Addition Of Lewis Bases Research Articles

Photodriven Sm(III)-to-Sm(II) Reduction for Catalytic Applications.

The selectivity of SmI2 as a one electron-reductant motivates the development of methods for reductive Sm-catalysis. Photochemical methods for SmI2 regeneration are desired for catalytic transformations. In particular, returning SmIII-alkoxides to SmII is a crucial step for Sm-turnover in many potential applications. To this end, photochemical conditions for reduction of both SmI3 and a model SmIII-alkoxide to SmI2(THF)n are described here. The Hantzsch ester can serve either as a direct photoreductant or as the reductive quencher for an Ir-based photoredox catalyst. In contrast to previous SmIII reduction methodologies, no Lewis acidic additives or byproducts are involved, facilitating selective ligand coordination to Sm. Accordingly, SmII species can be generated photochemically from SmI3 in the presence of protic, chiral, and/or Lewis basic additives. Both the photoreductant and photoredox methods for SmI2 generation translate to intermolecular ketone-acrylate coupling as a proof-of-concept demonstration of a photodriven, Sm-catalyzed reductive cross-coupling reaction.

Blade-Coating of High Crystallinity Cesium-Formamidinium Perovskite Formulations.

Up-scalable coating processes need to be developed to manufacture efficient and stable perovskite-based solar modules. In this work, we combine two Lewis base additives (N,N'-dimethylpropyleneurea and thiourea) to fabricate high-quality Cs0.15FA0.85PbI3 perovskite films by blade-coating on large areas. Selected-area electron diffraction patterns reveal a minimization of stacking faults in the α-FAPbI3 phase for this specific cesium-formamidinium composition in both spin-coated and blade-coated perovskite films, demonstrating its scaling potential. The underlying mechanism of the crystallization process and the specific role of thiourea are characterized by Fourier transform infrared spectroscopy and in situ optical absorption, showing clear interaction between thiourea and perovskite precursors and halved film-formation activation energy (from 114 to 49 kJ/mol), which contribute to the obtained specific morphology with the formation of large domain sizes on a short time scale. The blade-coated perovskite solar cells demonstrate a maximum efficiency of approximately 16.9% on an aperture area of 1 cm2.

Unlocking the Myths of Molecular Bonding State in Modulating Oxidation and Anderson Localization for Inorganic Sn/Pb‐based Perovskite Solar Cells

AbstractThe improvement of photovoltaic and stability performance of tin (Sn)‐based halide perovskite solar cells is impeded by notorious oxidation issues and Anderson localization. Despite previous implements in antioxidation through the incorporation of Lewis base additives, there still exist ongoing uncertainties surrounding its complex interaction mechanisms. A perplexing phenomenon regarding accelerated oxidation in acrylic acid is discovered that deviates from conventional Lewis base–acid reaction. The underlying insights into the deprotonation of acrylic acid followed by the formation of a “tripod” ionic bonding form are provided, which results in amplifying the delocalization effect of electrons of Sn2+. Furthermore, with the assistance of acrylamide and acrolein, synergistic enhancement in terms of the antioxidation and suppression of Anderson localization can be achieved — a concept referred to as “Dual Synergistic Engineering”. This suppresses the oxidation of Sn2+ and reduces Sn4+ content by ≈76%. Meanwhile, the diffusion length is prolonged significantly from 195.9 to 458.9 nm. The optimized all‐inorganic Sn/Pb‐based perovskite solar cells exhibit a power conversion efficiency of above 14% with enhanced stability. These findings provide an alternative viewpoint for comprehending the impact of chemical interaction on oxidation and crystal growth in Sn/Pb‐based perovskites.

A first-principles study of organic Lewis bases for passivating tin-based perovskite solar cells.

Tin-based perovskite solar cells (PSCs) are potential light absorbers for solar cell applications since they are less toxic compared to commonly used lead-based alternatives. Retaining the less stable Sn2+ state is key to improving the efficiency of tin-based PSCs. Organic Lewis base molecules have demonstrated potential to achieve this purpose. However, the critical factors influencing the performance of Lewis bases are largely unknown. In this study, we applied density functional theory (DFT) to investigate seven Lewis base materials, including methanol (MeOH), dimethyl ether (DME), ethyl methyl ether (EME), methyl acetate (MeOAc), methyl ammonium (MA), methyl sulfonic acid (MSA), and methyl phosphonic acid (MPA). Our results show that the effectiveness of passivation is linked to the gap between the HOMO and the LUMO (Egap). These findings provide theoretical guidance to screen Lewis base additives for enhancing energy conversion efficiencies of tin-based PSCs.

Synergistic Passivation via Lewis Coordination and Electrostatic Interaction for Efficient Perovskite Solar Cells

Non-radiative recombination has a negative impact on the device performance of perovskite solar cells (PSCs), and defect passivation can suppress the non-radiative recombination sufficiently. Herein, an innovative and effective synergistic passivation strategy is reported by introducing three kinds of maleic anhydride derivatives serving as Lewis base additives to the PbI2 precursor solution to obtain modified perovskite films and systematically investigating the synergistic effect of functional group passivation defects. Studies found that the electronic effect of the maleic anhydride derivatives would affect their interaction with defects. For example, the electrostatic interaction between the −CH3 positively charged by the conjugation effect and iodine(I) in 2,3-dimethylmaleic anhydride (M-MAH) enhances the coordination strength of the C═O bond with antisite lead (Pb) defects. Such synergetic passivation of M-MAH improves crystallinity and orientation and reduces defect state density. This modification also causes the edge of the perovskite band to bend upward, facilitating hole extraction and transport. These advantages enable the M-MAH-modified PSCs a champion power conversion efficiency (PCE) of 21.61% and significant environmental stability. Our findings not only provide new insights into the synergistic passivation associated with electrostatic interaction but also propose a simple strategy for fabricating high-performance perovskite optoelectronic devices.

K‐doped CuO/ZnO with dual active centers of synergism for highly efficient dimethyl carbonate synthesis

AbstractThe application of heterogeneous catalysts in dimethyl carbonate (DMC) synthesis from methanol is hindered by low activation efficiency of methanol to methoxy intermediates (CH3O*), which is the key intermediate for DMC generation. Herein, a catalyst of alkali metal K anchored on the CuO/ZnO oxide is rationally designed for offering Lewis acid–base pairs as dual active centers to improve the activation efficiency of methanol. Characterizations of CO2‐TPD, NH3‐TPD, XPS, and DRIFTS revealed that the addition of Lewis base K observably boosted the dissociation of methanol and combined with Lewis acid CuO/ZnO oxide to adsorb the formed CH3O* stably, thus synergistically promoted the transesterification. Finally, the CuO/ZnO‐9%K2O catalyst exhibited the optimal catalytic activity, achieving a high yield of 74.4% with an excellent selectivity of 98.9% for DMC at a low temperature of 90°C. The strategy of constructing Lewis acid–base pairs provides a reference for the design of heterogeneous catalysts.

Hard and Soft Acid and Base (HSAB) Engineering for Efficient and Stable Sn‐Pb Perovskite Solar Cells

AbstractRegulation of Lewis acid‐base adduct intermediate is more critical for the dual metal ions of Sn2+ and Pb2+ than for the single metal ion such as Pb2+ in preparing high quality perovskite films. It has been reported here that the photovoltaic performance of Sn‐Pb alloyed perovskite solar cells is dependent on the interaction between metal ions and Lewis base additives. Urea and thiourea are selected as an O‐ and a S‐donor, respectively, which is used as an additive in the precursor solution including equimolar SnI2 and PbI2 together with organic iodides of formamidinium iodide and methylammonium iodide, forming a nominal composition of FA0.5MA0.5Pb0.5Sn0.5I3. Open‐circuit voltage (Voc) is increased while maintaining short‐circuit photocurrent density (Jsc) after the addition of urea. On the other hand, both Jsc and Voc are simultaneously increased by adding thiourea, leading to a considerable increase in power conversion efficiency from 14.58% (control) to 18.59%. A strong interaction between the relatively soft Sn2+, compared to Sn4+, and the soft sulfur in thiourea, associated with hard and soft acid and base theory, suppresses effectively a disproportionation reaction of 2Sn2+→ Sn4+ + Sn0, which results in a substantial enhancement of carrier lifetime and consequently photovoltaic performance.

Thiourea with sulfur-donor as an effective additive for enhanced performance of lead-free double perovskite photovoltaic cells

Lead-free inorganic Cs2AgBiBr6 double perovskites have emerged as promising materials in perovskite solar cells (PSCs) to tackle the inferior stability and toxicity issues of organic–inorganic hybrid PSCs. However, the power conversion efficiencies (PCEs) of Cs2AgBiBr6 solar cells are remarkably restricted by the intrinsic and extrinsic defects of Cs2AgBiBr6 films. More specifically, the fast crystallization process in the formation of Cs2AgBiBr6 films strongly prevents the homogeneous growth of perovskite crystals, leading to inferior Cs2AgBiBr6 film quality. This work introduces a facile strategy to retard the crystallization of Cs2AgBiBr6 perovskites by introducing Lewis base additives into the precursor solution. The incorporation of a strongly coordinated thiourea additive with a sulfur donor leads to the generation of a Lewis acid base adduct, which retards the crystallization process for Cs2AgBiBr6 crystals, improves the quality of the Cs2AgBiBr6 film, decreases the defect density and inhibits charge carrier recombination. After optimization, the cell delivers a superior PCE of 3.07%, surpassing that reported for most Cs2AgBiBr6-based solar cells in the literature, and exhibits outstanding stability with a PCE retention rate of 95% after 20 days of storage in air. This work provides an effective strategy for further improvements in the performance of inorganic lead-free Cs2AgBiBr6-based photovoltaic cells.

Impact of surface-active site heterogeneity and surface hydroxylation in Ni doped ceria catalysts on oxidative dehydrogenation of propane

Using periodic Density Functional Theory calculations, propane oxidative dehydrogenation (ODH) and overoxidation over bare and hydroxylated Ni-doped CeO2 nanorods with predominantly exposed (110) facets were studied. Ab-initio thermodynamics-based surface phase analysis and computational Raman spectroscopic analysis predicted an 8.3 % surface oxygen vacancy concentration (Ce0.83Ni0.17O1.83) at typical ODH conditions. Only one-third of the surface oxygens, adjacent to the dopant, were selective for propene formation. Moreover, activated oxygen (O22–*) favored the formation of overoxidation products over propene. A monolayer hydroxyl coverage from water dissociation was stable at typical ODH conditions. This reduced the activation energy barrier for propene formation by 0.38 eV, increased the barrier for undesired acetone formation by 0.54 eV, and increased the barrier for propene activation by 0.6 eV. These promotional effects were due to the destabilization and induced hyperconjugation effects in the C3 adsorbates due to surface hydroxylation. Hence, surface hydroxylation (Lewis Base addition) is a potential strategy to improve propene selectivity.

Enhanced Reactivity for Aromatic Bromination via Halogen Bonding with Lactic Acid Derivatives.

We report a new method for regioselective aromatic bromination using lactic acid derivatives as halogen bond acceptors with N-bromosuccinimide (NBS). Several structural analogues of lactic acid affect the efficiency of aromatic brominations, presumably via Lewis acid/base halogen-bonding interactions. Rate comparisons of aromatic brominations demonstrate the reactivity enhancement available via catalytic additives capable of halogen bonding. Computational results demonstrate that Lewis basic additives interact with NBS to increase the electropositive character of bromine prior to electrophilic transfer. An optimized procedure using catalytic mandelic acid under aqueous conditions at room temperature was developed to promote aromatic bromination on a variety of arene substrates with complete regioselectivity.

Intermediate Chemistry of Halide Perovskites: Origin, Evolution, and Application.

The preparation of solution-processed metal halide perovskites is interwoven with research on their intermediate chemistry. In this Perspective, molecule-level insights are provided into how Lewis base additives (LBAs), e.g., DMSO and NMP, facilitate powder-to-film formation processes (i.e., the chemical origin of intermediate structures, structural evolution of intermediate-to-perovskite phase transition, and device-based application of intermediate-evolved perovskites). LBAs interact with Lewis acid species (cationic A+ or B2+ sites) of ABX3 structures with separate probability in terms of coordination bonds or hydrogen bonds to form two types of intermediate structures, inducing significant differences within intermediate-to-perovskite processes. In addition, in-depth understanding of intermediate chemistry favors the multifaceted applications of solution-processed perovskites. A brief summary is finally provided together with a perspective on how intermediate chemistry determines perovskite properties and applications.

Phosphine Oxide Additives for High‐Brightness Inorganic Perovskite Light‐Emitting Diodes

AbstractIn the search for cost‐efficient, simple, and solution processable light‐emitting diodes, metal halide perovskites show encouraging developments. In particular, the purely inorganic CsPbBr3 is a promising material with outstanding optoelectronic properties. However, the poor solubility of Cs‐salts leads to discontinuous film formation and a high density of defect states at the crystal surface. These problems are known to be reduced by Lewis base additives. In this work, a facile fabrication method using phosphine oxide ligands such as the trioctyl and triphenyl derivatives (TOPO and TPPO, respectively) is introduced. These additives reduce surface defect states, lead to an energetic confinement of charge carriers, and improve radiative recombination in the perovskite crystals. Using X‐ray diffraction, changes in crystallinity are observed, in particular the crystallinity of the 3D phase CsPbBr3 is reduced by addition of TOPO, while changes to the 0D phase (Cs4PbBr6) are much smaller. Overall, TOPO and TPPO containing films result in current efficiencies as high as 14 and 10 cd A−1 and an outstanding brightness of more than 57 800 and 18 300 cd m−2 in a relatively simple device stack.

Living Cationic Ring-Opening Homo- and Copolymerization of Cyclohexene Oxide by “Dormant” Species Generation Using Cyclic Ethers as Lewis Basic Additives

The living cationic ring-opening polymerization of cyclohexene oxide (CHO) was demonstrated to proceed using cyclic ethers as Lewis basic additives that potentially form “dormant” species through a reaction with the CHO-derived propagating species. The polymers obtained under suitable conditions had molecular weights close to the theoretical values and narrow molecular weight distributions. The formation of the dormant species was strongly supported by the generation of chain ends consisting of a cyclic ether additive and a quencher fragment, which was confirmed by 1H NMR and ESI-MS analysis of the product polymers. The use of additives with appropriate basicity, such as hexamethylene oxide and tetrahydropyran, is of considerable importance for living polymerization. In addition, the living copolymerization of CHO and 1,4-epoxycyclohexene and the synthesis of alternating-like acid-degradable polymers with aliphatic aldehydes were also achieved.

Hard and soft Lewis-base behavior for efficient and stable CsPbBr3 perovskite light-emitting diodes

Abstract All-inorganic CsPbBr3 perovskite is an attractive emission material for high-stability perovskite light-emitting diodes (PeLEDs), due to the high thermal and chemical stability. However, the external quantum efficiencies (EQEs) of CsPbBr3 based PeLEDs are still far behind their organic–inorganic congeners. Massive defect states on the surface of CsPbBr3 perovskite grains should be the main reason. Lewis base additives have been widely used to passivate surface defects. However, systematic investigations which relate to improving the passivation effect via rational molecule design are still lacking. Here, we demonstrate that the CsPbBr3 film’s optical and electrical properties can be significantly boosted by tailoring the hardness–softness of the Lewis base additives. Three carboxylate Lewis bases with different tail groups are selected to in-situ passivate CsPbBr3 perovskite films. Our research indicates that 4-(trifluoromethyl) benzoate acid anion (TBA−) with the powerful electron-withdrawing group trifluoromethyl and benzene ring possesses the softest COO− bonding head. TBA− thus acts as a soft Lewis base and possesses a robust combination with unsaturated lead atoms caused by halogen vacancies. Based on this, the all-inorganic CsPbBr3 PeLEDs with a maximum EQE up to 16.75% and a half-lifetime over 129 h at an initial brightness of 100 cd m−2 is thus delivered.

Effective lewis base additive with S-donor for efficient and stable CsPbI2Br based perovskite solar cells

• The coordination of S in TAA with Pb 2+ is more effective than O in AA. • The high crystallinity and efficient defects passivation are realized with TAA. • The PSC based on TAA exhibits the highest performance of 15.87% and improved stabilty. In perovskite solar cells, the Lewis acid-base additives function effectively in high crystalline perovskite film formation and defects passivation. Exploration of effective Lewis acid-base additive to prepare high quality inorganic CsPbI 2 Br perovskite films with few defects is quite imperative. Here, thioacetamide with S-donor and acetamide with O-donor as Lewis base additives are investigated. It is revealed that a high electron density on S results in better coordination ability with Pb 2+ in perovskite solution, leading to form high crystallinity film with lower defect states compared with O-donor. The inorganic CsPbI 2 Br based perovskite solar cells with thioacetamide additive exhibit the best performance of 15.87% (AM 1.5, 1 sun) and good ambient stability compared with the control device and device with acetamide. This work provides guidance for choosing and designing the effective additives for perovskite solar cells.

Chemical passivation of the under coordinated Pb2+ defects in inverted planar perovskite solar cells via β-diketone Lewis base additives.

Hybrid organic-inorganic perovskite solar cells (PSCs) are promising new generations of solar cells, which is low in cost with high power conversion efficiency (PCE). However, PSCs suffer from structural defects generated from the under coordinated ions at the surface, which limits their photovoltaic performances. Herein we report, two β-diketone Lewis base additives 2,4-pentanedione and 3-methyl-2,4-nonanedione within the chlorobenzene anti-solvent to passivate the surface defects generated from the under coordinated Pb2+ ions in CH3NH3PbI3 perovskite films. The incorporation of the two β-diketone passivators could successfully enhance the open-circuit voltage of the PSCs by 52mV and 17mV for 3-methyl-2,4-nonanedione and 2,4-pentanedione, respectively, with improved PCE by 45% for 3-methyl-2,4-nonanedione compared to the pristine PSC. This enhancement in the photovoltaic performance of the PSCs can be attributed to passivation of the defects through the interaction between two carbonyl groups of the β-diketone Lewis base additives and the under coordinated Pb2+ defects in the perovskite film, which improved the PSCs PCE and stability.

Manipulation of Perovskite Crystallization Kinetics via Lewis Base Additives

AbstractThe Lewis acid–base adduct approach has been widely used to form high‐crystalline perovskite films, but the complicated crystallization pathway and underlying film formation mechanism are still ambiguous. Here, the detailed crystallization process of perovskites manipulated by Lewis base additives has been revealed by in situ X‐ray scattering measurements. Through monitoring the film formation process, two distinct crystal growth stages have been definitely recognized: i) an intermediate phase‐dominated stage; and ii) a phase transformation stage from intermediates to crystalline perovskite phase. Incorporating Lewis base additives significantly prolongs the duration of stage 1 and induces a postponed phase transformation pathway, which could be responsible for retardant crystallization kinetics. Based on a series of experimental results and theoretical calculations, it is indicated that the manipulation of perovskite crystallization pathway is a result of the modulated molecular interactions between Lewis base additives and solution precursors. Owing to the retardant crystallization kinetics, enhanced‐quality perovskite films with reduced defect density and improved optoelectronic properties, as well as optimized photovoltaic performance have been demonstrated. This work provides in‐depth understanding with respect to perovskite crystallization pathway modulated by Lewis base additives and perceptive guidelines for precise regulation of crystallization kinetics of perovskite film toward high performance.

High‐Efficiency Tin Halide Perovskite Solar Cells: The Chemistry of Tin (II) Compounds and Their Interaction with Lewis Base Additives during Perovskite Film Formation

Lead (Pb)‐based perovskite solar cells (Pb‐PSCs) have been recorded with a fascinating power conversion efficiency (PCE) of 25.5%. However, the presence of toxic Pb in the perovskite absorber material hinders the commercial aspects of Pb‐PSCs as a promising and efficient new generation of solar cells. Fortunately, theoretical calculations have predicted that tin (Sn)‐based perovskite solar cells (Sn‐PSCs) could have superior performance comparable to the Pb‐PSCs. Recently, many approaches have been reported for developing efficient Sn‐PSCs but yet they have shown the best PCE of 13.24%. This low PCE compared to Pb‐PSCs might be because Sn‐PSCs have been approached in the same way as Pb‐PSCs. However, from a chemistry viewpoint, the understanding of Sn‐PSCs might be very different from that of Pb‐based ones. Herein, the fundamental knowledge of the chemistry and coordination chemistry of SnII compounds and their structural properties is described. Then, an insight is provided into understanding the recent trends of Sn perovskite formation using various Lewis base additives in the precursor solution and incorporation as a cation in the perovskite lattice. Finally, the influence of utilizing Lewis base additives on the device dynamics is discussed.

Z‐Selective α‐Arylation of α,β‐Unsaturated Nitriles via [3,3]‐Sigmatropic Rearrangement

AbstractThe Morita‐Baylis–Hillman (MBH) reaction and [3, 3]‐sigmatropic rearrangement are two paradigms in organic synthesis. We have merged the two types of reactions to achieve [3,3]‐rearrangement of aryl sulfoxides with α,β‐unsaturated nitriles. The reaction was achieved by sequentially treating both coupling partners with electrophilic activator (Tf2O) and base, offering an effective approach to prepare synthetically versatile α‐aryl α,β‐unsaturated nitriles with Z‐selectivity through direct α‐C‐H arylation of unmodified α,β‐unsaturated nitriles. The control experiments and DFT calculations support a four‐stage reaction sequence, including the assembly of Tf2O activated aryl sulfoxide with α,β‐unsaturated nitrile, MBH‐like Lewis base addition, [3,3]‐rearrangement, and E1cB‐elimination. Among these stages, the Lewis base addition is diastereoselective and E1cB‐elimination is cis‐selective, which could account for the remarkable Z‐selectivity of the reaction.

Z-Selective α-Arylation of α,β-Unsaturated Nitriles via [3,3]-Sigmatropic Rearrangement.

The Morita-Baylis-Hillman (MBH) reaction and [3, 3]-sigmatropic rearrangement are two paradigms in organic synthesis. We have merged the two types of reactions to achieve [3,3]-rearrangement of aryl sulfoxides with α,β-unsaturated nitriles. The reaction was achieved by sequentially treating both coupling partners with electrophilic activator (Tf2 O) and base, offering an effective approach to prepare synthetically versatile α-aryl α,β-unsaturated nitriles with Z-selectivity through direct α-C-H arylation of unmodified α,β-unsaturated nitriles. The control experiments and DFT calculations support a four-stage reaction sequence, including the assembly of Tf2 O activated aryl sulfoxide with α,β-unsaturated nitrile, MBH-like Lewis base addition, [3,3]-rearrangement, and E1cB-elimination. Among these stages, the Lewis base addition is diastereoselective and E1cB-elimination is cis-selective, which could account for the remarkable Z-selectivity of the reaction.