Porphyrins, graphitic carbon nitride and their hybrids for photocatalytic solar fuel generation

  • Lingling Li

Student thesis: Doctoral Thesis


Photocatalytic solar fuel generation is the most green, sustainable and viable approach to deal with both the ever-growing energy crisis and environmental issues, simultaneously. The work presented in this thesis is focused on the development of new organic carbonaceous semiconductors, typically, carbon quantum dots (CQDs) and graphitic carbon nitride (g-C3N4), and porphyrin small molecules and their hybrids with graphitic carbon nitride, meanwhile, their application in the field of photocatalytic solar fuel generation. In the chapter 1, a general review about background and mechanism of photocatalytic solar fuel generation are introduced first. Next, the features and developments of porphyrin and graphitic carbon nitride for the photocatalytic redox reaction are discussed. In chapter 2, the synthesis, characterization methods and photocatalytic experiment in details are described. In chapter 3, gram-scale CQDs are facilely synthesized by simple thermal treatment of citric acid monohydrate, and microporous 1D nanorods of g-C3N4 are prepared through template-free chemical approach. The photocatalytic properties of 1D protonated g-C3N4 (HCN) modified with different amount of CQDs were evaluated by the rate of H2- evolution under visible light irritation. The results demonstrate that g-C3N4/CQDs with the optimal CQDs amount of 0.25 wt.% afford the highest H2-production rate of 382 μmol h-1 g-1 with apparent quantum yield (AQY) of 1.9% which was about 3-fold of pure g- C3N4. The composite g-C3N4/CQDs show a remarkable stability against the photocorrosion within a continuous experiment period over 12h. The enhanced photocatalytic H2-production activity could be attribute to the intimate interface between CQDs and g-C3N4, which not only significantly improves the visible-light absorption, but also prolongs the lifetime of charge carriers and suppresses the recombination of photogenerated electron-hole pairs. This work showed that low-cost and metal-free CQDs could be an efficient photosensitizer to promote photocatalytic hydrogen generation. In chapter 4, we reported a new array of push-pull isomeric naphthalimide- porphyrins (ZnT(p-NI)PP) to investigate the effect of naphthalimide and molecular constitution on light driven hydrogen evolution from water splitting. These compounds were synthesized by integration of four naphthalimide moieties on meso-substituion of porphyrin macrocycle through para phenyl linker. Porphyrins were characterized by UV- Vis, Fluorescence and DFT calculations and compared with those of zinc tertapheylporphyrin (ZnTPP). When these porphyrins were employed as photocatalyst for the photocatalytic hydrogen production (PHP) with platinum co-catalyst, they delivered high hydrogen efficiency compared to that of ZnTPP. Particularly, ZnT(p-NI)PP exhibited 203 times higher hydrogen efficiency than the ZnTPP. This could be ascribed to the efficient exciton dissociation into holes and electrons at the photoexcited state of ZnT(p-NI)PP and then electrons were transferred to the proton through platinum. These results indicate that introduction of naphthalimide at meso-position of porphyrin through para phenyl linker is a versatile strategy to improve the photocatalytic hydrogen evolution of porphyrin based materials. In addition, the other two isomeric naphthalimide conjugated porphyrins through meta-and ortho-phenyl linker, ZnT(m-NI)PP and ZnT(o-NI)PP are also developed for photocatalytic H2 production. The para-linked isomer, ZnT(p-NI)PP delivered a much higher H2 production rate of 973 μmol h−1g -1 compared to that of ZnT(m-NI)PP (597 μmol h−1g −1) and ZnT(o-NI)PP (54 μmol h−1g −1), respectively. This could be attributed to the efficient intramolecular energy transfer from the naphthalimide to the porphyrin ring. In chapter 5, a series of NP/g-C3N4 hybrids of graphitic carbon nitride (g-C3N4) with naphthalimide-porphyrin (ZnT(p-NI)PP, labelled as NP) have been developed for photocatalytic hydrogen production. Planar naphthalimide-porphyrins are adsorbed onto flexible two-dimensional g-C3N4 through π-π stacking, which are characterized by scanning electronic microscopy and X-ray photoelectron spectroscopy. Except for its function as photosensitizer, NP in the hybrids could efficient inhibit the charge recombination by electron transfer for the lower lowest unoccupied molecular orbital of NP than g-C3N4, whereas facilitate energy transfer from g-C3N4 donor to NP acceptor for efficient overlap of emission spectrum of NP and absorption of g-C3N4. As a result, the hybrid containing weigh ratio of 2% NP (2%NP/g-C3N4) exhibits an enhanced photocatalytic hydrogen production rate (HPR) of 2297 μmol g−1 h −1, while pristine g- C3N4 shows a HPR of 698 μmol g−1 h −1. The 2%NP/g-C3N4 shows the best performance when compared with the reported hybrids of g-C3N4 with Zn(II) -tetrakis(4- carboxylphenyl) porphyrin (ZnTCPP/g-C3N4) and Zn(II)-tetrakis(4- hydroxyphenyl)porphyrin (ZnTHPP/g-C3N4) in photocatalytic hydrogen production under the same conditions. In the chapter 6, the future work on photocatalytic CO2 reduction, perspectives and conclusions are included

Date of Award20 May 2020
Original languageEnglish
SupervisorXunjin ZHU (Supervisor)

User-Defined Keywords

  • Porphyrins
  • Graphitic carbon nitride
  • Solar cells
  • Materials
  • Photocatalysis

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