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Introducing metal–sulfur active sites in metal–organic frameworks via post-synthetic modification for hydrogenation catalysis

Nature Chemistry volume 17, pages 1514–1523 (2025)Cite this article

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An Author Correction to this article was published on 23 September 2025

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Abstract

Metal–sulfur active sites play a central role in catalytic processes such as hydrogenation and dehydrogenation, yet the majority of active sites in these compounds reside on the surfaces and edges of catalyst particles, limiting overall efficiency. Here we present a strategy to embed metal–sulfur active sites into metal–organic frameworks (MOFs) by converting bridging or terminal chloride ligands into hydroxide and subsequently into sulfide groups through post-synthetic modification. We apply this method to two representative MOF families: one featuring one-dimensional metal–chloride chains and another containing discrete multinuclear metal clusters. Crystallographic and spectroscopic analyses confirm structural integrity and sulfide incorporation, and the transformation is monitored by in situ total scattering methods. The sulfided MOFs display enhanced catalytic activity in the selective hydrogenation of nitroarenes using molecular hydrogen. Density functional theory calculations indicate that sulfur incorporation promotes homolytic metal–ligand bond cleavage and facilitates H2 activation. This work establishes an approach to construct MOFs featuring accessible metal–sulfide sites.

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Fig. 1: Strategy and MOF platforms used for sulfur incorporation.
Fig. 2: Stepwise post-synthetic routes to embed metal–sulfide active sites into MOFs.
Fig. 3: Structural integrity and sulfur incorporation characterizations across MOF series.
Fig. 4: In situ structural evolution during sulfidation and catalytic hydrogenation performance.
Fig. 5: Computed mechanisms and energetics of hydrogenation catalysis in MOF-based systems.

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Data availability

Materials, general methods, instrumentation, synthetic protocols and DFT computational details are provided in the Supplementary Information PDF file. Crystallographic data for the structures reported in this Article have been deposited at the Cambridge Crystallographic Data Centre, under deposition numbers CCDC 2376631 (Co2Cl2BBTA), 2376626 (Co2(OH)2BBTA), 2376634 (Co2(SH)2BBTA), 2385609 (Ni2Cl2BBTA), 2385610 (Ni2(OH)2BBTA), 2385611 (Ni2(SH)2BBTA), 2376630 (Co-MFU-4l-Cl), 2376629 (Co-MFU-4l-OH), 2376628 (Co-MFU-4l-SH), 2376627 (Ni-MFU-4l-Cl), 2376633 (Ni-MFU-4l-OH) and 2376632 (Ni-MFU-4l-SH). Copies of the data can be obtained free of charge via https://www.ccdc.cam.ac.uk/structures/. The computational data supporting this study are available via Zenodo at https://doi.org/10.5281/zenodo.15074051 (ref. 88). PXRD patterns, N2 isotherms, XPS spectra and PDF data are available via Figshare at https://doi.org/10.6084/m9.figshare.27327783 (ref. 89). Source data are provided with this paper.

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Acknowledgements

This research was supported by the Catalyst Design for Decarbonization Center, an Energy Frontier Research Center funded by the US Department of Energy (DOE), Office of Science, Basic Energy Sciences (BES) under grant DE-SC0023383. Additionally, the IMSERC Crystallography facility at Northwestern University was utilized, with support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-2025633) and Northwestern University. The EPIC facility at Northwestern University’s NUANCE Center was also used, supported by the SHyNE Resource (NSF ECCS-2025633), the International Institute for Nanotechnology (IIN) and Northwestern’s Materials Research Science and Engineering Center (MRSEC) programme (NSF DMR-1720139). Lastly, the Keck-II facility at Northwestern University’s NUANCE Center was used, with backing from the SHyNE Resource (NSF ECCS-2025633), the IIN and Northwestern’s MRSEC programme (NSF DMR-1720139). This research used beamline 28-ID-1 of the National Synchrotron Light Source II, a US DOE Office of Science User Facility at Brookhaven National Laboratory under contract number DE-SC0012704. The computing resources were provided by the University of Chicago Research Computing Center (RCC).

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Authors and Affiliations

  1. Department of Chemistry and International Institute of Nanotechnology, Evanston, IL, USA

    Haomiao Xie, Milad Ahmadi Khoshooei, Kent O. Kirlikovali, Dawson A. Grimes, Seryeong Lee, Shengyi Su, Susanne Reischauer, Debabrata Sengupta, Kira Fahy, Kaikai Ma, Xiaoliang Wang, Fanrui Sha, Wei Gong, Yongwei Chen, Justin M. Notestein & Omar K. Farha

  2. Department of Chemistry, University of Chicago, Chicago, IL, USA

    Mukunda Mandal & John S. Anderson

  3. Department of Chemistry, Stony Brook University, Stony Brook, NY, USA

    Simon M. Vornholt, Jan Hofmann, Luke M. Tufaro & Karena W. Chapman

  4. Department of Science and High Technology and INSTM, Università degli Studi dell’Insubria, Como, Italy

    Jenny G. Vitillo

  5. Department of Chemistry and Pritzker School of Molecular Engineering, University of Chicago, Chicago, IL, USA

    Laura Gagliardi

  6. Department of Chemical and Biological Engineering, Northwestern University, Evanston, IL, USA

    Omar K. Farha

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  1. Haomiao Xie
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H.X., L.G. and O.K.F. conceived and supervised the project. H.X. designed and carried out the synthesis and catalytic experiments, and wrote the original draft together with M.M. M.A.K. contributed to catalysis methodology. M.M. performed theoretical calculations under the supervision of L.G. S.M.V., J.H. and L.M.T. carried out PDF measurements and analysis. K.F., D.A.G. and S.L. assisted with synthesis and materials preparation. S.S., S.R. and D.S. contributed to catalytic studies. K.M. participated in synthesis. X.W., F.S. and S.S. performed microscopy. J.M.N., K.M., W.G., J.G.V., Y.C., J.S.A. and K.O.K. contributed to the interpretation of results. J.M.N. also advised on catalysis. K.W.C. supervised PDF analysis. All authors discussed the results and contributed to revising the manuscript.

Corresponding authors

Correspondence to Haomiao Xie, Laura Gagliardi or Omar K. Farha.

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Competing interests

O.K.F. has financial interest in NuMat Technologies, a start-up company that is seeking to commercialize MOFs. The remaining authors declare no competing interests.

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Extended data

Extended Data Table 1 Energy Decomposition Analysis of NiII–X Homolytic Dissociation in MFU-4l-Ni-X (X = Cl, OH, SH) at M06-D3(0)/def2-TZVP Level
Full size table
Extended Data Table 2 Energy Decomposition Analysis of H2 Binding at an MI Site in both BBTA and MFU-4l Systems Calculated at the M06-D3(0)/def2-TZVP Level
Full size table

Extended Data Fig. 1 Periodic and cluster models used in theoretical studies of MOF catalysts.

a, Structural models of M2X2BBTA. b, Structural models of M-MFU-4l-X. Both periodic and cluster models were used to represent the local coordination environments and extended structures (M = Co, Ni; X = Cl, OH, SH). Colour coding follows that used in Fig. 2.

Extended Data Fig. 2 Schematic of open metal-site generation, hydrogen adsorption and dissociation for subsequent Ar–NO2 reduction with M-BBTA-X catalysts.

In the 1D BBTA system, MeOH initially coordinates to the square pyramidal metal centres, converting species A to B. Subsequent M–X bond cleavage (M = Co, Ni; X = Cl, OH, SH) can proceed either homolytically (C1) or heterolytically (C2), generating an open metal site for H2 adsorption (D1, D2). The H–H bond then dissociates, facilitated by a N-atom on the ligand, forming species E1 and E2. Although our computed results show relatively high energy requirements for the formation of active species E, our goal was to qualitatively understand trends related to MOF structure, metal node, and X ligand. The cluster models employed frozen C atoms in the linkers to maintain structural rigidity of the MOF, potentially overestimating energetic barriers where remarkable ligand relaxation would occur, particularly during the H–H dissociation on the ligand (Conversion of species D to E). Future studies using fully relaxed periodic models of all proposed reaction intermediates should yield lower energy requirements for E formation. Additionally, while intrinsic barriers appear high due to solvent stabilization of species B, the apparent activation energy (Eapp) observed experimentally can be lower when measured relative to separated reactants (Species A).

Supplementary information

Supplementary Information

Supplementary Figs. 1–57, Discussion and Tables 1–18.

Supplementary Data 1

Crystallographic Data of Co2Cl2BBTA (CCDC 2376631)

Supplementary Data 2

Crystallographic Data of Co2(OH)2BBTA (CCDC 2376626)

Supplementary Data 3

Crystallographic Data of Co2(SH)2BBTA (CCDC 2376634)

Supplementary Data 4

Crystallographic Data of Ni2Cl2BBTA (CCDC 2385609)

Supplementary Data 5

Crystallographic Data of Ni2(OH)2BBTA (CCDC 2385610)

Supplementary Data 6

Crystallographic Data of Ni2(SH)2BBTA (CCDC 2385611)

Supplementary Data 7

Crystallographic Data of Co-MFU-4l-Cl (CCDC 2376630)

Supplementary Data 8

Crystallographic Data of Co-MFU-4l-OH (CCDC 2376629)

Supplementary Data 9

Crystallographic Data of Co-MFU-4l-SH (CCDC 2376628)

Supplementary Data 10

Crystallographic Data of Ni-MFU-4l-Cl (CCDC 2376627)

Supplementary Data 11

Crystallographic Data of Ni-MFU-4l-OH (CCDC 2376633)

Supplementary Data 12

Crystallographic Data of Ni-MFU-4l-SH (CCDC 2376632)

Source data

Source Data Fig. 3

Statistical Source Data for plots in Fig. 3

Source Data Fig. 4

Statistical Source Data for plots in Fig. 4

Source Data Fig. 5

Statistical Source Data for plots in Fig. 5

Source Data Table 1

Statistical Source Data for Table 1

Source Data Extended Data Fig./Table 3

Statistical Source Data for Extended Data Table 1

Source Data Extended Data Fig./Table 4

Statistical Source Data for Extended Data Table 2

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Xie, H., Khoshooei, M.A., Mandal, M. et al. Introducing metal–sulfur active sites in metal–organic frameworks via post-synthetic modification for hydrogenation catalysis. Nat. Chem. 17, 1514–1523 (2025). https://doi.org/10.1038/s41557-025-01876-y

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