The worldwide replacement of the toxic mercuric chloride catalyst in vinyl chloride manufacture via acetylene hydrochlorination is slowed by the limited durability of alternative catalytic systems at high space velocities. Here, we demonstrate that platinum single atoms on carbon carriers are substantially more stable (up to 1,073 K) than their gold counterparts (up to 473 K), enabling facile and scalable preparation and precise tuning of their coordination environment by simple temperature control. By combining kinetic analysis, advanced characterization, and density functional theory, we assess how the Pt species determines the catalytic performance and thereby identify Pt(ii)−Cl as the active site, being three times more active than Pt nanoparticles. We show that Pt single atoms exhibit outstanding stability in acetylene hydrochlorination and surpass the space–time yields of their gold-based analogues after 25 h time-on-stream, qualifying them as a candidate for sustainable vinyl chloride production.
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The data that support the plots within this paper and other findings of this study are available from the corresponding author upon reasonable request. The DFT structures can be retrieved from the ioChem-BD database56.
Zhang, Z. et al. Thermally stable single atom Pt/m-Al2O3 for selective hydrogenation and CO oxidation. Nat. Commun. 8, 16100 (2017).
Zhang, L. et al. Single-atom catalyst: a rising star for green synthesis of fine chemicals. Natl Sci. Rev. 5, 653–672 (2018).
Zhang, J. & Alexandrova, A. N. The golden crown: a single Au atom that boosts the CO oxidation catalyzed by a palladium cluster on titania surfaces. J. Phys. Chem. Lett. 4, 2250–2255 (2013).
Yang, M. & Flytzani-Stephanopoulos, M. Design of single-atom metal catalysts on various supports for the low-temperature water-gas shift reaction. Catal. Today 298, 216–225 (2017).
Zhang, B. et al. Atomically dispersed Pt1-polyoxometalate catalysts: how does metal-support interaction affect stability and hydrogenation activity? J. Am. Chem. Soc. 141, 8185–8197 (2019).
Wang, A., Li, J. & Zhang, T. Heterogeneous single-atom catalysis. Nat. Rev. Chem. 2, 65–81 (2018).
Li, M. et al. Single-atom tailoring of platinum nanocatalysts for high-performance multifunctional electrocatalysis. Nat. Catal. 2, 495–503 (2019).
Xu, H., Cheng, D., Cao, D. & Zeng, X. C. A universal principle for a rational design of single-atom electrocatalysts. Nat. Catal. 1, 339–348 (2018).
Kaiser, S. K. et al. Controlling the speciation and reactivity of carbon-supported gold nanostructures for catalysed acetylene hydrochlorination. Chem. Sci. 10, 359–369 (2019).
Lin, R. et al. Design of single gold atoms on nitrogen-doped carbon for molecular recognition in alkyne semi-hydrogenation. Angew. Chem. Int. Ed. 58, 504–509 (2019).
Yin, X. P. et al. Engineering the coordination environment of single-atom platinum anchored on graphdiyne for optimizing electrocatalytic hydrogen evolution. Angew. Chem. Int. Ed. 57, 9382–9386 (2018).
Liu, W. et al. Discriminating catalytically active FeNx species of atomically dispersed Fe-N-C catalyst for selective oxidation of the C-H bond. J. Am. Chem. Soc. 139, 10790–10798 (2017).
Wang, X. et al. Regulation of coordination number over single Co sites: triggering the efficient electroreduction of CO2. Angew. Chem. Int. Ed. 57, 1944–1948 (2018).
Mitchell, S., Vorobyeva, E. & Pérez-Ramírez, J. The multifaceted reactivity of single-atom heterogeneous catalysts. Angew. Chem. Int. Ed. 57, 15316–15329 (2018).
Lin, R., Amrute, A. P. & Pérez-Ramírez, J. Halogen-mediated conversion of hydrocarbons to commodities. Chem. Rev. 117, 4182–4247 (2017).
Zhu, M. et al. Development of a heterogeneous non-mercury catalyst for acetylene hydrochlorination. ACS Catal. 5, 5306–5316 (2015).
Zhong, J., Xu, Y. & Liu, Z. Heterogeneous non-mercury catalysts for acetylene hydrochlorination: progress, challenges, and opportunities. Green Chem. 20, 2412–2427 (2018).
United Nations Environment Programme. Minamata Convention on Mercury www.mercuryconvention.org/ (accessed August 2019).
Malta, G., Freakley, S. J., Kondrat, S. A. & Hutchings, G. J. Acetylene hydrochlorination using Au/carbon: a journey towards single site catalysis. Chem. Commun. 53, 11733–11746 (2017).
Johnston, P., Carthey, N. & Hutchings, G. J. Discovery, development, and commercialization of gold catalysts for acetylene hydrochlorination. J. Am. Chem. Soc. 137, 14548–14557 (2015).
Shang, S. et al. Highly efficient Ru@IL/AC to substitute mercuric catalyst for acetylene hydrochlorination. ACS Catal. 7, 3510–3520 (2017).
Malta, G. et al. Identification of single-site gold catalysis in acetylene hydrochlorination. Science 355, 1399–1403 (2017).
Malta, G. et al. Deactivation of a single-site gold-on-carbon acetylene hydrochlorination catalyst: an X-ray absorption and inelastic neutron scattering study. ACS Catal. 8, 8493–8505 (2018).
Ye, L. et al. Self-regeneration of Au/CeO2 based catalysts with enhanced activity and ultra-stability for acetylene hydrochlorination. Nat. Commun. 10, 914 (2019).
Kaiser, S. K. et al. Preserved in a shell: the high performance of graphene-confined ruthenium nanoparticles in acetylene hydrochlorination. Angew. Chem. Int. Ed. 58, 12297–12304 (2019).
Zhou, K. et al. A low content Au-based catalyst for hydrochlorination of C2H2 and its industrial scale-up for future PVC processes. Green Chem. 17, 356–364 (2015).
Conte, M. et al. Hydrochlorination of acetylene using supported bimetallic Au-based catalysts. J. Catal. 257, 190–198 (2008).
Figueroba, A., Kovács, G., Bruix, A. & Neyman, K. M. Towards stable single-atom catalysts: strong binding of atomically dispersed transition metals on the surface of nanostructured ceria. Catal. Sci. Technol. 6, 6806–6813 (2016).
Pierre, D., Deng, W. & Flytzani-Stephanopoulos, M. The importance of strongly bound Pt–CeOx species for the water-gas shift reaction: catalyst activity and stability evaluation. Top. Catal. 46, 363–373 (2007).
O’Connor, N. J., Jonayat, A. S. M., Janik, M. J. & Senftle, T. P. Interaction trends between single metal atoms and oxide supports identified with density functional theory and statistical learning. Nat. Catal. 1, 531–539 (2018).
Daelman, N., Capdevila-Cortada, M. & López, N. Dynamic charge and oxidation state of Pt/CeO2 single-atom catalysts. Nat. Mater. 18, 1215–1221 (2019).
Leyva-Pérez, A. & Corma, A. Similarities and differences between the “relativistic” triad gold, platinum, and mercury in catalysis. Angew. Chem. Int. Ed. 51, 614–635 (2012).
London Bullion Market Association (LBMA). Precious metal prices. http://www.lbma.org.uk/precious-metal-prices (accessed September 2019).
Hu, J. et al. Confining noble metal (Pd, Au, Pt) nanoparticles in surfactant ionic liquids: active non-mercury catalysts for hydrochlorination of acetylene. ACS Catal. 5, 6724–6731 (2015).
Mitchenko, S. A., Krasnyakova, T. V., Mitchenko, R. S. & Korduban, A. N. Acetylene catalytic hydrochlorination over powder catalyst prepared by pre-milling of K2PtCl4 salt. J. Mol. Catal. A Chem. 275, 101–108 (2007).
Yang, L. et al. Metal nanoparticles in ionic liquid-cosolvent biphasic systems as active catalysts for acetylene hydrochlorination. AIChE J. 64, 2536–2544 (2018).
Yang, M. et al. A common single-site Pt(II)-O(OH)x- species stabilized by sodium on “active” and “inert” supports catalyzes the water-gas shift reaction. J. Am. Chem. Soc. 137, 3470–3473 (2015).
Spieker, W. A., Liu, J., Miller, J. T. & Regalbuto, J. R. An EXAFS study of the co-ordination chemistry of hydrogen hexachloroplatinate(IV) 1. Speciation in aqueous solution. Appl. Catal. A 232, 219–235 (2002).
Fraga, M. A. et al. Properties of carbon-supported platinum catalysts: role of carbon surface sites. J. Catal. 209, 355–364 (2002).
Chen, Z. et al. Stabilization of single metal atoms on graphitic carbon nitride. Adv. Funct. Mater. 27, 1605785 (2017).
Lei, Y. et al. Effect of particle size and adsorbates on the L3, L2 and L1 X-ray absorption near edge structure of supported Pt nanoparticles. Top. Catal. 54, 334–348 (2011).
Lin, R., Kaiser, S. K., Hauert, R. & Pérez-Ramírez, J. Descriptors for high-performance nitrogen-doped carbon catalysts in acetylene hydrochlorination. ACS Catal. 8, 1114–1121 (2018).
Bishop, P. T., Carthey, N. A. & Johnston, P. Catalyst comprising gold and a sulphur containing ligand on a support and method for its preparation. International patent WO 2013/008004A3 (2013).
Newville, M. IFEFFIT: interactive XAFS analysis and FEFF fitting. J. Synchrotron Rad. 8, 322–324 (2001).
Kresse, G. & Furthmüller, J. Efficiency of ab initio total energy calculations for metals and semiconductors using a plane-wave basis set. Comp. Mater. Sci. 6, 15–50 (1996).
Kresse, G. & Furthmüller, J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys. Rev. B 54, 11169–11186 (1996).
Perdew, J. P., Burke, K. & Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 77, 3865–3868 (1996).
Grimme, S. Semiempirical GGA-type density functional constructed with a long-range dispersion correction. J. Comput. Chem. 27, 1787–1799 (2006).
Grimme, S., Antony, J., Ehrlich, S. & Krieg, H. A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu. J. Chem. Phys. 132, 154104 (2010).
Blöchl, P. E. Projector augmented-wave method. Phys. Rev. B 50, 17953–17979 (1994).
Kresse, G. & Joubert, D. From ultrasoft pseudopotentials to the projector augmented-wave method. Phys. Rev. B 59, 1758–1775 (1999).
Makov, G. & Payne, M. C. Periodic boundary conditions in ab initio calculations. Phys. Rev. B 51, 4014–4022 (1995).
Henkelman, G. & Jónsson, H. Improved tangent estimate in the nudged elastic band method for finding minimum energy paths and saddle points. J. Chem. Phys. 113, 9978–9985 (2000).
Ravel, B. & Newville, M. ATHENA, ARTEMIS, HEPHAESTUS: data analysis for X-ray absorption spectroscopy using IFEFFIT. J. Synchrotron Radiat. 12, 537–541 (2005).
Álvarez-Moreno, M. et al. Managing the computational chemistry big data problem: the ioChem-BD platform. J. Chem. Inf. Model. 55, 95–103 (2015).
Fako, E. ioChem-BD Collection (Institute of Chemical Research of Catalonia, accessed 6 February 2020); https://doi.org/10.19061/iochem-bd-1-74.
This work was supported by an ETH research grant (ETH-40 17-1) and the Swiss National Science Foundation (project no. 200021–169679). E.F. thanks MINECO La Caixa Severo Ochoa for a predoctoral grant through Severo Ochoa Excellence Accreditation 2014–2018 (SEV 2013 0319). We thank BSC-RES for providing generous computational resources. We thank the Scientific Centre for Optical and Electron Microscopy (ScopeM) at ETH Zurich for the use of their facilities and the Micromeritics Grant Program for the award of the 3Flex instrument.
The authors declare no competing interests.
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Kaiser, S.K., Fako, E., Manzocchi, G. et al. Nanostructuring unlocks high performance of platinum single-atom catalysts for stable vinyl chloride production. Nat Catal 3, 376–385 (2020). https://doi.org/10.1038/s41929-020-0431-3
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