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Current understanding and challenges of solar-driven hydrogen generation using polymeric photocatalysts

Nature Energy volume 4, pages 746–760 (2019)Cite this article

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A Publisher Correction to this article was published on 19 June 2020

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Abstract

The use of hydrogen as a fuel, when generated from water using semiconductor photocatalysts and driven by sunlight, is a sustainable alternative to fossil fuels. Polymeric photocatalysts are based on Earth-abundant elements and have the advantage over their inorganic counterparts in that their electronic properties are easily tuneable through molecular engineering. Polymeric photocatalysts have developed rapidly over the past decade, resulting in the discovery of many active materials. However, our understanding of the key properties underlying their photoinitiated redox processes has not kept pace, and this impedes further progress to generate cost-competitive technologies. Here, we discuss state-of-the-art polymeric photocatalysts and our microscopic understanding of their activities. We conclude with a discussion of five outstanding challenges in this field: non-standardized reporting of activities, limited photochemical stability, insufficient knowledge of reaction mechanisms, balancing charge carrier lifetimes with catalysis timescales and the use of unsustainable sacrificial reagents.

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Fig. 1: Thermodynamics of water splitting.
Fig. 2: Structures of the different (hypothetical) carbon nitride polymorphs.
Fig. 3: Linear homo- and copolymeric photocatalysts.
Fig. 4: Nominal structure of CTFs.
Fig. 5: Nominal structure of CMP photocatalysts.
Fig. 6: Nominal structure of COFs.

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References

  1. Pinaud, B. A. et al. Technical and economic feasibility of centralized facilities for solar hydrogen production via photocatalysis and photoelectrochemistry. Energy Environ. Sci. 6, 1983–2002 (2013).

    Google Scholar 

  2. Zhang, J. & Wang, X. Solar water splitting at λ=600 nm: a step closer to sustainable hydrogen production. Angew. Chem. Int. Ed. 54, 7230–7232 (2015).

    Google Scholar 

  3. Martin, D. J., Reardon, P. J. T., Moniz, S. J. & Tang, J. Visible light-driven pure water splitting by a nature-inspired organic semiconductor-based system. J. Am. Chem. Soc. 136, 12568–12571 (2014). Overall water splitting was achieved in a Z-scheme system based on a polymeric photocatalyst for the first time.

    Google Scholar 

  4. Su, D. S. et al. Metal-free heterogeneous catalysis for sustainable chemistry. ChemSusChem 3, 169–180 (2010).

    Google Scholar 

  5. Chen, X. et al. Incorporating graphitic carbon nitride (g-C3N4) quantum dots into bulk-heterojunction polymer solar cells leads to efficiency enhancement. Adv. Funct. Mater. 26, 1719–1728 (2016).

    Google Scholar 

  6. Peng, G., Volokh, M., Tzadikov, J., Sun, J. & Shalom, M. Carbon nitride/reduced graphene oxide film with enhanced electron diffusion length: an efficient photo-electrochemical cell for hydrogen generation. Adv. Energy Mater. 8, 1800566 (2018).

    Google Scholar 

  7. Xu, J. et al. Color-tunable photoluminescence and NIR electroluminescence in carbon nitride thin films and light-emitting diodes. Adv. Opt. Mater. 3, 913–917 (2015).

    Google Scholar 

  8. Yanagida, S., Kabumoto, A., Mizumoto, K., Pac, C. & Yoshino, K. Poly (p-phenylene)-catalysed photoreduction of water to hydrogen. J. Chem. Soc. Chem. Commun. 474–475 (1985). This is the first example of photocatalytic hydrogen evolution on polymeric semiconductors in the presence of sacrificial donors under UV irradiation (λ > 290 nm).

  9. Matsuoka, S. et al. Photocatalysis of oligo(p-phenylenes): photoreductive production of hydrogen and ethanol in aqueous triethylamine. J. Phys. Chem. 95, 5802–5808 (1991).

    Google Scholar 

  10. Wang, X. et al. A metal-free polymeric photocatalyst for hydrogen production from water under visible light. Nat. Mater. 8, 76–80 (2009). This is the first report of carbon nitride photocatalysts for stable hydrogen production in the presence of sacrificial reagents under visible light, which stimulated the research on polymeric photocatalysts in the past decade.

    Google Scholar 

  11. Kuhn, P., Antonietti, M. & Thomas, A. Porous, covalent triazine-based frameworks prepared by ionothermal synthesis. Angew. Chem. Int. Ed. 47, 3450–3453 (2008).

    Google Scholar 

  12. Schwab, M. G. et al. Photocatalytic hydrogen evolution through fully conjugated poly(azomethine) networks. Chem. Commun. 46, 8932–8934 (2010).

    Google Scholar 

  13. Stegbauer, L., Schwinghammer, K. & Lotsch, B. V. A hydrazone-based covalent organic framework for photocatalytic hydrogen production. Chem. Sci. 5, 2789–2793 (2014).

    Google Scholar 

  14. Sprick, R. S. et al. Tunable organic photocatalysts for visible-light-driven hydrogen evolution. J. Am. Chem. Soc. 137, 3265–3270 (2015). The optical gap in a series of microporous copolymers was fine-tuned by varying monomer composition over a broad range (1.94−2.95 eV), which didn’t directly correlate with their efficiency for hydrogen evolution, indicating that more complex factors are at play.

    Google Scholar 

  15. Sprick, R. S. et al. Visible-light-driven hydrogen evolution using planarized conjugated polymer photocatalysts. Angew. Chem. Int. Ed. 55, 1792–1796 (2016).

    Google Scholar 

  16. Liu, J. et al. Metal-free efficient photocatalyst for stable visible water splitting via a two-electron pathway. Science 347, 970–974 (2015).

    Google Scholar 

  17. Ruan, Q. et al. A nanojunction polymer photoelectrode for efficient charge transport and separation. Angew. Chem. Int. Ed. 56, 8221–8225 (2017).

    Google Scholar 

  18. Zhang, G., Lan, Z.-A., Lin, L., Lin, S. & Wang, X. Overall water splitting by Pt/g-C3N4 photocatalysts without using sacrificial agents. Chem. Sci. 7, 3062–3066 (2016).

    Google Scholar 

  19. Schwarz, D. et al. Tailored band gaps in sulfur- and nitrogen-containing porous donor–acceptor polymers. Chem. Eur. J. 23, 13023–13027 (2017).

    Google Scholar 

  20. Kosco, J. et al. The effect of residual palladium catalyst contamination on the photocatalytic hydrogen evolution activity of conjugated polymers. Adv. Energy Mater. 8, 1802181 (2018). Residual Pd has been demonstrated to play a necessary role in the hydrogen evolution activity in a photocatalytic system of dispersed conjugated polymer nanoparticles.

    Google Scholar 

  21. Sprick, R. S. et al. Maximising the hydrogen evolution activity in organic photocatalysts by co-polymerisation. J. Mater. Chem. A 6, 11994–12003 (2018).

    Google Scholar 

  22. Roncali, J. Synthetic principles for bandgap control in linear pi-conjugated systems. Chem. Rev. 97, 173–206 (1997).

    Google Scholar 

  23. Guiglion, P., Butchosa, C. & Zwijnenburg, M. A. Polymer photocatalysts for water splitting: insights from computational modeling. Macromol. Chem. Phys. 217, 344–353 (2016).

    Google Scholar 

  24. Tamai, Y., Ohkita, H., Benten, H. & Ito, S. Exciton diffusion in conjugated polymers: from fundamental understanding to improvement in photovoltaic conversion efficiency. J. Phys. Chem. Lett. 6, 3417–3428 (2015).

    Google Scholar 

  25. Clarke, T. M. & Durrant, J. R. Charge photogeneration in organic solar cells. Chem. Rev. 110, 6736–6767 (2010).

    Google Scholar 

  26. Sprick, R. S. et al. Nitrogen containing linear poly(phenylene) derivatives for photo-catalytic hydrogen evolution from water. Chem. Mater. 30, 5733–5742 (2018).

    Google Scholar 

  27. Sprick, R. S., Bari, Y., Aitchison C. M., Woods, D. J. & Cooper, A. I. Photocatalytic hydrogen evolution from water using heterocyclic conjugated microporous polymers: porous or non-porous? Preprint at https://doi.org/10.26434/chemrxiv.6217451 (2018).

  28. Wang, Y. et al. Linker-controlled polymeric photocatalyst for highly efficient hydrogen evolution from water. Energy Environ. Sci. 10, 1643–1651 (2017).

    Google Scholar 

  29. Liu, G. et al. Nature-inspired environmental “phosphorylation” boosts photocatalytic h2 production over carbon nitride nanosheets under visible-light irradiation. Angew. Chem. Int. Ed. 54, 13561–13565 (2015).

    Google Scholar 

  30. Zhang, G. et al. Tailoring the grain boundary chemistry of polymeric carbon nitride for enhanced solar hydrogen production and CO2 reduction. Angew. Chem. Int. Ed. 131, 3471–3475 (2019).

    Google Scholar 

  31. Botari, T., Huhn, W. P., Lau, V. W.-h, Lotsch, B. V. & Blum, V. Thermodynamic equilibria in carbon nitride photocatalyst materials and conditions for the existence of graphitic carbon nitride g-C3N4. Chem. Mater. 29, 4445–4453 (2017).

    Google Scholar 

  32. Jorge, A. B. et al. H2 and O2 Evolution from water half-splitting reactions by graphitic carbon nitride materials. J. Phys. Chem. C. 117, 7178–7185 (2013).

    Google Scholar 

  33. Lotsch, B. V. et al. Unmasking melon by a complementary approach employing electron diffraction, solid-state NMR spectroscopy, and theoretical calculations—structural characterization of a carbon nitride polymer. Chem. Eur. J. 13, 4969–4980 (2007).

    Google Scholar 

  34. Liebig, J. Uber einige Stickstoff ‐ Verbindungen. Ann. der Pharm. 10, 1–47 (1834).

    Google Scholar 

  35. Wirnhier, E. et al. Poly(triazine imide) with intercalation of lithium and chloride ions [(C3N3)2(NHxLi1-x)3·LiCl]: A crystalline 2D carbon nitride network. Chem. Eur. J. 17, 3213–3221 (2011).

    Google Scholar 

  36. Martin, D. J. et al. Highly efficient photocatalytic H2 evolution from water using visible light and structure-controlled graphitic carbon nitride. Angew. Chem. Int. Ed. 53, 9240–9245 (2014).

    Google Scholar 

  37. Zhang, G. et al. Ionothermal synthesis of triazine-heptazine-based copolymers with apparent quantum yields of 60 % at 420 nm for solar hydrogen production from “sea water”. Angew. Chem. Int. Ed. 57, 9372–9376 (2018).

    Google Scholar 

  38. Zhou, Z., Zhang, Y., Shen, Y., Liu, S. & Zhang, Y. Molecular engineering of polymeric carbon nitride: advancing applications from photocatalysis to biosensing and more. Chem. Soc. Rev. 47, 2298–2321 (2018).

    Google Scholar 

  39. Yang, S. et al. Exfoliated graphitic carbon nitride nanosheets as efficient catalysts for hydrogen evolution under visible light. Adv. Mater. 25, 2452–2456 (2013).

    Google Scholar 

  40. Yang, Z., Zhang, Y. & Schnepp, Z. Soft and hard templating of graphitic carbon nitride. J. Mater. Chem. A 3, 14081–14092 (2015).

    Google Scholar 

  41. Bhunia, M. K., Yamauchi, K. & Takanabe, K. Harvesting solar light with crystalline carbon nitrides for efficient photocatalytic hydrogen evolution. Angew. Chem. Int. Ed. 126, 11181–11185 (2014).

    Google Scholar 

  42. Liu, G. et al. In situ bond modulation of graphitic carbon nitride to construct p–n homojunctions for enhanced photocatalytic hydrogen production. Adv. Funct. Mater. 26, 6822–6829 (2016).

    Google Scholar 

  43. Chen, Z. et al. Gradual carbon doping of graphitic carbon nitride towards metal-free visible light photocatalytic hydrogen evolution. J. Mater. Chem. A 6, 15310–15319 (2018).

    Google Scholar 

  44. Barrio, J., Lin, L., Wang, X. & Shalom, M. Design of a unique energy-band structure and morphology in a carbon nitride photocatalyst for improved charge separation and hydrogen production. ACS Sustain. Chem. Eng. 6, 519–530 (2018).

    Google Scholar 

  45. Fan, Q., Liu, J., Yu, Y., Zuo, S. & Li, B. A simple fabrication for sulfur doped graphitic carbon nitride porous rods with excellent photocatalytic activity degrading RhB dye. Appl. Surf. Sci. 391, 360–368 (2017).

    Google Scholar 

  46. Liao, Y. et al. Tailoring the morphology of g-C3N4 by self-assembly towards high photocatalytic performance. ChemCatChem 6, 3419–3425 (2014).

    Google Scholar 

  47. Jun, Y.-S. et al. From melamine-cyanuric acid supramolecular aggregates to carbon nitride hollow spheres. Adv. Funct. Mater. 23, 3661–3667 (2013).

    Google Scholar 

  48. Wan, S., Ou, M., Zhong, Q., Zhang, S. & Cai, W. Supramolecular synthesis of multifunctional holey carbon nitride nanosheet with high-efficiency photocatalytic performance. Adv. Opt. Mater. 5, 1700536 (2017).

    Google Scholar 

  49. Shi, L. et al. In site acid template induced facile synthesis of porous graphitic carbon nitride with enhanced visible-light photocatalytic activity. Catal. Commun. 89, 129–132 (2017).

    Google Scholar 

  50. Barrio, J., Grafmüller, A., Tzadikov, J. & Shalom, M. Halogen-hydrogen bonds: A general synthetic approach for highly photoactive carbon nitride with tunable properties. Appl. Catal., B 237, 681–688 (2018).

    Google Scholar 

  51. Xie, M., Wei, W., Jiang, Z., Xu, Y. & Xie, J. Carbon nitride nanowires/nanofibers: A novel template-free synthesis from a cyanuric chloride–melamine precursor towards enhanced adsorption and visible-light photocatalytic performance. Ceram. Int. 42, 4158–4170 (2016).

    Google Scholar 

  52. Hong, Y. et al. Precisely tunable thickness of graphitic carbon nitride nanosheets for visible-light-driven photocatalytic hydrogen evolution. Nanoscale 9, 14103–14110 (2017).

    Google Scholar 

  53. Barrio, J. et al. Unprecedented Centimeter-Long Carbon Nitride Needles: Synthesis, Characterization and Applications. Small 14, 1800633 (2018).

    Google Scholar 

  54. Bai, J., Han, Q., Cheng, Z. & Qu, L. Wall-mesoporous graphitic carbon nitride nanotubes for efficient photocatalytic hydrogen evolution. Chem. Asian J. 13, 3160–3164 (2018).

    Google Scholar 

  55. Wang, J. et al. Direct synthesis of porous nanorod-type graphitic carbon nitride/cuo composite from cu–melamine supramolecular framework towards enhanced photocatalytic performance. Chem. Asian J. 10, 1276–1280 (2015).

    Google Scholar 

  56. Lau, V. W.-h et al. Rational design of carbon nitride photocatalysts by identification of cyanamide defects as catalytically relevant sites. Nat. Commun. 7, 12165 (2016).

    Google Scholar 

  57. Lau, V. W.-h et al. Urea-modified carbon nitrides: enhancing photocatalytic hydrogen evolution by rational defect engineering. Adv. Energy Mater. 7, 1602251 (2017).

    Google Scholar 

  58. Lin, L., Ou, H., Zhang, Y. & Wang, X. Tri-s-triazine-based crystalline graphitic carbon nitrides for highly efficient hydrogen evolution photocatalysis. ACS Catal. 6, 3921–3931 (2016).

    Google Scholar 

  59. Wang, L. et al. Conjugated microporous polymer nanosheets for overall water splitting using visible light. Adv. Mater. 29, 1702428 (2017).

    Google Scholar 

  60. Yu, H. et al. Alkali-assisted synthesis of nitrogen deficient graphitic carbon nitride with tunable band structures for efficient visible-light-driven hydrogen evolution. Adv. Mater. 29, 1605148 (2017).

    Google Scholar 

  61. Guo, S. et al. Phosphorus-doped carbon nitride tubes with a layered micro-nanostructure for enhanced visible-light photocatalytic hydrogen evolution. Angew. Chem. Int. Ed. 55, 1830–1834 (2016).

    Google Scholar 

  62. Fang, J., Fan, H., Li, M. & Long, C. Nitrogen self-doped graphitic carbon nitride as efficient visible light photocatalyst for hydrogen evolution. J. Mater. Chem. A 3, 13819–13826 (2015).

    Google Scholar 

  63. Li, J. et al. A facile approach to synthesize novel oxygen-doped g-C3N4 with superior visible-light photoreactivity. Chem. Commun. 48, 12017–12019 (2012).

    Google Scholar 

  64. Wang, Y., Li, H., Yao, J., Wang, X. & Antonietti, M. Synthesis of boron doped polymeric carbon nitride solids and their use as metal-free catalysts for aliphatic C-H bond oxidation. Chem. Sci. 2, 446–450 (2011).

    Google Scholar 

  65. Wang, Y. et al. Excellent visible-light photocatalysis of fluorinated polymeric carbon nitride solids. Chem. Mater. 22, 5119–5121 (2010).

    Google Scholar 

  66. Zhang, J. et al. Synthesis of a carbon nitride structure for visible-light catalysis by copolymerization. Angew. Chem. Int. Ed. 49, 441–444 (2010).

    Google Scholar 

  67. Zhang, J. et al. Co-monomer control of carbon nitride semiconductors to optimize hydrogen evolution with visible light. Angew. Chem. Int. Ed. 124, 3237–3241 (2012).

    Google Scholar 

  68. Barrio, J. & Shalom, M. Rational design of carbon nitride materials by supramolecular preorganization of monomers. Chem. Cat. Chem. 10, 5573–5586 (2018).

    Google Scholar 

  69. Wang, Y. et al. Bandgap engineering of organic semiconductors for highly efficient photocatalytic water splitting. Adv. Energy Mater. 8, 1801084 (2018).

    Google Scholar 

  70. Li, M. et al. Graphene with atomic-level in-plane decoration of h-BN domains for efficient photocatalysis. Chem. Mater. 29, 2769–2776 (2017).

    Google Scholar 

  71. Zhang, G., Zhang, J., Zhang, M. & Wang, X. Polycondensation of thiourea into carbon nitride semiconductors as visible light photocatalysts. J. Mater. Chem. 22, 8083–8091 (2012).

    Google Scholar 

  72. Zhang, G., Huang, C. & Wang, X. Dispersing molecular cobalt in graphitic carbon nitride frameworks for photocatalytic water oxidation. Small 11, 1215–1221 (2015).

    Google Scholar 

  73. Zhao, G., Huang, X., Fina, F., Zhang, G. & Irvine, J. T. Facile structure design based on C3N4 for mediator-free Z-scheme water splitting under visible light. Catal. Sci. Technol. 5, 3416–3422 (2015).

    Google Scholar 

  74. Sui, Y., Liu, J., Zhang, Y., Tian, X. & Chen, W. Dispersed conductive polymer nanoparticles on graphitic carbon nitride for enhanced solar-driven hydrogen evolution from pure water. Nanoscale 5, 9150–9155 (2013).

    Google Scholar 

  75. Wang, L. et al. Organic polymer dots as photocatalysts for visible light-driven hydrogen generation. Angew. Chem. Int. Ed. 55, 12306–12310 (2016).

    Google Scholar 

  76. Shibata, T. et al. Novel visible-light-driven photocatalyst. Poly (p-phenylene)-catalyzed photoreductions of water, carbonyl compounds, and olefins. J. Phys. Chem. 94, 2068–2076 (1990).

    Google Scholar 

  77. Yamamoto, T., Yoneda, Y. & Maruyama, T. Ruthenium and nickel complexes of a π-conjugated electrically conducting polymer chelate ligand, poly(2,2′-bipyridine-5,5′-diyl), and their chemical and catalytic reactivity. J. Chem. Soc. Chem. Commun. 1652–1654 (1992).

  78. Yang, C. et al. Molecular engineering of conjugated polybenzothiadiazoles for enhanced hydrogen production by photosynthesis. Angew. Chem. Int. Ed. 55, 9202–9206 (2016).

    Google Scholar 

  79. Li, L. et al. Photocatalysts based on cobalt-chelating conjugated polymers for hydrogen evolution from water. Chem. Mater. 28, 5394–5399 (2016).

    Google Scholar 

  80. Woods, D. J., Sprick, R. S., Smith, C. L., Cowan, A. J. & Cooper, A. I. A solution-processable polymer photocatalyst for hydrogen evolution from water. Adv. Energy Mater. 7, 1700479 (2017).

    Google Scholar 

  81. Pati, P. B. et al. An experimental and theoretical study of an efficient polymer nano-photocatalyst for hydrogen evolution. Energy Environ. Sci. 10, 1372–1376 (2017).

    Google Scholar 

  82. Liu, M., Guo, L., Jin, S. & Tan, B. Covalent triazine frameworks: synthesis and applications. J. Mater. Chem. A 7, 5153–5172 (2019).

    Google Scholar 

  83. Schwinghammer, K., Hug, S., Mesch, M. B., Senker, J. & Lotsch, B. V. Phenyl-triazine oligomers for light-driven hydrogen evolution. Energy Environ. Sci. 8, 3345–3353 (2015).

    Google Scholar 

  84. Kuecken, S. et al. Fast tuning of covalent triazine frameworks for photocatalytic hydrogen evolution. Chem. Commun. 53, 5854–5857 (2017).

    Google Scholar 

  85. Kuhn, P., Thomas, A. & Antonietti, M. Toward tailorable porous organic polymer networks: a high-temperature dynamic polymerization scheme based on aromatic nitriles. Macromolecules 42, 319–326 (2009).

    Google Scholar 

  86. Bi, J. et al. Covalent triazine-based frameworks as visible light photocatalysts for the splitting of water. Macromol. Rapid Commun. 36, 1799–1805 (2015).

    Google Scholar 

  87. Meier, C. B. et al. Structure-property relationships for covalent triazine-based frameworks: The effect of spacer length on photocatalytic hydrogen evolution from water. Polymer 126, 283–290 (2017).

    Google Scholar 

  88. Li, L. et al. Rational design of porous conjugated polymers and roles of residual palladium for photocatalytic hydrogen production. J. Am. Chem. Soc. 138, 7681–7686 (2016).

    Google Scholar 

  89. Maeda, K. et al. Photocatalytic activities of graphitic carbon nitride powder for water reduction and oxidation under visible light. J. Phys. Chem. C. 113, 4940–4947 (2009).

    Google Scholar 

  90. Li, L. et al. Sulfur-doped covalent triazine-based frameworks for enhanced photocatalytic hydrogen evolution from water under visible light. J. Mater. Chem. A 4, 12402–12406 (2016).

    Google Scholar 

  91. Zhang, Z. et al. Organic semiconductor for artificial photosynthesis: water splitting into hydrogen by a bioinspired C3N3S3 polymer under visible light irradiation. Chem. Sci. 2, 1826–1830 (2011).

    Google Scholar 

  92. Chu, S. et al. Facile green synthesis of crystalline polyimide photocatalyst for hydrogen generation from water. J. Mater. Chem. 22, 15519–15521 (2012).

    Google Scholar 

  93. Jiang, J.-X. et al. Conjugated microporous poly(aryleneethynylene) networks. Angew. Chem. Int. Ed. 46, 8574–8578 (2007).

    Google Scholar 

  94. Sprick, R. S. et al. Extended conjugated microporous polymers for photocatalytic hydrogen evolution from water. Chem. Commun. 52, 10008–10011 (2016).

    Google Scholar 

  95. Bhunia, A. et al. A photoluminescent covalent triazine framework: CO2 adsorption, light-driven hydrogen evolution and sensing of nitroaromatics. J. Mater. Chem. A 4, 13450–13457 (2016).

    Google Scholar 

  96. Xu, Y. et al. Perylene-Containing conjugated microporous polymers for photocatalytic hydrogen evolution. Macromol. Chem. Phys. 218, 1700049 (2017).

    Google Scholar 

  97. Xu, Y. et al. Tetra-armed conjugated microporous polymers for gas adsorption and photocatalytic hydrogen evolution. Sci. China Chem. 60, 1075–1083 (2017).

    Google Scholar 

  98. Chaoui, N., Trunk, M., Dawson, R., Schmidt, J. & Thomas, A. Trends and challenges for microporous polymers. Chem. Soc. Rev. 46, 3302–3321 (2017).

    Google Scholar 

  99. Li, L. & Cai, Z. Structure control and photocatalytic performance of porous conjugated polymers based on perylene diimide. Polym. Chem. 7, 4937–4943 (2016).

    Google Scholar 

  100. Wang, L. et al. Photocatalytic oxygen evolution from low-bandgap conjugated microporous polymer nanosheets: a combined first-principles calculation and experimental study. Nanoscale 9, 4090–4096 (2017).

    Google Scholar 

  101. Wang, L., Zheng, X., Chen, L., Xiong, Y. & Xu, H. Van der Waals heterostructures comprised of ultrathin polymer nanosheets for efficient Z-scheme overall water splitting. Angew. Chem. Int. Ed. 130, 3512–3516 (2018).

    Google Scholar 

  102. Jiang, J.-X. et al. Conjugated microporous poly(phenylene butadiynylene)s. Chem. Commun., 486–488 (2008).

  103. Côté, A. P. et al. Porous, crystalline, covalent organic frameworks. Science 310, 1166–1170 (2005).

    Google Scholar 

  104. Vyas, V. S. et al. A tunable azine covalent organic framework platform for visible light-induced hydrogen generation. Nat. Commun. 6, 8508 (2015). Covalent organic frameworks have been demonstrated to be modified post-synthetically through the incorporation of a molecular co-catalyst for visible-light-driven hydrogen production.

    Google Scholar 

  105. Banerjee, T. et al. single-site photocatalytic h2 evolution from covalent organic frameworks with molecular cobaloxime co-catalysts. J. Am. Chem. Soc. 139, 16228–16234 (2017).

    Google Scholar 

  106. Pachfule, P. et al. Diacetylene functionalized covalent organic framework (cof) for photocatalytic hydrogen generation. J. Am. Chem. Soc. 140, 1423–1427 (2018).

    Google Scholar 

  107. Wang, X. et al. Sulfone-containing covalent organic frameworks for photocatalytic hydrogen evolution from water. Nat. Chem. 10, 1180–1189 (2018).

    Google Scholar 

  108. Bai, Y. et al. Accelerated discovery of organic polymer photocatalysts for hydrogen evolution from water through the integration of experiment and theory. J. Am. Chem. Soc. 141, 9063–9071 (2019).

    Google Scholar 

  109. Guiglion, P., Butchosa, C. & Zwijnenburg, M. A. Polymeric watersplitting photocatalysts; a computational perspective on the water oxidation conundrum. J. Mater. Chem. A 2, 11996–12004 (2014).

    Google Scholar 

  110. Butchosa, C., Guiglion, P. & Zwijnenburg, M. A. Carbon nitride photocatalysts for water splitting: a computational perspective. J. Phys. Chem. C. 118, 24833–24842 (2014).

    Google Scholar 

  111. Merschjann, C. et al. Photophysics of polymeric carbon nitride: An optical quasimonomer. Phys. Rev. B 87, 205204 (2013).

    Google Scholar 

  112. Godin, R., Wang, Y., Zwijnenburg, M. A., Tang, J. & Durrant, J. R. Time-resolved spectroscopic investigation of charge trapping in carbon nitrides photocatalysts for hydrogen generation. J. Am. Chem. Soc. 139, 5216–5224 (2017). This is the first spectroscopic investigation of trap states in urea-derived carbon nitride and shows that charge trapping significantly reduces the driving force and rate of charge transfer reactions and dictates the photocatalytic activity.

    Google Scholar 

  113. Merschjann, C. et al. Complementing graphenes: 1D interplanar charge transport in polymeric graphitic carbon nitrides. Adv. Mater. 27, 7993–7999 (2015).

    Google Scholar 

  114. Corp, K. L. & Schlenker, C. W. Ultrafast spectroscopy reveals electron-transfer cascade that improves hydrogen evolution with carbon nitride photocatalysts. J. Am. Chem. Soc. 139, 7904–7912 (2017).

    Google Scholar 

  115. Nogueira, A. F. et al. Charge recombination in conjugated polymer/fullerene blended films studied by transient absorption spectroscopy. J. Phys. Chem. B 107, 1567–1573 (2003).

    Google Scholar 

  116. Baxter, J. B., Richter, C. & Schmuttenmaer, C. A. Ultrafast carrier dynamics in nanostructures for solar fuels. Annu. Rev. Phys. Chem. 65, 423–447 (2014).

    Google Scholar 

  117. Wang, H. et al. Boosting hot-electron generation: exciton dissociation at the order–disorder interfaces in polymeric photocatalysts. J. Am. Chem. Soc. 139, 2468–2473 (2017).

    Google Scholar 

  118. Walsh, J. J., Jiang, C., Tang, J. & Cowan, A. J. Photochemical CO2 reduction using structurally controlled g-C3N4. Phys. Chem. Chem. Phys. 18, 24825–24829 (2016).

    Google Scholar 

  119. Kuriki, R. et al. Nature-inspired, highly durable CO2 reduction system consisting of a binuclear ruthenium(ii) complex and an organic semiconductor using visible light. J. Am. Chem. Soc. 138, 5159–5170 (2016).

    Google Scholar 

  120. Kasap, H. et al. Solar-driven reduction of aqueous protons coupled to selective alcohol oxidation with a carbon nitride-molecular Ni catalyst system. J. Am. Chem. Soc. 138, 9183–9192 (2016).

    Google Scholar 

  121. Moon, G.-h et al. Eco-friendly photochemical production of H2O2 through O2 reduction over carbon nitride frameworks incorporated with multiple heteroelements. ACS Catal. 7, 2886–2895 (2017).

    Google Scholar 

  122. Peng, G., Albero, J., Garcia, H. & Shalom, M. A Water-splitting carbon nitride photoelectrochemical cell with efficient charge separation and remarkably low onset potential. Angew. Chem. Int. Ed. 130, 16033–16037 (2018).

    Google Scholar 

  123. Zhang, W. et al. One-pot synthesis of nickel-modified carbon nitride layers toward efficient photoelectrochemical cells. ACS Appl. Mater. Interfaces 9, 32667–32677 (2017).

    Google Scholar 

  124. Jing, L., Zhu, R., Phillips, D. L. & Yu, J. C. Effective prevention of charge trapping in graphitic carbon nitride with nanosized red phosphorus modification for superior photo(electro)catalysis. Adv. Funct. Mater. 27, 1703484 (2017).

    Google Scholar 

  125. Elbanna, O., Fujitsuka, M. & Majima, T. g-C3N4/TiO2 mesocrystals composite for H2 evolution under visible-light irradiation and its charge carrier dynamics. ACS Appl. Mater. Interfaces 9, 34844–34854 (2017).

    Google Scholar 

  126. Lau, V. W.-h et al. Dark photocatalysis: storage of solar energy in carbon nitride for time-delayed hydrogen generation. Angew. Chem. Int. Ed. 56, 510–514 (2017).

    Google Scholar 

  127. Savateev, A., Kurpil, B., Mishchenko, A., Zhang, G. & Antonietti, M. A “waiting” carbon nitride radical anion: a charge storage material and key intermediate in direct C-H thiolation of methylarenes using elemental sulfur as the “S”-source. Chem. Sci. 9, 3584–3591 (2018).

    Google Scholar 

  128. Pellegrin, Y. & Odobel, F. Sacrificial electron donor reagents for solar fuel production. C. R. Chim. 20, 283–295 (2017).

    Google Scholar 

  129. Matsuoka, S. et al. Photocatalysis of oligo (p-phenylenes): photoreductive production of hydrogen and ethanol in aqueous triethylamine. J. Phys. Chem. 95, 5802–5808 (1991).

    Google Scholar 

  130. Yanagida, S. et al. Synthesis of 2,′:5′, 2″-terpyridine and 2,2′:5′, 2″:5″, 2‴-quaterpyridine and their photocatalysis of the reduction of water. J. Chem. Soc. Perkin Trans. 2, 1963–1969 (1996).

    Google Scholar 

  131. Yanagida, S. & Matsuoka, S. Effective photoreduction of CO2 catalyzed by oligo(p-phenylenes). In Proc. Optical Materials Technology for Energy Efficiency and Solar Energy Conversion XI: Photovoltaics, Photochemistry, Photoelectrochemistry 243–250 (SPIE, 1992).

  132. Reynal, A., Lakadamyali, F., Gross, M. A., Reisner, E. & Durrant, J. R. Parameters affecting electron transfer dynamics from semiconductors to molecular catalysts for the photochemical reduction of protons. Energy Environ. Sci. 6, 3291–3300 (2013).

    Google Scholar 

  133. Rodenberg, A. et al. Mechanism of photocatalytic hydrogen generation by a polypyridyl-based cobalt catalyst in aqueous solution. Inorg. Chem. 54, 646–657 (2015).

    Google Scholar 

  134. Pastor, E. et al. Spectroelectrochemical analysis of the mechanism of (photo)electrochemical hydrogen evolution at a catalytic interface. Nat. Commun. 8, 14280 (2017).

    Google Scholar 

  135. Pesci, F. M., Cowan, A. J., Alexander, B. D., Durrant, J. R. & Klug, D. R. Charge carrier dynamics on mesoporous WO3 during water splitting. J. Phys. Chem. Lett. 2, 1900–1903 (2011).

    Google Scholar 

  136. Wang, X. et al. Transient absorption spectroscopy of anatase and rutile: the impact of morphology and phase on photocatalytic activity. J. Phys. Chem. C. 119, 10439–10447 (2015).

    Google Scholar 

  137. Sachs, M. et al. Understanding structure-activity relationships in linear polymer photocatalysts for hydrogen evolution. Nat. Commun. 9, 4968 (2018).

    Google Scholar 

  138. Schwarze, M. et al. Quantification of photocatalytic hydrogen evolution. Phys. Chem. Chem. Phys. 15, 3466–3472 (2013).

    Google Scholar 

  139. Le, C. C. et al. A general small-scale reactor to enable standardization and acceleration of photocatalytic reactions. ACS Cent. Sci. 3, 647–653 (2017).

    Google Scholar 

  140. Kisch, H. & Bahnemann, D. Best practice in photocatalysis: comparing rates or apparent quantum yields? J. Phys. Chem. Lett. 6, 1907–1910 (2015).

    Google Scholar 

  141. Han, L., Lin, M. & Haussener, S. Reliable performance characterization of mediated photocatalytic water-splitting half reactions. ChemSusChem 10, 2158–2166 (2017).

    Google Scholar 

  142. Ehrmaier, J., Janicki, M. J., Sobolewski, A. L. & Domcke, W. Mechanism of photocatalytic water splitting with triazine-based carbon nitrides: insights from ab initio calculations for the triazine–water complex. Phys. Chem. Chem. Phys. 20, 14420–14430 (2018).

    Google Scholar 

  143. Godin, R., Kafizas, A. & Durrant, J. R. Electron transfer dynamics in fuel producing photosystems. Curr. Opin. Electrochem. 2, 136–143 (2017).

    Google Scholar 

  144. Ferreira, K. N., Iverson, T. M., Maghlaoui, K., Barber, J. & Iwata, S. Architecture of the photosynthetic oxygen-evolving center. Science 303, 1831–1838 (2004).

    Google Scholar 

  145. Zhang, J. et al. Photocatalytic oxidation of water by polymeric carbon nitride nanohybrids made of sustainable elements. Chem. Sci. 3, 443–446 (2012).

    Google Scholar 

  146. Wang, W., Jimmy, C. Y., Shen, Z., Chan, D. K. & Gu, T. gC3N4 quantum dots: direct synthesis, upconversion properties and photocatalytic application. Chem. Commun. 50, 10148–10150 (2014).

    Google Scholar 

  147. Kang, Y. et al. An amorphous carbon nitride photocatalyst with greatly extended visible‐light‐responsive range for photocatalytic hydrogen generation. Adv. Mater. 27, 4572–4577 (2015).

    Google Scholar 

  148. Yang, P., Ou, H., Fang, Y. & Wang, X. A facile steam reforming strategy to delaminate layered carbon nitride semiconductors for photoredox catalysis. Angew. Chem. Int. Ed. 56, 3992–3996 (2017).

    Google Scholar 

  149. Ou, H. et al. Tri-s-triazine-based crystalline carbon nitride nanosheets for an improved hydrogen evolution. Adv. Mater. 29, 1700008 (2017).

    Google Scholar 

  150. Aitchison, C. M., Sprick, R. S. & Cooper, A. I. Emulsion polymerization derived organic photocatalysts for improved light-driven hydrogen evolution. J. Mater. Chem. A 7, 2490–2496 (2019).

    Google Scholar 

  151. Vogel, A. et al. Photocatalytically active ladder polymers. Faraday Discuss. 215, 84–97 (2019).

    Google Scholar 

  152. Zong, X. et al. Structure defects assisted photocatalytic H2 production for polythiophene nanofibers. Appl. Catal. B 211, 98–105 (2017).

    Google Scholar 

  153. Xie, J. et al. Efficient visible light-driven water oxidation and proton reduction by an ordered covalent triazine-based framework. Energy Environ. Sci. 11, 1617–1624 (2018).

    Google Scholar 

  154. Sprick, R. S. et al. Photocatalytic hydrogen evolution from water using fluorene and dibenzothiophene sulfone-conjugated microporous and linear polymers. Chem. Mater. 31, 305–313 (2019).

    Google Scholar 

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Acknowledgements

Y.W. acknowledges the China Scholarship Council (CSC) for full PhD studentship. The UK Engineering and Physical Sciences Research Council (EPSRC) is acknowledged for funding through grant EP/N004884/1 (for R.S.S., L.W., M.A.Z. and A.I.C.). This work has received funding from the European Union’s Horizon 2020 research and innovation programme (Marie Skłodowska-Curie Individual Fellowship to A.V.) under grant agreement no. 796322. M.S. thanks the Imperial College President’s PhD Scholarship scheme. R.G. thanks the Fonds de recherche du Québec—Nature et technologies (FRQNT) for postdoctoral support and the University of British Columbia for start-up funds. J.R.D. acknowledges support from ERC AdG Intersolar (291482). Y.W., S.J.A.M. and J.T. acknowledge the financial supports from UK EPSRC (EP/N009533/1), Royal Society Newton Advanced Fellowship grant (NA170422) and the Leverhulme Trust (RPG-2017-122).

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Authors and Affiliations

  1. Department of Chemical Engineering, University College London, London, UK

    Yiou Wang, Savio J. A. Moniz & Junwang Tang

  2. Department of Chemistry, University of Liverpool, Liverpool, UK

    Anastasia Vogel, Reiner Sebastian Sprick & Andrew I. Cooper

  3. Centre for Materials Discovery, University of Liverpool, Liverpool, UK

    Anastasia Vogel, Reiner Sebastian Sprick & Andrew I. Cooper

  4. Department of Chemistry, Imperial College London, London, UK

    Michael Sachs, Robert Godin & James R. Durrant

  5. Centre for Plastic Electronics, Imperial College London, London, UK

    Michael Sachs, Robert Godin & James R. Durrant

  6. Department of Chemistry, University College London, London, UK

    Liam Wilbraham & Martijn A. Zwijnenburg

  7. Department of Chemistry, The University of British Columbia, Kelowna, British Columbia, Canada

    Robert Godin

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Wang, Y., Vogel, A., Sachs, M. et al. Current understanding and challenges of solar-driven hydrogen generation using polymeric photocatalysts. Nat Energy 4, 746–760 (2019). https://doi.org/10.1038/s41560-019-0456-5

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