Research Reveals Custom Metal Intercalation in Titanates

Abstract

Layered titanates (LTs) offer exceptional structural and chemical tunability, enabling precise modulation of their electronic states and catalytic properties. However, systematic studies on the range of cations that can serve as intercalants for LTs remain limited, and conventional synthesis methods often require additional treatments for cation intercaltion. In this study, we present a cation-free H+ (H3O+)-intercalated LT as a versatile platform for direct cation insertion. This LT can be intercalated with single metal cations (42 metals from five groups) or a combination of 5-30 cations without structural deformation. Intercalation with alkali metals (AMs) precisely tuned the charge density of Rh species when the prepared LTs are used as catalytic supports. Among the Rh-loaded AM-bearing LTs, Rh/K-LT delivered the highest turnover frequency (23 685 h-1), surpassing those of other AM-intercalated systems and previously reported Rh-based heterogeneous catalysts, during propylene hydroformylation. Combined in situ/ex situ analyses and density functional theory calculations revealed that AM intercalation promotes charge transfer to Rh, thereby enhancing adsorption behavior and catalytic activity. This work establishes not only a broad cation intercalation library but also a generalizable strategy for cation engineering in LTs, highlighting the potential of intercalation-driven charge modulation for rational catalyst design across diverse reactions.

A research team, affiliated with UNIST has reported a novel synthesis strategy that enables the direct intercalation of a wide range of metal cations into the interlayer spaces of layered titanate (LT) structures. This approach opens new possibilities for designing highly tailored catalysts and energy storage materials for specific industrial applications.

Professors Seungho Cho (Materials Science and Engineering), Kwangjin An (Energy and Chemical Engineering), and Hu Young Jeong (Semiconductor Materials and Devices Engineering) at UNIST, in collaboration with Professor Jeong Woo Han from Seoul National University, announced this advancement. Their method allows for the one-step synthesis of a flexible, H+-intercalated LT (called H-LT), which can undergo direct ion-exchange to incorporate a wide range of metal cations-from alkali metals (AMs) to lanthanides-without compromising structural integrity.

LTs are titanium oxide-based materials composed of thin, stacked layers. Their ability to host various metal ions has made them attractive as catalyst supports and electrode materials. However, traditional metal incorporation methods often involve high-temperature processing and harsh chemicals, limiting the types of metals that can be used and complicating large-scale production.

Figure 1. Preparation and characterization of LT and the M-LTs.

Figure 1. Preparation and characterization of LT and the M-LTs.

To address these challenges, the team developed a bottom-up approach using ammonium hydroxide. Precursor materials naturally organize into proton-rich LTs, which can then exchange protons for desired metal ions when immersed in solution. This technique can intercalate up to 42 different metals across five groups-including AMs and rare earth elements-and can even incorporate over 30 different metals simultaneously in a single structure.

The team demonstrated the practical potential by creating a rhodium(Rh)-supported catalyst. When tested for hydroformylation of propylene-a key step in plastics and detergent production-the catalyst supported on potassium-intercalated LT showed more than three times the activity of conventional Rh catalysts. Analyses and computational modeling suggested that the intercalated AMs facilitate charge transfer to Rh, improving adsorption and catalytic efficiency.

This work provides more than synthesizing new materials. Rather it offers a comprehensive platform-an intercalation library-that can be tailored for various catalytic and energy applications.

"Our work goes beyond just synthesizing a new material," said Professor Cho. "It is about establishing a flexible, scalable technology for selecting and combining metals, opening up new avenues for cost-effective catalysts and high-performance energy storage."

The research involved contributions from Hyoseok Kim (Department of Materials Science and Engineering, UNIST), Daewon Oh (School of Energy and Chemical Engineering, UNIST), and Miyeon Kim (Department of Materials Science and Engineering, SNU), as first authors. Their findings have been published in the online version of Advanced Materials on December 26, 2025.

The study has been supported by the Ministry of Science and ICT (MSIT), the National Research Foundation of Korea (NRF), the UNIST InnoCORE program, the Korea Institute for Advancement of Technology (KIAT), the Ulsan RISE Center, and the Korea Basic Science Institute.

Journal Reference

Hyoseok Kim, Daewon Oh, Miyeon Kim, et al., "Diverse Cation Exchange in Layered Titanate Nanostructures for Tailored Catalysis," Adv. Mater., (2025).

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