Authors: Giane Benvinda Damas, Fredrik von Kieseritzky, Jonas Hellberg, Cleber Fabiano N. Marchiori, Carlos Moyses Araujo
Small-molecules (SM) have attracted a great deal of attention in the field of solar energy conversion due to their unique properties compared to polymers, such as well-defined molecular weight and lack of regio-isomeric impurities. Furthermore, these materials can be synthesized in a variety of configurational architectures, representing an opportunity for tailoring chemical and optical properties that could lead to a better photocatalytic efficiency for hydrogen generation. Here, we evaluate by means of density functional theory (DFT) and time-dependent DFT methods a set of small-molecules with A-D-A architecture (A-acceptor; D- donor) based on well-known building blocks like thiophene (T), cyclopentadithiophene (CPT) and benzothiadiazole (BT) as potential candidates for photocatalytic hydrogen evolution reaction (HER). We also propose i) the replacement of the thiophene unit by 3,4-ethylenedioxythiophene (EDOT) to form with CPT unit an extended donor core ii) an additional acceptor unit, the 1,3,4-thiadiazole, in the extremities and iii) insertion of the difluoromethoxy (DFM) as substituent in the BT unit. Our outcomes reveal that these materials have a broad absorption spectrum with λ= 318-719 nm, being the most intense absorption peak originated from an electronic transition with charge-transfer nature, as the spatial distribution of LUMO is concentrated on the acceptor units for all materials. Moreover, these small-molecules not only present catalytic power or thermodynamic driving force to carry out the chemical reactions involved in the process of hydrogen production, but can be coupled in cooperative photocatalytic systems to promote intramolecular charge transfer that is expected to boost the overall photocatalytic efficiency of these materials.
J. Phys. Chem. C 2019,
Authors: Pascal Acker, Luisa Rzesny, Cleber F. N. Marchiori, C. Moyses Araujo and Birgit Esser
In recent years, organic battery cathode materials have emerged as an attractive alternative to metal oxide–based cathodes. Organic redox polymers that can be reversibly oxidized are particularly promising. A drawback, however, often is their limited cycling stability and rate performance in a high voltage range of more than 3.4 V versus Li/Li+. Herein, a conjugated copolymer design with phenothiazine as a redox‐active group and a bithiophene co‐monomer is presented, enabling ultra‐high rate capability and cycling stability. After 30 000 cycles at a 100C rate, >97% of the initial capacity is retained. The composite electrodes feature defined discharge potentials at 3.6 V versus Li/Li+ due to the presence of separated phenothiazine redox centers. The semiconducting nature of the polymer allows for fast charge transport in the composite electrode at a high mass loading of 60 wt%. A comparison with three structurally related polymers demonstrates that changing the size, amount, or nature of the side groups leads to a reduced cell performance. This conjugated copolymer design can be used in the development of advanced redox polymers for batteries.
Adv. Funct. Mater.2019, 1906436
Authors: Giane Benvinda Damas, Cleber Fabiano N. Marchiori, and Carlos Moyses Araujo
Polymeric materials containing an extended π-conjugated backbone have shown a wide range of applicability including photocatalytic activity for hydrogen evolution reaction (HER). The latter requires highly efficient materials with optimal light absorption and thermodynamic driving force for charge transfer processes, properties that are tailored by linking chemical units with distinct electron-affinity to form donor-acceptor architecture. Here, this concept is explored by means of ab initio theory in benzothiadiazole-based polymers with varying electron-rich moieties, viz. fluorene (PFO), cyclopentadithiophene (CPT), methoxybenzodithiophene (O-BzT), thiophenebenzodithiophene (T-BzT), thiophene- (T, VT) and thienethiophene (TT, VTT)-based units. All materials exhibit a red-shifted absorption spectrum with respect to the reference polymer (PFO-DT-BT), while keeping the catalytic power for hydrogen production almost unchanged. In particular, a displacement of ∆λ=167 nm in the first absorption maximum has been achieved upon combination of chemical units with high donating character in CPT-VTT-BT. Furthermore, the exciton binding energies (Eb) have been systematically investigated to unveil the effects of geometry relaxation, environment polarity and finite temperature contributions to the free energy. For instance, we show a significant change in Eb when going from the gas phase (Eb=1.43-1.85 eV) to the solvent environment (Eb=0.29-0.54 eV in 1-bromooctane with ε=5.02). Furthermore, we have found a linear correlation between the lowering of exciton binding energies and the increasing of the ratio between donor and acceptor contributions to the HOMO orbital. This is a consequence of increased donating ability and enhanced spatial separation of electron-hole pairs, which weakens their interaction. Finally, our findings reveal that the donor unit plays a crucial role on key properties that govern the photocatalytic activity of donor-acceptor polymers contributing to the development of a practical guideline to design more efficient photocatalysts for HER. This goes through a proper combination of electron-rich moieties to tune the optical gap, favor thermodynamic driving force for charge transfer and lower exciton binding energies.
J. Phys. Chem. C, 2019, 123, 42, 25531-25542
Authors: Leandro Benatto, Cleber F. N. Marchiori, C. Moyses Araujo and Marlus Koehler
Due to the strong exciton binding energy (Eb) of organic materials, the energy offset between donor (D) and acceptor (A) materials is essential to promote charge generation in organic solar cells (OSCs). Yet an efficient exciton dissociation from non-fullerene acceptors (NFAs) began to be observed in D/A blends even at very low driving force for hole transfer (ΔHh). The mechanism behind this efficient photoinduced hole transfer (PHT) remains unclear since current estimates from calculations of isolated molecules indicate that Eb > ΔHh. Here we rationalize these discrepancies using density functional theory (DFT), the total Gibbs free energy method and the extended Hückel theory (EHT). First, we employed DFT to calculate Eb for NFAs of three representative groups (perylene diimide derivatives, indacenodithiophene and subphthalocyanines) as well as for fullerene acceptors (FAs). Considering isolated molecules in the calculations, we verified that Eb for NFAs is lower than for FAs but still higher than the experimental ΔHh in which efficient PHT has been observed. Finding the molecular geometry of the excited state, we also obtain that the structural relaxation after photoexcitation tends to further decrease (increase) Eb for NFAs (FAs). This effect helps explain the delayed charge generation measured in some NFA systems. However, this effect is still not large enough for a significant decrease in Eb. We then applied EHT to quantify the decrease of Eb induced by energy levels coupling between stacked molecules in a model aggregate. We then estimated the number of stacked molecules so that Eb approaches ΔHh‘s. We found that small NFA aggregates, involving around 5 molecules, are already large enough to explain the experiments. Our results are justified by the low energy barrier to the generation of delocalized states in these systems (especially for the hole delocalization). Therefore, they indicate that molecular systems with certain characteristics can achieve efficient molecular orbital delocalization, which is a key factor to allow an efficient exciton dissociation in low-driving-force systems. These theoretical findings provide a sound explanation to very recent observations in OSCs.
J. Mat. Chem. C 2019, 2019,7, 12180-12193
Authors: Cleber F. N. Marchiori, Daniel Brandell, and C. Moyses Araujo
Organic electroactive materials are promising candidates to be used as lithium insertion electrodes in the next generation of environmentally friendly battery technologies. In this work, evolutionary algorithms at interplay with density functional theory calculations have been employed to predict the crystal structure for both delithiated and lithiated phases of dilithium thiophene dicarboxylate (Li2TDC). On the basis of the resulting crystals, electronic structure modifications and voltage profiles for the lithiation process have been calculated. The obtained structure for the delithiated phase showed a well-defined salt layer intercalating the organic components, forming a so-called lithium organic framework (LOF). Upon lithiation, new structures appear which deviate from the LOF as a consequence of the reduction of the S atoms, which coordinate with the additional Li ions. The calculated average potential of ∼1.00 V vs Li/Li+ is found to be in good agreement with experimental findings. An additional study at the molecular level has also been conducted aiming at gaining insight into the importance of the crystallographic environment on the structural and thermodynamics properties. This strategy is suitable for an initial assessment of the electrochemical process that underlies the lithiation mechanism of electrode materials. Moreover, the employed evolutionary algorithm emerges as a promising tool to predict crystal structures during lithiation, which are otherwise difficult to resolve experimentally.
J. Phys. Chem. C, 2019 123, 8, p. 4691-4700
Authors: Amina Mirsakiyeva, Mahsa Ebadi, C. Moyses Araujo, Daniel Brandell, Peter Broqvist, Jolla Kullgren
Poly(ethylene oxide) (PEO) is the most widely used compound as a solid-state (solvent-free) polymer electrolyte for Li batteries, mainly due to its low glass transition temperature (Tg) and ability to dissolve Li salts. It is also frequently suggested that its cathodic stability renders it possible to operate with Li metal anodes in the design of high energy density storage devices. However, little is still known about the true interfacial chemistry between Li metal and PEO and how these two materials interact with each other. We are here exploring this relationship by the means of density functional theory (DFT)-based modeling. Using bulk structures and isolated PEO chains, we have found that there is a strong thermodynamic driving force to oxidize Li metal into lithium oxide (Li2O) when PEO is decomposed into C2H4 and H2, irrespectively of the PEO oligomer length. Explicit modeling of PEO on a Li(100) surface reveals that all steps in the decomposition are exothermic and that the PEO/Li metal system should have a layer of Li2O between the polymer electrolyte and the metal surface. These insights and the computational strategy adopted here could be highly useful to better tailor polymer electrolytes with favorable interfacial properties.
J. Phys. Chem. C, 2019, 123, 37, p. 22851-22857