Filling metal-organic framework mesopores with TiO2 for CO2 photoreduction.

Metal-organic frameworks (MOFs)1-3 are known for their specific interactions with gas molecules4,5; this, combined with their rich and ordered porosity, makes them promising candidates for the photocatalytic conversion of gas molecules to useful products6. However, attempts to use MOFs or MOF-based composites for CO2 photoreduction6-13 usually result in far lower CO2 conversion efficiency than that obtained from state-of-the-art solid-state or molecular catalysts14-18, even when facilitated by sacrificial reagents. Here we create 'molecular compartments' inside MOF crystals by growing TiO2 inside different pores of a chromium terephthalate-based MOF (MIL-101) and its derivatives. This allows for synergy between the light-absorbing/electron-generating TiO2 units and the catalytic metal clusters in the backbones of MOFs, and therefore facilitates photocatalytic CO2 reduction, concurrent with production of O2. An apparent quantum efficiency for CO2 photoreduction of 11.3 per cent at a wavelength of 350 nanometres is observed in a composite that consists of 42 per cent TiO2 in a MIL-101 derivative, namely, 42%-TiO2-in-MIL-101-Cr-NO2. TiO2 units in one type of compartment in this composite are estimated to be 44 times more active than those in the other type, underlining the role of precise positioning of TiO2 in this system.

Self-assembly of a triply periodic continuous mesophase with Fddd symmetry in simple one-component liquids.

Triply periodic continuous morphologies (networks) arising as a result of the microphase separation in block copolymer melts have so far never been observed self-assembled in systems of particles with spherically symmetric interaction. We report a molecular dynamics simulation where two simple one-component liquids form upon cooling an equilibrium network with the Fddd space group symmetry. This complexity reduction in the liquid network formation in terms of the particle geometry and the number of components evidences the generic nature of this class of phase transition, suggesting opportunities for producing these structures in a variety of new systems.

Electron crystallography for determining the handedness of a chiral zeolite nanocrystal.

Chiral crystals can be exploited for applications in enantioselective separation and catalysis. However, the study of chirality at the atomic level in a sub-micrometre-sized crystal is difficult due to the lack of adequate characterization methods. Herein, we present two efficient and practical methods of characterization that are based on electron crystallography. These methods are successfully applied to reveal the handedness of a chiral, zeolite nanocrystal. The handedness is identified through either a comparison of two high-resolution transmission electron microscope images, taken from the same nanocrystal but along different zone axes by tilting it around its screw axis, or the intensity asymmetry of a Bijvoet pair of reflections in a single precession electron-diffraction pattern. These two approaches provide new ways to determine the handedness of small, chiral crystals.

A smectic dodecagonal quasicrystal.

We report a solid smectic phase that exhibits dodecagonal global order. It is composed of axially stacked hexagonally ordered particle layers, and its 12-fold rotational symmetry induced by the 30° rotation of adjacent layers with respect to each other. A quasicrystal was produced in a molecular-dynamics simulation of a single-component system of particles interacting via a spherically-symmetric potential. It was formed as a result of a first-order phase transition from an isotropic liquid state that occurred under constant-density cooling. This finding implies that a similarly structured quasicrystal can possibly be produced by the same class of systems as those forming smectic-B crystals. This quasicrystal can also be expected to arise in a system of spherically-shaped colloidal particles with appropriately tuned potential.

WO3 nanorods created by self-assembly of highly crystalline nanowires under hydrothermal conditions.

WO3 nanorods and wires were obtained via hydrothermal synthesis using sodium tungstate as a precursor and either oxalic acid, citric acid, or poly(methacrylic acid) as a stabilizing agent. Transmission electron microscopy images showed that the organic acids with different numbers of carboxylic groups per molecule influence the final sizes and stacking nanostructures of WO3 wires. Three-dimensional electron diffraction tomography of a single nanocrystal revealed a hexagonal WO3 structure with preferential growth along the c-axis, which was confirmed by high-resolution transmission electron microscopy. WO3 nanowires were also spin-coated onto an indium tin oxide/glass conducting substrate, resulting in the formation of a film that was characterized by scanning electron microscopy. Finally, cyclic voltammetry measurements performed on the WO3 thin film showed voltammograms typical for the WO3 redox process.

Phase identification and structure solution by three-dimensional electron diffraction tomography: Gd-phosphate nanorods.

Hydrothermal synthesis of GdPO4 in the presence of poly(methacrylic acid) yields nanorods with a diameter of 15 nm and an aspect ratio of 20. Powder X-ray diffraction patterns showed that the GdPO4 nanorods display peaks characteristics for both monoclinic and hexagonal structures. Three-dimensional electron diffraction tomography (3D EDT) was used to determine the structures ab initio on the basis of reciprocal volume reconstruction of electron diffraction data sets collected from single nanorods. The crystal structure of the monoclinic form was shown to be P21/n, corroborating previous work. We were able to solve the 3D structure of the hexagonal P6222 form, which has not been reported previously. Our work shows that 3D EDT is a powerful method that can be used for solving structures of single nanocrystals.

Formation of a new archetypal Metal-Organic Framework from a simple monatomic liquid.

We report a molecular-dynamics simulation of a single-component system of particles interacting via a spherically symmetric potential that is found to form, upon cooling from a liquid state, a low-density porous crystalline phase. Its structure analysis demonstrates that the crystal can be described by a net with a topology that belongs to the class of topologies characteristic of the Metal-Organic Frameworks (MOFs). The observed net is new, and it is now included in the Reticular Chemistry Structure Resource database. The observation that a net topology characteristic of MOF crystals, which are known to be formed by a coordination-driven self-assembly process, can be reproduced by a thermodynamically stable configuration of a simple single-component system of particles opens a possibility of using these models in studies of MOF nets. It also indicates that structures with MOF topology, as well as other low-density porous crystalline structures can possibly be produced in colloidal systems of spherical particles, with an appropriate tuning of interparticle interaction.

The determination of rotation axis in the rotation electron diffraction technique.

Methods to determine the rotation axis using the rotation electron diffraction technique are described. A combination of rotation axis tilt, beam tilt, and simulated experimental diffraction patterns with nonintegers zone axis has been used. Accurate knowledge of the crystallographic direction of the incident beam for deducing the excitation error of reflections simultaneously near Bragg positions is essential in quantitative electron diffraction. Experimental patterns from CoP3 are used as examples.

Docking MOF crystals on graphene support for highly selective electrocatalytic peroxide production.

Tailoring the reaction kinetics is the central theme of designer electrocatalysts, which enables the selective conversion of abundant and inert atmospheric species into useful products. Here we show a supporting effect in tuning the electrocatalytic kinetics of oxygen reduction reaction (ORR) from four-electron to two-electron mechanism by docking metalloporphyrin-based metal-organic frameworks (MOFs) crystals on graphene support, leading to highly selective peroxide production with faradaic efficiency as high as 93.4%. A magic angle of 38.1° tilting for the co-facial alignment was uncovered by electron diffraction tomography, which is attributed to the maximization of π-π interaction for mitigating the lattice and symmetry mismatch between MOF and graphene. The facilitated electron migration and oxygen chemisorption could be ascribed to the supportive effect of graphene that disperses of the electron state of the active center, and ultimately regulates rate-determining step. ELECTRONIC SUPPLEMENTARY MATERIAL: Supplementary material (synthesis protocols for control samples, morphological and structural characterizations, porosity, electrochemical properties and activities including SEM, TEM, XPS, Raman, AFM investigations) is available in the online version of this article at 10.1007/s12274-021-3382-3.

Synchronous quantitative analysis of chiral mesostructured inorganic crystals by 3D electron diffraction tomography.

Chiral mesostructures exhibit distinctive twisting and helical hierarchical stacking ranging from atomic to micrometre scales with fascinating structural-chiral anisotropy properties. However, the detailed determination of their multilevel chirality remains challenging due to the limited information from spectroscopy, diffraction techniques, scanning electron microscopy and the two-dimensional projections in transmission electron microscopy. Herein, we report a general approach to determine chiral hierarchical mesostructures based on three-dimensional electron diffraction tomography (3D EDT), by which the structure can be solved synchronously according to the quantitative measurement of diffraction spot deformations and their arrangement in reciprocal space. This method was verified on two samples-chiral mesostructured nickel molybdate and chiral mesostructured tin dioxide-revealing hierarchical chiral structures that cannot be determined by conventional techniques. This approach provides more precise and comprehensive identification of the hierarchical mesostructures, which is expected to advance our understanding of structural-chiral anisotropy at the fundamental level.

A complicated quasicrystal approximant epsilon16 predicted by the strong-reflections approach.

The structure of a complicated quasicrystal approximant epsilon(16) was predicted from a known and related quasicrystal approximant epsilon(6) by the strong-reflections approach. Electron-diffraction studies show that in reciprocal space, the positions of the strongest reflections and their intensity distributions are similar for both approximants. By applying the strong-reflections approach, the structure factors of epsilon(16) were deduced from those of the known epsilon(6) structure. Owing to the different space groups of the two structures, a shift of the phase origin had to be applied in order to obtain the phases of epsilon(16). An electron-density map of epsilon(16) was calculated by inverse Fourier transformation of the structure factors of the 256 strongest reflections. Similar to that of epsilon(6), the predicted structure of epsilon(16) contains eight layers in each unit cell, stacked along the b axis. Along the b axis, epsilon(16) is built by banana-shaped tiles and pentagonal tiles; this structure is confirmed by high-resolution transmission electron microscopy (HRTEM). The simulated precession electron-diffraction (PED) patterns from the structure model are in good agreement with the experimental ones. Epsilon(16) with 153 unique atoms in the unit cell is the most complicated approximant structure ever solved or predicted.

Pore structures of ordered large cage-type mesoporous silica FDU-12s.

The pore variations of ordered cage-type mesoporous silica FDU-12s have been analyzed in detail by PXRD, SAXS, nitrogen sorption, and electron crystallography. FDU-12s with a cubic symmetry (space group, Fmm) were templated by amphiphilic triblock copolymer F127 with the addition of 1,3,5-trimethylbenzene and KCl under an acidic condition. Three typical samples with different unit cell sizes, pore cage diameters, and entrance sizes were obtained from different synthesis and hydrothermal treatment temperatures, as indicated by the differences in the PXRD and SAXS patterns. The pore structure changes in the three materials were observed by nitrogen adsorption/desorption and 3-D reconstruction of HRTEM images taken from different crystal orientations. The approximate pore structures of FDU-12s can be regarded as a face-centered cubic (fcc) close-packing of spherical cages, each connected to 12 nearest neighboring cages. However, the ideal spherical model is only valid for the FDU-12s prepared at a low temperature (L-FDU-12-100). The cage shape of the FDU-12s synthesized at a high temperature deviates from perfect spheres and is accompanied by an entrance enlargement. The temperature-dependent behavior of the PEO block is discussed with regard to its influence on the micelles and hence the cage configuration. The better understanding of the formation mechanism via the combined characterization techniques and modeling may lead to a more rational approach for tuning the pore cages and entrances of the mesoporous FDU-12 materials.

A practical method to detect and correct for lens distortion in the TEM.

A practical, offline method for experimental detection and correction for projector lens distortion in the transmission electron microscope (TEM) operating in high-resolution (HR) and selected area electron diffraction (SAED) modes is described. Typical TEM works show that, in the simplest case, the distortion transforms on the recording device, which would be a circle into an ellipse. The first goal of the procedure described here is to determine the elongation and orientation of the ellipse. The second goal is to correct for the distortion using an ordinary graphic program. The same experimental data set may also be used to determine the actual microscope magnification and the rotation between SAED patterns and HR images. The procedure may be helpful in several quantitative applications of electron diffraction and HR imaging, for instance while performing accurate lattice parameter determination, or while determining possible metrical deviations (cell edges and angles) from a given symmetry.

Weaving of organic threads into a crystalline covalent organic framework.

A three-dimensional covalent organic framework (COF-505) constructed from helical organic threads, designed to be mutually weaving at regular intervals, has been synthesized by imine condensation reactions of aldehyde functionalized copper(I)-bisphenanthroline tetrafluoroborate, Cu(PDB)2(BF4), and benzidine (BZ). The copper centers are topologically independent of the weaving within the COF structure and serve as templates for bringing the threads into a woven pattern rather than the more commonly observed parallel arrangement. The copper(I) ions can be reversibly removed and added without loss of the COF structure, for which a tenfold increase in elasticity accompanies its demetalation. The threads in COF-505 have many degrees of freedom for enormous deviations to take place between them, throughout the material, without undoing the weaving of the overall structure.

CO2 capture from humid flue gases and humid atmosphere using a microporous coppersilicate.

Capturing CO2 from humid flue gases and atmosphere with porous materials remains costly because prior dehydration of the gases is required. A large number of microporous materials with physical adsorption capacity have been developed as CO2-capturing materials. However, most of them suffer from CO2 sorption capacity reduction or structure decomposition that is caused by co-adsorbed H2O when exposed to humid flue gases and atmosphere. We report a highly stable microporous coppersilicate. It has H2O-specific and CO2-specific adsorption sites but does not have H2O/CO2-sharing sites. Therefore, it readily adsorbs both H2O and CO2 from the humid flue gases and atmosphere, but the adsorbing H2O does not interfere with the adsorption of CO2. It is also highly stable after adsorption of H2O and CO2 because it was synthesized hydrothermally.

Probing planar defects in nanoparticle superlattices by 3D small-angle electron diffraction tomography and real space imaging.

We demonstrate how the acquisition and processing of 3D electron diffraction data can be extended to characterize structural features on the mesoscale, and show how lattice distortions in superlattices of self-assembled spherical Pd nanoparticles can be quantified by three-dimensional small-angle electron diffraction tomography (3D SA-EDT). Transmission electron microscopy real space imaging and 3D SA-EDT reveal a high density of stacking faults that was related to a competition between fcc and hcp arrangements during assembly. Information on the orientation of the stacking faults was used to make analogies between planar defects in the superlattices and Shockley partial dislocations in metallic systems.

π-π interaction of aromatic groups in amphiphilic molecules directing for single-crystalline mesostructured zeolite nanosheets.

One of the challenges in material science has been to prepare macro- or mesoporous zeolite. Although examples of their synthesis exist, there is a need for a facile yet versatile approach to such hierarchical structures. Here we report a concept for designing a single quaternary ammonium head amphiphilic template with strong ordered self-assembling ability through π-π stacking in hydrophobic side, which stabilizes the mesostructure to form single-crystalline mesostructured zeolite nanosheets. The concept is demonstrated for the formation of a new type of MFI (zeolite framework code by International Zeolite Association) nanosheets joined with a 90° rotational boundary, which results in a mesoporous zeolite with highly specific surface area even after calcination. Low binding energies for this self-assembling system are supported by a theoretical analysis. A geometrical matching between the arrangement of aromatic groups and the zeolitic framework is speculated for the formation of single-crystalline MFI nanosheets.

Cobalt phosphate-modified barium-doped tantalum nitride nanorod photoanode with 1.5% solar energy conversion efficiency.

Spurred by the decreased availability of fossil fuels and global warming, the idea of converting solar energy into clean fuels has been widely recognized. Hydrogen produced by photoelectrochemical water splitting using sunlight could provide a carbon dioxide lean fuel as an alternative to fossil fuels. A major challenge in photoelectrochemical water splitting is to develop an efficient photoanode that can stably oxidize water into oxygen. Here we report an efficient and stable photoanode that couples an active barium-doped tantalum nitride nanostructure with a stable cobalt phosphate co-catalyst. The effect of barium doping on the photoelectrochemical activity of the photoanode is investigated. The photoanode yields a maximum solar energy conversion efficiency of 1.5%, which is more than three times higher than that of state-of-the-art single-photon photoanodes. Further, stoichiometric oxygen and hydrogen are stably produced on the photoanode and the counter electrode with Faraday efficiency of almost unity for 100 min.

Structure and catalytic properties of the most complex intergrown zeolite ITQ-39 determined by electron crystallography.

Porous materials such as zeolites contain well-defined pores in molecular dimensions and have important industrial applications in catalysis, sorption and separation. Aluminosilicates with intersecting 10- and 12-ring channels are particularly interesting as selective catalysts. Many porous materials, especially zeolites, form only nanosized powders and some are intergrowths of different structures, making structure determination very challenging. Here, we report the atomic structures of an aluminosilicate zeolite family, ITQ-39, solved from nanocrystals only a few unit cells in size by electron crystallography. ITQ-39 is an intergrowth of three different polymorphs, built from the same layer but with different stacking sequences. ITQ-39 contains stacking faults and twinning with nano-sized domains, being the most complex zeolite ever solved. The unique structure of ITQ-39, with a three-dimensional intersecting pairwise 12-ring and 10-ring pore system, makes it a promising catalyst for converting naphtha into diesel fuel, a process of emerging interest for the petrochemical industry.