Unexpected “Spontaneous” Evolution of Catalytic, MOF-Supported Single Cu(II) Cations to Catalytic, MOF-Supported Cu(0) Nanoparticles

Yang, Ying; Zhang, Xuan; Kanchanakungwankul, Siriluk; Lu, Zhiyong; Noh, Hyunho; Syed, Zoha H.; Farha, Omar K.; Truhlar, Donald G.; Hupp, Joseph T.

doi:10.1021/jacs.0c10367

Title: Unexpected “Spontaneous” Evolution of Catalytic, MOF-Supported Single Cu(II) Cations to Catalytic, MOF-Supported Cu(0) Nanoparticles

Journal Article · Thu Dec 03 00:00:00 EST 2020 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.0c10367· OSTI ID:1735333

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Northwestern Univ., Evanston, IL (United States)
Univ. of Minnesota, Minneapolis, MN (United States)
Northwestern Univ., Evanston, IL (United States); Hohai Univ., Nanjing (China)

A desirable feature of metal–organic frameworks (MOFs) is their well-defined structural periodicity and the presence of well-defined catalyst grafting sites (e.g., reactive –OH and –OH₂ groups) that can support single-site heterogeneous catalysts. However, one should not overlook the potential role of residual organic moieties, specifically formate ions that can occupy the catalyst anchoring sites during MOF synthesis. Here we show how these residual formate species in a Zr-based MOF, NU-1000, critically alter the structure, redox capability, and catalytic activity of postsynthetically incorporated Cu(II) ions. Single-crystal X-ray diffraction measurements established that there are two structurally distinct types of Cu(II) ions in NU-1000: one type with residual formate and one without. In NU-1000 with formate, Cu(II) solely binds to the node via the formate-unoccupied, bridging μ₃–OH, whereas in the formate-free case, it displaces protons from two node hydroxo ligands and resides close to the terminal –OH₂. Under an inert atmosphere, node-bound formate facilitates the unanticipated reduction of isolated Cu(II) to nanoparticulate Cu(0)—a behavior which is essentially absent in the formate-free analogue because no other sacrificial reductant is present. When the two MOFs were tested as benzyl alcohol oxidation catalysts, we observed that residual formate boosts the catalytic turnover frequency. Density functional calculations showed that node-bound formate acts as a sacrificial two-electron donor and assists in reducing Cu(II) to Cu(0) by a nonradical pathway. The negative Gibbs free energy of reaction (ΔG) and enthalpy of reaction (ΔH) indicate that the reduction is thermodynamically favorable. Here, the work presented here highlights how the often-neglected residual formate prevalent in nearly all zirconium-based MOFs can significantly modulate the properties of supported catalysts.

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Research Organization:: Univ. of Minnesota, Minneapolis, MN (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Natural Science Foundation of China (NSFC); National Science Foundation (NSF)

Grant/Contract Number:: SC0012702; 21601047; DGE-1842165; AC02-06CH11357; FG02-03ER15457

OSTI ID:: 1735333

Journal Information:: Journal of the American Chemical Society, Vol. 142, Issue 50; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Title: Unexpected “Spontaneous” Evolution of Catalytic, MOF-Supported Single Cu(II) Cations to Catalytic, MOF-Supported Cu(0) Nanoparticles

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