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Asymmetric photooxidation of glycerol to hydroxypyruvic acid over Rb–Ir catalytic pairs on poly(heptazine imides)

Nature Nanotechnology volume 20, pages 815–824 (2025)Cite this article

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Abstract

Selective asymmetric oxidation of glycerol (GLY) to hydroxypyruvic acid (HPA) offers an attractive approach for chiral drug synthesis, but this process is highly challenging. Here we develop a photocatalytic method to achieve heterogeneous selective photooxidation of GLY to HPA over rubidium (Rb) and iridium (Ir) catalytic pairs decorated on a poly(heptazine imide) framework. The Rb sites effectively adsorb GLY molecules through the terminal –OH groups, thus inhibiting their oxidation during photoreaction, while the Ir sites enhance the oxygen reduction reaction and the in situ generated surficial oxygen-reduction radicals on Ir can protect the reactive C-centred radical intermediates produced during photooxidation. The spatial arrangement of Rb and Ir sites facilitates hydrogen extraction—an essential rate-determining step for GLY photooxidation—and protects C3 radical intermediates from overoxidation. This photocatalytic system achieves a remarkable productivity for HPA synthesis (~8,000 μmol of HPA per gram of photocatalyst per hour) under visible-light illumination.

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Fig. 1: Photooxidation of GLY for HPA synthesis.
Fig. 2: Structural characterization of IrRb-PHI.
Fig. 3: Photoexcitation and quenching properties.
Fig. 4: Reaction mechanism for oxidizing GLY to GLA.
Fig. 5: Pathway for HPA production.

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All source data for figures in the Article, extended data and Supplementary Information will be uploaded to the Nature publication system. The data that support the findings of this study are available from the corresponding author upon reasonable request. Source data are provided with this paper.

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Acknowledgements

We thank the financial support from the City University of Hong Kong startup fund (grant no. 9020003), ITF–RTH – Global STEM Professorship (grant no. 9446006), JC STEM lab of Advanced CO2 Upcycling (grant no. 9228005), National Natural Science Foundation of China (grant nos. 11904235, 22125604, 22372102 and 22436003), the National Key Research and Development Program of China (grant no. 2021YFA1600800), Educational Commission of Guangdong Province (grant no. 839-0000013131), Shenzhen Science and Technology Program (grant no. RCJC20200714114434086), Guangdong Basic and Applied Basic Research Foundation (grant no. 2024A1515010976), Shenzhen Peacock Plan (grant no. 20210802524B) and Research Team Cultivation Program of Shenzhen University (grant no. 2023QNT013). We also thank C. Chen (King Abdullah University of Science and Technology) and Y. Han (King Abdullah University of Science and Technology).

Author information

Author notes

  1. These authors contributed equally: Zhenyuan Teng, Zhenzong Zhang.

Authors and Affiliations

  1. Department of Materials Science and Engineering, City University of Hong Kong, Hong Kong, China

    Zhenyuan Teng, Jie Ding & Bin Liu

  2. International Collaborative Laboratory of 2D Materials for Optoelectronics Science and Technology of Ministry of Education, Institute of Microscale Optoelectronics, Shenzhen University, Shenzhen, China

    Zhenzong Zhang, Ying Tu, Qitao Zhang & Chenliang Su

  3. Hebei Key Laboratory of Close-to-Nature Restoration Technology of Wetlands, School of Eco-Environment, Hebei University, Baoding, China

    Zhenzong Zhang

  4. Guangdong-Hong Kong-Macao Greater Bay Area Environmental Technology Research Center, Shenzhen Research Institute of Nankai University, Shenzhen, China

    Zhenzong Zhang & Han Yu

  5. Electron Microscopy Center of Shenzhen University, Shenzhen University, Shenzhen, China

    Nan Jian

  6. College of Chemistry Chemical Engineering and Materials Science, Collaborative Innovation Center of Suzhou Nano Science and Technology, National United Engineering Laboratory of Functionalized Environmental Adsorption Materials, Soochow University, Suzhou, China

    Liujun Yang & Jianmei Lu

  7. School of Chemical Engineering, University of Chinese Academy of Sciences, Beijing, China

    Jiadong Xiao

  8. Innovation Institute of Carbon Neutrality, International Joint Laboratory of Catalytic Chemistry, State Key Laboratory of Advanced Special Steel, Department of Chemistry, College of Sciences, Shanghai University, Shanghai, China

    Longzhen Huang & Dengsong Zhang

  9. Department of Applied Chemistry, Faculty of Engineering, Kyushu Institute of Technology, Kitakyushu, Japan

    Ohno Teruhsia

  10. College of Chemistry and Chemical Engineering, Yangzhou University, Yangzhou, China

    Chengyin Wang

  11. Department of Chemistry, Hong Kong Institute for Clean Energy Center, Center of Super-Diamond and Advanced Films, City University of Hong Kong, Hong Kong, China

    Bin Liu

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  1. Zhenyuan Teng
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Contributions

Z.T. and B.L. conceptualized the project. D.Z., J.L., C.S. and B.L. supervised the project. Z.T. and Z.Z. synthesized the catalysts, conducted the catalytic tests and the related data processing, and performed materials characterization and analysis with help from Y.T., L.Y., L.H., C.W., Q.Z., O.T., H.Y., J.X. and J.D. Z.T. and Z.Z. performed the theoretical study. N.J. performed the microscopy measurement. Z.T. and B.L. wrote the manuscript with support from all authors.

Corresponding authors

Correspondence to Dengsong Zhang, Jianmei Lu, Chenliang Su or Bin Liu.

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Extended data

Extended Data Fig. 1 X-ray diffraction patterns of the as-prepared Rb-PHI and Ir0.5Rb-PHI.

a, Structural model of Rb-PHI along the zone axis of [001]. b, Structural model of Rb-PHI along the zone axis of [010]. c, XRD pattern of the as-prepared Rb-PHI. d, XRD pattern of the as-prepared Ir0.5Rb-PHI.

Source data

Extended Data Fig. 2 Influence of Ir and Rb species on chemical states of C and N.

a-b, Normalized carbon (a) and nitrogen (b) K-edge XANES spectra for PHI, Rb-PHI and Ir0.5Rb-PHI.

Source data

Extended Data Fig. 3 Extended X-ray absorption fine structure (EXAFS) spectra of Rb-PHI, Ir0.5-PHI and Ir0.5Rb-PHI.

a, Fourier transform extended X-ray absorption fine structure (FT-EXAFS) spectra of Rb-OH, Rb-PHI, Ir0.5Rb-PHI and RbCl. b, k3-weighted k-space spectrum of Rb for Ir0.5Rb-PHI. c, Fourier transform extended X-ray absorption fine structure (FT-EXAFS) spectra of IrO2, Ir0.5-PHI, Ir0.5Rb-PHI and Ir foil. d, k3-weighted k-space spectrum of Ir for Ir0.5Rb-PHI.

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Extended Data Fig. 4 Surface chemical states of C, N, Rb and Ir in Rb-PHI, Ir0.5-PHI and Ir0.5Rb-PHI.

a-c, High-resolution XPS spectra of N 1 s (a), C 1 s (b) and Rb 3 d (c) for Rb-PHI and Ir0.5Rb-PHI. d, High-resolution XPS spectra of Ir 4 f for Ir0.5-PHI and Ir0.5Rb-PHI. The almost no shift in the Rb 3 d XPS spectrum is attributed to the notably large content of Rb (~7% wt.%) species in Ir0.5Rb-PHI, which cannot be remarkably affected by the Ir species with a low concentration (~0.5 wt.%). On the other hand, the shift of the Ir 4 f XPS spectrum is notable for Ir0.5Rb-PHI as compared to that for Ir0.5-PHI.

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Extended Data Fig. 5 Post-structural characterization of Ir0.5Rb-PHI.

a, The Ir and Rb contents before and after the photoreaction. b, TEM image of Ir0.5Rb-PHI after 30 h of photoreaction. c, High-resolution image of b. d, HAADF-STEM image of Ir0.5Rb-PHI after the 30 h of photoreaction. e, HAADF-STEM image of Ir0.5Rb-PHI before photoreaction and the corresponding EDX mappings. f, HAADF-STEM image of Ir0.5Rb-PHI after 30 h of photoreaction and the corresponding EDX mappings. g-h, High-resolution Rb 3 d (g) and Ir 4 f (h) XPS spectra for Ir0.5Rb-PHI after 30 h of photoreaction.

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Extended Data Fig. 6 Density of states.

a-b, Total density of states (TDOS), partial density of states (PDOS) and overlapped density of states (ODOS) for a, Rb incorporated hexagonal heptazine imide (Rb-HHI) and b, Ir and Rb co-incorporated hexagonal heptazine imide (IrRb-HHI).

Source data

Extended Data Fig. 7 Adsorption of HPA, GLD and GLA on Rb-PHI and IrRb-PHI.

a, Adsorption energy of GLY-end-on (GLY-T), GLA, GLY-side-on (GLY-S) and GLD on Rb-PHI. b, Adsorption energy of GLY-T, GLA, GLY-S and GLD on IrRb-PHI. GLY-T refers to the adsorption configuration of attaching the terminal-OH of GLY to Rb site on Rb-PHI and IrRb-PHI. GLY-S refers to the adsorption configuration of attaching the secondary-OH of GLY to Rb site on Rb-PHI and IrRb-PHI. GLA refers to the adsorption configuration of attaching the terminal-OH of GLA to Rb site on Rb-PHI and IrRb-PHI. HPA refers to the adsorption configuration of attaching the terminal -OH groups of HPA to Rb site on Rb-PHI and IrRb-PHI.

Source data

Extended Data Fig. 8 Exploration of oxygen reduction intermediates.

Raman spectra recorded over Rb-PHI in O2 saturated GLY aqueous solution (0.1 M) during photoreaction for 0, 5, 10, 15 and 20 min from bottom to top.

Source data

Extended Data Fig. 9 Photooxidation of GLY for selective HPA synthesis under various O2 pressure.

a, Production rate under the reaction condition of 0.2 M GLY, 298 K, 2 atm O2 (left) and 1 atm O2 (right). c, Production rate under the reaction condition of 0.5 M GLY, 298 K, 5 atm O2 (left) and 1 atm O2 (right). e, Production rate under the reaction condition of 0.1 M GLY, 298 K, 5 atm O2 (left) and 1 atm O2 (right). b, d, f, HPA selectivity and GLY conversion under the reaction condition of 0.2 M GLY at 298 K in 2 atm O2 (left) and 1 atm O2 (right) (b), 0.5 M GLY at 298 K in 5 atm O2 (left) and 1 atm O2 (right) (d) and 0.1 M GLY at 298 K in 5 atm O2 (left) and 1 atm O2 (right) (f).

Source data

Extended Data Fig. 10 Partial density of states for various oxidation intermediates.

a-b, PDOS of CH2OH-·COH-COOH on Rb-PHI (a) and IrRb-PHI (b). c-d, PDOS of CH2OH-CHO on Rb-PHI (c) and IrRb-PHI (d).

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Supplementary information

Supplementary Information

Supplementary Figs. 1–64, Tables 1–14 and Notes 1–12.

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Teng, Z., Zhang, Z., Tu, Y. et al. Asymmetric photooxidation of glycerol to hydroxypyruvic acid over Rb–Ir catalytic pairs on poly(heptazine imides). Nat. Nanotechnol. 20, 815–824 (2025). https://doi.org/10.1038/s41565-025-01897-1

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