Metal/metal-oxide heterostructured nanoparticle arrays via block copolymer nanopatterning

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요약

J. Mater. Chem. A, 2026, Advance ArticleDOI: 10.1039/D6TA02839J, PaperJisoo Lim, Jiwoong Ham, Myeongbum Ko, Gyu Hui Jo, In Beom Heo, Kyoung Sun Kim, Hyungsub Kim, Jeonghoon Lim, Hyeyoung Shin, Nari Jeon, Hyeong Min JinA hybrid LPI/SIS strategy within block co…

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Metal/metal-oxide heterostructured nanoparticle arrays via block copolymer nanopatterning

* Corresponding authors

a Department of Organic Materials Engineering, Chungnam National University, Daejeon 34134, Republic of Korea
E-mail: [email protected]

b Department of Materials Science and Engineering, Chungnam National University, Daejeon 34134, Republic of Korea
E-mail: [email protected]

c Graduate School of Energy Science and Technology (GEST), Chungnam National University, Daejeon 34134, Republic of Korea

d Department of Chemistry, College of Sciences, Kyung Hee University, Seoul 02447, Republic of Korea
E-mail: [email protected]

e Neutron Science Division, Korea Atomic Energy Research Institute, Daejeon 34057, Republic of Korea

Abstract

Vertically oriented block copolymer cylindrical nanotemplates provide a constant-geometry route to periodic nanoparticle arrays with predefined size and pitch, yet an easy and general route to periodic, co-localized metal/metal-oxide (M–MO) nanoparticle arrays remains limited. Here we report a nanotemplate-guided hybrid infiltration strategy that sequentially couples liquid-phase infiltration (LPI) with sequential infiltration synthesis (SIS) to generate compositionally tunable M–MO nanoparticle arrays while preserving the template geometry. This sequential protocol expands the accessible precursor space beyond that of either method alone and yields clearly defined M–MO architectures across multiple metal and metal-oxide combinations, with mechanistic insights and scalable fabrication over large areas. As a proof of concept, the resulting arrays serve as highly active hydrogen evolution reaction (HER) catalyst substrates and outperform the corresponding single-metal arrays with identical geometric configurations. Coverage-dependent density functional theory (DFT) calculations on Pt and Pt-ZnO surfaces further rationalized the interfacial synergy by quantifying the hydrogen adsorption free energy as a function of hydrogen coverage. This hybrid infiltration platform enables geometry-matched M–MO libraries for quantitative evaluation of interfacial effects in electrocatalysis and related interfacial-function devices.