diazonium salts in these solvents are known in the literature. In this paper, we present the behavior of arenediazonium tetrafluoroborates in new halide salts/polyol-based DESs, the nature of which is investigated by means of a combined computational and experimental approach. A relatively fast (strictly depending on the electronic effects of the substituents bound to the aromatic ring) reduction reaction occurs initiated by the formation of a glycerolate-like species as proved by a thorough computational study aiming at elucidating the involved mechanism.
Tandem dye-sensitized solar cell shows higher photoconversion performances with respect to parent... more Tandem dye-sensitized solar cell shows higher photoconversion performances with respect to parent devices with single photoactive electrode thanks to careful photocurrent matching and complementarity of electrodes optical absorption.
Main DSSC components, along with their most critical materials and related issues are reviewed an... more Main DSSC components, along with their most critical materials and related issues are reviewed and feasible alternatives are envisaged.
In the quest for sustainable materials for quasisolid-state (QS) electrolytes in aqueous dye-sens... more In the quest for sustainable materials for quasisolid-state (QS) electrolytes in aqueous dye-sensitized solar cells (DSSCs), novel bioderived polymeric membranes were prepared in this work by reaction of preoxidized kraft lignin with poly(ethylene glycol)diglycidylether (PEGDGE). The effect of the PEGDGE/lignin relative proportions on the characteristics of the obtained membranes was thoroughly investigated, and clear structure−property correlations were highlighted. In particular, the glass transition temperature of the materials was found to decrease by increasing the amount of PEGDGE in the formulation, indicating that polyethylene glycol chains act as flexible segments that increase the molecular mobility of the three-dimensional polymeric network. Concurrently, their swelling ability in liquid electrolyte was found to increase with the concentration of PEGDGE, which was also shown to influence the ionic transport efficiency within the membrane. The incorporation of these lignin-based cross-linked systems as QS electrolyte frameworks in aqueous DSSCs allowed the preparation of devices with excellent long-term stability under UV−vis light, which were found to be superior to benchmark QS-DSSCs incorporating state-of-the-art carboxymethylcellulose membranes. This study provides the first demonstration of lignin-based QS electrolytes for stable aqueous DSSCs, establishing a straightforward strategy to exploit the potential of lignin as a functional polymer precursor for the field of sustainable photovoltaic devices.
Dye-sensitized solar cells (DSSCs) have become a strong reality in the field of hybrid photovolta... more Dye-sensitized solar cells (DSSCs) have become a strong reality in the field of hybrid photovoltaics. Their ability to operate in diffused light conditions and the possibility of fabrication of modules bearing different colors make these cells attractive for different applications, for example, wearable electronics, building integration, etc. This review focuses on one of the compounds rather often studied for DSSCs, namely, poly(3,4-ethylenedioxythiophene) (PEDOT). It has been introduced both as a substitute for liquid electrolytes, in order to facilitate cells fabrication and increase their durability, and as an alternative to platinum for counter electrodes. The literature counts many studies on PEDOT and this manuscript collects them following a classification criterion based on applications, functionalization/doping strategies, and deposition methods. In addition to comparing the performance obtained for PEDOT-based systems with those of traditional cells (i.e., assembled with liquid iodine-based electrolytes and platinum cathodes), the manuscript also offers a brief analysis of costs and sustainability aspects, built up on experimental data found in the literature; this latter is expected to constitute a precious resource to catalyze the attention of the scientific community on relevant and preliminary aspects when figuring out the industrial scalability of newly proposed cell components.
Abstract The unambiguous quantification of the proton transfer in Protic Ionic Liquids (PILs) and... more Abstract The unambiguous quantification of the proton transfer in Protic Ionic Liquids (PILs) and its differentiation from the concept of ionicity are still unsolved questions. Albeit researchers awfully quickly treat them as synonyms, the two concepts are intrinsically different and imply a dramatic modification in the expected chemical and physical properties of a PIL. Some attempts have been made to shed light on this discrimination, but single-technique-based approaches fail in giving a clear answer. Aiming at definitively figuring out the differentiation between proton transfer and ionicity, we performed a multi-technique analysis (NMR, Raman, IR, thermal and electrochemical analyses, among others). Indeed, thermal and spectroscopic analyses are employed to determine the acid strength's role in ions' complete formation. To overcome the ambiguity between ionicity and formation degree, we introduce a new paradigm where Reduced Ionicity accounts for both the quantities mentioned above. The reduced ionicity directly affects the thermal stability, the phase behavior, and the spectroscopic observations, resulting in particular features in NMR and vibrational spectra. The combination of physical-chemical analyses and Pulsed-Gradient Spin-Echo (PGSE) NMR allows determining the reduced ionicity (and not the ionicity, as reported so far) of the investigated systems. In this context, being the proton transfer not quantitatively accessible directly, the reduced ionicity of a reference series of triethylamine-based PILs is investigated through transport properties as a function of temperature. Our findings point towards a substantial dependence of the reduced ionicity by the acid strength and the anion's coordination power. Furthermore, some interesting insights about the proton transfer are obtained, combining all the findings collected.
While the commercialization of dye-sensitized solar cells (DSSCs) is finally proceeding taking ad... more While the commercialization of dye-sensitized solar cells (DSSCs) is finally proceeding taking advantage of their low cost and tunable optical features, such as colour and transparency for both indoor and building-integrated applications, the corresponding aqueous counterpart is still at its infancy. Being the TiO2 electrode a fundamental component for hybrid solar cells, this work investigates the effect of several molecular (α-terpineol, propylene carbonate) and polymeric (polyethylene oxide, polyethylene glycol, carboxymethyl cellulose and xanthan gum) additives when introduced in a commercial TiO2 paste for DSSCs, conceived for screen-printing (or doctor blade). Among all, the addition of polyethylene glycol leads to the best cell performances, with markedly increased short-circuit current density (+18%) and power conversion efficiency (+48%) with respect to the pristine (commercial) counterpart. When further explored at different concentration levels, electrodes fabricated from polyethylene glycol-based pastes show different morphologies, thicknesses and performances, that are here investigated through (photo)electrochemical, structural, physical-chemical and microscopic techniques.
Metal-organic frameworks (MOFs) and covalent organic frameworks (COFs) are two innovative classes... more Metal-organic frameworks (MOFs) and covalent organic frameworks (COFs) are two innovative classes of porous coordination polymers. MOFs are three-dimensional materials made up of secondary building blocks comprised of metal ions/clusters and organic ligands whereas COFs are 2D or 3D highly porous organic solids made up by light elements (i.e., H, B, C, N, O). Both MOFs and COFs, being highly conjugated scaffolds, are very promising as photoactive materials for applications in photocatalysis and artificial photosynthesis because of their tunable electronic properties, high surface area, remarkable light and thermal stability, easy and relative low-cost synthesis, and structural versatility. These properties make them perfectly suitable for photovoltaic application: throughout this review, we summarize recent advances in the employment of both MOFs and COFs in emerging photovoltaics, namely dye-sensitized solar cells (DSSCs) organic photovoltaic (OPV) and perovskite solar cells (PSCs)...
The investigation of innovative electrolytes based on nontoxic and nonflammable solvents is an up... more The investigation of innovative electrolytes based on nontoxic and nonflammable solvents is an up-to-date, intriguing challenge to push forward the environmental sustainability of dye-sensitized solar cells (DSSCs). Water is one of the best choices, thus 100% aqueous electrolytes are proposed in this work, which are gelled with xanthan gum. This well-known biosourced polymer matrix is able to form stable and easily processable hydrogel electrolytes based on the iodide/triiodide redox couple. An experimental strategy, also supported by the multivariate chemometric approach, is used here to study the main factors influencing DSSCs efficiency and stability, leading to an optimized system able to improve its efficiency by 20% even after a 1200 h aging test, and reaching an overall performance superior to 2.7%. In-depth photoelectrochemical investigation demonstrates that DSSCs performance based on hydrogel electrolytes depends on many factors (e.g., dipping conditions, redox mediator co...
Screen-printed NiO electrodes were sensitized with 11 different dyes and the respective electroch... more Screen-printed NiO electrodes were sensitized with 11 different dyes and the respective electrochemical properties were analyzed in a three-electrode cell with the techniques of cyclic voltammetry and electrochemical impedance spectroscopy. The dye sensitizers of NiO were organic molecules of different types (e.g., squaraines, coumarins, and derivatives of triphenyl-amines and erythrosine B), which were previously employed as sensitizers of the same oxide in dye-sensitized solar cells of p-type (p-DSCs). Depending on the nature of the sensitizer, diverse types of interactions occurred between the immobilized sensitizer and the screen-printed NiO electrode at rest and under polarization. The impedance data recorded at open circuit potential were interpreted in terms of two different equivalent circuits, depending on the eventual presence of the dye sensitizer on the mesoporous electrode. The fitting parameter of the charge transfer resistance through the electrode/electrolyte interface varied in accordance to the differences of the passivation action exerted by the various dyes against the electrochemical oxidation of NiO. Moreover, it has been observed that the resistive term R CT associated with the process of dark electron transfer between the dye and NiO substrate is strictly correlated to the overall efficiency of the photoconversion (η) of the corresponding p-DSC, which employs the same dye-sensitized electrode as photocathode.
Deep Eutectic Solvent (DES)-like mixtures, based on glycerol and different halide organic and ino... more Deep Eutectic Solvent (DES)-like mixtures, based on glycerol and different halide organic and inorganic salts, are successfully exploited as new media in copper-free halodediazoniation of arenediazonium salts. The reactions are carried out in absence of metal-based catalysts, at room temperature and in a short time. Pure target products are obtained without the need for chromatographic separation. The solvents are fully characterized, and a computational study is presented aiming to understand the reaction mechanism.
Before taking this position, she worked at Xi'an Jiaotong-Liverpool University (XJTLU, Suzhou, Ch... more Before taking this position, she worked at Xi'an Jiaotong-Liverpool University (XJTLU, Suzhou, China), at the Chemistry Department as Inorganic Chemistry Lecturer and prior to XJTLU, was senior researcher at WMG (Warwick Manufacturing Group), University of Warwick (UK), at the battery scale-up facility. Her current research aims to develop advanced functional materials covering the design, synthesis, characterization of novel compounds, with potential applications for electrochemical energy storage. Presently, her group's research focuses on electrospinning of nanofibers and nanocomposite materials.
Abstract Four novel diketopyrrolopyrrole (DPP) derivatives have been synthesized and characterize... more Abstract Four novel diketopyrrolopyrrole (DPP) derivatives have been synthesized and characterized: the dyes are based on a DPP electron acceptor core symmetrically functionalized with donor bi-furyl moieties and end capped with four different auxiliary electron-acceptor groups. Because of the alternation along the molecular backbone of electron acceptor and donor groups, all the dyes are characterized by optical absorption maxima approaching or exceeding 700 nm. In the solid state, this optical behavior determines for all the dyes a very low optical bandgap ranging from 1.57 eV to 1.29 eV, while electrochemical characterization shows a clear dependence of the LUMO energies on the strength of the auxiliary electron-acceptor groups. All the dyes are characterized by stable LUMO energies suitable for their application as n-type semiconductors. Organic field-effect transistors based on the reported compounds display actually n-type behavior and, in three cases, a very interesting and balanced ambipolar charge transport behavior was moreover observed.
The commercialization of perovskite solar cells (PSCs) has seen an important limitation in the in... more The commercialization of perovskite solar cells (PSCs) has seen an important limitation in the instability that afflicts the hole-transporting layer (HTL), namely, spiro-OMeTAD, used in high-efficiency devices. The latter is, in turn, relatively expensive, undermining the sustainability of the device. Its replacement with polymeric scaffolds, such as poly(3hexylthiophene) (P3HT), will solve these issues. In this work, we adopted various sustainable synthetic methods to obtain four different homemade P3HTs with different molecular weights (MWs) and regioregularities (RRs), leading to different structural properties. They are implemented as HTLs in PSCs, and the effect of their properties on the efficiency and thermal stability of devices is thoroughly discussed. The highest efficiency is obtained with the highest MW and low-RR polymer (17.6%) owing to the more sustainable approach, but a very promising value is also reached with a lower-MW but fully regioregular polymer (15%). Finally, large-area devices with an efficiency of 16.7%, fabricated with a high-MW P3HT, show more than 1000 h (T80 = 1108 h) of stability under accelerated thermal stress tests (85°C) out of glovebox while keeping over 85% of the initial efficiency of an unencapsulated device after more than 3000 min under continuous light soaking (AM 1.5G).
Since the introduction of Perovskite Solar Cells, their photovoltaic efficiencies have grown impr... more Since the introduction of Perovskite Solar Cells, their photovoltaic efficiencies have grown impressively, reaching over 25%. Besides the exceptional efficiencies, those solar cells need to be improved to overcome some concerns, such as their intrinsic instability when exposed to humidity. In this respect, the development of new and stable Hole Transporting Materials (HTMs) rose as a new hot topic. Since the doping agents for common HTM are hygroscopic, they bring water in contact with the perovskite layer, thus deteriorating it. In the last years, the research focused on “dopant-free” HTMs, which are inherently conductive without any addition of dopants. Dopant-free HTMs, being small molecules or polymers, have still been a relatively small set of compounds until now. This review collects almost all the relevant organic dopant-free small-molecule HTMs known so far. A general classification of HTMs is proposed, and structure analysis is used to identify structure–property relationsh...
Perovskite solar cells are a hot topic of photovoltaic research, reaching, in few years, an impre... more Perovskite solar cells are a hot topic of photovoltaic research, reaching, in few years, an impressive efficiency (25.5%), but their long-term stability still needs to be addressed for industrial production. One of the most sizeable reasons for instability is the doping of the Hole Transporting Material (HTM), being the salt commonly employed as a vector bringing moisture in contact with perovskite film and destroying it. With this respect, the research focused on new and stable “dopant-free” HTMs, which are inherently conductive, being able to effectively work without any addition of dopants. Notwithstanding, they show impressive efficiency and stability results. The dopant-free polymers, often made of alternated donor and acceptor cores, have properties, namely the filming ability, the molecular weight tunability, the stacking and packing peculiarities, and high hole mobility in absence of any dopant, that make them very attractive and a real innovation in the field. In this revie...
Abstract Despite the growing use of Deep Eutectic Solvents (DESs) as green reaction media in a nu... more Abstract Despite the growing use of Deep Eutectic Solvents (DESs) as green reaction media in a number of organic syntheses, no significant reactions of diazonium salts in these solvents are known in the literature. In this paper, we present the behavior of arenediazonium tetrafluoroborates in new halide salts/polyol-based DESs, the nature of which is investigated by means of a combined computational and experimental approach. A relatively fast (strictly depending on the electronic effects of the substituents bound to the aromatic ring) reduction reaction occurs initiated by the formation of a glycerolate-like species as proved by a thorough computational study aiming at elucidating the involved mechanism.
Tandem dye-sensitized solar cell shows higher photoconversion performances with respect to parent... more Tandem dye-sensitized solar cell shows higher photoconversion performances with respect to parent devices with single photoactive electrode thanks to careful photocurrent matching and complementarity of electrodes optical absorption.
Main DSSC components, along with their most critical materials and related issues are reviewed an... more Main DSSC components, along with their most critical materials and related issues are reviewed and feasible alternatives are envisaged.
In the quest for sustainable materials for quasisolid-state (QS) electrolytes in aqueous dye-sens... more In the quest for sustainable materials for quasisolid-state (QS) electrolytes in aqueous dye-sensitized solar cells (DSSCs), novel bioderived polymeric membranes were prepared in this work by reaction of preoxidized kraft lignin with poly(ethylene glycol)diglycidylether (PEGDGE). The effect of the PEGDGE/lignin relative proportions on the characteristics of the obtained membranes was thoroughly investigated, and clear structure−property correlations were highlighted. In particular, the glass transition temperature of the materials was found to decrease by increasing the amount of PEGDGE in the formulation, indicating that polyethylene glycol chains act as flexible segments that increase the molecular mobility of the three-dimensional polymeric network. Concurrently, their swelling ability in liquid electrolyte was found to increase with the concentration of PEGDGE, which was also shown to influence the ionic transport efficiency within the membrane. The incorporation of these lignin-based cross-linked systems as QS electrolyte frameworks in aqueous DSSCs allowed the preparation of devices with excellent long-term stability under UV−vis light, which were found to be superior to benchmark QS-DSSCs incorporating state-of-the-art carboxymethylcellulose membranes. This study provides the first demonstration of lignin-based QS electrolytes for stable aqueous DSSCs, establishing a straightforward strategy to exploit the potential of lignin as a functional polymer precursor for the field of sustainable photovoltaic devices.
Dye-sensitized solar cells (DSSCs) have become a strong reality in the field of hybrid photovolta... more Dye-sensitized solar cells (DSSCs) have become a strong reality in the field of hybrid photovoltaics. Their ability to operate in diffused light conditions and the possibility of fabrication of modules bearing different colors make these cells attractive for different applications, for example, wearable electronics, building integration, etc. This review focuses on one of the compounds rather often studied for DSSCs, namely, poly(3,4-ethylenedioxythiophene) (PEDOT). It has been introduced both as a substitute for liquid electrolytes, in order to facilitate cells fabrication and increase their durability, and as an alternative to platinum for counter electrodes. The literature counts many studies on PEDOT and this manuscript collects them following a classification criterion based on applications, functionalization/doping strategies, and deposition methods. In addition to comparing the performance obtained for PEDOT-based systems with those of traditional cells (i.e., assembled with liquid iodine-based electrolytes and platinum cathodes), the manuscript also offers a brief analysis of costs and sustainability aspects, built up on experimental data found in the literature; this latter is expected to constitute a precious resource to catalyze the attention of the scientific community on relevant and preliminary aspects when figuring out the industrial scalability of newly proposed cell components.
Abstract The unambiguous quantification of the proton transfer in Protic Ionic Liquids (PILs) and... more Abstract The unambiguous quantification of the proton transfer in Protic Ionic Liquids (PILs) and its differentiation from the concept of ionicity are still unsolved questions. Albeit researchers awfully quickly treat them as synonyms, the two concepts are intrinsically different and imply a dramatic modification in the expected chemical and physical properties of a PIL. Some attempts have been made to shed light on this discrimination, but single-technique-based approaches fail in giving a clear answer. Aiming at definitively figuring out the differentiation between proton transfer and ionicity, we performed a multi-technique analysis (NMR, Raman, IR, thermal and electrochemical analyses, among others). Indeed, thermal and spectroscopic analyses are employed to determine the acid strength's role in ions' complete formation. To overcome the ambiguity between ionicity and formation degree, we introduce a new paradigm where Reduced Ionicity accounts for both the quantities mentioned above. The reduced ionicity directly affects the thermal stability, the phase behavior, and the spectroscopic observations, resulting in particular features in NMR and vibrational spectra. The combination of physical-chemical analyses and Pulsed-Gradient Spin-Echo (PGSE) NMR allows determining the reduced ionicity (and not the ionicity, as reported so far) of the investigated systems. In this context, being the proton transfer not quantitatively accessible directly, the reduced ionicity of a reference series of triethylamine-based PILs is investigated through transport properties as a function of temperature. Our findings point towards a substantial dependence of the reduced ionicity by the acid strength and the anion's coordination power. Furthermore, some interesting insights about the proton transfer are obtained, combining all the findings collected.
While the commercialization of dye-sensitized solar cells (DSSCs) is finally proceeding taking ad... more While the commercialization of dye-sensitized solar cells (DSSCs) is finally proceeding taking advantage of their low cost and tunable optical features, such as colour and transparency for both indoor and building-integrated applications, the corresponding aqueous counterpart is still at its infancy. Being the TiO2 electrode a fundamental component for hybrid solar cells, this work investigates the effect of several molecular (α-terpineol, propylene carbonate) and polymeric (polyethylene oxide, polyethylene glycol, carboxymethyl cellulose and xanthan gum) additives when introduced in a commercial TiO2 paste for DSSCs, conceived for screen-printing (or doctor blade). Among all, the addition of polyethylene glycol leads to the best cell performances, with markedly increased short-circuit current density (+18%) and power conversion efficiency (+48%) with respect to the pristine (commercial) counterpart. When further explored at different concentration levels, electrodes fabricated from polyethylene glycol-based pastes show different morphologies, thicknesses and performances, that are here investigated through (photo)electrochemical, structural, physical-chemical and microscopic techniques.
Metal-organic frameworks (MOFs) and covalent organic frameworks (COFs) are two innovative classes... more Metal-organic frameworks (MOFs) and covalent organic frameworks (COFs) are two innovative classes of porous coordination polymers. MOFs are three-dimensional materials made up of secondary building blocks comprised of metal ions/clusters and organic ligands whereas COFs are 2D or 3D highly porous organic solids made up by light elements (i.e., H, B, C, N, O). Both MOFs and COFs, being highly conjugated scaffolds, are very promising as photoactive materials for applications in photocatalysis and artificial photosynthesis because of their tunable electronic properties, high surface area, remarkable light and thermal stability, easy and relative low-cost synthesis, and structural versatility. These properties make them perfectly suitable for photovoltaic application: throughout this review, we summarize recent advances in the employment of both MOFs and COFs in emerging photovoltaics, namely dye-sensitized solar cells (DSSCs) organic photovoltaic (OPV) and perovskite solar cells (PSCs)...
The investigation of innovative electrolytes based on nontoxic and nonflammable solvents is an up... more The investigation of innovative electrolytes based on nontoxic and nonflammable solvents is an up-to-date, intriguing challenge to push forward the environmental sustainability of dye-sensitized solar cells (DSSCs). Water is one of the best choices, thus 100% aqueous electrolytes are proposed in this work, which are gelled with xanthan gum. This well-known biosourced polymer matrix is able to form stable and easily processable hydrogel electrolytes based on the iodide/triiodide redox couple. An experimental strategy, also supported by the multivariate chemometric approach, is used here to study the main factors influencing DSSCs efficiency and stability, leading to an optimized system able to improve its efficiency by 20% even after a 1200 h aging test, and reaching an overall performance superior to 2.7%. In-depth photoelectrochemical investigation demonstrates that DSSCs performance based on hydrogel electrolytes depends on many factors (e.g., dipping conditions, redox mediator co...
Uploads
Papers by Matteo Bonomo