We constructed highly oriented and ordered macropores within metal-organic framework (MOF) single crystals, opening up the area of three-dimensional-ordered macro-microporous materials (that is, ...materials containing both macro- and micropores) in single-crystalline form. Our methodology relies on the strong shaping effects of a polystyrene nanosphere monolith template and a double-solvent-induced heterogeneous nucleation approach. This process synergistically enabled the in situ growth of MOFs within ordered voids, rendering a single crystal with oriented and ordered macro-microporous structure. The improved mass diffusion properties of such hierarchical frameworks, together with their robust single-crystalline nature, endow them with superior catalytic activity and recyclability for bulky-molecule reactions, as compared with conventional, polycrystalline hollow, and disordered macroporous ZIF-8.
Construction of organic semiconducting materials with in-plane π-conjugated structures and robustness through carbon-carbon bond linkages, alternatively as organic graphene analogs, is extremely ...desired for powerfully optoelectrical conversion. However, the poor reversibility for sp
carbon bond forming reactions makes them unavailable for building high crystalline well-defined organic structures through a self-healing process, such as covalent organic frameworks (COFs). Here we report a scalable solution-processing approach to synthesize a family of two-dimensional (2D) COFs with trans-disubstituted C = C linkages via condensation reaction at arylmethyl carbon atoms on the basis of 3,5-dicyano-2,4,6-trimethylpyridine and linear/trigonal aldehyde (i.e., 4,4″-diformyl-p-terphenyl, 4,4'-diformyl-1,1'-biphenyl, or 1,3,5-tris(4-formylphenyl)benzene) monomers. Such sp
carbon-jointed-pyridinyl frameworks, featuring crystalline honeycomb-like structures with high surface areas, enable driving two half-reactions of water splitting separately under visible light irradiation, comparable to graphitic carbon nitride (g-C
N
) derivatives.
High-resolution imaging of electron beam-sensitive materials is one of the most difficult applications of transmission electron microscopy (TEM). The challenges are manifold, including the ...acquisition of images with extremely low beam doses, the time-constrained search for crystal zone axes, the precise image alignment, and the accurate determination of the defocus value. We develop a suite of methods to fulfill these requirements and acquire atomic-resolution TEM images of several metal organic frameworks that are generally recognized as highly sensitive to electron beams. The high image resolution allows us to identify individual metal atomic columns, various types of surface termination, and benzene rings in the organic linkers. We also apply our methods to other electron beam-sensitive materials, including the organic-inorganic hybrid perovskite CH
NH
PbBr
.
Two-dimensional (2D) materials with highly ordered in-plane nanopores are crucial for numerous applications, but their rational synthesis and local structural characterization remain two grand ...challenges. We illustrate here that single-crystalline ultrathin 2D MOF nanosheets (MONs) with intrinsic porosity can be prepared by exfoliating layered metal–organic frameworks (MOFs), whose layers are stabilized by sterically bulky groups. As a result, three three-dimensional (3D) isostructural lanthanide MOFs possessing porous layer structures are constructed by coordinating metal ions with an angular dicarboxylate linker derived from chiral 1,1′-biphenyl phosphoric acid with pendant mesityl groups. The Eu-MOF is readily ultrasonic exfoliated into single-crystalline nanosheets with a thickness of ca. 6.0 nm (2 layers) and a lateral size of 1.5 × 3.0 μm2. The detailed structural information, i.e., the pore channels and individual organic and inorganic building units in the framework, is clearly visualized by a low-dose high-resolution transmission electron microscopy (HRTEM) technique. Benefiting from their ultrathin feature, the nanosheets are well embedded into the polymer matrix to form free-standing mixed-matrix membranes. In both the solution and membrane phase, the fluorescence of the MONs can be effectively quenched by a total of 17 chiral terpenes and terpenoids through supramolecular interactions with uncoordinated chiral phosphoric acids, leading to a chiral optical sensor for detecting vapor enantiomers, which is among the most challenging molecular recognition tasks.
Hollow nanostructures are widely used in chemistry, materials, bioscience, and medicine, but their fabrication remains a great challenge. In particular, there is no effective strategy for their ...assembly and interconnection. We bring pottery, the oldest and simplest method of fabricating hollow containers, into the nanoscale. By exploiting the liquid nature of the xylene template, fullerene hollow nanostructures of tailored shapes, such as bowls, bottles, and cucurbits, are readily synthesized. The liquid templates permit stepwise and versatile manipulation and hence, modular assembly of nodes and junctions leads to interconnected hollow systems. As a proof-of-concept, we create multi-compartment nano-containers, with different nanoparticles isolated in the separate pockets. This methodology expands the synthetic freedom for hollow nanostructures, building a bridge from isolated hollow units to interconnected hollow systems.
Oxide-/hydroxide-derived copper electrodes exhibit excellent selectivity toward C2+ products during the electrocatalytic CO2 reduction reaction (CO2RR). However, the origin of such enhanced ...selectivity remains controversial. Here, we prepared two Cu-based electrodes with mixed oxidation states, namely, HQ-Cu (containing Cu, Cu2O, CuO) and AN-Cu (containing Cu, Cu(OH)2). We extracted an ultrathin specimen from the electrodes using a focused ion beam to investigate the distribution and evolution of various Cu species by electron microscopy and electron energy loss spectroscopy. We found that at the steady stage of the CO2RR, the electrodes have all been reduced to Cu0, regardless of the initial states, suggesting that the high C2+ selectivities are not associated with specific oxidation states of Cu. We verified this conclusion by control experiments in which HQ-Cu and AN-Cu were pretreated to fully reduce oxides/hydroxides to Cu0, and the pretreated electrodes showed even higher C2+ selectivity compared with their unpretreated counterparts. We observed that the oxide/hydroxide crystals in HQ-Cu and AN-Cu were fragmented into nanosized irregular Cu grains under the applied negative potentials. Such a fragmentation process, which is the consequence of an oxidation–reduction cycle and does not occur in electropolished Cu, not only built an intricate network of grain boundaries but also exposed a variety of high-index facets. These two features greatly facilitated the C–C coupling, thus accounting for the enhanced C2+ selectivity. Our work demonstrates that the use of advanced characterization techniques enables investigating the structural and chemical states of electrodes in unprecedented detail to gain new insights into a widely studied system.
Direct conversion of methane to methanol is an effective and practical process to improve the efficiency of natural gas utilization. Copper (Cu)-based catalysts have attracted great research ...attention, due to their unique ability to selectively catalyze the partial oxidation of methane to methanol at relatively low temperatures. In recent decades, many different catalysts have been studied to achieve a high conversion of methane to methanol, including the Cu-based enzymes, Cu-zeolites, Cu-MOFs (metal-organic frameworks) and Cu-oxides. In this mini review, we will detail the obtained evidence on the exact state of the active Cu sites on these various catalysts, which have arisen from the most recently developed techniques and the results of DFT calculations. We aim to establish the structure–performance relationship in terms of the properties of these materials and their catalytic functionalities, and also discuss the unresolved questions in the direct conversion of methane to methanol reactions. Finally, we hope to offer some suggestions and strategies for guiding the practical applications regarding the catalyst design and engineering for a high methanol yield in the methane oxidation reaction.
Metal–organic frameworks (MOFs) are often synthesized using various additives to modulate the crystallization. Here, we report the direct imaging of the crystal surface of MOF MIL-101 synthesized ...with different additives, using low-dose high-resolution transmission electron microscopy (HRTEM), and identify three distinct surface structures, at subunit cell resolution. We find that the mesoporous cages at the outermost surface of MIL-101 can be opened up by vacuum heating treatment at different temperatures, depending on the MIL-101 samples. We monitor the structural evolution of MIL-101 upon vacuum heating, using in situ X-ray diffraction, and find the results to be in good agreement with HRTEM observations, which leads us to speculate that additives have an influence not only on the surface structure but also on the stability of framework. In addition, we observe solid–solid phase transformation from MIL-101 to MIL-53 taking place in the sample synthesized with hydrofluoric acid.
Hybrid nanostructures integrating electroactive materials with functional species, such as metal-organic frameworks, covalent organic frameworks, graphdiyne etc., are of significance for both ...fundamental research and energy conversion/storage applications. Here, hierarchical triple-layered nanotube arrays, which consist of hydrogen-substituted graphdiyne frameworks seamlessly sandwiched between an outer layer of nickel-cobalt co-doped molybdenum disulfide nanosheets and an inner layer of mixed cobalt sulfide and nickel sulfide (Co
S
/Ni
S
), are directly fabricated on conductive carbon paper. The elaborate triple-layered structure emerges as a useful hybrid electrode for energy conversion and storage, in which the organic hydrogen-substituted graphdiyne middle layer, with an extended π-conjugated system between the electroactive nanomaterials, provides built-in electron and ion channels that are crucial for performance enhancement. This dual-template synthetic method, which makes use of microporous organic networks to confine a self-template, is shown to be versatile and thus provides a promising platform for advanced nanostructure-engineering of hierarchical multi-layered nanostructures towards a wide range of electrochemical applications.
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