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Open-channel metal particle superlattices

Abstract

Although tremendous advances have been made in preparing porous crystals from molecular precursors1,2, there are no general ways of designing and making topologically diversified porous colloidal crystals over the 10–1,000 nm length scale. Control over porosity in this size range would enable the tailoring of molecular absorption and storage, separation, chemical sensing, catalytic and optical properties of such materials. Here, a universal approach for synthesizing metallic open-channel superlattices with pores of 10 to 1,000 nm from DNA-modified hollow colloidal nanoparticles (NPs) is reported. By tuning hollow NP geometry and DNA design, one can adjust crystal pore geometry (pore size and shape) and channel topology (the way in which pores are interconnected). The assembly of hollow NPs is driven by edge-to-edge rather than face-to-face DNA–DNA interactions. Two new design rules describing this assembly regime emerge from these studies and are then used to synthesize 12 open-channel superlattices with control over crystal symmetry, channel geometry and topology. The open channels can be selectively occupied by guests of the appropriate size and that are modified with complementary DNA (for example, Au NPs).

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Fig. 1: Reaction pathway for the synthesis of hollow NPs (NFs and NCs) and open-channel superlattices.
Fig. 2: Edge-bonding of NFs that outline space-filling shapes.
Fig. 3: Edge-bonding of NFs that outline one shape of a space-filling pair.
Fig. 4: Adjusting pore topologies of open-channel superlattices and encapsulation of guests in open lattices.

Data availability

All data are available in the main article and Supplementary Information, or from the corresponding author on request.

References

  1. Kong, L., Zhong, M., Shuang, W., Xu, Y. & Bu, X.-H. Electrochemically active sites inside crystalline porous materials for energy storage and conversion. Chem. Soc. Rev. 49, 2378–2407 (2020).

    CAS  PubMed  Google Scholar 

  2. Slater, A. G. & Cooper, A. I. Function-led design of new porous materials. Science 348, aaa8075 (2015).

    PubMed  Google Scholar 

  3. Wang, J. et al. New insights into the structure–performance relationships of mesoporous materials in analytical science. Chem. Soc. Rev. 47, 8766–8803 (2018).

    CAS  PubMed  Google Scholar 

  4. Geng, K. et al. Covalent organic frameworks: design, synthesis, and functions. Chem. Rev. 120, 8814–8933 (2020).

    CAS  PubMed  Google Scholar 

  5. Lee, J.-S. M. & Cooper, A. I. Advances in conjugated microporous polymers. Chem. Rev. 120, 2171–2214 (2020).

    CAS  PubMed  PubMed Central  Google Scholar 

  6. Finnefrock, A. C., Ulrich, R., Toombes, G. E. S., Gruner, S. M. & Wiesner, U. The plumber’s nightmare: a new morphology in block copolymer−ceramic nanocomposites and mesoporous aluminosilicates. J. Am. Chem. Soc. 125, 13084–13093 (2003).

    CAS  PubMed  Google Scholar 

  7. Meza, L. R., Das, S. & Greer, J. R. Strong, lightweight, and recoverable three-dimensional ceramic nanolattices. Science 345, 1322–1326 (2014).

    ADS  CAS  PubMed  Google Scholar 

  8. Zhou, J. & Wang, B. Emerging crystalline porous materials as a multifunctional platform for electrochemical energy storage. Chem. Soc. Rev. 46, 6927–6945 (2017).

    CAS  PubMed  Google Scholar 

  9. Sun, M.-H. et al. Applications of hierarchically structured porous materials from energy storage and conversion, catalysis, photocatalysis, adsorption, separation, and sensing to biomedicine. Chem. Soc. Rev. 45, 3479–3563 (2016).

    CAS  PubMed  Google Scholar 

  10. Vyatskikh, A. et al. Additive manufacturing of 3D nano-architected metals. Nat. Commun. 9, 593 (2018).

    ADS  PubMed  PubMed Central  Google Scholar 

  11. Hirt, L., Reiser, A., Spolenak, R. & Zambelli, T. Additive manufacturing of metal structures at the micrometer scale. Adv. Mater. 29, 1604211 (2017).

    Google Scholar 

  12. Ullal, C. K. et al. Photonic crystals through holographic lithography: simple cubic, diamond-like, and gyroid-like structures. Appl. Phys. Lett. 84, 5434–5436 (2004).

    ADS  CAS  Google Scholar 

  13. Park, H. & Lee, S. Double gyroids for frequency-isolated Weyl points in the visible regime and interference lithographic design. ACS Photonics 7, 1577–1585 (2020).

    CAS  Google Scholar 

  14. Phan, A. et al. Synthesis, structure, and carbon dioxide capture properties of zeolitic imidazolate frameworks. Acc. Chem. Res. 43, 58–67 (2010).

    CAS  PubMed  Google Scholar 

  15. Furukawa, H., Cordova, K. E., O’Keeffe, M. & Yaghi, O. M. The chemistry and applications of metal–organic frameworks. Science 341, 1230444 (2013).

    PubMed  Google Scholar 

  16. Armstrong, E. & O’Dwyer, C. Artificial opal photonic crystals and inverse opal structures—fundamentals and applications from optics to energy storage. J. Mater. Chem. C 3, 6109–6143 (2015).

    CAS  Google Scholar 

  17. Hoeven, J. E. S., van der, Shneidman, A. V., Nicolas, N. J. & Aizenberg, J. Evaporation-induced self-assembly of metal oxide inverse opals: from synthesis to applications. Acc. Chem. Res. 55, 1809–1820 (2022).

    PubMed  PubMed Central  Google Scholar 

  18. Friedrichs, O. D., Dress, A. W. M., Huson, D. H., Klinowski, J. & Mackay, A. L. Systematic enumeration of crystalline networks. Nature 400, 644–647 (1999).

    ADS  CAS  Google Scholar 

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

    ADS  CAS  PubMed  Google Scholar 

  20. Hoffmann, F. Introduction to Crystallography (Springer Nature, 2020).

  21. Mirkin, C. A., Letsinger, R. L., Mucic, R. C. & Storhoff, J. J. A DNA-based method for rationally assembling nanoparticles into macroscopic materials. Nature 382, 607–609 (1996).

    ADS  CAS  PubMed  Google Scholar 

  22. Samanta, D., Zhou, W., Ebrahimi, S. B., Petrosko, S. H. & Mirkin, C. A. Programmable matter: the nanoparticle atom and DNA bond. Adv. Mater. 34, e2107875 (2022).

    ADS  PubMed  Google Scholar 

  23. Macfarlane, R. J. et al. Nanoparticle superlattice engineering with DNA. Science 334, 204–208 (2011).

    ADS  CAS  PubMed  Google Scholar 

  24. O’Brien, M. N., Lin, H. X., Girard, M., Olvera De La Cruz, M. & Mirkin, C. A. Programming colloidal crystal habit with anisotropic nanoparticle building blocks and DNA bonds. J. Am. Chem. Soc. 138, 14562–14565 (2016).

    PubMed  Google Scholar 

  25. Tian, Y. et al. Lattice engineering through nanoparticle–DNA frameworks. Nat. Mater. 15, 654–661 (2016).

    ADS  CAS  PubMed  PubMed Central  Google Scholar 

  26. Zhang, T. et al. 3D DNA origami crystals. Adv. Mater. 30, 1800273 (2018).

    Google Scholar 

  27. Ham, S., Jang, H.-J., Song, Y., Shuford, K. L. & Park, S. Octahedral and cubic gold nanoframes with platinum framework. Angew. Chem. Int. Edn Engl. 54, 9025–9028 (2015).

    CAS  Google Scholar 

  28. Yang, T.-H. et al. Noble-metal nanoframes and their catalytic applications. Chem. Rev. 121, 796–833 (2021).

    CAS  PubMed  Google Scholar 

  29. Wang, Y. et al. Synthesis of silver octahedra with controlled sizes and optical properties via seed-mediated growth. ACS Nano 7, 4586–4594 (2013).

    CAS  PubMed  Google Scholar 

  30. Auyeung, E. et al. DNA-mediated nanoparticle crystallization into Wulff polyhedra. Nature 505, 73–77 (2014).

    ADS  PubMed  Google Scholar 

  31. Auyeung, E., Macfarlane, R. J., Choi, C. H. J., Cutler, J. I. & Mirkin, C. A. Transitioning DNA-engineered nanoparticle superlattices from solution to the solid state. Adv. Mater. 24, 5181–5186 (2012).

    CAS  PubMed  Google Scholar 

  32. Oh, T. et al. Stabilization of colloidal crystals engineered with DNA. Adv. Mater. 31, 1805480 (2019).

    Google Scholar 

  33. Jones, M. R. et al. DNA-nanoparticle superlattices formed from anisotropic building blocks. Nat. Mater. 9, 913–917 (2010).

    ADS  CAS  PubMed  Google Scholar 

  34. Senesi, A. J. et al. Oligonucleotide flexibility dictates crystal quality in DNA-programmable nanoparticle superlattices. Adv. Mater. 26, 7235–7240 (2014).

    CAS  PubMed  Google Scholar 

  35. Gong, J. et al. Shape-dependent ordering of gold nanocrystals into large-scale superlattices. Nat. Commun. 8, 14038 (2017).

    ADS  CAS  PubMed  PubMed Central  Google Scholar 

  36. Tian, Y. et al. Ordered three-dimensional nanomaterials using DNA-prescribed and valence-controlled material voxels. Nat. Mater. 19, 789–796 (2020).

    ADS  CAS  PubMed  Google Scholar 

  37. Smith, D. R., Pendry, J. B. & Wiltshire, M. C. K. Metamaterials and negative refractive index. Science 305, 788–792 (2004).

    ADS  CAS  PubMed  Google Scholar 

  38. Shelby, R. A., Smith, D. R. & Schultz, S. Experimental verification of a negative index of refraction. Science 292, 77–79 (2001).

    ADS  CAS  PubMed  Google Scholar 

  39. Sun, L. et al. Position- and orientation-controlled growth of Wulff-shaped colloidal crystals engineered with DNA. Adv. Mater. 32, 2005316 (2020).

    CAS  Google Scholar 

  40. Millstone, J. E., Wei, W., Jones, M. R., Yoo, H. & Mirkin, C. A. Iodide ions control seed-mediated growth of anisotropic gold nanoparticles. Nano Lett. 8, 2526–2529 (2008).

    ADS  CAS  PubMed  PubMed Central  Google Scholar 

  41. Young, K. L. et al. Assembly of reconfigurable one-dimensional colloidal superlattices due to a synergy of fundamental nanoscale forces. Proc. Natl Acad. Sci. USA 109, 2240–2245 (2012).

    ADS  CAS  PubMed  PubMed Central  Google Scholar 

  42. O’Brien, M. N., Jones, M. R., Brown, K. A. & Mirkin, C. A. Universal noble metal nanoparticle seeds realized through iterative reductive growth and oxidative dissolution reactions. J. Am. Chem. Soc. 136, 7603–7606 (2014).

    PubMed  Google Scholar 

  43. Li, Y. et al. Corner-, edge-, and facet-controlled growth of nanocrystals. Sci. Adv. 7, eabf1410 (2021).

    ADS  CAS  PubMed  PubMed Central  Google Scholar 

  44. Kremer, J. R., Mastronarde, D. N. & McIntosh, J. R. Computer visualization of three-dimensional image data using IMOD. J. Struct. Biol. 116, 71–76 (1996).

    CAS  PubMed  Google Scholar 

  45. Yan, R., Venkatakrishnan, S. V., Liu, J., Bouman, C. A. & Jiang, W. MBIR: a cryo-ET 3D reconstruction method that effectively minimizes missing wedge artifacts and restores missing information. J. Struct. Biol. 206, 183–192 (2019).

    PubMed  PubMed Central  Google Scholar 

  46. Johnson, P. B. & Christy, R. W. Optical constants of the noble metals. Phys. Rev. B 6, 4370–4379 (1972).

    ADS  CAS  Google Scholar 

  47. Werner, W. S. M., Glantschnig, K. & Ambrosch-Draxl, C. Optical constants and inelastic electron-scattering data for 17 elemental metals. J. Phys. Chem. Ref. Data 38, 1013–1092 (2009).

    ADS  CAS  Google Scholar 

Download references

Acknowledgements

We acknowledge S. H. Petrosko (Northwestern University (NU)) for providing editorial input, E. W. Roth (NU) for ultramicrotomy and S. Krishnaswamy (NU) for providing the NIR laser. This material is based on work supported by the Air Force Office of Scientific Research under awards FA9550-17-1-0348 (hollow nanoparticle synthesis and DNA functionalization) and FA9550-16-1-0150 (SEM characterization and optical simulation), and the Center for Bio-Inspired Energy Science, an Energy Frontier Research Center funded by the US Department of Energy, Office of Science, Basic Energy Sciences under award DE-SC0000989 (assembly of hollow nanoparticles). X-ray experiments were carried out at beamlines sector 12-ID-B and the DuPont-Northwestern-Dow Collaborative Access Team (DND-CAT) sector 5 of the Advanced Photon Source (APS) (DOE DE-AC02-06CH11357). This work made use of the EPIC facility of Northwestern University’s NUANCE Center, which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-2025633); the MRSEC program (NSF DMR-1720139) at the Materials Research Center; the International Institute for Nanotechnology (IIN); the Keck Foundation; and the State of Illinois, through the IIN.

Author information

Authors and Affiliations

Authors

Contributions

Y.L. and C.A.M. conceived the idea. Y.L. and W.Z. designed and performed experiments and analysed the data. I.T. and W.H. did the optical simulation. X.H. and J.L. performed the 3D reconstruction. B.L. performed the SAXS simulations. C.A.M. and K.A. supervised the project. Y.L. wrote the initial draft. Y.L., W.Z., B.E.P., H.L., I.T., W.H., X.H., B.L., J.L., V.P.D., K.A. and C.A.M. all analysed the data, interpreted the data and contributed to the writing of the manuscript.

Corresponding author

Correspondence to Chad A. Mirkin.

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Nature thanks Seungwoo Lee, Vinothan Manoharan 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 Edge-bonding of NFs and face-packing of solid NPs that outline space-filling shapes.

a, Models of sc crystals assembled from cubic NFs. b, Models of sc crystals constructed from solid cubes. c, Models of bcc crystals assembled from truncated octahedral NFs. d, Models of bcc crystals constructed from solid truncated octahedra. e, Schematic showing that when the building blocks are derived from space-filling shapes (e.g., cubic, truncated octahedral, and triangular prism NFs), maximizing area sharing maximizes edge sharing at the same time, which drives the thermodynamically stable structure based on CCM. Therefore, NFs that derive from space-filling shapes assemble into the corresponding space-filling construction via edge-bonding. Note that the solid cases are built based on the uniform tessellation of polyhedra.

Extended Data Fig. 2 Edge-bonding of NFs that outline one shape of a space-filling pair.

a, Octahedra and tetrahedra represent one space-filling pair for ccp symmetry. b, The edge-bonding assembly of only octahedral NFs gives the corresponding dual-shape lattice, the ccp structure, with triangular channels of different sizes, and two sets of tetrahedral voids in alternating orientations (shown in yellow and orange). c, Cuboctahedra and square pyramids form a space-filling pair for bct symmetry. d, The edge-bonding assembly of only cuboctahedral NFs gives the corresponding dual-shape lattice, the bct structure, with quadrilateral and triangular channels, and two sets of square pyramidal voids with alternating orientations (highlighted in yellow and orange). e, Truncated cubes and octahedra form a space-filling pair for sc symmetry. f, The edge-bonding assembly of only truncated cubic NFs gives the corresponding dual-shape lattice, the sc structure, with triangular, hexagonal, and octagonal channels, and octahedral voids (highlighted in yellow). Therefore, NFs that outline one shape of a convex space-filling pair can assemble into the corresponding space-filling cocrystal lattice via edge-bonding. Note that the solid cases are built based on uniform tessellation of polyhedra.

Extended Data Fig. 3 Pore sizes can be deliberately tailored by changing the dimensions of the hollow NP building blocks.

a–i, Open channel superlattices with ccp symmetry and different channel sizes. Models (a, d, g) and SEM images (b, c, e, f, h, i) of ccp crystals assembled from Au-Pt octahedral NFs in different sizes. Scale bars: 200 nm (c, f, i); 5 µm (b, e, h). L: NF size; l: pore size.

Extended Data Fig. 4 The pore geometry and topology of the superlattices can be tuned by employing NCs where specific facets are solid (compared to NFs).

a, b, Models of bcc crystals assembled from truncated octahedral NFs and NCs, respectively. c, d, Models of sc crystals assembled from truncated cubic NFs and NCs respectively. e, f, Models of bct crystals assembled from cuboctahedral NFs and NCs, respectively. From left to right, each panel contains models showing the building blocks, the assembled porous crystals, and the pore topologies of the corresponding crystals.

Extended Data Fig. 5 Pore topologies are programmed by both the shape of the building blocks and the crystal symmetry.

a–l, A library of open channel superlattices include: a, 1D chain assembled from triangular prism NFs; b, ih crystal assembled from triangular prism NFs; c, ccp crystal assembled from octahedral NFs; d, sc crystal assembled form cubic NFs; ebcc crystal assembled from truncated octahedral NCs; f, sc crystal assembled from cuboctahedral NCs; g, bcc crystal assembled from truncated octahedral NFs; h, sc crystal assembled from truncated cubic NFs; i, bcc crystal assembled from slightly truncated octahedral NCs; j, sc crystal assembled from truncated cubic NCs; k, bct crystal assembled from cuboctahedral NFs; and l, bct crystal assembled from cuboctahedral NCs. From left to right, each panel contains models shown in perspective view, projected along the indicated lattice directions (including <111>, <100> and <110> directions (cj); <001>, <011>, <111>, <100>, and <110> directions (k,l)], and models showing the pore topologies.

Extended Data Fig. 6 Experimental (red) and simulated (black) SAXS profiles of open channel superlattices with different symmetries.

a, Porous crystals with sc symmetry assembled from cubic NFs. b, Porous crystals with bcc symmetry assembled from truncated octahedral NFs. c, Porous crystals with ccp symmetry assembled from octahedral NFs. d, Porous crystals with bct symmetry assembled from cuboctahedral NFs. e, Porous crystals with sc symmetry assembled from cuboctahedral NCs. f, Porous crystals with bcc symmetry assembled from truncated octahedral NCs. g, Porous crystals with sc symmetry assembled from truncated cubic NCs. h, Porous crystals with bct symmetry assembled from cuboctahedral NCs. i, Porous crystals with sc symmetry assembled from truncated cubic NFs. It is worth noting that the signal of the peaks is not strong owing to the porous and anisotropic nature of the crystals.

Extended Data Fig. 7 Reconstructed 3D models of open channel superlattices from electron microscopy tomography.

a, Porous crystals with ccp symmetry assembled from octahedral NFs viewed from different angles. b, Porous crystals with bct symmetry assembled from cuboctahedral NFs viewed from different angles. Tomographic reconstruction is consistent with symmetry considerations.

Extended Data Fig. 8 Negative effective index simulation of the porous ccp crystal assembled from Au-Pt octahedral NFs.

a, Calculated effective refractive index (n, blue line) and extinction coefficient (k, red line) of a porous Au-Pt ccp crystal. b, Electric field phase accumulated throughout the Au-Pt ccp crystal at wavelengths corresponding to positive (blue line), near-zero (red line), and negative index (black and purple lines) regions.

Supplementary information

Supplementary Information

Supplementary materials and methods, text, figures, tables and references.

Supplementary Video 1 Topological diagrams of open-channel superlattices.

This video shows expanding empty spaces of different types of open-channel superlattices, growing inside out. From top left to bottom right, these diagrams represent—top column: 1D column formed from prism NFs, ih crystal formed from prism NFs, bct crystal formed from cuboctahedral NFs, bct crystal formed from cuboctahedral NCs. Middle column: sc crystal formed from cubic NFs, sc crystal formed from cuboctahedral NCs, sc crystal formed from truncated cubic NFs, sc crystal formed from truncated cubic NCs. Bottom column: ccp crystal formed from octahedral NFs, bcc crystal formed from truncated octahedral NFs, bcc crystal formed from truncated octahedral NCs, bcc crystal formed from slighted truncated octahedral NCs.

Supplementary Video 2 Phase propagation in time in the case of effective negative index.

This video shows the change of the electric field phase in time over the xz plane at 1,550 nm wavelength. A ten-layer ccp structure assembled from octahedral NFs is located inside the vacuum, where the white dashed lines denote the structure. The structure is illuminated by an x polarized plane wave source. The plane waves are injected towards the +z direction (from bottom to top). Phase values are represented by MATLAB’s standard colour map ‘jet’.

Supplementary Video 3 Phase propagation in time in the case of effective positive index.

This video shows the change of the electric field phase in time over the xz plane at 840 nm wavelength. A ten-layer ccp structure assembled from octahedral NFs is located inside the vacuum, where the white dashed lines denote the structure. The structure is illuminated by an x polarized plane wave source. The plane waves are injected towards the +z direction (from bottom to top). Phase values are represented by MATLAB’s standard colour map ‘jet’.

Supplementary Video 4 3D reconstructed structures of representative NFs.

This video shows the computer-reconstructed 3D structures of octahedral (left) and cuboctahedral (right) NFs, based on a series of tilted HAADF-STEM images.

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Li, Y., Zhou, W., Tanriover, I. et al. Open-channel metal particle superlattices. Nature 611, 695–701 (2022). https://doi.org/10.1038/s41586-022-05291-y

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