An All-in-One Lignin-Based Artificial Thylakoid Nanovesicle Via In-Situ Confined Growth Strategy for High-Efficient and Selectivity CO₂ Photoreduction

Abstract

Selective CO₂ photoreduction via artificial photocatalysis into high-value chemical feedstocks such as CO is a productive strategy for remitting environmental problems and energy crises. Nevertheless, photocatalysts generally endure low activity and poor product selectivity due to the low light/CO₂ capture and slow dynamic transfer of photogenerated electrons. Herein, we describe an all-in-one lignin-based artificial thylakoid nanovesicle (AiO-L-ATN) using the confined growth strategy of lignin molecules, inspired by the chloroplast's photosynthesis mechanism. Such AiO-L-ATN possesses a high CO generation rate of 98.8 μmol g⁻¹ h⁻¹ at normalized active mass with a satisfactory selectivity of 92.1% in a gas-solid system with H₂O, exceeding 26 times that of the primary ZnCdS. Besides, introducing carbon nanovesicles significantly improves CO₂ capture performance, narrows the band gap, expands the wavelength range of light absorption, and accelerates the separation of photogenerated electrons. Density functional theory (DFT) calculation reveals that the carbon nanovesicles with various functional groups favor *CO₂ adsorption, *COOH production and conversion, as well as accelerate the dynamic transfer of photogenerated electrons, thereby endowing the outstanding CO₂ reduction rate and CO selectivity of AiO-L-ATN. This study not only provides valuable insights into the preparation of highly efficient photocatalysts but also offers novel avenues for CO₂ photoreduction.

Keywords

all-in-one / artificial photocatalysis / carbon nanovesicle / CO₂ reduction / confined growth / lignin

References

[1] H. Li, M. E. Zick, T. Trisukhon, et al., “Capturing Carbon Dioxide From Air With Charged-Sorbents,” Nature 630, no. 8017 (2024): 654–659.

[2] C. Song, Q. Liu, S. Deng, H. Li, and Y. Kitamura, “Cryogenic-Based CO₂ Capture Technologies: State-of-the-Art Developments and Current Challenges,” Renewable and Sustainable Energy Reviews 101 (2019): 265–278.

[3] Y. Li, S. L. Zhang, W. Cheng, et al., “Loading Single-Ni Atoms on Assembled Hollow N-Rich Carbon Plates for Efficient CO₂ Electroreduction,” Advanced Materials 34, no. 1 (2022): e2105204.

[4] X. She, L. Zhai, Y. Wang, et al., “Pure-Water-Fed, Electrocatalytic CO₂ Reduction to Ethylene Beyond 1,000 h Stability at 10 A,” Nature Energy 9, no. 1 (2024): 81–91.

[5] Q. Chen, X. Wang, Y. Zhou, et al., “Electrocatalytic CO₂ Reduction to C₂₊ Products in Flow Cells,” Advanced Materials 36, no. 5 (2023): 2303902.

[6] Q. Wang, J. Warnan, S. Rodríguez-Jiménez, et al., “Molecularly Engineered Photocatalyst Sheet for Scalable Solar Formate Production From Carbon Dioxide and Water,” Nature Energy 5, no. 9 (2020): 703–710.

[7] G. Wang, Y. Wu, Z. Li, et al., “Engineering a Copper Single-Atom Electron Bridge to Achieve Efficient Photocatalytic CO₂ Conversion,” Angewandte Chemie International Edition 62, no. 13 (2023): e202218460.

[8] X. Li, L. Li, G. Chen, et al., “Accessing Parity-Forbidden d-d Transitions for Photocatalytic CO₂ Reduction Driven by Infrared Light,” Nature Communications 14, no. 1 (2023): 4034.

[9] H. Liu, Y. Chen, H. Li, et al., “Construction of Asymmetrical Dual Jahn–Teller Sites for Photocatalytic CO₂ Reduction,” Angewandte Chemie International Edition 62, no. 31 (2023): e202304562.

[10] V. Andrei, G. M. Ucoski, C. Pornrungroj, et al., “Floating Perovskite-BiVO₄ Devices for Scalable Solar Fuel Production,” Nature 608, no. 7923 (2022): 518–522.

[11] B. Weng, M. Zhang, Y. Lin, et al., “Photo-Assisted Technologies for Environmental Remediation,” Nature Reviews Clean Technology 1, no. 3 (2025): 201–215.

[12] B. Weng, M.-Y. Qi, C. Han, Z.-R. Tang, and Y.-J. Xu, “Photocorrosion Inhibition of Semiconductor-Based Photocatalysts: Basic Principle, Current Development, and Future Perspective,” ACS Catalysis 9, no. 5 (2019): 4642–4687.

[13] Y. Wang, S. Wang, and X. W. Lou, “Dispersed Nickel Cobalt Oxyphosphide Nanoparticles Confined in Multichannel Hollow Carbon Fibers for Photocatalytic CO₂ Reduction,” Angewandte Chemie International Edition 58, no. 48 (2019): 17236–17240.

[14] D. Liu, H. Ma, C. Zhu, et al., “Molecular Co-Catalyst Confined Within a Metallacage for Enhanced Photocatalytic CO₂ Reduction,” Journal of the American Chemical Society 146, no. 3 (2024): 2275–2285.

[15] Z. Wang, S. Akter Monny, and L. Wang, “Hollow Structure for Photocatalytic CO₂ Reduction,” ChemNanoMat 6, no. 6 (2020): 881–888.

[16] Y. Ma, X. Yi, S. Wang, et al., “Selective Photocatalytic CO₂ Reduction in Aerobic Environment by Microporous Pd-Porphyrin-Based Polymers Coated Hollow TiO₂,” Nature Communications 13, no. 1 (2022): 1400.

[17] R. Zeng, T. Liu, M. Qiu, et al., “High-Volumetric Density Atomic Cobalt on Multishell Zn_xCd_1–xS Boosts Photocatalytic CO₂ Reduction,” Journal of the American Chemical Society 146, no. 14 (2024): 9721–9727.

[18] R. Zeng, K. Lian, B. Su, et al., “Versatile Synthesis of Hollow Metal Sulfides via Reverse Cation Exchange Reactions for Photocatalytic CO₂ Reduction,” Angewandte Chemie International Edition 60, no. 47 (2021): 25055–25062.

[19] Y. Wang, J. Hu, T. Ge, et al., “Gradient Cationic Vacancies Enabling Inner-To-Outer Tandem Homojunctions: Strong Local Internal Electric Field and Reformed Basic Sites Boosting CO₂ Photoreduction,” Advanced Materials 35, no. 31 (2023): 2302538.

[20] Y. N. Gong, J. H. Mei, W. J. Shi, J. Liu, D. Zhong, and T. Lu, “Boosting CO₂ Photoreduction to Formate or CO With High Selectivity over a Covalent Organic Framework Covalently Anchored on Graphene Oxide,” Angewandte Chemie International Edition 63, no. 10 (2024): e202318735.

[21] J. Xu, M. Chong, W. Li, et al., “Guiding Electron Transfer for Selective C₂H₆ Photoproduction From CO₂,” Chem 11, no. 1 (2024): 1–9.

[22] S. Xiao, D. Zhang, D. Pan, et al., “A Chloroplast Structured Photocatalyst Enabled by Microwave Synthesis,” Nature Communications 10, no. 1 (2019): 1570.

[23] J. Lv, J. Xie, A. G. A. Mohamed, et al., “Solar Utilization Beyond Photosynthesis,” Nature Reviews Chemistry 7, no. 2 (2022): 91–105.

[24] R. Croce and H. van Amerongen, “Light Harvesting in Oxygenic Photosynthesis: Structural Biology Meets Spectroscopy,” Science 369, no. 6506 (2020): eaay2058.

[25] R. Croce and H. van Amerongen, “Natural Strategies for Photosynthetic Light Harvesting,” Nature Chemical Biology 10, no. 7 (2014): 492–501.

[26] R. D. Britt and D. A. Marchiori, “Photosystem II, Poised for O₂ Formation,” Science 366, no. 6463 (2019): 305–306.

[27] H. Wang, S. Tan, Z. Su, M. Li, X. Hao, and F. Peng, “Perforin-Mimicking Molecular Drillings Enable Macroporous Hollow Lignin Spheres for Performance-Configurable Materials,” Advanced Materials 36, no. 15 (2024): 2311073.

[28] F. Xiong, H. Wang, H. Xu, Y. Qing, Z. Wu, and Y. Wu, “Self-Assembled Lignin Nanospheres With Solid and Hollow Tunable Structures,” Industrial Crops and Products 144 (2020): 112063.

[29] Y. Fan, X. Hao, N. Yi, and Z. Jin, “Strong Electronic Coupling of Mo₂TiC₂ MXene/ZnCdS Ohmic Junction for Boosting Photocatalytic Hydrogen Evolution,” Applied Catalysis B: Environment and Energy 357 (2024): 124313.

[30] X. Wang, B. Liu, S. Ma, et al., “Induced Dipole Moments in Amorphous ZnCdS Catalysts Facilitate Photocatalytic H₂ Evolution,” Nature Communications 15, no. 1 (2024): 2600.

[31] F. Kang, C. Shi, Y. Zhu, et al., “Dual-Functional Marigold-Like Zn Cd1S Homojunction for Selective Glucose Photoreforming With Remarkable H2 Coproduction,” Journal of Energy Chemistry 79 (2023): 158–167.

[32] K. Ai, Y. Liu, C. Ruan, L. Lu, and G. Lu, “Sp² C-Dominant N-Doped Carbon Sub-Micrometer Spheres With a Tunable Size: A Versatile Platform for Highly Efficient Oxygen-Reduction Catalysts,” Advanced Materials 25, no. 7 (2013): 998–1003.

[33] M. Bonchio, J. Bonin, O. Ishitani, et al., “Best Practices for Experiments and Reporting in Photocatalytic Co₂ Reduction,” Nature Catalysis 6, no. 8 (2023): 657–665.

[34] B. Su, H. Huang, Z. Ding, et al., “S-Scheme CoTiO₃/Cd_9.51Zn_0.49S₁₀ Heterostructures for Visible-Light Driven Photocatalytic CO₂ Reduction,” Journal of Materials Science & Technology 124 (2022): 164–170.

[35] H. Huang, J. Zhao, B. Weng, et al., “Site-Sensitive Selective CO₂ Photoreduction to CO over Gold Nanoparticles,” Angewandte Chemie International Edition 61, no. 28 (2022): e202204563.

[36] J. Yu, L. Huang, Q. Tang, et al., “Artificial Spherical Chromatophore Nanomicelles for Selective CO₂ Reduction in Water,” Nature Catalysis 6, no. 6 (2023): 464–475.

[37] S. Hu, P. Qiao, X. Yi, et al., “Selective Photocatalytic Reduction of CO₂ to CO Mediated by Silver Single Atoms Anchored on Tubular Carbon Nitride,” Angewandte Chemie International Edition 62, no. 26 (2023): e202304585.

[38] J. Zhou, X. Zha, Z. Chen, et al., “Tailoring the Coordination Microenvironment of Single-Atom W for Efficient Photocatalytic CO₂ Reduction,” Applied Catalysis B: Environment and Energy 350 (2024): 123911.

[39] Z. Ma, H. Yin, P. Lyu, and Y. Xu, “Protruding-Shaped Co Polarization Field on Ultrathin Covalent Triazine Framework Nanosheets for Efficient CO₂ Photoreduction,” Advanced Energy Materials 14, no. 33 (2024): 2401619.

[40] K. Lai, Y. Sun, N. Li, et al., “Photocatalytic CO₂-To-CH₄ Conversion With Ultrahigh Selectivity of 95.93% on S-Vacancy Modulated Spatial In₂S₃/In₂O₃ Heterojunction,” Advanced Functional Materials 34, no. 49 (2024): 2409031.

[41] F. Liu, J. Deng, B. Su, et al., “Poly(Triazine Imide) Crystals for Efficient CO₂ Photoreduction: Surface Pyridine Nitrogen Dominates the Performance,” ACS Catalysis 15, no. 2 (2025): 1018–1026.

[42] Y. Yang, H. Y. Zhang, Y. Wang, et al., “Integrating Enrichment, Reduction, and Oxidation Sites in One System for Artificial Photosynthetic Diluted CO₂ Reduction,” Advanced Materials 35, no. 40 (2023): 2304170.

[43] J. Guo, D. Li, Z. Qian, et al., “Carbon Vesicles: A Symmetry-Breaking Strategy for Wide-Band and Solvent-Processable Ultrablack Coating Materials,” Advanced Functional Materials 30, no. 17 (2020): 1909877.

[44] C. Huang, Y. Wen, J. Ma, et al., “Unraveling Fundamental Active Units in Carbon Nitride for Photocatalytic Oxidation Reactions,” Nature Communications 12, no. 1 (2021): 320.

[45] J. Wang, T. Heil, B. Zhu, et al., “A Single Cu-Center Containing Enzyme-Mimic Enabling Full Photosynthesis under CO₂ Reduction,” ACS Nano 14, no. 7 (2020): 8584–8593.

[46] W. Wu, M. Chen, C. Feng, et al., “Metal-Free Polymer Photocatalysts for Efficient Gas-Phase Reduction of Atmospheric CO₂ and Simultaneous H₂O₂ Production,” Green Chemistry 27, no. 10 (2025): 2766–2775.

[47] G. D. Qi, D. Ba, Y. J. Zhang, et al., “Constructing an Asymmetric Covalent Triazine Framework to Boost the Efficiency and Selectivity of Visible-Light-Driven CO₂ Photoreduction,” Advanced Science 11, no. 28 (2024): 2402645.

[48] J. Liang, H. Yu, J. Shi, B. Li, L. Wu, and M. Wang, “Dislocated Bilayer MOF Enables High-Selectivity Photocatalytic Reduction of CO₂ to CO,” Advanced Materials 35, no. 10 (2023): 2209814.

[49] F. Zhou, Y. Zhang, J. Wu, et al., “Utilizing Er-Doped ZnIn₂S₄ for Efficient Photocatalytic CO₂ Conversion,” Applied Catalysis, B: Environmental 341 (2024): 123347.

[50] X. Deng, J. Zhang, K. Qi, G. Liang, F. Xu, and J. Yu, “Ultrafast Electron Transfer at the In₂O₃/Nb₂O₅ S-Scheme Interface for CO₂ Photoreduction,” Nature Communications 15, no. 1 (2024): 4807.

[51] B. Su, M. Zheng, W. Lin, et al., “S-Scheme Co₉S₈@Cd_0.8Zn_0.2S-DETA Hierarchical Nanocages Bearing Organic CO₂ Activators for Photocatalytic Syngas Production,” Advanced Energy Materials 13, no. 15 (2023): 2203290.

[52] Y. Wang, Y. Liu, L. Tan, et al., “Confining Ultrafine Pt Nanoparticles on In₂O₃ Nanotubes for Enhanced Selective Methanol Production by CO₂ Hydrogenation,” Journal of Materials Chemistry A 11, no. 48 (2023): 26804–26811.

[53] W. Zou, Y. Cheng, Y. X. Ye, et al., “Metal-Free Photocatalytic CO₂ Reduction to CH₄ and H₂O₂ Under Non-Sacrificial Ambient Conditions,” Angewandte Chemie International Edition 62, no. 49 (2023): e202313392.

[54] B. Su, Y. Kong, S. Wang, et al., “Hydroxyl-Bonded Ru on Metallic TiN Surface Catalyzing CO₂ Reduction With H₂O by Infrared Light,” Journal of the American Chemical Society 145, no. 50 (2023): 27415–27423.

[55] X. Wang, Y. Tong, W. Feng, et al., “Embedding Oxophilic Rare-Earth Single Atom in Platinum Nanoclusters for Efficient Hydrogen Electro-Oxidation,” Nature Communications 14, no. 1 (2023): 3767.

[56] Y. Li, B. Li, D. Zhang, L. Cheng, and Q. Xiang, “Crystalline Carbon Nitride Supported Copper Single Atoms for Photocatalytic CO₂ Reduction With Nearly 100% CO Selectivity,” ACS Nano 14, no. 8 (2020): 10552–10561.

[57] Y. Duan, Y. Wang, W. Zhang, et al., “Simultaneous CO₂ and H₂O Activation via Integrated Cu Single Atom and N Vacancy Dual-Site for Enhanced CO Photo-Production,” Advanced Functional Materials 33, no. 28 (2023): 2301729.

[58] H. Wang, M. He, Y. Qing, F. Chu, Y. Wu, and F. Xiong, “A Molecular-Chemistry-Manipulation Strategy Toward Functional Lignin-Based Porous Carbon Nanospheres With Tunable-Pore Structure,” Chemical Engineering Journal 499 (2024): 156615.

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