Synthesis of carboxylated chlorophylls and their application as functional materials

Sasaki, Shin‐ichi; Ikeuchi, Toshitaka; Tamiaki, Hitoshi

doi:10.1142/s1088424615500418

Cited by 25 publications

(9 citation statements)

References 11 publications

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“…As one of the most abundant natural photosynthetic pigmentsonearth, chlorophylls (Chls) were selected to convert solar energy into chemical energy based on absorbing sunlight and transferring absorbed energy,d ue to the delocalization of their excited electrons around the p-conjugated tetrapyrrole ring. [8][9][10] The remarkable properties of the charge-transfer ability of Chls have been reported previously.I tw as shown that they could form aggregates to efficiently captures unlight and transport chargec ompared with their monomers. Such properties of Chl derivatives have been applied in solar cells, [11][12][13] energys torage, [14] and photocatalytic hydrogen evolution.…”

Section: Introductionmentioning

confidence: 63%

“…This potential Z‐scheme of particular concern in photoinduced electron‐transport chain processes led us to design dual photoexcitation‐based photocatalysts. As one of the most abundant natural photosynthetic pigments on earth, chlorophylls (Chls) were selected to convert solar energy into chemical energy based on absorbing sunlight and transferring absorbed energy, due to the delocalization of their excited electrons around the π‐conjugated tetrapyrrole ring [8–10] . The remarkable properties of the charge‐transfer ability of Chls have been reported previously.…”

Section: Introductionmentioning

confidence: 99%

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Chlorophyll‐Based Organic Heterojunction on Ti₃C₂T_x MXene Nanosheets for Efficient Hydrogen Production

Sun

Zheng

et al. 2021

Chemistry A European J

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The Z‐scheme process is a photoinduced electron‐transfer pathway in natural oxygenic photosynthesis involving electron transport from photosystem II (PSII) to photosystem I (PSI). Inspired by the interesting Z‐scheme process, herein a photocatalytic hydrogen evolution reaction (HER) employing chlorophyll (Chl) derivatives, Chl‐1 and Chl‐2, on the surface of Ti3C2Tx MXene with two‐dimensional accordion‐like morphology, forming Chl‐1@Chl‐2@Ti3C2Tx composite, is demonstrated. Due to the frontier molecular orbital energy alignments of Chl‐1 and Chl‐2, sublayer Chl‐1 is a simulation of PSI, whereas upper layer Chl‐2 is equivalent to PSII, and the resultant electron transport can take place from Chl‐2 to Chl‐1. Under the illumination of visible light (>420 nm), the HER performance of Chl‐1@Chl‐2@Ti3C2Tx photocatalyst was found to be as high as 143 μmol h−1 gcat−1, which was substantially higher than that of photocatalysts of either Chl‐1@Ti3C2Tx (20 μmol h−1 g−1) or Chl‐2@Ti3C2Tx (15 μmol h−1 g−1).

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Section: Introductionmentioning

confidence: 63%

Section: Introductionmentioning

confidence: 99%

Chlorophyll‐Based Organic Heterojunction on Ti₃C₂T_x MXene Nanosheets for Efficient Hydrogen Production

Sun

Zheng

et al. 2021

Chemistry A European J

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“…Direct introduction of a carboxy group on the Chl macrocycle as in Chl‐15, 16, and 17 showed improved efficiency compared with the reported Chl‐2 but later Chl derivatives with C3‐acrylic acid was found to show better performance . The effects of tetrapyrrole skeleton (BChl‐2 and 3), steric and electronic substituent at the C20‐ (Chl‐18, 19, 20, and 21) and C13‐position (Chl‐18, 22, and 23), central metal ((Zn)Chl‐18, 24, and 25), C17‐ (Chl‐26, 27, 28, and 29) or C13/15/17‐alkyl chain (Chl‐30, 31, 32, and 33) were investigated in detail, and PCE of 8% was achieved after optimization. Because a carboxy group at the C3‐position of Chl‐15 caused PCE of 3.8% and increased to 6.5% upon insertion of an ethenylene group between the carboxy group and the C3‐position of the Chl π‐skeleton as in Chl‐18, the effect of spacer length and π‐conjugation was further investigated.…”

Section: Application Of Carboxylated Chlorophyll Derivatives To Dsscsmentioning

confidence: 93%

Semisynthetic Chlorophyll Derivatives Toward Solar Energy Applications

Duan

Zhou

et al. 2020

Solar RRL

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Plenty of thin‐film solar cell technologies using organic materials have been developed to alleviate energy shortages. As developing devices for solar energy applications, artificial photosynthesis is a trend inspired from natural photosynthesis. Although the sophisticated system that exists in nature is fascinating, the development of photovoltaic devices focusing on the usage of natural chlorophylls has been quite limited, compared with the application of other counterparts such as artificial porphyrins or phthalocyanines. Herein, the development of semisynthetic chlorophyll derivatives as functional materials for solar cells are focused on. (Bacterio)chlorins possessing a carboxylic acid moiety as a binding site to semiconductors are synthesized to improve the efficiencies of dye‐sensitized solar cells, which are now leading to another application: photocatalysts for hydrogen evolution. In contrast, derivatives without a carboxy group can be applied to organic solar cells. As for the application for perovskite solar cells, self‐assembling aggregates of a kind of derivatives are proven to be suitable as hole‐transporting materials. In addition, a new type of solid‐state biosolar cells is proposed, in which chlorophyll derivatives act solely as the photoactive materials. This Report can enlarge the scope of advanced functional materials in the field of solar energy applications.

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“…For introducing the C3 2 -carboxylic acid moiety as a binding and electron-injecting site to TiO 2 , Wittig reaction of the C3-formyl group with (tertbutoxycarbonylmethylene)triphenylphosphoran, and the following cleavage of the tert-butyl ester in TFA were applied. [51] To obtain tert-butyl ester 7 from 8, initial Wittig reaction (8→9: 86%) followed by ester formation (9+Car-COOH: 69%) showed a slightly better yield compared to 8→6→7 (60% × 90% = 54%). The subsequent cleavage of tert-butyl ester in 7 gave Dyad-COOH in 80% yield, which was better than the direct conversion of C3-formyl to C3-acrylic acid group by excess maleic acid [52] resulting in 41% yield in the case of carotenoid-chlorin 6 to Dyad-COOH.…”

Section: Design and Synthesis Of Dyad Sensitizersmentioning

confidence: 98%

Semi‐Synthetic Chlorophyll‐Carotenoid Dyad for Dye‐Sensitized Photocatalytic Hydrogen Evolution

Liu

Chen

et al. 2021

Adv Materials Inter

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attractive and challenging researches in the field of artificial photosynthesis. [1][2][3] Photocatalytic hydrogen evolution (PHE) has been in the spotlight as it is a highly prospective approach to convert and store the solar energy into hydrogen energy efficiently to meet future global energy demand. Thus development of photocatalysis for PHE is considered to be a matter of central focus to solve the problem of energy shortage and environmental pollution. [4][5][6] PHE systems based on various kinds of semiconductors have been extensively investigated so far, [7,8] among which Pt/TiO 2 has been regarded as one of the most major photocatalysts. [9][10][11][12][13] To overcome the inherent defects of TiO 2 such as large band gap which leads to low photocatalytic efficiency, some research groups reported the development of dye-sensitized Pt/TiO 2 photocatalysts for hydrogen evolution. [14][15][16][17] A recent trend for sensitizing Pt/TiO 2 is the use of metal-free organic dyes with strong absorptivity and panchromatic sensitization properties. [18][19][20] For example, perylene-quinoxaline, [21] porphyrin-BODIPY, [22] phenothiazine-BODIPY, [23] thienopyrazine-triarylamine, [24] or multicarbazole [25] have been developed as covalently-linked multichromophore sensitizers for Pt/TiO 2 -based catalysts to realize efficient light absorption. In this context, we recently reported a dyad sensitizer of chlorophyll derivative connected with indoline dye for panchromatic PHE. [26] The high photocatalytic activity of dyad was attributed to not only an excellent A chlorin-carotenoid dyad Dyad-COOH possessing a C3 2 -carboxylic acid group and a carotenoid moiety at the terminal end of C17-substituent is synthesized from naturally occurring chlorophyll-a as a new sensitizer for photocatalytic hydrogen evolution (PHE). Under the same experimental conditions, a maximum turnover number (TON) of PHE based on Dyad-COOH/Pt/TiO 2 is much higher than those of Pt/TiO 2 -based photocatalysts sensitized by the corresponding chlorin carboxylic acid (Chl-COOH) without carotenoid side chain, sole carotenoic acid (Car-COOH), or their 1:1 (mol/mol) mixture. By coadsorbing different types of carboxylic acid, the TON of Chl-COOH is found to be increased probably due to the suppression of chlorin aggregates on the TiO 2 surface. The Dyad-COOH/Pt/TiO 2 exhibits excellent photocatalytic performance with the hydrogen evolution of 9147 µmol g −1 h −1 with TON of 425 when 43 µmol g −1 of dye is loaded on the Pt/TiO 2 catalyst, while a better TON of 556 is achieved by preparing the photocatalyst with 10 µmol g −1 of Dyad-COOH. This study provides new ideas for utilizing traditional photosynthetic dyes to a low-cost and highly-efficient photosensitizer for PHE.

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Synthesis of carboxylated chlorophylls and their application as functional materials

Cited by 25 publications

References 11 publications

Chlorophyll‐Based Organic Heterojunction on Ti₃C₂T_x MXene Nanosheets for Efficient Hydrogen Production

Chlorophyll‐Based Organic Heterojunction on Ti₃C₂T_x MXene Nanosheets for Efficient Hydrogen Production

Semisynthetic Chlorophyll Derivatives Toward Solar Energy Applications

Semi‐Synthetic Chlorophyll‐Carotenoid Dyad for Dye‐Sensitized Photocatalytic Hydrogen Evolution

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Synthesis of carboxylated chlorophylls and their application as functional materials

Cited by 25 publications

References 11 publications

Chlorophyll‐Based Organic Heterojunction on Ti3C2Tx MXene Nanosheets for Efficient Hydrogen Production

Chlorophyll‐Based Organic Heterojunction on Ti3C2Tx MXene Nanosheets for Efficient Hydrogen Production

Semisynthetic Chlorophyll Derivatives Toward Solar Energy Applications

Semi‐Synthetic Chlorophyll‐Carotenoid Dyad for Dye‐Sensitized Photocatalytic Hydrogen Evolution

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Chlorophyll‐Based Organic Heterojunction on Ti₃C₂T_x MXene Nanosheets for Efficient Hydrogen Production

Chlorophyll‐Based Organic Heterojunction on Ti₃C₂T_x MXene Nanosheets for Efficient Hydrogen Production