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At least 145 records · Page 8

Selective Bidentate Coordination Reconstructs Residual PbI 2 to Homogenize Interfacial Energetics in Perovskite Solar Cells

Spatially heterogeneous interfacial energetics, often originating from residual lead iodide (PbI 2 ), represent a fundamental bottleneck to both the efficiency and operational stability of perovskite photovoltaics. Conventional PbI 2 passivation strategies based on monodentate ligands or highly polar solvents either interact weakly with PbI 2 or undesirably perturb the underlying three-dimensional perovskite lattice. Here, we report a diammonium bidentate strategy that selectively reconstructs residual PbI 2 into corner-sharing PbI 6 octahedra while preserving the bulk perovskite. Enabled by dual-site coordination, a newly designed thiophene-based bidentate ligand (MeXT) stabilizes PbI 6 units during passivation and establishes spatially homogeneous interfacial energetics. Perovskite solar cells incorporating MeXT achieve 26.19% power conversion efficiency and retain over 80% of their initial efficiency after 1000 h of continuous 1-sun illumination at 75 °C. This dual-anchor coordination passivation strategy establishes a general design principle for selectively treating residual PbI 2 and creating electronically coherent and operationally stable interfaces in perovskite photovoltaics.

ligands↗

High performance polymerized small molecule acceptor by synergistic optimization on $\pi$-bridge linker and side chain

The polymerized small-molecule acceptors have attracted great attention for application as polymer acceptor in all-polymer solar cells recently. The modification of small molecule acceptor building block and the π-bridge linker is an effective strategy to improve the photovoltaic performance of the polymer acceptors. In this work, we synthesized a new polymer acceptor PG-IT2F which is a modification of the representative polymer acceptor PY-IT by replacing its upper linear alkyl side chains on the small molecule building block with branched alkyl chains and attaching difluorene substituents on its thiophene π-bridge linker. Through this synergistic optimization, PG-IT2F possesses more suitable phase separation, increased charge transportation, better exciton dissociation, lower bimolecular recombination, and longer charge transfer state lifetime than PY-IT in their polymer solar cells with PM6 as polymer donor. Therefore, the devices based on PM6:PG-IT2F demonstrated a high power conversion efficiency of 17.24%, which is one of the highest efficiency reported for the binary all polymer solar cells to date. This work indicates that the synergistic regulation of small molecule acceptor building block and π-bridge linker plays a key role in designing and developing highly efficient polymer acceptors.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Near-infrared absorbing acceptor with suppressed triplet exciton generation enabling high performance tandem organic solar cells

Reducing the energy loss of sub-cells is critical for high performance tandem organic solar cells, while it is limited by the severe non-radiative voltage loss via the formation of non-emissive triplet excitons. Herein, we develop an ultra-narrow bandgap acceptor BTPSeV-4F through replacement of terminal thiophene by selenophene in the central fused ring of BTPSV-4F, for constructing efficient tandem organic solar cells. The selenophene substitution further decrease the optical bandgap of BTPSV-4F to 1.17 eV and suppress the formation of triplet exciton in the BTPSV-4F-based devices. The organic solar cells with BTPSeV-4F as acceptor demonstrate a higher power conversion efficiency of 14.2% with a record high short-circuit current density of 30.1 mA cm –2 and low energy loss of 0.55 eV benefitted from the low non-radiative energy loss due to the suppression of triplet exciton formation. We also develop a high-performance medium bandgap acceptor O1-Br for front cells. By integrating the PM6:O1-Br based front cells with the PTB7-Th:BTPSeV-4F based rear cells, the tandem organic solar cell demonstrates a power conversion efficiency of 19%. The results indicate that the suppression of triplet excitons formation in the near-infrared-absorbing acceptor by molecular design is an effective way to improve the photovoltaic performance of the tandem organic solar cells.

14 SOLAR ENERGY↗

Auxiliary sequential deposition enables 19%-efficiency organic solar cells processed from halogen-free solvents

High-efficiency organic solar cells are often achieved using toxic halogenated solvents and additives that are constrained in organic solar cells industry. Therefore, it is important to develop materials or processing methods that enabled highly efficient organic solar cells processed by halogen free solvents. In this paper, we report an innovative processing method named auxiliary sequential deposition that enables 19%-efficiency organic solar cells processed by halogen free solvents. Our auxiliary sequential deposition method is different from the conventional blend casting or sequential deposition methods in that it involves an additional casting of dithieno[3,2-b:2’,3’-d]thiophene between the sequential depositions of the donor (D18-Cl) and acceptor (L8-BO) layers. The auxiliary sequential deposition method enables dramatic performance enhancement from 15% to over 18% compared to the blend casting and sequential deposition methods. Furthermore, by incorporating a branched-chain-engineered acceptor called L8-BO-X, device performance can be boosted to over 19% due to increased intermolecular packing, representing top-tier values for green-solvent processed organic solar cells. Comprehensive morphological and time-resolved characterizations reveal that the superior blend morphology achieved through the auxiliary sequential deposition method promotes charge generation while simultaneously suppressing charge recombination. This research underscores the potential of the auxiliary sequential deposition method for fabricating highly efficient organic solar cells using environmentally friendly solvents.

14 SOLAR ENERGY↗

Tuning polymer-backbone coplanarity and conformational order to achieve high-performance printed all-polymer solar cells

Abstract All-polymer solar cells (all-PSCs) offer improved morphological and mechanical stability compared with those containing small-molecule-acceptors (SMAs). They can be processed with a broader range of conditions, making them desirable for printing techniques. In this study, we report a high-performance polymer acceptor design based on bithiazole linker (PY-BTz) that are on par with SMAs. We demonstrate that bithiazole induces a more coplanar and ordered conformation compared to bithiophene due to the synergistic effect of non-covalent backbone planarization and reduced steric encumbrances. As a result, PY-BTz shows a significantly higher efficiency of 16.4% in comparison to the polymer acceptors based on commonly used thiophene-based linkers (i.e., PY-2T, 9.8%). Detailed analyses reveal that this improvement is associated with enhanced conjugation along the backbone and closer interchain π-stacking, resulting in higher charge mobilities, suppressed charge recombination, and reduced energetic disorder. Remarkably, an efficiency of 14.7% is realized for all-PSCs that are solution-sheared in ambient conditions, which is among the highest for devices prepared under conditions relevant to scalable printing techniques. This work uncovers a strategy for promoting backbone conjugation and planarization in emerging polymer acceptors that can lead to superior all-PSCs.

14 SOLAR ENERGY↗

Mechanistic insights into a heterobifunctional degrader-induced PTPN2/N1 complex

PTPN2 (protein tyrosine phosphatase non-receptor type 2, or TC-PTP) and PTPN1 are attractive immuno-oncology targets, with the deletion of Ptpn1 and Ptpn2 improving response to immunotherapy in disease models. Targeted protein degradation has emerged as a promising approach to drug challenging targets including phosphatases. We developed potent PTPN2/N1 dual heterobifunctional degraders (Cmpd-1 and Cmpd-2) which facilitate efficient complex assembly with E3 ubiquitin ligase CRL4 CRBN , and mediate potent PTPN2/N1 degradation in cells and mice. To provide mechanistic insights into the cooperative complex formation introduced by degraders, we employed a combination of structural approaches. Our crystal structure reveals how PTPN2 is recognized by the tri-substituted thiophene moiety of the degrader. We further determined a high-resolution structure of DDB1-CRBN/Cmpd-1/PTPN2 using single-particle cryo-electron microscopy (cryo-EM). This structure reveals that the degrader induces proximity between CRBN and PTPN2, albeit the large conformational heterogeneity of this ternary complex. The molecular dynamic (MD)-simulations constructed based on the cryo-EM structure exhibited a large rigid body movement of PTPN2 and illustrated the dynamic interactions between PTPN2 and CRBN. Together, our study demonstrates the development of PTPN2/N1 heterobifunctional degraders with potential applications in cancer immunotherapy. Furthermore, the developed structural workflow could help to understand the dynamic nature of degrader-induced cooperative ternary complexes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Integrated linker-regulation and ring-fusion engineering for efficient additive-free non-fullerene organic solar cells

The rational molecular design and structural modification of quasi-two-dimensional fused perylene diimide (quasi-2D FPDI) acceptors have received growing attention for application in non-fullerene organic solar cells (NF-OSCs). Herein, we designed and synthesized two pairs of FPDI acceptors, one in the form of FPDI–π-bridge–FPDI with the π-bridge being either an axisymmetric thiophene (T) or a centrosymmetric thienothiophene (TT) unit, and the other being the corresponding ring-fusion counterpart. Additionally, four small molecule acceptors, namely T-FPDI, TT-FPDI, FT-FPDI and FTT-FPDI, were paired with a common PTB7-Th polymeric electron donor as active materials for a comparative study of the effects of linkers and ring fusion on their photovoltaic performances. The T-FPDI-based NF-OSC exhibited a decent power conversion efficiency (PCE) of 5.50%, while a higher PCE of 7.17% with a simultaneous enhancement in the open circuit voltage ( V oc ), the short-circuit current density ( J sc ) and the fill factor (FF) was achieved for the TT-FPDI-based solar cells. The solar cells based on the ring-fused FT-FPDI and FTT-FPDI acceptors displayed PCEs of 6.75% and 7.66%, respectively, both higher than those of the corresponding non-fused counterparts. Notably, the trade-off between the J sc and V oc , commonly observed in fullerene OSCs, is alleviated in these systems. It is also worth noting that the NF-OSCs based on these FPDI acceptors do not need any solvent additives. Overall, this successful molecular engineering based on novel quasi-2D FPDI building blocks may inspire the development of emergent electron acceptors for high performance additive-free NF-OSCs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Charge generation mechanism tuned via film morphology in small molecule bulk-heterojunction photovoltaic materials

Small organic molecules have emerged as promising component materials for organic photovoltaic devices. Compared to most conjugated polymers for the same application, small molecules have unique morphologies that promote electronic processes relevant to organic solar cell (OSC) function that can be significantly different from those of conjugated polymeric materials. Here we investigate constituent loading-dependent effects on OSC morphology and function using the classical fullerene acceptor, PC 61 BM, in a heterojunction blend with the small molecule donor, NDT (thiophene-capped diketopyrrolopyrrole naphthodithiophene). The evolution of active layer morphology as well as exciton speciation and dynamics as a function of the PC 61 BM content are examined in combined structural studies using GIWAXS and spectroscopic studies using transient absorption spectroscopy. We observe evidence for three types of coexisting excitons and details of the interplay between them determines the yield of charge separated states that afford sustained device efficiency.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Influence of shape on crystal structure and optical properties of heterocyclic conjugated molecules

Organic optoelectronics are increasingly important due to their tunablilty, flexibility, and solution processability. Tuning optical properties of these materials as solids relies on the balance of weak non-covalent interactions that dictate crystal structure, but are difficult to predict. Our research aims to improve our understanding of how electrostatic interactions can direct and facilitate intramolecular interactions that dictate emergent properties of crystalline materials. This paper focuses on exploring how multi-fused thiophene ring systems that are popular in modern organic optoelectronic materials impact intramolecular interactions, while also investigating the role of molecular shape. In these examples, the shape of heterocyclic systems correlate with the crystal structures: while the bent heterocyclics show no discrete and discernable intramolecular interactions, those with bent shapes interact cofacially with one of the electron poor ArF pendants by twisting the arylene ethynylene backbone. Two of the control molecules, which bear non-fluorinated benzyl ester substituents, show intramolecular edge-face interactions, and several of these molecules show clear polymorphic behavior. Furthermore, these findings further our understanding of how discrete interactions can be altered not only by electrostatics, but also by shape, allowing for increasingly nuanced control over the crystal structures and optical properties of optoelectronic materials.

Guzmán, Elisa↗

Long-lived charge separation in two-dimensional ligand-perovskite heterostructures

Rational design of heterojunctions using nanostructured materials is a useful strategy for achieving efficient interfacial charge separation in photovoltaics. Heterojunctions can be constructed between organic ligands and inorganic layer in two-dimensional (2D) perovskites, taking advantage of their highly programmable structures. We investigate electron and hole transfer at the interface between the thiophene-based semiconducting ligands and the lead halide inorganic sublattices using time-resolved photoluminescence and transient reflection spectroscopy in single 2D perovskite crystals. Here, these measurements demonstrate charge transfer time of ~ 10 ps and long-lived charge-separated state over the nanosecond timescale in 2D ligand-perovskite heterostructures. The efficient charge transfer processes with slow charge recombination suggest the potential for improving exciton dissociation and charge transport in 2D perovskite solar cells.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Spin-dependent charge transmission through chiral 2T3N self-assembled monolayer on Au

In this study, a gold surface is functionalized by chemisorption of the enantiopure N,N'-bis-[2,2';5',2"]tert-thiophene-5-yl methylcyclohexane-1,2-diamine (2T3N), a chiral oligothiophene derivative, via overnight incubation in a 2T3N ethanol solution. The Au|2T3N interface is characterized by x-ray photoelectron circular dichroism and comparing x-ray photoemission spectroscopy and electro-desorption results. Charge transmission at the Au|2T3N| solution interface is characterized by recording the cyclic voltammetry of the Fe(III)/Fe(II) reversible redox couple, finding a charge transfer rate constant, k°, variation from 1 × 10 -1 to 3.3 × 10 -2 cm s -1 , when comparing the bare Au and the Au|2T3N interfaces, respectively. The “anomalous” high value of k° found for the chiral Au|2T3N interface can be rationalized on the basis of the chiral-induced spin selectivity effect, as further proved by magnetic–conductive atomic force microscopy measurements at room temperature. A spin polarization of about 30% is found.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Ultrafast x-ray scattering of photodissociation dynamics in 2-iodothiophene

Here, a time-resolved x-ray scattering (TRXS) investigation of the photodissociation dynamics of gas-phase 2-iodothiophene molecules following 252 nm excitation is presented. Structural evolution of the molecule and dynamical information on the resulting photofragments were captured using femtosecond x-ray free-electron laser pulses. Two dissociation pathways were identified, arising via excitation to ππ* and (n/π)σ* states, respectively, yielding distinct interfragment recoil velocities of ∼6.4 Åps −1 and 17.0 Åps −1 . A comparison of asymptotic scattering data with simulated patterns indicates that the thiophene ring remains closed following dissociation at this wavelength. Modeling the experimental data yields a branching ratio of ∼3:1 in favor of the high velocity channel. These findings demonstrate the capability of TRXS to disentangle concurrent ultrafast reaction pathways and provide detailed structural insight into energy redistribution during photoinduced bond fission in complex molecular systems.

Razmus, Weronika O. [Univ. of Southampton (United ↗

Electrochemical Characterization of Biomolecular Electron Transfer at Conductive Polymer Interfaces

Bio-electrochemical systems (BESs) are promising for renewable energy generation but remain hindered by inefficient electron transfer at electrode surfaces. As the toolbox of bio-anode materials increases, rigorous electrochemical characterization of emerging materials is needed. Here, we holistically characterize the electrochemical interaction of flavin mononucleotide (FMN), an electron shuttle in biological systems and a cofactor for oxidoreductase enzymes, with the bio-inspired mixed conducting polymer poly{3-[6'-(N-methylimidazolium)hexyl]thiophene} (P3HT-Im + ). The behavior of this polymer is compared to the equivalent polymer without the histidine-like imidazolium. We find improved conductivity and charge storage in imidazolium-containing polymers beyond what is explained by differences in the electroactive area. The P3HT-Im + further shows internal charge storage but with negligible faradaic contribution, indicating that charge storage capacity may translate to improved biocatalysis non-intuitive ways. Finally, one-electron transfer is observed between FMN and glassy carbon, while a bio-similar two-electron transfer is observed for the P3HT-Im + . To our knowledge, this is the first example of a concerted two-electron transfer between FMN and an electrode interface, which we attribute to the bio-inspired, histidine-like imidazolium functional groups in the polymer. These studies demonstrate the importance of bio-relevant materials characterization when such materials are deployed in BESs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Unifying principles for catalytic hydrotreating processes (Final Technical Report)

This project builds on the hypothesis that the hydrotreating processes for the removal of oxygen and sulfur are fundamentally similar at the atomic-scale and existing knowledge from the treatment of petroleum derived feedstock can be leveraged for the design of novel catalysts for the upgrade of bio-oil. We tested this hypothesis by comparing computed potential energy diagrams for hydrodesulfurization (HDS) of thiophene over MoS 2 with hydrodeoxygenation (HDO) of furan over MoO 3 and concluded that certain aspects, such as catalyst promotion with transition metals, are valid strategies for both reactions. On the other hand, we also noticed significant differences in the mechanism for hydrogen (H 2 ) activation, which requires sites with metallic character. While MoS 2 is known to have metallic edge states that can catalyze H 2 dissociation, this elementary step is prohibitively slow on defect-free oxides. Only in the presence of vacancies or by creating metal/oxide interfaces can efficient H 2 activation sites during HDO be formed. The need for bifunctional catalyst when it comes to efficient and selective HDO or dehydrogenation reactions was further corroborated in joint experimental and theoretical studies of the Guerbet reaction for the coupling of biomass derived oxygenates over PdCu alloys, nitrate reduction over In-promoted Pd nanoparticles, and ethylene dehydroaromatization over Ga-exchanged ZSM-5 zeolites. All of these catalytic systems have in common that catalytic sites with distinct functional requirements are needed to create a working catalyst. Detailed computational studies were carried out for HDO of m -cresol and phenol on Ru-modified TiO 2 surfaces, which allowed us to attribute catalytic activity to the metal/oxide interface. A surprising finding was that heterolytic cleavage of the H-H bond across the Ru/TiO 2 interface was critically important, despite lower barriers for homolytic H 2 activation on Ru metal. The explanation lies in the high barriers for hydrogen spillover from Ru to TiO 2 , which becomes unnecessary in the heterolytic activation pathway. Moreover, we also reported that proton transfer steps between metal and oxide sites are mediated by weakly adsorbed surface water. During attempts to develop and validate a kinetic Monte Carlo (kMC) model for HDO reactions at the Ru/TiO 2 interface, it became clear that lateral interactions are paramount to describe realistic surface chemistry and without these interactions, the reduction and hydroxylation behavior from our simulations was inconsistent with reported experiments. To assess the importance of lateral interactions in popular computational catalyst design strategies relying on the identification of reactivity descriptors, which can be used along with Brønsted–Evans–Polanyi (BEP) and scaling relations as input to a microkinetic model (MKM) to make predictions for activity or selectivity trends, we compared predicted trends with those obtained from descriptor-based kMC models. We critically evaluated the benefits of kMC over MKM in terms of trend predictions and computational cost when using only a small set of input parameters. After confirming that in the absence of lateral interactions the kMC and MKM approaches yield identical trends and mechanistic information, we observed substantial differences between the two kinetic models when lateral interactions were introduced. The mean-field implementation applies coverage corrections directly to the descriptors, causing an artificial overprediction of the activity of strongly binding metals. In contrast, the cluster expansion in kMC implementation can differentiate among the highly active metals but it is very sensitive to the set of included interaction parameters. Considering that computational screening relies on a minimal set of descriptors, for which MKM makes reasonable trend predictions at a ca. three orders of magnitude lower computational cost than kMC, we concluded that the MKM approach does provide an overall better entry point for computational catalyst design. Overall, this project has led to 11 peer-reviewed publications, and their scientific is impact is well illustrated by their combined 702 citations.

08 HYDROGEN↗

Benzoimidazolium-derived dimeric and hydride n-dopants for organic electron-transport materials: impact of substitution on structures, electrochemistry, and reactivity

1,3-Dimethyl-2,3-dihydrobenzo[ d ]imidazoles, 1H , and 1,1',3,3'-tetramethyl-2,2',3,3'-tetrahydro-2,2'-bibenzo[ d ]imidazoles, 1 2 , are of interest as n-dopants for organic electron-transport materials. Salts of 2-(4-(dimethylamino)phenyl)-4,7-dimethoxy-, 2-cyclohexyl-4,7-dimethoxy-, and 2-(5-(dimethylamino)thiophen-2-yl)benzo[ d ]imidazolium ( 1g–i + , respectively) have been synthesized and reduced with NaBH 4 to 1gH , 1hH , and 1iH , and with Na:Hg to 1g 2 and 1h 2 . Their electrochemistry and reactivity were compared to those derived from 2-(4-(dimethylamino)phenyl)- ( 1b + ) and 2-cyclohexylbenzo[ d ]imidazolium ( 1e + ) salts. E ( 1 + / 1 • ) values for 2-aryl species are less reducing than for 2-alkyl analogues, i.e., the radicals are stabilized more by aryl groups than the cations, while 4,7-dimethoxy substitution leads to more reducing E ( 1 + / 1 • ) values, as well as cathodic shifts in E ( 1 2 •+ / 1 2 ) and E ( 1H •+ / 1H ) values. Both the use of 3,4-dimethoxy and 2-aryl substituents accelerates the reaction of the 1H species with PC 61 BM. Because 2-aryl groups stabilize radicals, 1b 2 and 1g 2 exhibit weaker bonds than 1e 2 and 1h 2 and thus react with 6,13-bis(triisopropylsilylethynyl)pentacene ( VII ) via a “cleavage-first” pathway, while 1e 2 and 1h 2 react only via “electron-transfer-first”. 1h 2 exhibits the most cathodic E ( 1 2 •+ / 1 2 ) value of the dimers considered here and, therefore, reacts more rapidly than any of the other dimers with VII via “electron-transfer-first”. Crystal structures show rather long central C–C bonds for 1b 2 (1.5899(11) and 1.6194(8) Å) and 1h 2 (1.6299(13) Å).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Origin of organic matter in early solar system. V - Further studies of meteoritic hydrocarbons and a discussion of their origin.

The Murchison meteorite contains aliphatic and aromatic hydrocarbons similar to those made in static Fischer-Tropsch-type syntheses. Principal compound classes above C8 are n-alkanes, mono- and dimethylalkanes, alkenes, alkylbenzenes and -naphthalenes. Below C8, n-alkanes are virtually absent; instead, benzene, toluene, branched alkanes dominate. The CH4/C2H6 ratio is greater than 30, possibly greater than 700. Isoprenoids from C17 to C20 occur in a surface rinse but not in subsequent extracts and appear to be terrestrial contaminants. Thiophenes, porphyrin-like pigments, and chlorobenzenes were also found; the latter appear to be contaminants. In the Allende meteorite, only methane, benzene, toluene and an aromatic polymer seem to be indigeneous. A comprehensive review of current evidence shows that Fischer-Tropsch-type reactions can account for most principal features of meteorite organic matter.

Studier, M. H.↗

The polymer-like organic material in the Orgueil meteorite

Results are reported for analysis of polymeric organic material contained in powder from the Orgueil chondrite, using a stepwise high-vacuum pyrolysis-gas chromatography-mass spectrometry technique. Pyrolysis products obtained include a series of alkanes and alkenes to C8, an extensive series of alkylbenzene isomers, thiophene, alkylthiophenes, benzothiophene, acetonitrile, acrylonitrile, benzonitrile, acetone, and phenol. Most of these products are shown to be similar both qualitatively and quantitatively to those previously obtained from solvent-extracted Allende powder, indicating a basically aromatic and heteroaromatic polymer matrix with short aliphatic bridges or side chains. The production of acrylonitrile, acetonitrile, and benzonitrile (common breakdown products of amino acids) from the insoluble organic material is taken to suggest that amino acids exist in an insoluble form, perhaps as peptides, in the meteorite's polymeric component. Similarities between the structure of the Orgueil polymeric material and terrestrial kerogen are discussed which raise the possibility that both might have been produced in part by similar reactions.

Bandurski, E. L.↗