Dynamic structural twist in metal–organic frameworks enhances solar overall water splitting (2024)

1. Hisatomi, T. & Domen, K. Reaction systems for solar hydrogen production via water splitting with particulate semiconductor photocatalysts. Nat. Catal. 2, 387–399 (2019).

   CAS Google Scholar

2. Liu, M. et al. Photocatalytic hydrogen production using twinned nanocrystals and an unanchored NiS_x co-catalyst. Nat. Energy 1, 16151 (2016).

   CAS Google Scholar

3. Ran, J. et al. NiPS₃ ultrathin nanosheets as versatile platform advancing highly active photocatalytic H₂ production. Nat. Commun. 13, 4600 (2022).

   PubMed PubMed Central CAS Google Scholar

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

   PubMed CAS Google Scholar

5. Kosco, J. et al. Generation of long-lived charges in organic semiconductor heterojunction nanoparticles for efficient photocatalytic hydrogen evolution. Nat. Energy 7, 340–351 (2022).

   CAS Google Scholar

6. Wang, Z., Li, C. & Domen, K. Recent developments in heterogeneous photocatalysts for solar-driven overall water splitting. Chem. Soc. Rev. 48, 2109–2125 (2019).

   PubMed CAS Google Scholar

7. Wang, Q., p*rnrungroj, C., Linley, S. & Reisner, E. Strategies to improve light utilization in solar fuel synthesis. Nat. Energy 7, 13–24 (2022).

   Google Scholar

8. Zou, Z., Ye, J., Sayama, K. & Arakawa, H. Direct splitting of water under visible light irradiation with an oxide semiconductor photocatalyst. Nature 414, 625–627 (2001).

   PubMed CAS Google Scholar

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

   PubMed CAS Google Scholar

10. Takata, T. et al. Photocatalytic water splitting with a quantum efficiency of almost unity. Nature 581, 411–414 (2020).

    PubMed CAS Google Scholar

11. Nishiyama, H. et al. Photocatalytic solar hydrogen production from water on a 100-m² scale. Nature 598, 304–307 (2021).

    PubMed CAS Google Scholar

12. Zhou, P. et al. Solar-to-hydrogen efficiency of more than 9% in photocatalytic water splitting. Nature 613, 66–70 (2023).

    PubMed CAS Google Scholar

13. 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).

    PubMed PubMed Central CAS Google Scholar

14. Song, X. et al. Overall photocatalytic water splitting by an organolead iodide crystalline material. Nat. Catal. 3, 1027–1033 (2020).

    CAS Google Scholar

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15. Larom, S., Salama, F., Schuster, G. & Adir, N. Engineering of an alternative electron transfer path in photosystem II. Proc. Natl Acad. Sci. USA 107, 9650–9655 (2010).

    PubMed PubMed Central CAS Google Scholar

16. Dods, R. et al. Ultrafast structural changes within a photosynthetic reaction centre. Nature 589, 310–314 (2021).

    PubMed CAS Google Scholar

17. Grabowski, Z. R., Rotkiewicz, K. & Rettig, W. Structural changes accompanying intramolecular electron transfer: focus on twisted intramolecular charge-transfer states and structures. Chem. Rev. 103, 3899–4032 (2003).

    PubMed Google Scholar

18. Wang, Y. et al. Current understanding and challenges of solar-driven hydrogen generation using polymeric photocatalysts. Nat. Energy 4, 746–760 (2019).

    CAS Google Scholar

19. Furukawa, H., Cordova, K. E., O’Keeffe, M. & Yaghi, O. M. The chemistry and applications of metal–organic frameworks. Science 341, 1230444 (2013).

    PubMed Google Scholar

20. Li, G., Zhao, S., Zhang, Y. & Tang, Z. Metal–organic frameworks encapsulating active nanoparticles as emerging composites for catalysis: recent progress and perspectives. Adv. Mater. 30, 1800702 (2018).

    Google Scholar

21. Hu, H. et al. Metal–organic frameworks embedded in a liposome facilitate overall photocatalytic water splitting. Nat. Chem. 13, 358–366 (2021).

    PubMed CAS Google Scholar

22. Stanley, P. M., Haimerl, J., Shustova, N. B., Fischer, R. A. & Warnan, J. Merging molecular catalysts and metal–organic frameworks for photocatalytic fuel production. Nat. Chem. 14, 1342–1356 (2022).

    PubMed CAS Google Scholar

23. Navalón, S., Dhakshinamoorthy, A., Álvaro, M., Ferrer, B. & García, H. Metal–organic frameworks as photocatalysts for solar-driven overall water splitting. Chem. Rev. 123, 445–490 (2023).

    PubMed Google Scholar

24. Nguyen, H. L. Metal–organic frameworks for photocatalytic water splitting. Sol. RRL 5, 2100198 (2021).

    CAS Google Scholar

25. Nguyen, H. L. Metal–organic frameworks can photocatalytically split water—why not? Adv. Mater. 34, 2200465 (2022).

    CAS Google Scholar

26. Jiao, L., Wang, J. & Jiang, H.-L. Microenvironment modulation in metal–organic framework-based catalysis. Acc. Mater. Res. 2, 327–339 (2021).

    CAS Google Scholar

27. Schmieder, P. et al. CFA-1: the first chiral metal–organic framework containing Kuratowski-type secondary building units. Dalton Trans. 42, 10786–10797 (2013).

    PubMed CAS Google Scholar

28. Braslavsky, S. E. et al. Glossary of terms used in photocatalysis and radiation catalysis (IUPAC Recommendations 2011). Pure Appl. Chem. 83, 931–1014 (2011).

    CAS Google Scholar

29. Lachmanová, Š. et al. Kinetics of multielectron transfers and redox-induced structural changes in N-aryl-expanded pyridiniums: establishing their unusual, versatile electrophoric activity. J. Am. Chem. Soc. 137, 11349–11364 (2015).

    PubMed Google Scholar

30. Damrauer, N. H. et al. Effects of intraligand electron delocalization, steric tuning, and excited-state vibronic coupling on the photophysics of aryl-substituted bipyridyl complexes of Ru(II). J. Am. Chem. Soc. 119, 8253–8268 (1997).

    CAS Google Scholar

31. Wang, H. et al. High quantum efficiency of hydrogen production from methanol aqueous solution with PtCu–TiO₂ photocatalysts. Nat. Mater. 22, 619–626 (2023).

    PubMed CAS Google Scholar

32. Fu, C. et al. Spontaneous bulk-surface charge separation of TiO₂-{001} nanocrystals leads to high activity in photocatalytic methane combustion. ACS Catal. 12, 6457–6463 (2022).

    CAS Google Scholar

33. An, Y. et al. Ni^II coordination to an Al-based metal-organic framework made from 2-aminoterephthalate for photocatalytic overall water splitting. Angew. Chem. Int. Ed. 56, 3036–3040 (2017).

    CAS Google Scholar

34. Zhang, J. et al. Metal–organic-framework-based photocatalysts optimized by spatially separated cocatalysts for overall water splitting. Adv. Mater. 32, 2004747 (2020).

    CAS Google Scholar

35. Salcedo-Abraira, P. et al. A novel porous Ti-squarate as efficient photocatalyst in the overall water splitting reaction under simulated sunlight irradiation. Adv. Mater. 33, 2106627 (2021).

    CAS Google Scholar

36. Nyakuchena, J. et al. Direct evidence of photoinduced charge transport mechanism in 2D conductive metal organic frameworks. J. Am. Chem. Soc. 142, 21050–21058 (2020).

    PubMed CAS Google Scholar

37. Shi, M. et al. Intrinsic facet-dependent reactivity of well-defined BiOBr nanosheets on photocatalytic water splitting. Angew. Chem. Int. Ed. 59, 6590–6595 (2020).

    CAS Google Scholar

38. Liu, Y. et al. Phase-enabled metal–organic framework hom*ojunction for highly selective CO₂ photoreduction. Nat. Commun. 12, 1231 (2021).

    PubMed PubMed Central CAS Google Scholar

39. Bottaro, S. & Lindorff-Larsen, K. Biophysical experiments and biomolecular simulations: a perfect match? Science 361, 355–360 (2018).

    PubMed CAS Google Scholar

40. Hu, S. et al. Proton transport through one-atom-thick crystals. Nature 516, 227–230 (2014).

    PubMed CAS Google Scholar

41. Santaclara, J. G. et al. Organic linker defines the excited-state decay of photocatalytic MIL-125(Ti)-type materials. ChemSusChem 9, 388–395 (2016).

    PubMed CAS Google Scholar

42. Rachuri, Y., Parmar, B., Bisht, K. K. & Suresh, E. Mixed ligand two dimensional Cd(II)/Ni(II) metal organic frameworks containing dicarboxylate and tripodal N-donor ligands: Cd(II) MOF is an efficient luminescent sensor for detection of picric acid in aqueous media. Dalton Trans. 45, 7881–7892 (2016).

    PubMed CAS Google Scholar

43. Huang, G.-Q. et al. Mixed-linker isoreticular Zn(II) metal–organic frameworks as Brønsted acid–base bifunctional catalysts for Knoevenagel condensation reactions. Inorg. Chem. 61, 8339–8348 (2022).

    PubMed CAS Google Scholar

44. Bien, C. E. et al. Bioinspired metal–organic framework for trace CO₂ capture. J. Am. Chem. Soc. 140, 12662–12666 (2018).

    PubMed CAS Google Scholar

45. Ketchie, W., Murayama, M. & Davis, R. Promotional effect of hydroxyl on the aqueous phase oxidation of carbon monoxide and glycerol over supported Au catalysts. Top. Catal. 44, 307 (2007).

    CAS Google Scholar

46. Kühne, T. D. et al. CP2K: an electronic structure and molecular dynamics software package—Quickstep: efficient and accurate electronic structure calculations. J. Chem. Phys. 152, 194103 (2020).

    PubMed Google Scholar

47. VandeVondele, J. et al. QUICKSTEP: fast and accurate density functional calculations using a mixed Gaussian and plane waves approach. Comput. Phys. Commun. 167, 103–128 (2005).

    CAS Google Scholar

48. Kohn, W. & Sham, L. J. Self-consistent equations including exchange and correlation effects. J. Phys. Rev. 140, A1133–A1138 (1965).

    Google Scholar

49. VandeVondele, J. & Hutter, J. Gaussian basis sets for accurate calculations on molecular systems in gas and condensed phases. J. Chem. Phys. 127, 114105 (2007).

    PubMed Google Scholar

50. Goedecker, S., Teter, M. & Hutter, J. Separable dual-space Gaussian pseudopotentials. Phys. Rev. B 54, 1703–1710 (1996).

    CAS Google Scholar

51. Heyd, J., Scuseria, G. E. & Ernzerhof, M. Hybrid functionals based on a screened Coulomb potential. J. Chem. Phys. 118, 8207–8215 (2003).

    CAS Google Scholar

52. Blochl, P. E., Jepsen, O. & Andersen, O. K. Improved tetrahedron method for Brillouin-zone integrations. Phys. Rev. B 50, 17953–17979 (1994).

    CAS Google Scholar

53. Perdew, J. P., Burke, K. & Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 77, 3865–3868 (1996).

    PubMed CAS Google Scholar

54. Nørskov, J. K. et al. Origin of the overpotential for oxygen reduction at a fuel-cell cathode. J. Phys. Chem. B 108, 17886–17892 (2004).

    Google Scholar

55. Chu, W. et al. Ultrafast dynamics of photongenerated holes at a CH₃OH/TiO₂ rutile interface. J. Am. Chem. Soc. 138, 13740–13749 (2016).

    PubMed CAS Google Scholar

56. Craig, C. F., Duncan, W. R. & Prezhdo, O. V. Trajectory surface hopping in the time-dependent Kohn–Sham approach for electron-nuclear dynamics. Phys. Rev. Lett. 95, 163001 (2005).

    PubMed Google Scholar

57. Akimov, A. V. & Prezhdo, O. V. The PYXAID program for non-adiabatic molecular dynamics in condensed matter systems. J. Chem. Theory and Comput. 9, 4959–4972 (2013).

    CAS Google Scholar

58. Akimov, A. V. & Prezhdo, O. V. Advanced capabilities of the PYXAID program: integration schemes, decoherence effects, multiexcitonic states, and field–matter interaction. J. Chem. Theory Comput. 10, 789–804 (2014).

    PubMed CAS Google Scholar

59. Nose, S. A unified formulation of the constant temperature molecular-dynamics methods. J. Chem. Phys. 81, 511–519 (1984).

    CAS Google Scholar

60. Barducci, A., Bussi, G. & Parrinello, M. Well-tempered metadynamics: a smoothly converging and tunable free-energy method. Phys. Rev. Lett. 100, 020603 (2008).

    PubMed Google Scholar

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