Abstract
Constructing regioselective architectures in heterostructures is important for many applications; however, the targeted design of regioselective architectures is challenging due to the sophisticated processes, impurity pollution and an unclear growth mechanism. Here we successfully realized a one-pot kinetically controlled synthetic framework for constructing regioselective architectures in metallic heterostructures. The key objective was to simultaneously consider the reduction rates of metal precursors and the lattice matching relationship at heterogeneous interfaces. More importantly, this synthetic method also provided phase- and morphology-independent behaviours as foundations for choosing substrate materials, including phase regulation from Pd20Sb7 hexagonal nanoplates (HPs) to Pd8Sb3 HPs, and morphology regulation from Pd20Sb7 HPs to Pd20Sb7 rhombohedra and Pd20Sb7 nanoparticles. Consequently, the activity of regioselective epitaxially grown Pt on Pd20Sb7 HPs was greatly enhanced towards the ethanol oxidation reaction; its activity was 57 times greater than that of commercial Pt/C, and the catalyst showed increased stability (decreasing by 16.3% after 2,000 cycles) and selectivity (72.4%) compared with those of commercial Pt/C (56.0%, 18.2%). This work paves the way for the design of unconventional well-defined heterostructures for use in various applications.
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Data availability
All data supporting the findings of this study are available in the Supplementary Information. Additional data are also available from the corresponding authors upon reasonable request. Source data are provided with this paper.
Code availability
The computational codes used in this work are available from the corresponding authors on reasonable request.
References
Mitchell, S. et al. Nanoscale engineering of catalytic materials for sustainable technologies. Nat. Nanotechnol. 16, 129–139 (2020).
Guan, Q. et al. Bimetallic monolayer catalyst breaks the activity–selectivity trade−off on metal particle size for efficient chemoselective hydrogenations. Nat. Catal. 4, 840–849 (2021).
van der Hoeven, J. E. S. et al. Unlocking synergy in bimetallic catalysts by core−shell design. Nat. Mater. 20, 1216–1220 (2021).
He, T. et al. Mastering the surface strain of platinum catalysts for efficient electrocatalysis. Nature 598, 76–81 (2021).
Chang, J. et al. Improving Pd–N–C fuel cell electrocatalysts through fluorination-driven rearrangements of local coordination environment. Nat. Energy 6, 1144–1153 (2021).
Oyedele, A. D. et al. PdSe2: pentagonal two-dimensional layers with high air stability for electronics. J. Am. Chem. Soc. 139, 14090–14097 (2017).
Li, Y. et al. Anomalous resistive switching in memristors based on two-dimensional palladium diselenide using heterophase grain boundaries. Nat. Electron. 4, 348–356 (2021).
Sancho-Albero, M. et al. Cancer-derived exosomes loaded with ultrathin palladium nanosheets for targeted bioorthogonal catalysis. Nat. Catal. 2, 864–872 (2019).
Sebastian, V. et al. Nondestructive production of exosomes loaded with ultrathin palladium nanosheets for targeted bio-orthogonal catalysis. Nat. Protoc. 16, 131–163 (2021).
Chen, Z. et al. Bioorthogonal catalytic patch. Nat. Nanotechnol. 16, 933–941 (2021).
Novoselov, K. S., Mishchenko, A., Carvalho, A. & Castro Neto, A. H. 2D materials and van der Waals heterostructures. Science 353, aac9439 (2016).
Lu, Q. et al. Crystal phase-based epitaxial growth of hybrid noble metal nanostructures on 4H/fcc Au nanowires. Nat. Chem. 10, 456–461 (2018).
Zhai, L. et al. Epitaxial growth of highly symmetrical branched noble metal-semiconductor heterostructures with efficient plasmon-induced hot-electron transfer. Nat. Commun. 14, 2538 (2023).
Mistry, H., Varela, A. S., Kühl, S., Strasser, P. & Cuenya, B. R. Nanostructured electrocatalysts with tunable activity and selectivity. Nat. Rev. Mater. 1, 16009 (2016).
Seh, Z. W. et al. Combining theory and experiment in electrocatalysis: insights into materials design. Science 355, eaad4998 (2017).
Yang, Y. et al. Metal surface and interface energy electrocatalysis: fundamentals, performance engineering, and opportunities. Chem 4, 2054–2083 (2018).
Luo, M. & Guo, S. Strain-controlled electrocatalysis on multimetallic nanomaterials. Nat. Rev. Mater. 2, 17059 (2017).
Xu, Q. et al. Atomic heterointerface engineering overcomes the activity limitation of electrocatalysts and promises highly-efficient alkaline water splitting. Energy Environ. Sci. 14, 5228–5259 (2021).
Park, J. et al. Flattening bent Janus nanodiscs expands lattice parameters. Chem 9, 948–962 (2023).
Bu, L. et al. Biaxially strained PtPb/Pt core/shell nanoplate boosts oxygen reduction catalysis. Science 354, 1410–1414 (2016).
Li, M. et al. Ultrafine jagged platinum nanowires enable ultrahigh mass activity for the oxygen reduction reaction. Science 354, 1414–1419 (2016).
Zhao, M. et al. Selective epitaxial growth of oriented hierarchical metal–organic framework heterostructures. J. Am. Chem. Soc. 142, 8953–8961 (2020).
Huang, L. et al. Regioselective deposition of metals on seeds within a polymer matrix. J. Am. Chem. Soc. 144, 4792–4798 (2022).
Zhuang, T. et al. Regioselective magnetization in semiconducting nanorods. Nat. Nanotechnol. 15, 192–197 (2020).
Steimle, B. C. et al. Rational construction of a scalable heterostructured nanorod megalibrary. Science 367, 418–424 (2020).
Oh, M. H. et al. Design and synthesis of multigrain nanocrystals via geometric misfit strain. Nature 577, 359–363 (2020).
Chen, L. et al. Improved ethanol electrooxidation performance by shortening Pd–Ni active site distance in Pd–Ni–P nanocatalysts. Nat. Commun. 8, 14136 (2017).
Zhang, Y. et al. Atomically isolated Rh sites within highly branched Rh2Sb nanostructures enhance bifunctional hydrogen electrocatalysis. Adv. Mater. 33, e2105049 (2021).
Zhou, M. et al. Improvement of oxygen reduction performance in alkaline media by tuning phase structure of Pd–Bi nanocatalysts. J. Am. Chem. Soc. 143, 15891–15897 (2021).
Lide, D. R. et al. CRC Handbook of Chemistry and Physics 90th edn, 9–68 (CRC, 2010).
Wang, C. et al. Facet-controlled synthesis of platinum-group-metal quaternary alloys: the case of nanocubes and 100 facets. J. Am. Chem. Soc. 145, 2553–2560 (2023).
Qiu, X. et al. Twin proliferation and prolongation under kinetic control: Pd–Au Janus icosahedra versus Pd@Au core–shell starfishes. J. Am. Chem. Soc. 145, 13400–13410 (2023).
Harada, M. & Katagiri, E. Mechanism of silver particle formation during photoreduction using in situ time-resolved SAXS analysis. Langmuir 26, 17896–17905 (2010).
Li, J. & Deepak, F. L. In situ kinetic observations on crystal nucleation and growth. Chem. Rev. 122, 16911–16982 (2022).
Lu, N., Wang, J., Xie, S., Xia, Y. & Kim, M. J. Enhanced shape stability of Pd–Rh core–frame nanocubes at elevated temperature: in situ heating transmission electron microscopy. Chem. Commun. 49, 11806–11808 (2013).
Gilroy, K. D. et al. Bimetallic nanocrystals: syntheses, properties, and applications. Chem. Rev. 116, 10414–10472 (2016).
Kwon, S. G. et al. Heterogeneous nucleation and shape transformation of multicomponent metallic nanostructures. Nat. Mater. 14, 215–223 (2015).
Lin, M. et al. One-pot heterointerfacial metamorphosis for synthesis and control of widely varying heterostructured nanoparticles. J. Am. Chem. Soc. 143, 3383–3392 (2021).
Acknowledgements
This work was financially supported by the National Key R&D Program of China (grant no. 2022YFA1504500 to Xiaoqing Huang), the National Natural Science Foundation of China (grant nos. 22025108, U21A20327 and 22121001 to Xiaoqing Huang), the start-up funding from Xiamen University National Key Research, National Key Research and Development Program of China (grant no. 2021YFB2500303 to D.S.), National Natural Science Foundation of China (grant nos. 22075317, U21A20328, 22105220 and 52101277 to D.S.), the major project of Basic Science (natural science) of Jiangsu Province (21KJA430001 to Q.S.), Jiangsu Provincial Natural Science Foundation (grant no. BK20211316 to Q.S.), the Suzhou Municipal Science and Technology Bureau (grant no. SYG202125 to Q.S.), Young Elite Scientists Sponsorship Program by CAST (grant no. 2023QNRC001 to Q.S.) and the Priority Academic Program Development of Jiangsu Higher Education Institutions (PAPD to Q.S.), Strategic Priority Research Program (B) (grant no. XDB33030200 to D.S.) of Chinese Academy of Sciences and the Project Funded by China Postdoctoral Science Foundation (grant no. 2021M703457 to X.L.). We acknowledge support from the Max Planck-POSTECH-Hsinchu Center for Complex Phase Materials.
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Xuan Huang, Q.S. and Xiaoqing Huang conceived and supervised the research. Xuan Huang, Xiaoqing Huang and B.X. designed the experiments. Xuan Huang and Xiaoqing Huang performed most of the experiments and data analysis. J.F., Y.J. and Youyong Li performed the theoretical calculations. S.H. and N.T. performed in situ FTIR tests. Xuan Huang performed in situ FTIR data analyses. M.H. and Yinshi Li performed a membrane electrode assembly test. Y.W. performed the NMR test. X.L. and D.S. performed aberration-corrected HAADF-STEM imaging. Xuan Huang performed aberration-corrected HAADF-STEM image analysis. Y.H., T.-S.C. and Z.H. performed the XAFS measurements. Xuan Huang performed XAFS data analysis. Xuan Huang, Q.S. and Xiaoqing Huang wrote the paper. All authors discussed the results and commented on the paper.
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Nature Nanotechnology thanks Bin Cai, Weiping Ding and Dingsheng Wang for their contribution to the peer review of this work.
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Extended data
Extended Data Fig. 1 Phase regulation used to validate the regioselective growth mechanism.
(a) XRD patterns of r-Pt/Pd8Sb3 HPs and u-Pt/Pd8Sb3 HPs. (b) Schematic illustration of r-Pt/Pd8Sb3 HPs and u-Pt/Pd8Sb3 HPs. (c) TEM image, (d) HRTEM image from the labelled area of Extended Data Fig. 1c, and (e, f) corresponding FFT images of r-Pt/Pd8Sb3 HPs. (g) EDS line scanning, and (h) elemental mapping image of single r-Pt/Pd8Sb3 HP. (i) TEM image, and (j) HRTEM image of u-Pt/Pd8Sb3 HPs from the labelled area of Extended Data Fig. 1i, inset of the corresponding FFT image. (k) EDS line scanning, and (l) elemental mapping image of single u-Pt/Pd8Sb3 HP.
Supplementary information
Supplementary Information
Supplementary Figs. 1–52 and Tables 1–7.
Supplementary Data 1
The NMR spectra of Pt/C, u-Pt/Pd20Sb7 HPs/C and r-Pt/Pd20Sb7 HPs/C for EOR at 0.7 V versus RHE.
Source data
Source Data Fig. 2
Statistical source data for Fig. 2.
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Statistical source data for Fig. 3.
Source Data Fig. 4
Statistical source data for Fig. 4.
Source Data Fig. 5
Statistical source data for Fig. 5.
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Statistical source data for Fig. 6.
Source Data Extended Data Fig.1
Statistical source data for Extended Data Fig. 1.
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Huang, X., Feng, J., Hu, S. et al. Regioselective epitaxial growth of metallic heterostructures. Nat. Nanotechnol. (2024). https://doi.org/10.1038/s41565-024-01696-0
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DOI: https://doi.org/10.1038/s41565-024-01696-0