Electrostatic Attraction-Driven Assembly of Non-Noble Metallo-Supramolecular Polymers With Single-Walled Carbon Nanotubes for Boosting Photocatalytic Hydrogen Evolution

Abstract

The search for photoactive materials that are able to efficiently produce solar fuels is a growing research field to tackle the current energy crisis. Herein, we have prepared two ionic non-noble metallo-supramolecular polymers Se-MTpy (M = Co or Ni), and constructed their composites with single-walled carbon nanotubes (CNTs) via electrostatic attraction and π–π interactions for efficient and stable photocatalytic hydrogen evolution. In the photocatalytic system, the cationic Se-MTpy as host and anionic CNTs as guest are assembled into a binary composite, which exhibits superior photocatalytic activity under visible light irradiation (> 420 nm). The optimized CNT@Se-CoTpy composite, containing 1.2 wt% metal loading, achieves 7 times higher hydrogen evolution rate (2.47 mmol g⁻¹ h⁻¹) than bare Se-CoTpy (0.35 mmol g⁻¹ h⁻¹). This is attributed to the constructive formation of junctions between polymer and CNTs, facilitating interfacial charge transfer and transport for efficient proton reduction. The composite system also shows high photostability after continuous irradiation for ~30 h. The combination of experimental and theoretical analysis demonstrates the higher activity for reducing H₂O to H₂ of Se-CoTpy than Se-NiTpy. The feasible interfacial architecture proposed in this study represents an effective approach to achieve high photocatalytic performance.

Keywords

electrostatic attraction / hybrid heterojunction / metallo-supramolecular polymers / photocatalytic hydrogen evolution / single-walled carbon nanotubes

References

[1] A. Kudo and Y. Miseki, “Heterogeneous Photocatalyst Materials for Water Splitting,” Chemical Society Reviews 38, no. 1 (2009): 253-278.

[2] T. He, K. Geng, and D. Jiang, “Engineering Covalent Organic Frameworks for Light-Driven Hydrogen Production From Water,” ACS Materials Letters 1, no. 2 (2019): 203-208.

[3] T. Takata, J. Jiang, Y. Sakata, et al., “Photocatalytic Water Splitting With a Quantum Efficiency of Almost Unity,” Nature 581, no. 7809 (2020): 411-414.

[4] R. S. Sprick, J.-X. Jiang, B. Bonillo, et al., “Tunable Organic Photocatalysts for Visible-Light-Driven Hydrogen Evolution,” Journal of the American Chemical Society 137, no. 9 (2015): 3265-3270.

[5] S. Chabi, K. M. Papadantonakis, N. S. Lewis, and M. S. Freund, “Membranes for Artificial Photosynthesis,” Energy & Environmental Science 10, no. 6 (2017): 1320-1338.

[6] D. J. Woods, R. S. Sprick, C. L. Smith, A. J. Cowan, and A. I. Cooper, “A Solution-Processable Polymer Photocatalyst for Hydrogen Evolution From Water,” Advanced Energy Materials 7, no. 22 (2017): 1700479.

[7] Y. J. Gao, X. B. Li, H. L. Wu, et al., “Exceptional Catalytic Nature of Quantum Dots for Photocatalytic Hydrogen Evolution Without External Cocatalysts,” Advanced Functional Materials 28, no. 33 (2018): 1801769.

[8] M. Liras, M. Barawi, and V. A. de la Peña O'Shea, “Hybrid Materials Based on Conjugated Polymers and Inorganic Semiconductors As Photocatalysts: From Environmental to Energy Applications,” Chemical Society Reviews 48, no. 22 (2019): 5454-5487.

[9] A. Fujishima and K. Honda, “Electrochemical Photolysis of Water at a Semiconductor Electrode,” Nature 238, no. 5358 (1972): 37-38.

[10] X. Wang, X. Wang, J. Huang, S. Li, A. Meng, and Z. Li, “Interfacial Chemical Bond and Internal Electric Field Modulated Z-Scheme S_V-ZnIn₂S₄/MoSe₂ Photocatalyst for Efficient Hydrogen Evolution,” Nature Communications 12, no. 1 (2021): 4112.

[11] D. Ma, J.-W. Shi, D. Sun, et al., “Au Decorated Hollow ZnO@ZnS Heterostructure for Enhanced Photocatalytic Hydrogen Evolution: The Insight Into the Roles of Hollow Channel and Au Nanoparticles,” Applied Catalysis, B: Environmental 244 (2019): 748-757.

[12] H. S. Moon, K.-C. Hsiao, M.-C. Wu, Y. Yun, Y.-J. Hsu, and K. Yong, “Spatial Separation of Cocatalysts on Z-Scheme Organic/Inorganic Heterostructure Hollow Spheres for Enhanced Photocatalytic H₂ Evolution and In-Depth Analysis of the Charge-Transfer Mechanism,” Advanced Materials 35, no. 4 (2023): 2200172.

[13] W.-J. Ong, L.-L. Tan, Y. H. Ng, S.-T. Yong, and S.-P. Chai, “Graphitic Carbon Nitride (g-C₃N₄)-Based Photocatalysts for Artificial Photosynthesis and Environmental Remediation: Are We a Step Closer to Achieving Sustainability?,” Chemical Reviews 116, no. 12 (2016): 7159-7329.

[14] J. Fu, J. Yu, C. Jiang, and B. Cheng, “g-C₃N₄-Based Heterostructured Photocatalysts,” Advanced Energy Materials 8, no. 3 (2018): 1701503.

[15] Q. Liu, J. Shen, X. Yu, et al., “Unveiling the Origin of Boosted Photocatalytic Hydrogen Evolution in Simultaneously (S, P, O)-Codoped and Exfoliated Ultrathin g-C₃N₄ Nanosheets,” Applied Catalysis B: Environmental 248 (2019): 84-94.

[16] L. Wang, R. Fernández-Terán, L. Zhang, et al., “Organic Polymer Dots as Photocatalysts for Visible Light-Driven Hydrogen Generation,” Angewandte Chemie International Edition 55, no. 40 (2016): 12306-12310.

[17] P.-J. Tseng, C.-L. Chang, Y.-H. Chan, et al., “Design and Synthesis of Cycloplatinated Polymer Dots as Photocatalysts for Visible-Light-Driven Hydrogen Evolution,” ACS Catalysis 8, no. 9 (2018): 7766-7772.

[18] M. V. Pavliuk, S. Wrede, A. Liu, et al., “Preparation, Characterization, Evaluation and Mechanistic Study of Organic Polymer Nano-Photocatalysts for Solar Fuel Production,” Chemical Society Reviews 51, no. 16 (2022): 6909-6935.

[19] Y. Wang, A. Vogel, M. Sachs, et al., “Current Understanding and Challenges of Solar-Driven Hydrogen Generation Using Polymeric Photocatalysts,” Nature Energy 4, no. 9 (2019): 746-760.

[20] M. Barawi, L. Collado, M. Gomez-Mendoza, F. E. Oropeza, M. Liras, and V. A. de la Peña O'Shea, “Conjugated Porous Polymers: Ground-Breaking Materials for Solar Energy Conversion,” Advanced Energy Materials 11, no. 43 (2021): 2101530.

[21] L. Li, Z. Cai, Q. Wu, et al., “Rational Design of Porous Conjugated Polymers and Roles of Residual Palladium for Photocatalytic Hydrogen Production,” Journal of the American Chemical Society 138, no. 24 (2016): 7681-7686.

[22] A. Dhakshinamoorthy, A. M. Asiri, and H. García, “Metal-Organic Framework (MOF) Compounds: Photocatalysts for Redox Reactions and Solar Fuel Production,” Angewandte Chemie International Edition 55, no. 18 (2016): 5414-5445.

[23] A. García-Sánchez, M. Gomez-Mendoza, M. Barawi, et al., “Fundamental Insights Into Photoelectrocatalytic Hydrogen Production With a Hole-Transport Bismuth Metal-Organic Framework,” Journal of the American Chemical Society 142, no. 1 (2020): 318-326.

[24] X. Feng, Y. Pi, Y. Song, et al., “Metal-Organic Frameworks Significantly Enhance Photocatalytic Hydrogen Evolution and CO₂ Reduction With Earth-Abundant Copper Photosensitizers,” Journal of the American Chemical Society 142, no. 2 (2020): 690-695.

[25] X. Wang, L. Chen, S. Y. Chong, et al., “Sulfone-Containing Covalent Organic Frameworks for Photocatalytic Hydrogen Evolution From Water,” Nature Chemistry 10, no. 12 (2018): 1180-1189.

[26] H. Zhang, Z. Lin, P. Kidkhunthod, and J. Guo, “Stable Immobilization of Nickel Ions on Covalent Organic Frameworks for Panchromatic Photocatalytic Hydrogen Evolution,” Angewandte Chemie International Edition 62, no. 21 (2023): e202217527.

[27] H. Wang, H. Wang, Z. Wang, et al., “Covalent Organic Framework Photocatalysts: Structures and Applications,” Chemical Society Reviews 49, no. 12 (2020): 4135-4165.

[28] P. Pachfule, A. Acharjya, J. Roeser, et al., “Diacetylene Functionalized Covalent Organic Framework (COF) for Photocatalytic Hydrogen Generation,” Journal of the American Chemical Society 140, no. 4 (2018): 1423-1427.

[29] Z. Li, T. Deng, S. Ma, et al., “Three-Component donor−π-acceptor Covalent-Organic Frameworks for Boosting Photocatalytic Hydrogen Evolution,” Journal of the American Chemical Society 145, no. 15 (2023): 8364-8374.

[30] V. S. Vyas, F. Haase, L. Stegbauer, et al., “A Tunable Azine Covalent Organic Framework Platform for Visible Light-Induced Hydrogen Generation,” Nature Communications 6, no. 1 (2015): 8508.

[31] K. Gottschling, G. Savasci, H. Vignolo-González, et al., “Rational Design of Covalent Cobaloxime-Covalent Organic Framework Hybrids for Enhanced Photocatalytic Hydrogen Evolution,” Journal of the American Chemical Society 142, no. 28 (2020): 12146-12156.

[32] R. Chen, Y. Wang, Y. Ma, et al., “Rational Design of Isostructural 2D Porphyrin-Based Covalent Organic Frameworks for Tunable Photocatalytic Hydrogen Evolution,” Nature Communications 12, no. 1 (2021): 1354.

[33] S. Ma, T. Deng, Z. Li, et al., “Photocatalytic Hydrogen Production on a sp²-Carbon-Linked Covalent Organic Framework,” Angewandte Chemie International Edition 61, no. 42 (2022): e202208919.

[34] L. Collado, T. Naranjo, M. Gomez-Mendoza, et al., “Conjugated Porous Polymers Based on Bodipy and Bophy Dyes in Hybrid Heterojunctions for Artificial Photosynthesis,” Advanced Functional Materials 31, no. 51 (2021): 2105384.

[35] C. Cui, X. Zhao, X. Su, et al., “Porphyrin-Based Donor-Acceptor Covalent Organic Polymer/ZnIn₂S₄ Z-Scheme Heterostructure for Efficient Photocatalytic Hydrogen Evolution,” Advanced Functional Materials 32, no. 47 (2022): 2208962.

[36] T. Naranjo, L. Collado, M. Gomez-Mendoza, et al., “Solar-Driven Hydrogen Production Using a Bodipy Covalent Organic Framework Hybrid Photocatalyst,” ACS Catalysis 14, no. 1 (2024): 283-291.

[37] Y. Qian, D. Li, Y. Han, and H.-L. Jiang, “Photocatalytic Molecular Oxygen Activation by Regulating Excitonic Effects in Covalent Organic Frameworks,” Journal of the American Chemical Society 142, no. 49 (2020): 20763-20771.

[38] X. Yang, Y. Zhang, B. Zhang, et al., “Electron-Accepting Carborane Viologen and Iron Based-Supramolecular Polymers for Electrochromism and Enhanced Photocatalytic Hydrogen Evolution,” Journal of Materials Chemistry C 8, no. 46 (2020): 16326-16332.

[39] P. Verma, F. A. Rahimi, D. Samanta, A. Kundu, J. Dasgupta, and T. K. Maji, “Visible-Light-Driven Photocatalytic CO₂ Reduction to CO/CH₄ Using a Metal-Organic “Soft” Coordination Polymer Gel,” Angewandte Chemie International Edition 61, no. 16 (2022): e202116094.

[40] N. Yoshimura, M. Yoshida, and A. Kobayashi, “Efficient Hydrogen Production by a Photoredox Cascade Catalyst Comprising Dual Photosensitizers and a Transparent Electron Mediator,” Journal of the American Chemical Society 145, no. 11 (2023): 6035-6038.

[41] Y. Fang, T. Liu, L. Chen, and D. Chao, “Morphology Control of Supramolecular Assembly for Superior CO₂ Photoreduction,” ACS Catalysis 13, no. 3 (2023): 2086-2093.

[42] L. Li, R. G. Hadt, S. Yao, et al., “Photocatalysts Based on Cobalt-Chelating Conjugated Polymers for Hydrogen Evolution From Water,” Chemistry of Materials 28, no. 15 (2016): 5394-5399.

[43] P. Verma, A. Singh, F. A. Rahimi, et al., “Charge-Transfer Regulated Visible Light Driven Photocatalytic H₂ Production and CO₂ Reduction in Tetrathiafulvalene Based Coordination Polymer Gel,” Nature Communications 12, no. 1 (2021): 7313.

[44] L. Ran, Z. Li, B. Ran, et al., “Engineering Single-Atom Active Sites on Covalent Organic Frameworks for Boosting CO₂ Photoreduction,” Journal of the American Chemical Society 144, no. 37 (2022): 17097-17109.

[45] Q. Zhang, S. Gao, Y. Guo, et al., “Designing Covalent Organic Frameworks With Co-O₄ Atomic Sites for Efficient CO₂ Photoreduction,” Nature Communications 14, no. 1 (2023): 1147.

[46] Z. Li, X. Shi, H. Cheng, et al., “Atomically Dispersed Iron Active Sites on Covalent Organic Frameworks for Artificial Photosynthesis of Hydrogen Peroxide,” Advanced Energy Materials 14, no. 7 (2024): 2302797.

[47] X. Zhou, Y. Liu, Z. Jin, et al., “Solar-Driven Hydrogen Generation Catalyzed by g-C₃N₄ With poly(Platinaynes) as Efficient Electron Donor at Low Platinum Content,” Advanced Science 8, no. 4 (2021): 2002465.

[48] D. Chaudhary, S. Singh, V. D. Vankar, and N. Khare, “A Ternary Ag/TiO₂/CNT Photoanode for Efficient Photoelectrochemical Water Splitting Under Visible Light Irradiation,” International Journal of Hydrogen Energy 42, no. 12 (2017): 7826-7835.

[49] J.-Y. Jung, D. Lee, and Y.-S. Lee, “CNT-Embedded Hollow TiO₂ Nanofibers With High Adsorption and Photocatalytic Activity Under UV Irradiation,” Journal of Alloys and Compounds 622 (2015): 651-656.

[50] Y. Xu, H. Xu, L. Wang, et al., “The CNT Modified White C₃N₄ Composite Photocatalyst With Enhanced Visible-Light Response Photoactivity,” Dalton Transactions 42, no. 21 (2013): 7604-7613.

[51] U. Bharagav, N. R. Reddy, V. Navakoteswara Rao, et al., “Z-Scheme Driven Photocatalytic Activity of CNTs-Integrated Bi₂S₃/WO₃ Nanohybrid Catalysts for Highly Efficient Hydrogen Evolution Under Solar Light Irradiation,” Chemical Engineering Journal 465 (2023): 142886.

[52] J. Zhang, M. Dai, S. Zhang, et al., “Recent Progress on Carbon-Nanotube-Based Materials for Photocatalytic Applications: A Review,” Solar RRL 6, no. 9 (2022): 2200243.

[53] N. Ramesh Reddy, U. Bhargav, M. Mamatha Kumari, K. K. Cheralathan, and M. Sakar, “Review on the Interface Engineering in the Carbonaceous Titania for the Improved Photocatalytic Hydrogen Production,” International Journal of Hydrogen Energy 45, no. 13 (2020): 7584-7615.

[54] C. Shu, C. Han, X. Yang, et al., “Boosting the Photocatalytic Hydrogen Evolution Activity for D-π-A Conjugated Microporous Polymers by Statistical Copolymerization,” Advanced Materials 33, no. 26 (2021): 2008498.

[55] X. Lan, X. Liu, Y. Zhang, et al., “Unveiling Charge Dynamics in Acetylene-Bridged donor−π-acceptor Covalent Triazine Framework for Enhanced Photoredox Catalysis,” ACS Catalysis 11, no. 12 (2021): 7429-7441.

[56] Y. Qin, P. She, Y. Wang, and W.-Y. Wong, “An All-in-One Integrating Strategy for Designing Platinum(II)-Based Supramolecular Polymers for Photocatalytic Hydrogen Evolution,” Small 20, no. 35 (2024): 2400259.

[57] L. Y. Jun, N. M. Mubarak, L. S. Yon, C. H. Bing, M. Khalid, and E. C. Abdullah, “Comparative Study of Acid Functionalization of Carbon Nanotube via Ultrasonic and Reflux Mechanism,” Journal of Environmental Chemical Engineering 6, no. 5 (2018): 5889-5896.

[58] L. Liang, X. Wang, M. Wang, Z. Liu, G. Chen, and G. Sun, “Flexible Poly(3,4-ethylenedioxythiophene)-tosylate/SWCNT Composite Films With Ultrahigh Electrical Conductivity for Thermoelectric Energy Harvesting,” Composites Communications 25 (2021): 100701.

[59] M. S. Dresselhaus, G. Dresselhaus, R. Saito, and A. Jorio, “Raman Spectroscopy of Carbon Nanotubes,” Physics Reports 409, no. 2 (2005): 47-99.

[60] Y. Hao, Y. Wang, L. Wang, et al., “Probing Layer Number and Stacking Order of Few-Layer Graphene by Raman Spectroscopy,” Small 6, no. 2 (2010): 195-200.

[61] A. Bhardwaj, J. Kaur, M. Wuest, and F. Wuest, “In Situ Click Chemistry Generation of Cyclooxygenase-2 Inhibitors,” Nature Communications 8, no. 1 (2017): 1.

[62] A. L. M. Reddy, A. Srivastava, S. R. Gowda, H. Gullapalli, M. Dubey, and P. M. Ajayan, “Synthesis of Nitrogen-Doped Graphene Films for Lithium Battery Application,” ACS Nano 4, no. 11 (2010): 6337-6342.

[63] Y. Qin, Q. Zhang, and G. Chen, “Organic Borate Doped Carbon Nanotube for Enhancement of Thermoelectric Performance,” Carbon 182 (2021): 742-748.

[64] S. L. Kim, K. Choi, A. Tazebay, and C. Yu, “Flexible Power Fabrics Made of Carbon Nanotubes for Harvesting Thermoelectricity,” ACS Nano 8, no. 3 (2014): 2377-2386.

[65] D. Chaudhary, V. D. Vankar, and N. Khare, “Noble Metal-Free g-C₃N₄/TiO₂/CNT Ternary Nanocomposite With Enhanced Photocatalytic Performance Under Visible-Light Irradiation via Multi-Step Charge Transfer Process,” Solar Energy 158 (2017): 132-139.

[66] E. Zhou, X. Zhang, L. Zhu, et al., “Ultrathin Covalent Organic Framework Nanosheets for Enhanced Photocatalytic Water Oxidation,” Science Advances 10, no. 3 (2024): eadk8564.

[67] K. Kitamoto and K. Sakai, “Pigment-Acceptor-Catalyst Triads for Photochemical Hydrogen Evolution,” Angewandte Chemie International Edition 53, no. 18 (2014): 4618-4622.

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