Filling metal–organic framework mesopores with TiO2 for CO2 photoreduction

Abstract

Metal–organic frameworks (MOFs)1,2,3 are known for their specific interactions with gas molecules4,5; this, combined with their rich and ordered porosity, makes them promising candidates for the photocatalytic conversion of gas molecules to useful products6. However, attempts to use MOFs or MOF-based composites for CO2 photoreduction6,7,8,9,10,11,12,13 usually result in far lower CO2 conversion efficiency than that obtained from state-of-the-art solid-state or molecular catalysts14,15,16,17,18, even when facilitated by sacrificial reagents. Here we create ‘molecular compartments’ inside MOF crystals by growing TiO2 inside different pores of a chromium terephthalate-based MOF (MIL-101) and its derivatives. This allows for synergy between the light-absorbing/electron-generating TiO2 units and the catalytic metal clusters in the backbones of MOFs, and therefore facilitates photocatalytic CO2 reduction, concurrent with production of O2. An apparent quantum efficiency for CO2 photoreduction of 11.3 per cent at a wavelength of 350 nanometres is observed in a composite that consists of 42 per cent TiO2 in a MIL-101 derivative, namely, 42%-TiO2-in-MIL-101-Cr-NO2. TiO2 units in one type of compartment in this composite are estimated to be 44 times more active than those in the other type, underlining the role of precise positioning of TiO2 in this system.

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Fig. 1: Illustration of molecular compartments generated by positioning of TiO2 within specific pores of MOFs.
Fig. 2: Control over the number and location of TiO2 units in TiO2-in-MOF composites.
Fig. 3: Visualization of TiO2 locations within MOF single crystals by electron microscopy.
Fig. 4: CO2 photoreduction performance of TiO2-in-MOF composites and correlation with TiO2 locations.

Data availability

The following are available in Supplementary Information: additional crystallographic information and PXRD data; data from SEM, TEM, selected-area electron diffraction, STEM; results of gas-sorption measurements; diffuse reflectance UV–visible spectra; elemental analyses; CO2 reduction and O2 production data; results from TAS, X-ray absorption fine structure measurements, and XPS; and DFT simulations.

References

  1. 1.

    Yaghi, O. M. et al. Reticular synthesis and the design of new materials. Nature 423, 705–714 (2003).

    ADS  CAS  Article  Google Scholar 

  2. 2.

    Kitagawa, S., Kitaura, R. & Noro, S. I. Functional porous coordination polymers. Angew. Chem. Int. Edn 43, 2334–2375 (2004).

    CAS  Article  Google Scholar 

  3. 3.

    Férey, G. et al. A chromium terephthalate-based solid with unusually large pore volumes and surface area. Science 309, 2040–2042 (2005).

    ADS  Article  Google Scholar 

  4. 4.

    Eddaoudi, M. et al. Systematic design of pore size and functionality in isoreticular MOFs and their application in methane storage. Science 295, 469–472 (2002).

    ADS  CAS  Article  Google Scholar 

  5. 5.

    Cui, X. et al. Pore chemistry and size control in hybrid porous materials for acetylene capture from ethylene. Science 353, 141–144 (2016).

    ADS  CAS  Article  Google Scholar 

  6. 6.

    Logan, M. W. et al. Systematic variation of the optical bandgap in titanium based isoreticular metal–organic frameworks for photocatalytic reduction of CO2 under blue light. J. Mater. Chem. A 5, 11854–11863 (2017).

    CAS  Article  Google Scholar 

  7. 7.

    Fu, Y. H. et al. An amine-functionalized titanium metal–organic framework photocatalyst with visible-light-induced activity for CO2 reduction. Angew. Chem. Int. Edn 124, 3420–3423 (2012).

    Article  Google Scholar 

  8. 8.

    Li, R. et al. Integration of an inorganic semiconductor with a metal–organic framework: a platform for enhanced gaseous photocatalytic reactions. Adv. Mater. 26, 4783–4788 (2014).

    ADS  CAS  Article  Google Scholar 

  9. 9.

    Yan, S. S. et al. Co-ZIF-9/TiO2 nanostructure for superior CO2 photoreduction activity. J. Mater. Chem. A 4, 15126–15133 (2016).

    CAS  Article  Google Scholar 

  10. 10.

    Wang, M. T., Wang, D. K. & Li, Z. H. Self-assembly of CPO-27-Mg/TiO2 nanocomposite with enhanced performance for photocatalytic CO2 reduction. Appl. Catal. B 183, 47–52 (2016).

    CAS  Article  Google Scholar 

  11. 11.

    Sheng, H. et al. Urchin-inspired TiO2@MIL-101 double-shell hollow particles: adsorption and highly efficient photocatalytic degradation of hydrogen sulfide. Chem. Mater. 29, 5612–5616 (2017).

    CAS  Article  Google Scholar 

  12. 12.

    Crake, A. et al. CO2 capture and photocatalytic reduction using bifunctional TiO2/MOF nanocomposites under UV–vis irradiation. Appl. Catal. B 210, 131–140 (2017).

    CAS  Article  Google Scholar 

  13. 13.

    Huang, Z. F. et al. A ZIF-8 decorated TiO2 grid-like film with high CO2 adsorption for CO2 photoreduction. J. CO 2 Util. 24, 369–375 (2018).

    CAS  Article  Google Scholar 

  14. 14.

    Gao, S. et al. Highly efficient and exceptionally durable CO2 photoreduction to methanol over freestanding defective single-unit-cell bismuth vanadate layers. J. Am. Chem. Soc. 139, 3438–3445 (2017).

    CAS  Article  Google Scholar 

  15. 15.

    Won, D. I. et al. Highly robust hybrid photocatalyst for carbon dioxide reduction: tuning and optimization of catalytic activities of dye/TiO2/Re(I) organic-inorganic ternary systems. J. Am. Chem. Soc. 137, 13679–13690 (2015).

    CAS  Article  Google Scholar 

  16. 16.

    Wang, W. N. et al. Size and structure matter: enhanced CO2 photoreduction efficiency by size-resolved ultrafine Pt nanoparticles on TiO2 single crystals. J. Am. Chem. Soc. 134, 11276–11281 (2012).

    CAS  Article  Google Scholar 

  17. 17.

    Wang, L. et al. Anchored Cu(II) tetra(4-carboxylphenyl)porphyrin to P25 (TiO2) for efficient photocatalytic ability in CO2 reduction. Appl. Catal. B 239, 599–608 (2018).

    CAS  Article  Google Scholar 

  18. 18.

    Liang, L. et al. Infrared light-driven CO2 overall splitting at room temperature. Joule 2, 1004–1016 (2018).

    CAS  Article  Google Scholar 

  19. 19.

    Ohnishi, N., Ohsuna, T., Sakamoto, Y., Terasaki, O. & Hiraga, K. Quantitative HRTEM study of zeolite. Microporous Mesoporous Mater. 21, 581–588 (1998).

    CAS  Article  Google Scholar 

  20. 20.

    Choi, M. et al. Stable single-unit-cell nanosheets of zeolite MFI as active and long-lived catalysts. Nature 461, 246–249 (2009).

    ADS  CAS  Article  Google Scholar 

  21. 21.

    Deng, H. et al. Large-pore apertures in a series of metal–organic frameworks. Science 336, 1018–1023 (2012).

    ADS  CAS  Article  Google Scholar 

  22. 22.

    Wiktor, C., Meledina, M., Turner, S., Lebedev, O. I. & Fischer, R. A. Transmission electron microscopy on metal–organic frameworks: a review. J. Mater. Chem. A 5, 14969–14989 (2017).

    CAS  Article  Google Scholar 

  23. 23.

    Zhang, D. et al. Atomic-resolution transmission electron microscopy of electron beam-sensitive crystalline materials. Science 359, 675–679 (2018).

    ADS  CAS  Article  Google Scholar 

  24. 24.

    Lazić, I., Bosch, E. G. & Lazar, S. Phase contrast STEM for thin samples: integrated differential phase contrast. Ultramicroscopy 160, 265–280 (2016).

    Article  Google Scholar 

  25. 25.

    Weckhuysen, B. M., Wachs, I. E. & Schoonheydt, R. A. Surface chemistry and spectroscopy of chromium in inorganic oxides. Chem. Rev. 96, 3327–3350 (1996).

    CAS  Article  Google Scholar 

  26. 26.

    Modrow, A. et al. Introducing a photo-switchable azo-functionality inside Cr-MIL-101-NH2 by covalent post-synthetic modification. Dalton Trans. 41, 8690–8696 (2012).

    CAS  Article  Google Scholar 

  27. 27.

    Li, P. et al. Rationally “clicked” post-modification of a highly stable metal–organic framework and its high improvement on CO2-selective capture. RSC Advances 3, 15566–15570 (2013).

    CAS  Article  Google Scholar 

  28. 28.

    Dong, Z. et al. Multivariate metal–organic frameworks for dialing-in the binding and programming the release of drug molecules. J. Am. Chem. Soc. 139, 14209–14216 (2017).

    CAS  Article  Google Scholar 

  29. 29.

    Serra-Crespo, P. et al. Synthesis and characterization of an amino functionalized MIL-101 (Al): separation and catalytic properties. Chem. Mater. 23, 2565–2572 (2011).

    CAS  Article  Google Scholar 

  30. 30.

    Gallington, L. C. et al. Regioselective atomic layer deposition in metal−organic frameworks directed by dispersion interactions. J. Am. Chem. Soc. 138, 13513–13516 (2016).

    CAS  Article  Google Scholar 

  31. 31.

    Cho, H. S. et al. Extra adsorption and adsorbate superlattice formation in metal–organic frameworks. Nature 527, 503–507 (2015).

    ADS  Article  Google Scholar 

  32. 32.

    Cho, H. S. et al. Isotherms of individual pores by gas adsorption crystallography. Nat. Chem. 11, 562–570 (2019).

    CAS  Article  Google Scholar 

  33. 33.

    Yang, T. Y. et al. Introduction of the X-ray diffraction beamline of SSRF. Nucl. Sci. Tech. 26, 20101–020101 (2015).

    Google Scholar 

  34. 34.

    Marra, G. L. et al. Cation location in dehydrated Na–Rb–Y zeolite: an XRD and IR study. J. Phys. Chem. B 101, 10653–10660 (1997).

    CAS  Article  Google Scholar 

  35. 35.

    Petříček, V., Dušek, M. & Palatinus, L. Crystallographic computing system JANA2006: general features. Z. Krist. Cryst. Mater. 229, 345–352 (2014).

    Google Scholar 

  36. 36.

    Momma, K. & Izumi, K. VESTA 3 for three-dimensional visualization of crystal, volumetric and morphology data. J. Appl. Crystallogr. 44, 1272–1276 (2011).

    CAS  Article  Google Scholar 

  37. 37.

    Ohara, K. et al. Time-resolved pair distribution function analysis of disordered materials on beamlines BL04B2 and BL08W at SPring-8. J. Synchrotron Radiat. 25, 1627 (2018).

    Article  Google Scholar 

  38. 38.

    Gemmi, M. & Oleynikov, P. Scanning reciprocal space for solving unknown structures: Energy filtered diffraction tomography and rotation diffraction tomography methods. Z. Krist. Cryst. Mater. 228, 51–58 (2013).

    CAS  Article  Google Scholar 

Download references

Acknowledgements

We thank staff at beamlines BL14B1, BL14W1, BL15U1 and BL08U1-A (Shanghai Synchrotron Radiation Facility), and at beamline BL04B (National Synchrotron Radiation Laboratory, Hefei, China), for providing the beam time and assistance with synchrotron experiments. We also thank staff of the High Magnetic Field Laboratory of the Chinese Academy of Sciences (CHMFL) for collecting EPR data. We thank S. Osami, T. Masahiko, Y. Katsuya and K. J. Ohara for collecting the absorption coefficient and PDF data at BL04B2 and BL15XU in the National Institute for Materials Science in Japan; Y. Yang and J. Huang at the Dalian Institute of Chemical Physics for collecting nanosecond TAS data; and A. Carlsson and S. Lazar from Thermo Fisher, I. Onishi from JEOL Ltd, and P. Liu from Shanghai Jiaotong University for their invaluable assistance with TEM. Other characterizations were provided by the test centre and Core Research Facilities of Wuhan University. We thank W. Zhang, J. Cao, X. Cai, Z. Dong, H. Jiang, Q. Liu, B. Bie, F. Ke and H. Cong from Wuhan University and Z. Pan and W. Hong from Xiamen University for their help. Financial support was provided by the Natural Science Foundation of China (21471118, 91545205, 91622103, 21971199) and the National Key Basic Research Program of China (2014CB239203, 2018YFA0704000). L.Z. thanks the National Natural Science Foundation of Jiangsu Province for support (BK20151248). T.P. thanks the Natural Science Foundation of China for support (21573166). Y.M. thanks the Commission for Science and Technology of Shanghai Municipality (17ZR1418600), the Shanghai Pujiang Program (17PJ1406400) and the Young Elite Scientist Sponsorship Program by CAST (2017QNRC001) for support. The Recruitment Program for Foreign Experts, China (O.T.) and the grant EM02161943 from CħEM, SPST, ShanghaiTech are acknowledged by Y.M., H.S.C., P.O. and O.T. We also thank the scientists at Berkeley Global Science Institute, UC-Berkeley, for discussions.

Author information

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Authors

Contributions

H.D. and L.Z. conceived the idea for the project and led the studies of synthesis and mechanisms. H.D. and O.T. led the structural characterizations. X.X., Z.J., J.W. and D.D. synthesized MOFs. Z.J. synthesized TiO2-in-MOF composites with the assistance of X.X., H.D., L.Z., J.W. and D.D. in optimizing the conditions. X.X. and Z.J. collected the PXRD data. X.X. and H.S.C. analysed the PXRD data to generate the 3D electron-density map of TiO2 within MOF pores. Y.M., X.X., C.W., P.O., O.T. and H.D. carried out electron diffraction experiments and TEM imaging under the TEM mode. X.X. and Y.M. analysed the electron diffraction data to generate 3D electrostatic potential maps. C.W. performed SEM analysis. X.X., Y.M., Y.Z., O.T. and H.D. analysed iDPC and HAADF images under the STEM mode. Z.J. performed the CO2 photoreduction experiments, O2 capturing and analysed the data with L.Z. and H.D. Z.J. collected and analysed EPR data. X.X. collected and analysed gas adsorption isotherms. Z.J. and X.X. collected and analysed data from XPS, XAS and EXAFS. X.X., H.D., M.J. and J.C. performed the DFT calculations. X.X., H.D., Z.J. and L.Z. prepared the first version of the manuscript and all authors contributed to the final version. The order of the two co-first authors was determined by the alphabetic order of their last names.

Corresponding authors

Correspondence to Osamu Terasaki or Ling Zan or Hexiang Deng.

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The authors declare no competing interests.

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Peer review information Nature thanks Matthew Cliffe, Fernando Uribe Romo and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Extended data figures and tables

Extended Data Fig. 1 Electron diffraction data from the MOF and the TiO2-in-MOF samples.

a, b, 2D projection of the reconstructed reciprocal space of the MOF (MIL-101-Cr; a) and the TiO2-in-MOF (23%-TiO2-in-MIL-101-Cr; b) samples along the [100] direction. The inset in b is the differential electrostatic potential obtained from the 3D diffraction data of 23%-TiO2-in-MIL-101-Cr subtracted from that of MIL-101-Cr. The yellow circles at top right in a and b indicate the diffraction points with highest resolution. Scale bars, 1 nm−1.

Extended Data Fig. 2 Elemental maps of TiO2-in-MOF samples revealed by EDS analysis.

a, b, Elemental maps of single-crystal 23%-TiO2-in-MIL-101-Cr (a) and 42%-TiO2-in-MIL-101-Cr (b); the elements are given at the top right of each coloured map. The uniform TiO2 distribution in both samples is clear. Also shown (bottom right in a and b) is the atomic ratio Ti/Cr (in %) for the five sampling points indicated at top left of a and b. The green dashes in these plots indicate the Ti/Cr ratio of the bulk materials. The Ti/Cr atomic ratios at the five distinct positions in one single crystal are almost identical. Scale bars: a, 100 nm; b, 50 nm.

Extended Data Fig. 3 STEM images of MIL-101-Cr taken from [110] incidence.

a, HAADF and b, iDPC images. The sample thicknesses are indicated on the left in yellow. Red and blue outlines (bottom right of each panel) are overlaid on the images to highlight the position of molecular compartments, with the unit cell in orange. Scale bars, 20 nm.

Extended Data Fig. 4 STEM images of 23%-TiO2-in-MIL-101-Cr taken from [110] incidence.

As Extended Data Fig. 3 but for 23%-TiO2-in-MIL-101-Cr.

Extended Data Fig. 5 STEM images of 42%-TiO2-in-MIL-101-Cr taken from [110] incidence.

As Extended Data Fig. 3 but for 42%-TiO2-in-MIL-101-Cr.

Extended Data Fig. 6 Fourier diffractograms of the images of MOF and TiO2-in-MOF samples in Extended Data Figs. 35.

ac, Fourier diffractograms of the iDPC images in Extended Data Figs. 35, respectively; df, Fourier diffractograms of the HAADF images in Extended Data Figs. 35, respectively. Insets, contrast plots for the spots used to derive the resolution (boxed, labelled with indices). The dashed yellow circles indicate the resolution of each sample.

Extended Data Fig. 7 Line profiles for pure MOF and TiO2-in-MOF samples at different sample thickness in the HAADF images.

a, Illustration of the mesopore distribution in MOF single crystal in different directions, from which the sample thickness is derived. b, Line profiles across mesopores of different types in HAADF images at identical sample thickness. The line profiles of MIL-101-Cr, 23%-TiO2-in-MIL-101-Cr and 42%-TiO2-in-MIL-101-Cr are marked in green, red and blue, respectively. The black lines represent those obtained from the symmetry averaged image of pure MIL-101-Cr as references.

Extended Data Fig. 8 Electron transfer pathway in TiO2-in-MOF composite.

a, The energy level diagram of TiO2, reaction intermediates and products. h+, holes; e, electrons. b, Electron transfer pathway of the photocatalytic reaction illustrated in TiO2-in-MOF compartments composed of Cr clusters.

Extended Data Table 1 Comparison of CO2 conversion performance of various catalysts
Extended Data Table 2 Comparison of excited electron lifetime for CO2 reduction photocatalysts

Supplementary information

Supplementary Information

This file contains Supplementary Methods, Supplementary Discussions, Supplementary Figures 1 to 102, Supplementary Tables 1 to 16, and Supplementary References, and provides information about materials synthesis, identification of TiO2 within the pores of MOF, discussion of catalytic performance and mechanism.

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Jiang, Z., Xu, X., Ma, Y. et al. Filling metal–organic framework mesopores with TiO2 for CO2 photoreduction. Nature 586, 549–554 (2020). https://doi.org/10.1038/s41586-020-2738-2

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