We have prepared the first crystalline and 3D periodically ordered mesoporous quaternary semiconductor photocatalyst in an evaporation-induced self-assembly assisted soft-templating process. Using lab synthesized triblock-terpolymer poly(isoprene- b -styrene- b -ethylene oxide) (ISO) a highly ordered 3D interconnected alternating gyroid morphology was achieved exhibiting near and long-range order, as evidenced by small angle X-ray scattering (SAXS) and electron microscopy (TEM/SEM). Moreover, we reveal the formation process on the phase-pure construction of the material's pore-walls with its high crystallinity, which proceeds along a highly stable W 5+ compound, by both in situ and ex situ analyses, including X-ray powder diffraction (XRPD), Fourier transform infrared spectroscopy (FTIR) and electron paramagnetic resonance (EPR). The resulting photocatalyst CsTaWO 6 with its optimum balance between surface area and ordered mesoporosity ultimately shows superior hydrogen evolution rates over its non-ordered reference in photocatalytic hydrogen production. This work will help to advance new self-assembly preparation pathways towards multi-element multifunctional compounds for different applications, including improved battery and sensor electrode materials.
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Inside polyMOFs: layered structures in polymer-based metal–organic frameworks
In this report, we explore the internal structural features of polyMOFs consisting of equal mass ratios of metal-coordinating poly(benzenedicarboxylic acid) blocks and non-coordinating poly(ethylene glycol) (PEG) blocks. The studies reveal alternating lamellae of metal-rich, crystalline regions and metal-deficient non-crystalline polymer, which span the length of hundreds of nanometers. Polymers consisting of random PEG blocks, PEG end-blocks, or non-coordinating poly(cyclooctadiene) (COD) show similar alternation of metal-rich and metal-deficient regions, indicating a universal self-assembly mechanism. A variety of techniques were employed to interrogate the internal structure of the polyMOFs, including transmission electron microscopy (TEM), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), and small-angle synchrotron X-ray scattering (SAXS). Independent of the copolymer architecture or composition, the internal structure of the polyMOF crystals showed similar lamellar self-assembly at single-nanometer length scales.
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- Award ID(s):
- 2039044
- NSF-PAR ID:
- 10287816
- Date Published:
- Journal Name:
- Chemical Science
- Volume:
- 11
- Issue:
- 38
- ISSN:
- 2041-6520
- Page Range / eLocation ID:
- 10523 to 10528
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Abstract Although challenging, assembling and orienting non-spherical nanomaterials into two- and three-dimensional (2D and 3D) ordered arrays can facilitate versatile collective properties by virtue of their shape-dependent properties that cannot be realized with their spherical counterparts. Here, we report on the self-assembly of gold nanorods (AuNRs) into 2D films at the vapor/liquid interface facilitated by grafting them with poly(ethylene glycol) (PEG). Using surface sensitive synchrotron grazing incidence small angle X-ray scattering (GISAXS) and specular X-ray reflectivity (XRR), we show that PEG-AuNRs in aqueous suspensions migrate to the vapor/liquid interface in the presence of salt, forming a uniform monolayer with planar-to-surface orientation. Furthermore, the 2D assembled PEG functionalized AuNRs exhibit short range order into rectangular symmetry with side-by-side and tail-to-tail nearest-neighbor packing. The effect of PEG chain length and salt concentration on the 2D assembly are also reported.
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The ternary manganese pnictide phases, MnAs 1− x Sb x , are of interest for magnetic refrigeration and waste heat recovery due to their magnetocaloric properties, maximized at the Curie temperature ( T C ), which varies from 580–240 K, depending on composition. Nanoparticles potentially enable application in microelectronics (cooling) or graded composites that can operate over a wide temperature range, but manganese pnictides are synthetically challenging to realize as discrete nanoparticles and their fundamental magnetic properties have not been extensively studied. Accordingly, colloidal synthesis methods were employed to target discrete MnAs x Sb 1− x nanoparticles ( x = 0.1–0.9) by arrested precipitation reactions of Mn 2 (CO) 10 with (C 6 H 5 ) 3 AsO and (C 6 H 5 ) 3 Sb in coordinating solvents. The MnAs x Sb 1− x particles are spherical in morphology with average diameters 10–13 nm (standard deviations <20% based on transmission electron microscopy analysis). X-Ray fluorescence spectroscopy measurements on ensembles showed that all phases had an excess of Sb relative to the targeted composition, whereas energy dispersive spectroscopic mapping data of single particles revealed that the nanoparticles are inhomogeneous, adopting a core–shell structure, with the amorphous shell rich in Mn and O (and sometimes Sb) while the crystalline core is rich in Mn, As, and Sb. Magnetization measurements of the nanoparticle ensemble demonstrated the presence of both ferromagnetic and paramagnetic phases. By combining the magnetization measurements with precision chemical mapping and simple modeling, we were able to unambiguously attribute ferromagnetism to the MnAs x Sb 1− x crystalline core, whereas paramagnetism was attributed to the amorphous shell. Magnetization measurements at variable temperatures were used to determine the superparamagnetic transition of the nanoparticles, although for some compositions and particle sizes the blocking temperature exceeded room temperature. Preliminary magnetic studies also revealed a conventional dependence between core size and coercivity, in spite of variable compositions of the nanoparticles, an unexpected result.more » « less
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Abstract The interactions between uranium and non‐innocent organic species are an essential component of fundamental uranium redox chemistry. However, they have seldom been explored in the context of multidimensional, porous materials. Uranium‐based metal–organic frameworks (MOFs) offer a new angle to study these interactions, as these self‐assembled species stabilize uranium species through immobilization by organic linkers within a crystalline framework, while potentially providing a method for adjusting metal oxidation state through coordination of non‐innocent linkers. We report the synthesis of the MOF
NU‐1700 , assembled from U4+‐paddlewheel nodes and catecholate‐based linkers. We propose this highly unusual structure, which contains two U4+ions in a paddlewheel built from four linkers—a first among uranium materials—as a result of extensive characterization via powder X‐ray diffraction (PXRD), sorption, transmission electron microscopy (TEM), and thermogravimetric analysis (TGA), in addition to density functional theory (DFT) calculations. -
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Abstract The interactions between uranium and non‐innocent organic species are an essential component of fundamental uranium redox chemistry. However, they have seldom been explored in the context of multidimensional, porous materials. Uranium‐based metal–organic frameworks (MOFs) offer a new angle to study these interactions, as these self‐assembled species stabilize uranium species through immobilization by organic linkers within a crystalline framework, while potentially providing a method for adjusting metal oxidation state through coordination of non‐innocent linkers. We report the synthesis of the MOF
NU‐1700 , assembled from U4+‐paddlewheel nodes and catecholate‐based linkers. We propose this highly unusual structure, which contains two U4+ions in a paddlewheel built from four linkers—a first among uranium materials—as a result of extensive characterization via powder X‐ray diffraction (PXRD), sorption, transmission electron microscopy (TEM), and thermogravimetric analysis (TGA), in addition to density functional theory (DFT) calculations.
- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/d0sc03651j
