Morphogenesis of Magnetite Mesocrystals: Interplay between Nanoparticle Morphology and Solvation Shell

Brunner, Julian; Maier, Britta; Thomä, Sabrina L. J.; Kirner, Felizitas; Baburin, Igor A.; Lapkin, Dmitry; Rosenberg, Rose; Sturm, Sebastian; Assalauova, Dameli; Carnis, Jérôme; Kim, Young Yong; Ren, Zhe; Westermeier, Fabian; Theiß, Sebastian; Borrmann, Horst; Polarz, Sebastian; Eychmüller, Alexander; Lubk, Axel; Vartanyants, Ivan A.; Cölfen, Helmut; Zobel, Mirijam; Sturm, Elena V.

doi:10.1021/acs.chemmater.1c01941

Cited by 13 publications

(24 citation statements)

References 69 publications

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“…Furthermore, a variation in the crystallographic arrangement of the PtNCs in mesocrystals from OLA, LOA, or LLA is unlikely given the results of preceding work where it is shown that the crystal structure of a gas‐phase diffusion self‐assembled mesocrystal is dictated by the solvent and stabilizer concentration rather than its number of C═C double bonds [14a,19] . These findings conclude that the increasing facet‐to‐facet particle distance, which we examined in the 2D self‐assemblies, must be taking effect within the 3D mesocrystals as well and are the primary contributor to the decrease in conductivity.…”

Section: Discussionmentioning

confidence: 57%

Tuning the Electronic Properties of Mesocrystals

Jenewein

Schupp

et al. 2022

Small Science

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Colloidal crystals are arguably one of the most promising candidates when it comes to the fabrication of nanostructured metamaterials. Especially mesocrystals show exciting new properties that emerge from their inherent directional oriented assembly. With this work, the electrical conductivity of well‐defined micrometer‐sized platinum nanocube‐based mesocrystals is demonstrated and tuned through the variation of different capping agents. Herein, a method is presented to reproducibly quantify the intrinsic resistance of individual mesocrystals through electrical nanoprobing and focused ion beam deposition contacting. A thermally activated tunneling mechanism is identified as the main effect for electron propagation. In addition, the mesocrystals are altered through organically linking and mineral bridging the individual nanoparticles. This results in an increase in mesocrystal rigidity and, more importantly, conductivity by seven orders of magnitude while retaining shape, structure, and composition. In addition, these observations are transferred onto multicomponent superstructures in the form of binary mesocrystals. There, it is demonstrated that the electrical properties could be tuned through the ratio of nanoparticles incorporated into a mesocrystalline host system while simultaneously maintaining potential catalytic or superparamagnetic features of the guest particles.

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Section: Discussionmentioning

confidence: 57%

Tuning the Electronic Properties of Mesocrystals

Jenewein

Schupp

et al. 2022

Small Science

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“…This approach was already successfully applied for the analysis of the averaged structures and defects in single colloidal grains of gold and magnetite nanocrystals Schlotheuber ne ´Brunner et al, 2021). We expect that it will find applications for understanding the structure of colloidal grains and single crystals in future.…”

Section: Discussionmentioning

confidence: 98%

“…Here, we demonstrated an application of the AXCCA for qualitative determination of the crystalline structure of a colloidal crystal, including the present planar defects. AXCCA provides a complementary view on the structure when CDI reconstruction does not work (Schlotheuber ne ´Brunner et al, 2021). The results can be interpreted by means of a simple geometrical model of the crystalline lattice and defects.…”

Section: Discussionmentioning

confidence: 99%

“…Although such a reconstruction provides full information about the structure, the method is highly demanding in terms of experimental requirements and data quality. AXCCA is based on the analysis of angular correlations of scattered intensities in reciprocal space and can be applied to datasets of much lower quality, for which the phase retrieval algorithms fail, to reveal the structural features averaged over the sample without the need to perform a reconstruction (Schlotheuber ne ´Brunner et al, 2021).…”

Section: Introductionmentioning

confidence: 99%

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Angular X-ray cross-correlation analysis applied to the scattering data in 3D reciprocal space from a single crystal

Lapkin¹,

Shabalin²,

Meijer³

et al. 2022

Int Union Crystallogr J

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An application of angular X-ray cross-correlation analysis (AXCCA) to the scattered intensity distribution measured in 3D reciprocal space from a single-crystalline sample is proposed in this work. Contrary to the conventional application of AXCCA, when averaging over many 2D diffraction patterns collected from different randomly oriented samples is required, the proposed approach provides an insight into the structure of a single specimen. This is particularly useful in studies of defect-rich samples that are unlikely to have the same structure. The application of the method is shown on an example of a qualitative structure determination of a colloidal crystal from simulated as well as experimentally measured 3D scattered intensity distributions.

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“…In this sense, solvent quality plays a significant role in the extension of the ligand layer and the hydrodynamical shape (i.e., the volume of the surface ligand shell increases when its solvation degree increases). 2,3,27,50,51 Notably, depending on the mesocrystals under investigation, other factors need to be considered for the eventual controlled growth of 3D binary mesocrystals. For instance, in some cases, high nanoparticle concentrations can favor the formation of bcc structures 53,54 (i.e., generally associated with the absence of long-range order at the atomic level).…”

Section: Effective Shapementioning

confidence: 99%

Self-Assembly of Colloidal Nanocrystals into 3D Binary Mesocrystals

González‐Rubio

Cölfen

2022

Acc. Chem. Res.

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Conspectus Biominerals are unique materials found in many living organisms that often display outstanding functionalities attributed to their mesocrystalline structure. Mesocrystals are nanocrystal superstructures with mutual crystallographic alignment of the building units. One could thus imagine these optimized evolutionary systems as archetypes to fabricate advanced materials. The main advantage of such systems relies on their ability to combine the features of the nanocrystals with those of single crystalline microscopic structures, yielding assemblies with directional, enhanced, and potentially emergent properties. Moreover, fueled by the promises of multifunctional materials with unprecedented and tunable properties, the rational design of mesocrystals assembled from two distinct colloidal nanocrystal ensembles has become a recent focus of research. However, the combination of dissimilar nanocrystals into ordered binary superstructures is still a major scientific challenge due to the nature of the coassembly process. We focus this Account on the growth of tridimensional (3D) binary mesocrystals and the understanding of the self-assembly of two colloidal nanocrystal ensembles with the ultimate goal to serve as a basis for more rational mesocrystal syntheses in the future. The formation of mesocrystals demands nanocrystals with defined surface faceting, the primary factor influencing their oriented self-assembly. Notably, such a process cannot be successfully afforded without functionalized nanocrystals with high and, in many cases, tunable colloidal stability. Besides, the nature and solvation degree of the surface ligand shell influences the effective shape of the nanocrystals and the kinetics of self-assembly. If the assembly is triggered by reducing the colloidal stability with nonsolvents, 3D single-component mesocrystals are often grown. Here, the different magnitude of the van der Waals attraction forces between nanocrystals with differing compositions, dimensions, and morphologies generally favors the segregation and growth of single component mesocrystals. This phenomenon was illustrated during the successful preparation of 3D binary mesocrystals composed of iron oxide and platinum nanocubes. Although the building blocks possessed comparable sizes and were stabilized by similar ligands, the amount of the second component could only be arbitrarily tuned up to some extent, even when the assembly conditions were rationally optimized to achieve 3D binary mesocrystals. Only a small amount of it was effectively incorporated into the matrix of the initial mesocrystal. The 3D binary mesocrystal growth process demands a delicate control over the size, shape, and surface chemistry of the nanocrystals, the solvent nature, and the self-assembly process. Hence, the improvement of our ability to control the synthesis of 3D binary mesocrystalline materials is critical to exploit their potential toward technological applications in catalysis, energy storage, or structural materials.

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Morphogenesis of Magnetite Mesocrystals: Interplay between Nanoparticle Morphology and Solvation Shell

Cited by 13 publications

References 69 publications

Tuning the Electronic Properties of Mesocrystals

Tuning the Electronic Properties of Mesocrystals

Angular X-ray cross-correlation analysis applied to the scattering data in 3D reciprocal space from a single crystal

Self-Assembly of Colloidal Nanocrystals into 3D Binary Mesocrystals

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