Oxides and Nitrides with Asymmetric Pore Structure from Block Copolymer Co–Assembly and Non–Solvent Induced Phase Separation

Hesse, Sarah A.; Fritz, Kevin E.; Beaucage, Peter A.; Susca, Ethan M.; Suntivich, Jin; Wiesner, Ulrich

doi:10.1002/macp.202200304

Title: Oxides and Nitrides with Asymmetric Pore Structure from Block Copolymer Co–Assembly and Non–Solvent Induced Phase Separation

Journal Article · 06 October 2022 · Macromolecular Chemistry and Physics

DOI: https://doi.org/10.1002/macp.202200304 · OSTI ID:2006628

^[1]; Fritz, Kevin E. ^[2]; Beaucage, Peter A. ^[3]; Susca, Ethan M. ^[2]; Suntivich, Jin ^[2];

^[2]

Cornell Univ., Ithaca, NY (United States); SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States); SLAC
Cornell Univ., Ithaca, NY (United States)
Cornell Univ., Ithaca, NY (United States); National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States)

Materials combining an asymmetric pore structure with mesopores everywhere enable high surface area accessibility and fast transport, making them attractive for e.g., energy conversion and storage applications. Block copolymer (BCP)/inorganic precursor co-assembly combined with non-solvent induced phase separation (NIPS) provides a route to materials in which a mesoporous top surface layer merges into an asymmetric support with graded porosity along the film normal and mesopores throughout. Here, the co-assembly and non-solvent-induced phase separation (CNIPS) of poly(isoprene)-b-poly(styrene)-b-poly(4-vinylpyridine) (ISV) triblock terpolymer and titanium dioxide (TiO₂) sol-gel nanoparticlesare reported. Heat-treatment in air results in free-standing asymmetric porous TiO₂. Further thermal processing in ammonia results in free-standing asymmetric porous titanium nitride (TiN). processing changes alter structural membrane characteristics is demonstrated. Changing the CNIPS evaporation time results in various membrane cross-sections ( finger-like to sponge-like). Further, oxide and nitride material composition, crystallinity, and porosity are tuned by varying thermal processing conditions. Finally, thermal processing condition effects are probed on phase-pure asymmetric nitride membrane behavior using cyclic voltammetry to elucidate their influence, e.g., on specific capacitance. Results provide further insights into improving asymmetric and porous materials for applications including energy conversion and storage, separation, and catalysis and motivate a further expansion of CNIPS to other (in)organic materials.

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Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Center for Alkaline-Based Energy Solutions (CABES); SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-76SF00515; SC0019445

OSTI ID:: 2006628

Journal Information:: Macromolecular Chemistry and Physics, Journal Name: Macromolecular Chemistry and Physics Journal Issue: 3 Vol. 224; ISSN 1022-1352

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

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Title: Oxides and Nitrides with Asymmetric Pore Structure from Block Copolymer Co–Assembly and Non–Solvent Induced Phase Separation

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