Metal–Organic Frameworks@Calcite Composite Crystals

Liu, Ziqing; Xiong, Biao; Dong, Yingxiang; Ning, Yin; Li, Dan

doi:10.1021/acs.inorgchem.2c02859

Cited by 10 publications

(7 citation statements)

References 61 publications

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“…are essential for successful nanoparticle incorporation. – Moreover, the polymer chain length has to be long enough so as to provide sufficient binding sites to drive nanoparticle incorporation and the chain density ideally should be optimized. , When these parameters are satisfied, nanoparticle incorporation can be realized. Undoubtably, surface modification of the guest nanoparticles is tedious, time-consuming and sometimes irreproducible. – In the present study, the PMAA 84 -P(St- alt -NMI) 100 nanoparticles played a key role in promoting the incorporation of CNPs into calcite crystals. Such anionic polymeric nanoparticles bridge the MSNs-NH 2 and the growing calcite.…”

Section: Discussionmentioning

confidence: 71%

Interfacial Supra-Assembly of Copolymer Nanoparticles Enables the Formation of Nanocomposite Crystals with a Tunable Internal Structure

Zhao,

Chen,

et al. 2023

J. Am. Chem. Soc.

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It is highly desirable but technically challenging to precisely control the spatial composition and internal structure of crystalline nanocomposite materials, especially in a one-pot synthetic route. Herein, we demonstrate a versatile pathway to tune the spatial distribution of guest species within a host inorganic crystal via an incorporation strategy. Specifically, welldefined block copolymer nanoparticles, poly(methacrylic acid) x -block-poly-(styrene-alt-N-phenylmaleimide) y [PMAA x -P(St-alt-NMI) y ], are synthesized by polymerization-induced self-assembly. Such anionic nanoparticles can supraassemble onto the surface of larger cationic nanoparticles via an electrostatic interaction, forming colloidal nanocomposite particles (CNPs). Remarkably, such CNPs can be incorporated into calcite single crystals in a spatially controlled manner: the depth of CNPs incorporation into calcite is tunable. Systematic investigation indicates that this interesting phenomenon is governed by the colloidal stability of CNPs, which in turn is dictated by the PMAA x -P(St-alt-NMI) y adsorption density and calcium ion concentration. This study opens up a general and efficient route for the preparation of a wide range of crystalline nanocomposite materials with a controlled internal composition and structure.

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Section: Discussionmentioning

confidence: 71%

Interfacial Supra-Assembly of Copolymer Nanoparticles Enables the Formation of Nanocomposite Crystals with a Tunable Internal Structure

Zhao,

Chen,

et al. 2023

J. Am. Chem. Soc.

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“…5C). 104 The MOF nanoparticles were incorporated into calcite single crystals to form a uniform structure, opening up an efficient route to directly incorporate MOFs into host crystals.…”

Section: Growth Of Mof Nanocompositesmentioning

confidence: 99%

Surface ligand-assisted synthesis and biomedical applications of metal–organic framework nanocomposites

Wang

et al. 2023

Nanoscale

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“…[ 3 ] More importantly, varying the guest/host pairs enables a wide range of nanocomposite materials to be prepared in a controlled manner. [ 4 ] These nanocomposite materials have found various applications in the areas of catalysis, [ 5 ] controlled release, [ 3,6 ] defluoridation, [ 7 ] optoelectronics, [ 8 ] biomimetic synthesis, [ 2,9 ] and property regulation in magnetization, band gap, and chemical stability. [ 10 ]…”

Section: Introductionmentioning

confidence: 99%

“…

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confidence: 99%

Synergistic Effect of Hydroxyl and Carboxyl Groups on Promoting Nanoparticle Occlusion within Calcite

Zhang

Xiong

et al. 2023

Small

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defluoridation, [7] optoelectronics, [8] biomimetic synthesis, [2,9] and property regulation in magnetization, band gap, and chemical stability. [10] However, it has been a great challenge to efficiently occlude nanoparticles into inorganic host crystals because the crystallization of the latter phase is favorable for excluding impurities rather than incorporation. [11] Over the past decade, tremendous efforts have been placed in elucidating the fundamental design rules that determine efficient nanoparticle occlusion within inorganic crystals. [12] Owing to the large difference in surface energy, the guest nanoparticles are not compatible with the growing host crystals. Nonetheless, surface-modification of the guest nanoparticles with suitable polymers has been proven to be a feasible way to minimize this surface energy difference. [1b] Notably, only those polymers with required composition and functionality can drive nanoparticle occlusion. For example, the polymer chain density on the surface of the nanoparticles has played a key role in facilitating the efficient occlusion of sulfate-based copolymer nanoparticles within calcite (CaCO 3 ) crystals. [12d] On the other hand, polymer chain length has to be sufficiently long enough to achieve uniform occlusion. [12b] Otherwise, no occlusion or non-uniform occlusion occurred. [13] In term of chemical functionality, systematic investigation has revealed that carboxylate group has strong affinity with calcite and exhibits a superior performance (compared with phosphate, sulfate or sulfonate groups, etc.) in promoting nanoparticle occlusion within calcite crystals. [14] So far as we are aware, poly(methacrylic acid) is the most studied and well-established polymer that was used to drive polymeric nanoparticle occlusion into calcite crystals. [1b,4a] Unfortunately, as a weak polyelectrolyte, polycarboxylate cannot maintain colloidal stability at a high concentration of metal ions (e.g., calcium ions in the case of CaCO 3 host crystals). As a result, the concentration of the precursor ions must be kept at a very low level (typically below 1.5 mM) in order to achieve uniform nanoparticle occlusion. [4a] Obviously, this intrinsic drawback significantly limits the application of polycarboxylate in promoting nanoparticle occlusion. To solve this issue, we herein introduce multiple functionalities into the polymer stabilizer of the guest nanoparticles, aiming to endow such nanoparticles with both colloidal stability and outstanding capability in driving nanoparticle occlusion. To this end, three types of polymers with comparable mean degree of polymerization (DP) Direct occlusion of guest nanoparticles into host crystals enables the straightforward preparation for various of nanocomposite materials with emerging properties. Therefore, it is highly desirable to elucidate the 'design rules' that govern efficient nanoparticle occlusion. Herein, a series of stericallystabilized nanoparticles are rationally prepared, where the surface stabilizer chains of such nanoparticles...

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Metal–Organic Frameworks@Calcite Composite Crystals

Cited by 10 publications

References 61 publications

Interfacial Supra-Assembly of Copolymer Nanoparticles Enables the Formation of Nanocomposite Crystals with a Tunable Internal Structure

Interfacial Supra-Assembly of Copolymer Nanoparticles Enables the Formation of Nanocomposite Crystals with a Tunable Internal Structure

Surface ligand-assisted synthesis and biomedical applications of metal–organic framework nanocomposites

Synergistic Effect of Hydroxyl and Carboxyl Groups on Promoting Nanoparticle Occlusion within Calcite

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