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Photochemical tuning of dynamic defects for high-performance atomically dispersed catalysts

Nature Materials volume 23, pages 552–559 (2024)Cite this article

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Abstract

Developing active and stable atomically dispersed catalysts is challenging because of weak non-specific interactions between catalytically active metal atoms and supports. Here we demonstrate a general method for synthesizing atomically dispersed catalysts via photochemical defect tuning for controlling oxygen-vacancy dynamics, which can induce specific metal–support interactions. The developed synthesis method offers metal-dynamically stabilized atomic catalysts, and it can be applied to reducible metal oxides, including TiO2, ZnO and CeO2, containing various catalytically active transition metals, including Pt, Ir and Cu. The optimized Pt-DSA/TiO2 shows unprecedentedly high photocatalytic hydrogen evolution activity, producing 164 mmol g−1 h−1 with a turnover frequency of 1.27 s−1. Furthermore, it generates 42.2 mmol gsub−1 of hydrogen via a non-recyclable-plastic-photoreforming process, achieving a total conversion of 98%; this offers a promising solution for mitigating plastic waste and simultaneously producing valuable energy sources.

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Fig. 1: DFT simulation of Ti3+ formation at VO.
Fig. 2: Characterization of Pt-DSA/TiO2.
Fig. 3: Generalization of the DSA synthesis method to other supports and metal atoms.
Fig. 4: Photocatalytic HER.
Fig. 5: Hydrogen generation by PET photoreforming.

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All data that support the findings of this study are included in this Article. All other data that support the findings of this study are available from the corresponding authors upon reasonable request. Source data are provided with this paper.

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Acknowledgements

This research was supported by the Institute for Basic Science (IBS-R006-D1) and the National Supercomputing Center with supercomputing resources (KSC-2022-CRE-0146).

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Author notes

  1. These authors contributed equally: Chan Woo Lee, Byoung-Hoon Lee, Sunghak Park.

Authors and Affiliations

  1. Center for Nanoparticle Research, Institute for Basic Science (IBS), Seoul, Republic of Korea

    Chan Woo Lee, Byoung-Hoon Lee, Yoon Jung, Junhyeok Heo, Kangjae Lee, Wonjae Ko, Seungwoo Yoo, Megalamane S. Bootharaju & Taeghwan Hyeon

  2. School of Chemical and Biological Engineering, and Institute of Chemical Processes, Seoul National University, Seoul, Republic of Korea

    Chan Woo Lee, Yoon Jung, Junhyeok Heo, Kangjae Lee, Wonjae Ko, Seungwoo Yoo, Jaeyune Ryu & Taeghwan Hyeon

  3. KU-KIST Graduate School of Converging Science and Technology, Korea University, Seoul, Republic of Korea

    Byoung-Hoon Lee

  4. Department of Materials Science and Engineering, Seoul National University, Seoul, Republic of Korea

    Sunghak Park & Ki Tae Nam

  5. Department of Applied Chemistry, Kyung Hee University, Yongin, Republic of Korea

    Jaebeom Han & Minho Kim

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Contributions

C.W.L. and B.-H.L. conceived the idea and designed the research. C.W.L., B.-H.L. and S.P. designed the experiments. C.W.L. and S.P. conducted the photocatalytic measurements and analysis. J. Han and M.K. performed the DFT calculations and analysis. C.W.L., Y.J., J. Heo, K.L., W.K. and S.Y. conducted the data acquisition for material characterization and the subsequent analysis. C.W.L., B.-H.L., S.P. and M.K. wrote the original paper. M.S.B., J.R., K.T.N. and T.H. reviewed and edited the paper. T.H. supervised the research.

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Correspondence to Byoung-Hoon Lee, Minho Kim or Taeghwan Hyeon.

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Extended data

Extended Data Fig. 1 Schematic illustration of synthesizing Pt-DSA/TiO2 by photochemical defect tuning process.

A schematic illustration with photographs for the synthesis of Pt-DSA/TiO2 through the photochemical defect tuning process.

Extended Data Fig. 2 STEM and STEM-EDS elemental mapping images of Pt/TiO2 and Pt-NP/TiO2.

a, The Pt/TiO2 catalyst was produced through direct light irradiation on a mixture of Pt precursor (0.7 wt%) and anatase TiO2. In this particular case, Pt particles agglomerated severely, resulting in an irregular dispersion of Pt. b, The Pt-NP/TiO2 catalyst was prepared by physisorption of pre-made Pt nanoparticle on anatase TiO2.

Extended Data Fig. 3 Characterization of Pt-SA/hydrogenated TiO2.

Pt deposition on hydrogenated TiO2, which is a conventional atomic metal deposition technique, was conducted and subsequently analyzed. a, EPR spectra of hydrogenated commercial anatase TiO2 and Pt-SA/hydrogenated TiO2. b, STEM and STEM-EDS elemental mapping images of Pt-SA/hydrogenated TiO2. c, XPS spectra of Pt-SA/hydrogenated TiO2. In (b) and (c), agglomeration of Pt was detected. d, Schematic illustration of the deposition of Pt metals on TiO2 through conventional wet-impregnation method on hydrogenated TiO2. The loading amount of Pt-SA/hydrogenated TiO2 was 0.1 wt%, with identical concentrations of the Pt precursor solution and stabilization time as the conditions used for Pt-DSA 0.7 wt%/TiO2.

Source data

Extended Data Fig. 4 EPR spectra of air regeneration process of irradiated ZnO and CeO2.

a, b, the EPR signal related to surface VOs vanished upon exposure to the air. This phenomenon suggests that photochemically induced surface VOs can naturally (a) revert back to bulk VOs for ZnO and (b) be refilled for CeO2, through the contact with oxygen in the air.

Source data

Extended Data Fig. 5 The pictures of synthesized M (Pt, Ir and Cu)-DSA/supports (TiO2, ZnO and CeO2) catalysts.

a, The pictures of pristine TiO2 (left) and Pt-DSA/TiO2 (right). b, c, d, The samples in the left, middle and right side represent Pt, Ir and Cu-DSA/ (b) TiO2, (c) ZnO and (d) CeO2, respectively.

Extended Data Fig. 6 XPS spectra and XRD patterns of Pt-DSA/TiO2, ZnO and CeO2.

XPS spectrum of Pt-DSA/TiO2 is provided in Fig. 2f. a, The Pt-DSA/TiO2 showed identical XRD patterns which corresponded with anatase TiO2 (JCPDS card 96-720-6076). b,c, XPS spectra of the Pt-DSA/ (b) ZnO (a pink line is Al 2p signal which comes from residual Al in commercial ZnO (Supplementary Fig. 1b)) and (c) CeO2. d,e, XRD patterns of Pt-DSA/ (d) ZnO and (e) CeO2 showed identical patterns with bare ZnO (JCPDS card 96-900-4182) and CeO2 (JCPDS card 96-900-9009), respectively.

Source data

Extended Data Fig. 7 XPS spectra and XRD patterns of M(Ir and Cu)-DSA/TiO2, ZnO and CeO2.

a, b, c, XPS spectra of the Ir-DSA/ (a) TiO2 (a pink line is Na 2 s signal which comes from residual Na in commercial anatase TiO2 (Supplementary Fig. 1c)), (b) ZnO and (c) CeO2. The resulting Ir peak occurred between the position of Ir4+ and Ir0. d,e,f, XPS spectra of the Cu-DSA/ (d) TiO2, (e) ZnO and (f) CeO2 (a pink line is signal which comes from residual elements in commercial CeO2 (Supplementary Fig. 1d)). g,h,i, XRD patterns of Ir and Cu-DSA/ (g) TiO2, (h) ZnO and (i) CeO2 showed identical patterns with bare TiO2 (JCPDS card 96-720-6076), ZnO (JCPDS card 96-900-4182) and CeO2 (JCPDS card 96-900-9009), respectively.

Source data

Extended Data Fig. 8 Quantification of the consumed reactants before and after the photo-reforming of PET through the analysis of 1H NMR spectra.

The amount of EG and TPA consumed after 40 h of the reaction in Fig. 5e was calculated using the calibration curves in (b) and (d). The calculated amounts of EG and TPA before the reaction were 111 μmol and 20.6 μmol, respectively. After 40 h of the reaction, 100% of EG (111 μmol) and 91% of TPA (18.7 μmol) were consumed. a,b,c,d, The calibration curves for (b) EG and (d) TPA were obtained based on 1H NMR data from different concentrations of (a) EG and (c) TPA, respectively. The normalized areas of EG and TPA against DMSO (internal standard) were plotted depending on concentrations, and linear regression equations were obtained. TPA was detected as a form of terephthalate in the 1H NMR (D2O condition) data.

Source data

Extended Data Table 1 Comparison between recent TiO2 based photocatalysts on the photocatalytic HER activity51,52,53
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Extended Data Table 2 Comparison between recently reported photocatalysts on the hydrogen evolution activity through photo-reforming of non-recyclable plastics
Full size table

Supplementary information

Supplementary Information

Supplementary Figs. 1–9.

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Lee, C.W., Lee, BH., Park, S. et al. Photochemical tuning of dynamic defects for high-performance atomically dispersed catalysts. Nat. Mater. 23, 552–559 (2024). https://doi.org/10.1038/s41563-024-01799-y

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