Synthetic Access to a Framework-Stabilized and Fully Sulfided Analogue of an Anderson Polyoxometalate that is Catalytically Competent for Reduction Reactions

Jiaxin Duan, Hafeera Shabbir, Zhihengyu Chen, Wentuan Bi, Qin Liu*, Jingyi Sui, Luka Đorđević, Samuel I. Stupp, Karena W. Chapman, Alex B.F. Martinson, Alice Li, Richard D. Schaller, Subhadip Goswami, Rachel B. Getman, Joseph T. Hupp*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

2 Scopus citations


Polyoxometalates (POMs) featuring 7, 12, 18, or more redox-accessible transition metal ions are ubiquitous as selective catalysts, especially for oxidation reactions. The corresponding synthetic and catalytic chemistry of stable, discrete, capping-ligand-free polythiometalates (PTMs), which could be especially attractive for reduction reactions, is much less well developed. Among the challenges are the propensity of PTMs to agglomerate and the tendency for agglomeration to block reactant access of catalyst active sites. Nevertheless, the pervasive presence of transition metal sulfur clusters metalloenzymes or cofactors that catalyze reduction reactions and the justifiable proliferation of studies of two-dimensional (2D) metal-chalcogenides as reduction catalysts point to the promise of well-defined and controllable PTMs as reduction catalysts. Here, we report the fabrication of agglomeration-immune, reactant-accessible, capping-ligand-free CoIIMo6IVS24n- clusters as periodic arrays in a water-stable, hierarchically porous Zr-metal-organic framework (MOF; NU1K) by first installing a disk-like Anderson polyoxometalate, CoIIIMo6VIO24m-, in size-matched micropores where the siting is established via difference electron density (DED) X-ray diffraction (XRD) experiments. Flowing H2S, while heating, reduces molybdenum(VI) ions to Mo(IV) and quantitatively replaces oxygen anions with sulfur anions (S2-, HS-, S22-). DED maps show that MOF-templated POM-to-PTM conversion leaves clusters individually isolated in open-channel-connected micropores. The structure of the immobilized cluster as determined, in part, by X-ray photoelectron spectroscopy (XPS), X-ray absorption fine structure (XAFS) analysis, and pair distribution function (PDF) analysis of total X-ray scattering agrees well with the theoretically simulated structure. PTM@MOF displays both electrocatalytic and photocatalytic competency for hydrogen evolution. Nevertheless, the initially installed PTM appears to be a precatalyst, gaining competency only after the loss of ∼3 to 6 sulfurs and exposure to hydride-forming metal ions.

Original languageEnglish (US)
Pages (from-to)7268-7277
Number of pages10
JournalJournal of the American Chemical Society
Issue number13
StatePublished - Apr 5 2023

ASJC Scopus subject areas

  • Chemistry(all)
  • Biochemistry
  • Catalysis
  • Colloid and Surface Chemistry


Dive into the research topics of 'Synthetic Access to a Framework-Stabilized and Fully Sulfided Analogue of an Anderson Polyoxometalate that is Catalytically Competent for Reduction Reactions'. Together they form a unique fingerprint.

Cite this