Molecular Ligands Control Superlattice Structure and Crystallite Orientation in Colloidal Quantum Dot Solids

Colloidal quantum dot solids represent a new materials platform that has garnered interest for a variety of electronic, optoelectronic, and photovoltaic applications. In such solids, individual quantum dots must be coupled with each other to facilitate charge transport through the solid. Past improvements on charge transport of colloidal quantum dot solids have been achieved primarily through the control of the interparticle spacing. However, the role of morphological ordering of the crystalline facets of individual quantum dots on the charge transport of the quantum dot solid is unknown. Here, we show for the first time that small passivating ligand molecules around the quantum dots can control the arrangement of different facets of quantum dots within the quantum dot solid. The insights from this study provide important directions for future enhancement in orientation of quantum dots in colloidal quantum dot solids

<i>In Situ</i> X‑ray Scattering Guides the Synthesis of Uniform PtSn Nanocrystals

Compared to monometallic nanocrystals (NCs), bimetallic ones often exhibit superior properties due to their wide tunability in structure and composition. A detailed understanding of their synthesis at the atomic scale provides crucial knowledge for their rational design. Here, exploring the Pt–Sn bimetallic system as an example, we study in detail the synthesis of PtSn NCs using <i>in situ</i> synchrotron X-ray scattering. We show that when Pt­(II) and Sn­(IV) precursors are used, in contrast to a typical simultaneous reduction mechanism, the PtSn NCs are formed through an initial reduction of Pt­(II) to form Pt NCs, followed by the chemical transformation from Pt to PtSn. The kinetics derived from the <i>in situ</i> measurements shows fast diffusion of Sn into the Pt lattice accompanied by reordering of these atoms into intermetallic PtSn structure within 300 s at the reaction temperature (∼280 °C). This crucial mechanistic understanding enables the synthesis of well-defined PtSn NCs with controlled structure and composition via a seed-mediated approach. This type of <i>in situ</i> characterization can be extended to other multicomponent nanostructures to advance their rational synthesis for practical applications

Activity of Silica-Alumina for the Conversion of Polyethylene into Tunable Aromatics Below Pyrolytic Temperatures

Plastic waste is a mounting problem that lacks global strategy, largely due to inadequate recycling capabilities. One alternative gaining traction in the heterogeneous catalysis community is the upcycling of polyolefins into value-added products, such as hydrogen-free conversion to alkylaromatic compounds over Pt/Al2O3. Here, we examined the activity of nominally metal-free, mesoporous silica-alumina mixed oxide materials (SiO2–Al2O3) for the conversion of polyethylene into aromatic compounds at temperatures of and below 280 °C. Yields with the silica-alumina catalysts are comparable to those obtained over Pt(1 wt %)/Al2O3 under identical conditions, and product selectivity can be tuned by altering reaction conditions or the acid site density of the SiO2–Al2O3. Notably, the fraction of polyaromatic products increases with the Brønsted acid site density of the catalyst, as does the degree of polymer deconstruction. These catalysts can be reused without regeneration, and their activity improves with each recycling event, producing soluble product yields up to 83%. Preliminary work on the mechanism of the reaction suggests that acid sites are responsible for initiating depolymerization and aromatization reactions, in analogy to previous work in the literature. This work showcases the activity of SiO2–Al2O3 for polyolefin deconstruction/aromatization at subpyrolytic temperatures and lays the foundation for future studies involving solid acid and bifunctional catalysts

Chemical Annealing of Zinc Tetraphenylporphyrin Films: Effects on Film Morphology and Organic Photovoltaic Performance

We present a chemical annealing process for organic thin films. In this process, a thin film of a molecular material, such as zinc tetraphenylporphyrin (ZnTPP), is exposed to a vapor of nitrogen-based ligand (e.g., pyrazine, pz, and triazine, tz), forming a film composed of the metal–ligand complex. Fast and quantitative formation of the complex leads to marked changes in the morphology and optical properties of the film. X-ray diffraction studies show that the chemical annealing process converts amorphous ZnTPP films to crystalline ZnTPP·ligand films, whose porphryin planes lie nearly parallel to the substrate (average deviation is 8° for the ZnTPP·pz film). Organic solar cells were prepared with ZnTPP donor and C₆₀ acceptor layers. Devices were prepared with and without chemical annealing of the ZnTPP layer with a pyrazine ligand. The devices with chemically annealed ZnTPP donor layer show an increase in short-circuit current (<i>J</i>_SC) and fill factor (<i>FF</i>) relative to analogous unannealed devices, presumably because of enhanced exciton diffusion length and improved charge conductivity. The open circuit voltages (<i>V</i>_OC) of the chemically annealed devices are lower than their unannealed counterpart because of enhanced polaron pair recombination at the donor/acceptor heterojunction. A net improvement of 5–20% in efficiency has been achieved, after chemical annealing of ZnTPP films with pyrazine

Effect of Backbone Chemistry on the Structure of Polyurea Films Deposited by Molecular Layer Deposition

An experimental investigation into the growth of polyurea films by molecular layer deposition was performed by examining trends in the growth rate, crystallinity, and orientation of chains as a function of backbone flexibility. Growth curves obtained for films containing backbones of aliphatic and phenyl groups indicate that an increase in backbone flexibility leads to a reduction in growth rate from 4 to 1 Å/cycle. Crystallinity measurements collected using grazing incidence X-ray diffraction and Fourier transform infrared spectroscopy suggest that some chains form paracrystalline, out-of-plane stacks of polymer segments with packing distances ranging from 4.4 to 3.7 Å depending on the monomer size. Diffraction intensity is largely a function of the homogeneity of the backbone. Near-edge X-ray absorption fine structure measurements for thin and thick samples show an average chain orientation of ∼25° relative to the substrate across all samples, suggesting that changes in growth rate are not caused by differences in chain angle but instead may be caused by differences in the frequency of chain terminations. These results suggest a model of molecular layer deposition-based chain growth in which films consist of a mixture of upward growing chains and horizontally aligned layers of paracrystalline polymer segments

Systematic Identification of Promoters for Methane Oxidation Catalysts Using Size- and Composition-Controlled Pd-Based Bimetallic Nanocrystals

Promoters enhance the performance of catalytic active phases by increasing rates, stability, and/or selectivity. The process of identifying promoters is in most cases empirical and relies on testing a broad range of catalysts prepared with the random deposition of active and promoter phases, typically with no fine control over their localization. This issue is particularly relevant in supported bimetallic systems, where two metals are codeposited onto high-surface area materials. We here report the use of colloidal bimetallic nanocrystals to produce catalysts where the active and promoter phases are colocalized to a fine extent. This strategy enables a systematic approach to study the promotional effects of several transition metals on palladium catalysts for methane oxidation. In order to achieve these goals, we demonstrate a single synthetic protocol to obtain uniform palladium-based bimetallic nanocrystals (PdM, M = V, Mn, Fe, Co, Ni, Zn, Sn, and potentially extendable to other metal combinations) with a wide variety of compositions and sizes based on high-temperature thermal decomposition of readily available precursors. Once the nanocrystals are supported onto oxide materials, thermal treatments in air cause segregation of the base metal oxide phase in close proximity to the Pd phase. We demonstrate that some metals (Fe, Co, and Sn) inhibit the sintering of the active Pd metal phase, while others (Ni and Zn) increase its intrinsic activity compared to a monometallic Pd catalyst. This procedure can be generalized to systematically investigate the promotional effects of metal and metal oxide phases for a variety of active metal-promoter combinations and catalytic reactions

Tuning Precursor Reactivity toward Nanometer-Size Control in Palladium Nanoparticles Studied by in Situ Small Angle X‑ray Scattering

Synthesis of monodisperse nanoparticles (NPs) with precisely controlled size is critical for understanding their size-dependent properties. Although significant synthetic developments have been achieved, it is still challenging to synthesize well-defined NPs in a predictive way due to a lack of in-depth mechanistic understanding of reaction kinetics. Here we use synchrotron-based small-angle X-ray scattering (SAXS) to monitor in situ the formation of palladium (Pd) NPs through thermal decomposition of Pd–TOP (TOP: trioctylphosphine) complex via the “heat-up” method. We systematically study the effects of different ligands, including oleylamine, TOP, and oleic acid, on the formation kinetics of Pd NPs. Through quantitative analysis of the real-time SAXS data, we are able to obtain a detailed picture of the size, size distribution, and concentration of Pd NPs during the syntheses, and these results show that different ligands strongly affect the precursor reactivity. We find that oleylamine does not change the reactivity of the Pd–TOP complex but promote the formation of nuclei due to strong ligand–NP binding. On the other hand, TOP and oleic acid substantially change the precursor reactivity over more than an order of magnitude, which controls the nucleation kinetics and determines the final particle size. A theoretical model is used to demonstrate that the nucleation and growth kinetics are dependent on both precursor reactivity and ligand–NP binding affinity, thus providing a framework to explain the synthesis process and the effect of the reaction conditions. Quantitative understanding of the impacts of different ligands enables the successful synthesis of a series of monodisperse Pd NPs in the broad size range from 3 to 11 nm with nanometer-size control, which serve as a model system to study their size-dependent catalytic properties. The in situ SAXS probing can be readily extended to other functional NPs to greatly advance their synthetic design

Monitoring a Silent Phase Transition in CH₃NH₃PbI₃ Solar Cells via <i>Operando</i> X‑ray Diffraction

The relatively modest temperature of the tetragonal-to-cubic phase transition in CH₃NH₃PbI₃ perovskite is likely to occur during real world operation of CH₃NH₃PbI₃ solar cells. In this work, we simultaneously monitor the structural phase transition of the active layer along with solar cell performance as a function of the device operating temperature. The tetragonal to cubic phase transition is observed in the working device to occur reversibly at temperatures between 60.5 and 65.4 °C. In these <i>operando</i> measurements, no discontinuity in the device performance is observed, indicating electronic behavior that is insensitive to the structural phase transition. This decoupling of device performance from the change in long-range order across the phase transition suggests that the optoelectronic properties are primarily determined by the local structure in CH₃NH₃PbI₃. That is, while the average crystal structure as probed by X-ray diffraction shows a transition from tetragonal to cubic, the local structure generally remains well characterized by uncorrelated, dynamic octahedral rotations that order at elevated temperatures but are unchanged locally

Polypeptide Composite Particle-Assisted Organization of π‑Conjugated Polymers into Highly Crystalline “Coffee Stains”

We demonstrate that homopolypeptides covalently tethered to anisotropically shaped silica particles induce crystalline ordering of representative semiconducting polymers. Films drop-cast from chloroform dispersions of poly­(γ-stearyl-l-glutamate) (PSLG) composite particles and poly­(3-hexythiophene) (P3HT) led to highly ordered crystalline structures of P3HT. Hydrophobic–hydrophobic interactions between the alkyl side chains of P3HT and PSLG were the main driving force for P3HT chain ordering into the crystalline assemblies. It was found that the orientation of rigid P3HT fibrils on the substrate adopted the directionality of the evaporating front. Regardless of the PSLG-coated particle dimensions used, the drop-cast films displayed patterns that were shaped by the coffee ring and Marangoni effects. PSLG-coated particles of high axial ratio (4.2) were more efficient in enhancing the electronic performance of P3HT than low axial ratio (2.6) homologues. Devices fabricated from the ordered assemblies displayed improved charge-carrier transport performance when compared to devices fabricated from P3HT alone. These results suggest that PSLG can favorably mediate the organization of semiconducting polymers

Protein-Assisted Assembly of π‑Conjugated Polymers

In an aqueous suspension process, protein dispersions facilitated improved alignment and organization of poly­(3-hexylthiophene) (P3HT) chains into highly ordered crystalline structures. A solution of P3HT in 1,2,4-trichlorobenzene (TCB) was added to an aqueous dispersion of the hydrophobin, Cerato ulmin (CU). Upon gentle agitation, the semiconductor solution was readily confined within CU membrane-stabilized microstructures, often with extended shapes. UV–vis and polarized micro-Raman spectroscopy suggested complex, enhanced molecular alignment due to a transition from isotropic to liquid crystalline fluid to polycrystalline states. Grazing-incidence X-ray diffraction corroborates this interpretation. On aging, the initial CU:P3HT/TCB structures develop dendritic architectures that slowly release polymer-containing capsules. The counterintuitive evolution from large structures to smaller ones suggests the initial structures were nonequilibrium, and it opens the door to latex-like processing of semiconducting polymers into crystalline, high-performance thin films for device applications. Preliminary studies using an organic field-effect transistor architecture suggest that optimized processing and device configuration will enable highly crystalline active materials with efficient charge transport characteristics