Journal article Lewis Acid–Base-Driven Anisotropic Crystal Growth of Pyrochlore Pb 2 Ti 2 O 5.4 F 1.2 with Enhanced Visible-Light H 2 Evolution Activity
Gentoku Kido (author) (Search by this author)
;
Hiroto Ueki (author) (Search by this author)
;
Megumi Okazaki (author) (Search by this author)
ORCID ; ORCID SAMURAI ; ORCID SAMURAI ;
Ryosuke Nishikubo (author) (Search by this author)
ORCID ;
Akinori Saeki (author) (Search by this author)
ORCID ;
Kazuhiko Maeda (author) (Search by this author)
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Citation
Gentoku Kido, Hiroto Ueki, Megumi Okazaki, Jun Kikkawa, Koji Kimoto, Ryosuke Nishikubo, Akinori Saeki, Kazuhiko Maeda. Lewis Acid–Base-Driven Anisotropic Crystal Growth of Pyrochlore Pb 2 Ti 2 O 5.4 F 1.2 with Enhanced Visible-Light H 2 Evolution Activity. Chemistry of Materials. 2026, 38 (4), 1980-1990. https://doi.org/10.1021/acs.chemmater.5c03153

Description:

(abstract)

Mixed-anion compounds offer unique functionalities unattainable with single-anion materials, yet rational morphology control remains largely unexplored. Here, we report a Lewis acid–base-driven strategy that enables low-temperature, solution-phase morphology control of the oxyfluoride photocatalyst Pb2Ti2O5.4F1.2 (PTOF). A microwave-assisted solvothermal method with monoethanolamine (MEA) was used to tune the particle morphology and size via the precursor-solution pH, which was adjusted by the addition of formic acid or acetic acid. PTOF, an A2B2X6X′0.5-type pyrochlore with intrinsic anion vacancies (X′2, 4d site), has exposed {111} facets composed of alternating Pb-rich and Ti-rich layers. Lewis basic MEA is proposed to bind selectively to undercoordinated, strongly acidic Pb2+ sites adjacent to Ti4+ and vacancies on Ti-rich {111} facets, suppressing growth along the surface direction and stabilizing these facets, thereby driving anisotropic crystal growth and forming plate-like nanoparticles. At pH 10 (formic acid), PTOF nanoparticles (∼30 nm) with a specific surface area of 37 m2 g–1 were obtained. Compared with an analogous PTOF synthesized by a conventional solid–state reaction, the optimized sample exhibited ∼29-fold higher H2 evolution activity in an aqueous solution containing dissolved disodium ethylenediaminetetraacetate under visible-light (λ > 400 nm) with the aid of a Pt cocatalyst. Lewis acid–base-directed facet stabilization is thus shown to be a promising approach for the rational morphological design of mixed-anion oxyfluorides via solution processing.

Rights:

Keyword: Catalytic activity, Nanoparticles, Organic acids, pH, Photocatalysis

Date published: 2026-02-24

Publisher: American Chemical Society (ACS)

Journal:

  • Chemistry of Materials (ISSN: 08974756) vol. 38 issue. 4 p. 1980-1990

Funding:

  • Japan Society for the Promotion of Science JP25H00899
  • Japan Society for the Promotion of Science JP22H05142
  • Japan Society for the Promotion of Science JP22H05145
  • Japan Society for the Promotion of Science JP22H05148
  • Japan Society for the Promotion of Science JP23H04626

Manuscript type: Publisher's version (Version of record)

MDR DOI:

First published URL: https://doi.org/10.1021/acs.chemmater.5c03153

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Updated at: 2026-04-13 09:22:40 +0900

Published on MDR: 2026-04-13 10:23:12 +0900