One-Pot Self-Assembly of Sequence-Controlled Mesoporous Heterostructures via Structure-Directing Agents

Taylor Larison; Eric R. Williams; Mason Wright; Mengxue Zhang; John Tengco; Matthew G. Boebinger; Chuanbing Tang; Morgan Stefik

doi:10.1021/acsnano.4c01855

One-Pot Self-Assembly of Sequence-Controlled Mesoporous Heterostructures via Structure-Directing Agents

Taylor Larison
, Eric R. Williams
, Mason Wright
, Mengxue Zhang
, John Tengco
, Matthew G. Boebinger
, Chuanbing Tang
, Morgan Stefik

Materials MicroAnalysis

Research output: Contribution to journal › Article › peer-review

4 Scopus citations

Abstract

Multimaterial heterostructures have led to characteristics surpassing the individual components. Nature controls the architecture and placement of multiple materials through biomineralization of nanoparticles (NPs); however, synthetic heterostructure formation remains limited and generally departs from the elegance of self-assembly. Here, a class of block polymer structure-directing agents (SDAs) are developed containing repeat units capable of persistent (covalent) NP interactions that enable the direct fabrication of nanoscale porous heterostructures, where a single material is localized at the pore surface as a continuous layer. This SDA binding motif (design rule 1) enables sequence-controlled heterostructures, where the composition profile and interfaces correspond to the synthetic addition order. This approach is generalized with 5 material sequences using an SDA with only persistent SDA-NP interactions (“P-NP₁-NP₂”; NP_i = TiO₂, Nb₂O₅, ZrO₂). Expanding these polymer SDA design guidelines, it is shown that the combination of both persistent and dynamic (noncovalent) SDA-NP interactions (“PD-NP₁-NP₂”) improves the production of uniform interconnected porosity (design rule 2). The resulting competitive binding between two segments of the SDA (P- vs D-) requires additional time for the first NP type (NP₁) to reach and covalently attach to the SDA (design rule 3). The combination of these three design rules enables the direct self-assembly of heterostructures that localize a single material at the pore surface while preserving continuous porosity.

Original language	English
Pages (from-to)	20133-20141
Number of pages	9
Journal	ACS Nano
Volume	18
Issue number	31
DOIs	https://doi.org/10.1021/acsnano.4c01855
State	Published - Aug 6 2024

Funding

T. Larison, E. Williams, M. Zhang, and M. Stefik acknowledge support by the NSF CAREER program, NSF Award No. DMR-1752615. Several STEM imaging and EDS characterization experiments were conducted at the Center for Nanophase Materials Sciences (CNMS), which is a US Department of Energy (DOE), Office of Science User Facility under Award CNMS2023-R-01970. This work was performed in part at the Analytical Instrument Facility (AIF) at North Carolina State University, which is supported by the State of North Carolina and the National Science Foundation (award number ECCS-2025064). The AIF is a member of the North Carolina Research Triangle Nanotechnology Network (RTNN), a site in the National Nanotechnology Coordinated Infastructure (NNCI). This work made use of the South Carolina SAXS Collaborative (SCSC). T. Larison acknowledges Cameron Centers for his artwork contributions.

Keywords

heterostructure
mesoporous
phosphonic acid
self-assembly
sequence control

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10.1021/acsnano.4c01855

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abstract = "Multimaterial heterostructures have led to characteristics surpassing the individual components. Nature controls the architecture and placement of multiple materials through biomineralization of nanoparticles (NPs); however, synthetic heterostructure formation remains limited and generally departs from the elegance of self-assembly. Here, a class of block polymer structure-directing agents (SDAs) are developed containing repeat units capable of persistent (covalent) NP interactions that enable the direct fabrication of nanoscale porous heterostructures, where a single material is localized at the pore surface as a continuous layer. This SDA binding motif (design rule 1) enables sequence-controlled heterostructures, where the composition profile and interfaces correspond to the synthetic addition order. This approach is generalized with 5 material sequences using an SDA with only persistent SDA-NP interactions (“P-NP1-NP2”; NPi = TiO2, Nb2O5, ZrO2). Expanding these polymer SDA design guidelines, it is shown that the combination of both persistent and dynamic (noncovalent) SDA-NP interactions (“PD-NP1-NP2”) improves the production of uniform interconnected porosity (design rule 2). The resulting competitive binding between two segments of the SDA (P- vs D-) requires additional time for the first NP type (NP1) to reach and covalently attach to the SDA (design rule 3). The combination of these three design rules enables the direct self-assembly of heterostructures that localize a single material at the pore surface while preserving continuous porosity.",

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author = "Taylor Larison and Williams, \{Eric R.\} and Mason Wright and Mengxue Zhang and John Tengco and Boebinger, \{Matthew G.\} and Chuanbing Tang and Morgan Stefik",

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One-Pot Self-Assembly of Sequence-Controlled Mesoporous Heterostructures via Structure-Directing Agents

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Keywords

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