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Designing single-site alloy catalysts using a degree-of-isolation descriptor

Nature Nanotechnology volume 18, pages 611–616 (2023)Cite this article

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Abstract

Geometrically isolated metal atoms in alloy catalysts can target efficient and selective catalysis. However, the geometric and electronic disturbance between the active atom and its neighbouring atoms, that is, diverse microenvironments, makes the active site ambiguous. Herein, we demonstrate a methodology to describe the microenvironment and determine the effectiveness of active sites in single-site alloys. A simple descriptor, degree-of-isolation, is proposed, considering both electronic regulation and geometric modulation within a PtM ensemble (M = transition metal). The catalytic performance of PtM single-site alloy is examined thoroughly using this descriptor for an industrially important reaction, propane dehydrogenation. The volcano-shaped isolation–selectivity plot reveals a Sabatier-type principle for designing selective single-site alloys. Specifically, for a single-site alloy with a high degree-of-isolation, alternation of the active centre has a great impact on tuning selectivity, validated by the outstanding consistency between experimental propylene selectivity and the computational descriptor.

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Fig. 1: Electronic regulation of Pt site.
Fig. 2: Geometric modulation of Pt site.
Fig. 3: Volcano-shaped isolation–selectivity plot.
Fig. 4: Experimental synthesis, characterization and PDH performance.

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Data availability

The data that support the findings of this study are available within this Article and its Supplementary Information files or from the corresponding author upon reasonable request. Source data are provided with this paper.

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Acknowledgements

We acknowledge the National Key R&D Program of China (2021YFA1500704), the National Natural Science Foundation of China (22121004, U22A20409, U1862207), the Haihe Laboratory of Sustainable Chemical Transformations, the Program of Introducing Talents of Discipline to Universities (BP0618007) and the XPLORER PRIZE for financial support. We also acknowledge generous computing resources at the High Performance Computing Center of Tianjin University.

Author information

Author notes

  1. Shenjun Zha

    Present address: Institute of Catalysis Research and Technology, Karlsruhe Institute of Technology, Eggenstein-Leopoldshafen, Germany

  2. These authors contributed equally: Xin Chang, Zhi-Jian Zhao.

Authors and Affiliations

  1. School of Chemical Engineering & Technology, Key Laboratory for Green Chemical Technology of Ministry of Education, Tianjin University, Tianjin, China

    Xin Chang, Zhi-Jian Zhao, Zhenpu Lu, Sai Chen, Shenjun Zha, Lulu Li, Guodong Sun, Chunlei Pei & Jinlong Gong

  2. Collaborative Innovation Center for Chemical Science & Engineering (Tianjin), Tianjin, China

    Xin Chang, Zhi-Jian Zhao, Zhenpu Lu, Sai Chen, Shenjun Zha, Lulu Li, Guodong Sun, Chunlei Pei & Jinlong Gong

  3. Haihe Laboratory of Sustainable Chemical Transformations, Tianjin, China

    Zhi-Jian Zhao & Jinlong Gong

  4. National Industry–Education Platform of Energy Storage, Tianjin University, Tianjin, China

    Zhi-Jian Zhao & Jinlong Gong

  5. Joint School of National University of Singapore and Tianjin University, Fuzhou, China

    Zhi-Jian Zhao, Ran Luo & Jinlong Gong

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Contributions

J.G. conceived and coordinated the research. X.C. and Z.-J.Z. designed and performed the DFT calculations. R.L., S.Z. and L.L. assisted with the DFT calculations. Z.L., S.C., G.S., X.C. and C.P. contributed to the experiments. All authors wrote the manuscript and have reviewed, discussed and approved the results and conclusions of this Article.

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Correspondence to Jinlong Gong.

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Nature Nanotechnology thanks Sharon Mitchell and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Extended data

Extended Data Fig. 1 Electronic regulation of Pt site.

a, The surface structure of PtNi(110), PtCo(110), PtFe(110), Pt3Ni(111), Pt3Co(111) and Pt3Fe(111). Color: Pt-blue, Ni-green, Co-red, Fe-yellow. The interatomic distance of Pt–Pt is annotated (unit: Å). b, Crystal orbital Hamilton populations (COHP) between Pt atom and C atom for π or di-σ adsorbed C3H6. The fermi level is at 0 eV. c, The relationship between Δχ and electron transfer from M to Pt for Pt(111), Pt3M(111) and PtM(110). The relationship between Δχ and antibonding occupation of Pt–C bond for top-adsorbed CH3 on Pt(111), Pt3M(111) and PtM(110). M = 3d transition metals. The mole ratio (k = cM/cPt) is introduced as a constant term to differentiate alloy composition.

Source data

Extended Data Fig. 2 PtZn intermetallic alloy with the atom colored with charge density (unit: |e|).

a, The surface structure of PtZn(110). b, The surface structure of PtZn(101). The interatomic distance of Pt–Pt is annotated (unit: Å). The elementary steps of PDH are investigated along two directions consisting of the closest Pt atoms. The red arrow indicates electron transfer from M to Pt. The ordered arrangement of constituent atoms in intermetallic alloy brings about homogeneous geometric and electronic structures.

Source data

Extended Data Fig. 3 The transformation of the most stable adsorption configurations of C3H5 on the close-packed surface of PtM.

a, The alternation of active center for alloys with different ϕ and different alloying elements. b, A schematic diagram to illustrate the change of active center. The most stable adsorption manner on PtHf and PtZr are calculated using a constrained structure to avoid surface reconstruction. PtAu and PtW with a negative ϕ are not discussed in the main text as they are directly excluded due to unfavorable electronic structure (a negative Δχ) for designing selective catalyst.

Source data

Extended Data Fig. 4 Segregation energy of Pt and Mn to the surface.

a, Optimized geometries of PtMn particle. b, The segregation energy of Pt and Mn to the surface of PtMn particle. The lowest segregation energy is used. c, Different number of segregation atom to the surface is calculated. The insets show the structure after optimization. For a certain number of atoms that segregates to the surface, the structure with lower energy is used. Color: Pt-blue, Mn-orange.

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Extended Data Fig. 5 AIMD simulations of PtMn particle.

a, Temperature and energy profiles of AIMD simulation for PtMn particle, which is modelled by 32 Pt atom and 31 Mn atom. b, Radius distribution functions (RDFs) between Pt and Mn atoms of PtMn particle. The last 8 ps and every 2 ps are used to perform RDFs to compare the equilibrium. The trends of four times RDFs are the same, which means the system is in an equilibrium state. c-f, The snapshots (top and side view) at 22, 24, 26, and 28 ps. The structure of PtMn particle is maintained despite of slight movement. Color: Pt-blue, Mn-orange.

Source data

Extended Data Fig. 6 AIMD simulations at 873 K of PtMn(110).

a, Temperature and energy profiles of AIMD simulation for PtMn(110), which is modelled by (4 × 4) supercell with five layers. The inset shows the structure of PtMn(110) before simulation. b, Radius distribution functions (RDFs) between Pt and Mn atoms of PtMn(110). The last 8 ps and every 2 ps are used to perform RDFs to compare the equilibrium. The trends of four times RDFs are the same, which means the system is in an equilibrium state. c-f, The snapshots (top and side view) at 42, 62, 72, and 82 ps. The structure of PtMn is maintained despite of slight movement. The bonding with bond length below 3 Å is shown. Color: Pt-blue, Mn-orange.

Source data

Extended Data Fig. 7 The volcano-shaped relationship between ϕ and experimental C3H6 selectivity.

a, Experimental test under different reaction temperature and WHSV of propane (823 K, WHSV of propane = 8.5 h−1, C3H8:H2=1:1, with N2 balance). b, Experimental test under a higher propane partial pressure and WHSV of propane (873 K, WHSV of propane = 8.5 h−1, C3H8:H2=2:1, without N2 balance). The data of PtZn is a quote of reference13. The experimental selectivity of C3H6 under different reaction conditions maintains a similar volcanic relationship with the descriptor (ϕ), further enhancing the reliability of ϕ.

Source data

Extended Data Fig. 8 The comparison of dehydrogenation behavior over PtMn(110), Pt(111), and PtMn particle.

The potential diagram of propylene dehydrogenation at a, edge site of PtMn particle, and b, corner site of PtMn particle. The insets show the geometries of the adsorbed C3H6, the transition state (TS) of C3H6 dehydrogenation, and the adsorbed C3H5 over PtMn particle. Color: Pt-blue, Mn-orange. c, d, The selectivity comparison between PtMn(110), Pt(111), and PtMn particle. Pt(111) is taken as the reference. The potential diagram shows that the adsorption strength of C3H6 at edge or corner site of PtMn particle becomes stronger than PtMn(110). Especially, the corner site exhibits stronger adsorption of the coke precursor (C3H5) compared with PtMn(110). Moreover, the transition states of C3H6 dehydrogenation are more stable over the low-coordinated sites than PtMn(110). This leads to a decreased selectivity, which can facilitate coke formation and contribute to the deactivation at the initial stage of catalysis.

Source data

Extended Data Fig. 9 Extension and applicability of ‘degree-of-isolation’.

a, The relationship between ϕe and experimental ethylene selectivity for Au-, Ag-, and Cu-alloyed Pd SAA catalyst in the semi-hydrogenation of acetylene. The experimental data is a quote from references16,17,18. b, The relationship between ϕe and experimental propylene selectivity for subsurface alloy with Pt-skin structure, and Fe, Co, or Ni as alloying elements in subsurface regions. The experimental data is a quote from reference38.

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Supplementary information

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Chang, X., Zhao, ZJ., Lu, Z. et al. Designing single-site alloy catalysts using a degree-of-isolation descriptor. Nat. Nanotechnol. 18, 611–616 (2023). https://doi.org/10.1038/s41565-023-01344-z

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