Understanding and Tuning the Electronic Properties of Prussian Blue Analogues

Liang, Liangbo; Robinson, Donald Arlington; Wu, Nova; Foster, Michael E.; Maksymovych, Petro; Talin, Albert Alec; Sumpter, Bobby G.

doi:10.1021/acs.chemmater.5c00596

Understanding and Tuning the Electronic Properties of Prussian Blue Analogues

Journal Article · Tue Aug 05 00:00:00 EDT 2025 · Chemistry of Materials

DOI:https://doi.org/10.1021/acs.chemmater.5c00596· OSTI ID:2589627

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Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Sandia National Lab. (SNL-CA), Livermore, CA (United States)
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States); Clemson Univ., SC (United States)

Prussian blue analogues (PBAs) have attracted increasing interest owing to their potential applications in various fields such as energy storage and conversion, neuromorphic computing, and magnetic switching. With a general formula of A_xM_N[M_C(CN)₆], they feature an open framework that provides abundant channels for diffusion of alkali metal ions A and allows flexible compositional control of transition metal ions M_N and M_C. The oxidation states of transition metal ions can be tuned by adjusting the amount (x) of alkali ions A. Here, we carried out density functional theory calculations combined with experimental measurements to investigate the effects of transition metal ions, alkali ions, and oxidation states on the electronic properties of PBAs. Our calculations found that the band gaps of PBAs can be tuned from close to 0 eV to more than 4 eV. Experimentally, we introduced the synthesis/characterization of five previously unreported PBAs (M_N = Ru, Os; M_C = Fe, Ru, and Os) to complete the nine stable M_N:M_C transition metal combinations in group VIII of the periodic table. The optically measured intervalence charge transfer excitation energies of group VIII PBAs are consistent with calculated band gaps. They demonstrate wide band gap tunability by adjusting transition metals and oxidation states, enabling semiconductor-to-metal transitions for memristor applications and enhancing electronic conductivity for battery applications. In conclusion, this work provides a computational/experimental database of electronic properties versus structural compositions for PBAs.

View Accepted Manuscript (DOE)

Research Organization:: Sandia National Lab. (SNL-CA), Livermore, CA (United States); Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF); National Energy Research Scientific Computing Center (NERSC); USDOE National Nuclear Security Administration (NNSA); USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Advanced Scientific Computing Research (ASCR); USDOE Office of Science (SC), High Energy Physics (HEP); USDOE Office of Science (SC), Nuclear Physics (NP); USDOE Office of Science (SC), Fusion Energy Sciences (FES)

Grant/Contract Number:: AC02-05CH11231; NA0003525; SC0023353; AC05-00OR22725

OSTI ID:: 2589627

Alternate ID(s):: OSTI ID: 3002794

Report Number(s):: SAND--2025-12044J; 1772015

Journal Information:: Chemistry of Materials, Journal Name: Chemistry of Materials Journal Issue: 16 Vol. 37; ISSN 1520-5002; ISSN 0897-4756

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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