Abstract
Chiral surfaces are critical components of enantioselective heterogeneous processes such as those used to prepare enantiomerically pure pharmaceuticals. While the majority of chiral surfaces in practical use are based on achiral materials whose surfaces have been modified with enantiomerically pure chiral adsorbates, there are many inorganic materials with valuable surface properties that could be rendered enantiospecific, if their surfaces were intrinsically chiral. This Perspective discusses recent developments in the fabrication of intrinsically chiral surfaces exhibiting enantiospecific adsorption, surface chemistry and electron emission. We propose possible paths to the scalable fabrication of high-surface-area, enantiomerically pure surfaces and discuss opportunities for future progress.
This is a preview of subscription content, access via your institution
Access options
Access Nature and 54 other Nature Portfolio journals
Get Nature+, our best-value online-access subscription
$29.99 / 30 days
cancel any time
Subscribe to this journal
Receive 12 print issues and online access
$259.00 per year
only $21.58 per issue
Buy this article
- Purchase on Springer Link
- Instant access to full article PDF
Prices may be subject to local taxes which are calculated during checkout
Similar content being viewed by others
References
Lang, J. C. & Armstrong, D. W. Chiral surfaces: the many faces of chiral recognition. Curr. Opin. Colloid Interface Sci. 32, 94–107 (2017).
Ahuja, S. Chiral Separations by Chromatography (Oxford Univ. Press, 2000).
Maier, N. M., Franco, P. & Lindner, W. Separation of enantiomers: needs, challenges, perspectives. J. Chromatogr. A 906, 3–33 (2001).
Baiker, A. Chiral catalysis on solids. Curr. Opin. Solid State Mater. Sci. 3, 86–93 (1998).
Dressler, D. H. & Mastai, Y. Enantioselective crystallization of histidine on chiral self-assembled films of cysteine. J. Colloid Interface Sci. 310, 653–660 (2007).
Gellman, A. J., Tysoe, W. T. & Zaera, F. Surface chemistry for enantioselective catalysis. Catal. Lett. 145, 220–232 (2015).
Kawasaki, T. & Soai, K. Asymmetric autocatalysis triggered by chiral crystals formed from achiral compounds and chiral isotopomers. Isr. J. Chem. 52, 582–590 (2012).
Kettner, M. et al. Chirality-dependent electron spin filtering by molecular monolayers of helicenes. J. Phys. Chem. Lett. 9, 2025–2030 (2018).
Mastai, Y. Enantioselective crystallization on nanochiral surfaces. Chem. Soc. Rev. 38, 772–780 (2009).
Rosenberg, R. A., Mishra, D. & Naaman, R. Chiral selective chemistry induced by natural selection of spin-polarized electrons. Angew. Chem. Int. Ed. 54, 7295–7298 (2015).
Meemken, F. & Baiker, A. Recent progress in heterogeneous asymmetric hydrogenation of C=O and C=C bonds on supported noble metal catalysts. Chem. Rev. 117, 11522–11569 (2017).
Jenkins, S. J. & Pratt, S. J. Beyond the surface atlas: a roadmap and gazetteer for surface symmetry and structure. Surf. Sci. Rep. 62, 373–429 (2007).
Jenkins, S. R. Chirality at Solid Surfaces 1st edn (John Wiley & Sons, 2018).
Baber, A. E., Gellman, A. J., Sholl, D. S. & Sykes, E. C. H. The real structure of naturally chiral Cu{643}. J. Phys. Chem. C 112, 11086–11089 (2008).
Gellman, A. J. Chiral surfaces: accomplishments and challenges. ACS Nano 4, 5–10 (2010).
Gellman, A. J., Horvath, J. D. & Buelow, M. T. Chiral single crystal surface chemistry. J. Mol. Catal. A 167, 3–11 (2001).
Hazen, R. M. & Sholl, D. S. Chiral selection on inorganic crystalline surfaces. Nat. Mater. 2, 367–374 (2003).
McFadden, C. F., Cremer, P. S. & Gellman, A. J. Adsorption of chiral alcohols on “chiral” metal surfaces. Langmuir 12, 2483–2487 (1996).
Ahmadi, A., Attard, G., Feliu, J. & Rodes, A. Surface reactivity at “chiral” platinum surfaces. Langmuir 15, 2420–2424 (1999).
Attard, G. A. et al. Temperature effects in the enantiomeric electro-oxidation of d- and l-glucose on Pt{643}(S). J. Phys. Chem. B 103, 1381–1385 (1999).
Gellman, A. J., Huang, Y., Koritnik, A. J. & Horvath, J. D. Structure-sensitive enantiospecific adsorption on naturally chiral Cu(hkl)R&S surfaces. J. Phys. Condens. Matter 29, 034001–034001 (2017).
Horvath, J. D. & Gellman, A. J. Enantiospecific desorption of R- and S-propylene oxide from a chiral Cu(643) surface. J. Am. Chem. Soc. 123, 7953–7954 (2001).
Horvath, J. D. & Gellman, A. J. Enantiospecific desorption of chiral compounds from chiral Cu(643) and achiral Cu(111) surfaces. J. Am. Chem. Soc. 124, 2384–2392 (2002).
Greber, T., Sljivancanin, Z., Schillinger, R., Wider, J. & Hammer, B. Chiral recognition of organic molecules by atomic kinks on surfaces. Phys. Rev. Lett. 96, 056103 (2006).
Horvath, J. D., Baker, L. & Gellman, A. J. Enantiospecific orientation of R-3-methylcyclohexanone on the chiral Cu(643)R&S surfaces. J. Phys. Chem. C 112, 7637–7643 (2008).
Schillinger, R., Sljivancanin, Z., Hammer, B. & Greber, T. Probing enantioselectivity with X-ray photoelectron spectroscopy and density functional theory. Phys. Rev. Lett. 98, 136102 (2007).
Horvath, J. D., Koritnik, A., Kamakoti, P., Sholl, D. S. & Gellman, A. J. Enantioselective separation on a naturally chiral surface. J. Am. Chem. Soc. 126, 14988–14994 (2004).
Yun, Y. J. & Gellman, A. J. Enantioselective separation on naturally chiral metal surfaces: d,l-aspartic acid on Cu(3,1,17)R&S. surfaces. Angew. Chem. Int. Ed. 52, 3394–3397 (2013).
Yun, Y. J. & Gellman, A. J. Enantiospecific adsorption of amino acids on naturally chiral Cu{3,1,17}R&S surfaces. Langmuir 31, 6055–6063 (2015).
Fleming, C., King, M. & Kadodwala, M. Highly efficient electron beam induced enantioselective surface chemistry. J. Phys. Chem. C 112, 18299–18302 (2008).
Rampulla, D. M., Francis, A. J., Knight, K. S. & Gellman, A. J. Enantioselective surface chemistry of R-2-bromobutane on Cu(643)R&S and Cu(531)R&S. J. Phys. Chem. B 110, 10411–10420 (2006).
Rampulla, D. M. & Gellman, A. J. Enantioselective decomposition of chiral alkyl bromides on Cu(643)R&S: effects of moving the chiral center. Surf. Sci. 600, 2823–2829 (2006).
Gellman, A. J. et al. Superenantioselective chiral surface explosions. J. Am. Chem. Soc. 135, 19208–19214 (2013).
Mhatre, B. S., Dutta, S., Reinicker, A., Karagoz, B. & Gellman, A. J. Explosive enantiospecific decomposition of aspartic acid on Cu surfaces. Chem. Commun. 52, 14125–14128 (2016).
Mhatre, B. S. et al. A window on surface explosions: tartaric acid on Cu(110). J. Phys. Chem. C 117, 7577–7588 (2013).
de Alwis, A. et al. Surface structure spread single crystals (S4Cs): preparation and characterization. Surf. Sci. 608, 80–87 (2013).
Karagoz, B., Payne, M., Reinicker, A., Kondratyuk, P. & Gellman, A. J. A most enantioselective chiral surface: tartaric acid on all surfaces vicinal to Cu(110). Langmuir 35, 16438–16443 (2019).
Reinicker, A. D. et al. Influence of step faceting on the enantiospecific decomposition of aspartic acid on chiral Cu surfaces vicinal to Cu{111}. Chem. Commun. 52, 11263–11266 (2016).
Kelso, M. V., Tubbesing, J. Z., Chen, Q. Z. & Switzer, J. A. Epitaxial electrodeposition of chiral metal surfaces on silicon(643). J. Am. Chem. Soc. 140, 15812–15819 (2018).
Francis, A. J., Koritnik, A. J., Gellman, A. J. & Salvador, P. A. Chiral surfaces and metal/ceramic heteroepitaxy in the Pt/SrTiO3(621) system. Surf. Sci. 601, 1930–1936 (2007).
Francis, A. J. & Salvador, P. A. Chirally oriented heteroepitaxial thin films grown by pulsed laser deposition: Pt(621) on SrTiO3(621). J. Appl. Phys. 96, 2482–2493 (2004).
Bohannan, E. W., Kothari, H. M., Nicic, I. M. & Switzer, J. A. Enantiospecific electrodeposition of chiral CuO films on single-crystal Cu(111). J. Am. Chem. Soc. 126, 488–489 (2004).
Gudavarthy, R. V. et al. Epitaxial electrodeposition of chiral CuO films from copper(ii) complexes of malic acid on Cu(111) and Cu(110) single crystals. J. Mater. Chem. 21, 6209–6216 (2011).
Kothari, H. M. et al. Enantiospecific electrodeposition of chiral CuO films from copper(ii) complexes of tartaric and amino acids on single-crystal Au(001). Chem. Mater. 16, 4232–4244 (2004).
Switzer, J. A., Kothari, H. M., Poizot, P., Nakanishi, S. & Bohannan, E. W. Enantiospecific electrodeposition of a chiral catalyst. Nature 425, 490–493 (2003).
Woodruff, D. P. Adsorbate-induced reconstruction of surfaces — an atomistic alternative to microscopic faceting. J. Phys. Condens. Matter 6, 6067–6094 (1994).
Woodruff, D. P. Solved and unsolved problems in surface structure determination. Surf. Sci. 500, 147–171 (2002).
Chen, Q. & Richardson, N. V. Surface facetting induced by adsorbates. Prog. Surf. Sci. 73, 59–77 (2003).
Gellman, A. J. & Ernst, K. H. Chiral autocatalysis and mirror symmetry breaking. Catal. Lett. 148, 1610–1621 (2018).
Lawton, T. J. et al. Long range chiral imprinting of Cu(110) by tartaric acid. J. Phys. Chem. C 117, 22290–22297 (2013).
Schunack, M., Laegsgaard, E., Stensgaard, I., Johannsen, I. & Besenbacher, F. A chiral metal surface. Angew. Chem. Int. Ed. 40, 2623–2626 (2001).
Schunack, M. et al. Anchoring of organic molecules to a metal surface: HtBDC on Cu(110). Phys. Rev. Lett. 86, 456–459 (2001).
Zhao, X. Y. Fabricating homochiral facets on Cu(001) with l-lysine. J. Am. Chem. Soc. 122, 12584–12585 (2000).
Zhao, X. Y., Zhao, R. G. & Yang, W. S. Scanning tunneling microscopy investigation of l-lysine adsorbed on Cu(001). Langmuir 16, 9812–9818 (2000).
Cheong, W. Y. & Gellman, A. J. Energetics of chiral imprinting of Cu(100) by lysine. J. Phys. Chem. C 115, 1031–1035 (2011).
Behar-Levy, H., Neumann, O., Naaman, R. & Avnir, D. Chirality induction in bulk gold and silver. Adv. Mater. 19, 1207–1211 (2007).
Pachon, L. D. et al. Chiral imprinting of palladium with cinchona alkaloids. Nat. Chem. 1, 160–164 (2009).
Gautier, C. & Burgi, T. Chiral gold nanoparticles. ChemPhysChem 10, 483–492 (2009).
Jadzinsky, P. D., Calero, G., Ackerson, C. J., Bushnell, D. A. & Kornberg, R. D. Structure of a thiol monolayer-protected gold nanoparticle at 1.1 angstrom resolution. Science 318, 430–433 (2007).
Zeng, C. J. & Jin, R. C. Chiral gold nanoclusters: atomic level origins of chirality. Chem. Asian J. 12, 1839–1850 (2017).
Shukla, N., Bartel, M. A. & Gellman, A. J. Enantioselective separation on chiral Au nanoparticles. J. Am. Chem. Soc. 132, 8575–8580 (2010).
Shukla, N. et al. Polarimetric detection of enantioselective adsorption by chiral Au nanoparticles — effects of temperature, wavelength and size. Nanomater. Nanotechnol. 5, 1 (2015).
Tian, N., Zhou, Z. Y., Sun, S. G., Ding, Y. & Wang, Z. L. Synthesis of tetrahexahedral platinum nanocrystals with high-index facets and high electro-oxidation activity. Science 316, 732–735 (2007).
Lee, H. E. et al. Concave rhombic dodecahedral Au nanocatalyst with multiple high-index facets for CO2 reduction. ACS Nano 9, 8384–8393 (2015).
Ming, T. et al. Growth of tetrahexahedral gold nanocrystals with high-index facets. J. Am. Chem. Soc. 131, 16350–16351 (2009).
Hong, J. W., Lee, S. U., Lee, Y. W. & Han, S. W. Hexoctahedral Au nanocrystals with high-index facets and their optical and surface-enhanced Raman scattering properties. J. Am. Chem. Soc. 134, 4565–4568 (2012).
Zhang, L. et al. Synthesis of convex hexoctahedral palladium@gold core-shell nanocrystals with {431} high-index facets with remarkable electrochemiluminescence activities. ACS Nano 8, 5953–5958 (2014).
Lee, H. E. et al. Amino-acid- and peptide-directed synthesis of chiral plasmonic gold nanoparticles. Nature 556, 360–365 (2018).
Deng, J. H., Fu, J. X., Ng, J. & Huang, Z. F. Tailorable chiroptical activity of metallic nanospiral arrays. Nanoscale 8, 4504–4510 (2016).
Gibbs, J. G. et al. Nanohelices by shadow growth. Nanoscale 6, 9457–9466 (2014).
Goyal, A. in Second Generation HTS Conductors (ed. Goyal, A.) Ch. 2, 347 (Springer, 2005).
Goyal, A., Paranthaman, M. P. & Schoop, U. The RABiTS approach: using rolling-assisted biaxially textured substrates for high-performance YBCO superconductors. MRS Bull. 29, 552–561 (2004).
Acknowledgements
The authors’ work in the field of chiral surface chemistry and catalysis has been funded by the US Department of Energy under grant number DE-SC0008703 and by the US National Science Foundation under grant number NSF CHE1764252.
Author information
Authors and Affiliations
Corresponding author
Ethics declarations
Competing interests
The authors declare no competing interests.
Additional information
Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Rights and permissions
About this article
Cite this article
Shukla, N., Gellman, A.J. Chiral metal surfaces for enantioselective processes. Nat. Mater. 19, 939–945 (2020). https://doi.org/10.1038/s41563-020-0734-4
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1038/s41563-020-0734-4
This article is cited by
-
Investigating chiral morphogenesis of gold using generative cellular automata
Nature Materials (2024)
-
The pseudochiral Fermi surface of α-RuI3
Communications Physics (2024)
-
Realization of large-area ultraflat chiral blue phosphorene
Nature Communications (2024)
-
Heteroepitaxial growth of Au@Pd core–shell nanocrystals with intrinsic chiral surfaces for enantiomeric recognition
Rare Metals (2024)
-
Bioinspired chiral inorganic nanomaterials
Nature Reviews Bioengineering (2023)