高分子铝卟啉催化下环氧化物与二氧化碳的光热聚合

周浩; 刘顺杰; 陈佩; 曹瀚; 卓春伟; 王献红

doi:10.11777/j.issn1000-3304.2025.25143

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高分子铝卟啉催化下环氧化物与二氧化碳的光热聚合

研究论文 | 更新时间：2025-08-05

- 高分子铝卟啉催化下环氧化物与二氧化碳的光热聚合
- Photothermal Polymerization of Epoxides and Carbon Dioxide Catalyzed by Polymeric Aluminum Porphyrin
- 高分子学报 2025年页码：1-11
- 作者机构：
  
  1.中国科学技术大学应用化学与工程学院合肥 230026
  2.中国科学院长春应用化学研究所高分子科学与技术全国重点实验室长春 130022
- 作者简介：
  
  E-mail: sjliu@ciac.ac.cn
  xhwang@ciac.ac.cn
- 基金信息：
  
  本文附有电子支持信息，与正文一并刊登在本刊网站(www.gfzxb.org)
- DOI：10.11777/j.issn1000-3304.2025.25143
  中图分类号：
- CSTR：32057.14.GFZXB.2025.7446
- 收稿日期：2025-06-10，
  
  录用日期：2025-07-04，
  
  网络出版日期：2025-08-04，
- 稿件说明：
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周浩, 刘顺杰, 陈佩, 曹瀚, 卓春伟, 王献红. 高分子铝卟啉催化下环氧化物与二氧化碳的光热聚合. 高分子学报, doi: 10.11777/j.issn1000-3304.2025.25143

Zhou, H.; Liu, S. J.; Chen, P.; Cao, H.; Zhuo, C. W.; Wang, X. H. Photothermal polymerization of epoxides and carbon dioxide catalyzed by polymeric aluminum porphyrin. Acta Polymerica Sinica, doi: 10.11777/j.issn1000-3304.2025.25143
周浩, 刘顺杰, 陈佩, 曹瀚, 卓春伟, 王献红. 高分子铝卟啉催化下环氧化物与二氧化碳的光热聚合. 高分子学报, doi: 10.11777/j.issn1000-3304.2025.25143 DOI： CSTR： 32057.14.GFZXB.2025.7446.

Zhou, H.; Liu, S. J.; Chen, P.; Cao, H.; Zhuo, C. W.; Wang, X. H. Photothermal polymerization of epoxides and carbon dioxide catalyzed by polymeric aluminum porphyrin. Acta Polymerica Sinica, doi: 10.11777/j.issn1000-3304.2025.25143 DOI： CSTR： 32057.14.GFZXB.2025.7446.

摘要

光热聚合兼备光响应的时空可控性与热聚合的高效性，具有广阔的应用前景. 本研究设计开发了铝卟啉主链型高分子催化剂(P

(

-Cat)用于催化环氧化物与CO

的高效光热聚合. P

(

-Cat采用模块化合成策略，为系统研究其结构与性能关系提供了基础. 研究表明，随着活性中心间距的增大(

10)，P

(

-Cat的分子内协同效应减弱，而光热效率保持稳定(

≈23.8%). 随着卟啉meso位苯环对位取代基吸电子能力增强(R=

Br)，催化剂的协同效应增强，但光热效率依次下降(30.9%、23.8%、15.8%). 综合催化剂的协同效应与光热转换能力，P

-Cat在催化环氧丙烷(PO)与CO

光热聚合时具有最佳的性能(TOF=660 h

-1

，聚合物选择性

99%). 此外，多活性中心的局部富集效应使其在极低催化剂用量下([PO

]

/[Al

]

=20000/1)仍能保持催化性能. 本研究不仅优化了光热聚合体系，也为催化剂的模块化设计提供了新思路.

Abstract

Photothermal polymerization offers both the spatiotemporal controllability of light-responsive processes and the high efficiency of thermal polymerization

making it highly promising for practical applications. In this work

an aluminum porphyrin backbone polymeric catalyst (P

(

-Cat) was developed for the efficient photothermal copolymerization of epoxides and CO

. The modular synthesis strategy provides a basis for systematically studying the structure-performance relationship of P

(

-Cat. The study showed that increasing the spatial distance of the active centers (

10) impaired the synergistic effect of P

(

-Cat

but the photothermal efficiency remained stable (

≈23.8%). Meanwhile

as the electron-withdrawing ability of the

para

-substituent of porphyrin meso-benzene increases (R =

Br)

the synergistic effect of the catalyst increases

but the

decreases (30.9%

23.8%

15.8%). Taking into account both synergistic catalysis and photothermal performance

-Cat exhibited the best catalytic activity in the photothermal copolymerization of propylene oxide (PO) and CO

(TOF=660 h⁻

polymer selectivity

99%). Moreover

due to the local enrichment of multiple active centers

-Cat maintained catalytic performance even at extremely low loadings ([PO

]

/[Al

]

=20000/1). This study not only optimizes photothermal polymerization systems but also offers a new perspective on the modular design of polymer catalysts.

关键词

Keywords

references

Saini N. ; Malik A. ; Jain S. L. Light driven chemical fixation and conversion of CO 2 into cyclic carbonates using transition metals: A review on recent advancements . Coord. Chem. Rev. , 2024 , 502 , 215636 . doi: 10.1016/j.ccr.2023.215636 http://dx.doi.org/10.1016/j.ccr.2023.215636

Chen G. B. ; Waterhouse G. I. N. ; Shi R. ; Zhao J. Q. ; Li Z. H. ; Wu L. Z. ; Tung C. H. ; Zhang T. R. From solar energy to fuels: recent advances in light-driven C1 chemistry . Angew. Chem. Int. Ed. , 2019 , 58 ( 49 ), 17528 - 17551 . doi: 10.1002/anie.201814313 http://dx.doi.org/10.1002/anie.201814313

Dai L. ; Zhang Z. F. ; Chen X. Y. Reduction of unactivated alkyl chlorides enabled by light-induced single electron transfer . Sci. China Chem. , 2024 , 67 ( 2 ), 471 - 481 . doi: 10.1007/s11426-023-1787-3 http://dx.doi.org/10.1007/s11426-023-1787-3

Steinhardt R. C. ; Steeves T. M. ; Wallace B. M. ; Moser B. ; Fishman D. A. ; Esser-Kahn A. P. Photothermal nanoparticle initiation enables radical polymerization and yields unique, uniform microfibers with broad spectrum light . ACS Appl. Mater. Interfaces , 2017 , 9 ( 44 ), 39034 - 39039 . doi: 10.1021/acsami.7b12230 http://dx.doi.org/10.1021/acsami.7b12230

Rejeb R. ; Lenormand P. ; Bichot G. ; Gigmes D. ; Dumur F. ; Schmitt M. ; Pinaud J. ; Lalevée J. NIR photothermal activation in epoxy/anhydride systems for advanced polymerization . Eur. Polym. J. , 2025 , 222 , 113589 . doi: 10.1016/j.eurpolymj.2024.113589 http://dx.doi.org/10.1016/j.eurpolymj.2024.113589

Bonardi A. H. ; Bonardi F. ; Noirbent G. ; Dumur F. ; Gigmes D. ; Dietlin C. ; Lalevée J. Free-radical polymerization upon near-infrared light irradiation, merging photochemical and photothermal initiating methods . J. Polym. Sci. , 2020 , 58 ( 2 ), 300 - 308 . doi: 10.1002/pol.20190079 http://dx.doi.org/10.1002/pol.20190079

Chen P. ; Zhou H. ; Cao H. ; Zhuo C. W. ; Liu S. J. ; Wang X. H. Polymeric catalyst with polymerization-enhanced lewis acidity for CO 2 -based copolymers . Chin. Chem. Lett. , 2023 , 34 ( 12 ), 108630 . doi: 10.1016/j.cclet.2023.108630 http://dx.doi.org/10.1016/j.cclet.2023.108630

Diment W. T. ; Lindeboom W. ; Fiorentini F. ; Deacy A. C. ; Williams C. K. Synergic heterodinuclear catalysts for the ring-opening copolymerization (ROCOP) of epoxides, carbon dioxide, and anhydrides . Acc. Chem. Res. , 2022 , 55 ( 15 ), 1997 - 2010 . doi: 10.1021/acs.accounts.2c00197 http://dx.doi.org/10.1021/acs.accounts.2c00197

Cao H. ; Liu S. J. ; Wang X. H. Environmentally benign metal catalyst for the ring-opening copolymerizati on of epoxide and CO 2 : state-of-the-art, opportunities, and challenges . Green Chem. Eng. , 2022 , 3 ( 2 ), 111 - 124 . doi: 10.1016/j.gce.2021.11.005 http://dx.doi.org/10.1016/j.gce.2021.11.005

Inoue S. ; Koinuma H. ; Tsuruta T. Copolymerization of carbon dioxide and epoxide . J. Polym. Sci., Part B : Polym. Lett., 1969 , 7 ( 4 ), 287 - 292 . doi: 10.1002/pol.1969.110070408 http://dx.doi.org/10.1002/pol.1969.110070408

Yang G. W. ; Xie R. ; Zhang Y. Y. ; Xu C. K. ; Wu G. P. Evolution of copolymers of epoxides and CO 2 : catalysts, monomers, architectures, and applications . Chem. Rev. , 2024 , 124 ( 21 ), 12305 - 12380 . doi: 10.1021/acs.chemrev.4c00517 http://dx.doi.org/10.1021/acs.chemrev.4c00517

Bhat G. A. ; Darensbourg D. J. Coordination complexes as catalysts for the coupling reactions of oxiranes and carbon dioxide . Coord. Chem. Rev. , 2023 , 492 , 215277 . doi: 10.1016/j.ccr.2023.215277 http://dx.doi.org/10.1016/j.ccr.2023.215277

Wang X. H. Biodegradable polymers, history tells polymer science's fortune . Chin. J. Polym. Sci. , 2022 , 40 ( 5 ), 431 - 432 . doi: 10.1007/s10118-022-2737-x http://dx.doi.org/10.1007/s10118-022-2737-x

Zhuo C. W. ; Cao H. ; You H. ; Liu S. J. ; Wang X. H. ; Wang F. S. Two-in-one: photothermal ring-opening copolymerization of CO 2 and epoxides . ACS Macro Lett. , 2022 , 11 ( 7 ), 941 - 947 . doi: 10.1021/acsmacrolett.2c00365 http://dx.doi.org/10.1021/acsmacrolett.2c00365

Guo B. ; Feng G. X. ; Manghnani P. N. ; Cai X. L. ; Liu J. ; Wu W. B. ; Xu S. D. ; Cheng X. M. ; Teh C. ; Liu B. A porphyrin-based conjugated polymer for highly efficient in vitro and in vivo photothermal therapy . Small , 2016 , 12 ( 45 ), 6243 - 6254 . doi: 10.1002/smll.201602293 http://dx.doi.org/10.1002/smll.201602293

Zou Q. L. ; Abbas M. ; Zhao L. Y. ; Li S. K. ; Shen G. Z. ; Yan X. H. Biological photothermal nanodots based on self-assembly of peptide-porphyrin conjugates for antitumor therapy . J. Am. Chem. Soc. , 2017 , 139 ( 5 ), 1921 - 1927 . doi: 10.1021/jacs.6b11382 http://dx.doi.org/10.1021/jacs.6b11382

Wu F. ; Sun Y. F. ; Gao H. ; Zhi X. ; Zhao Y. ; Shen Z. Boosting near-infrared photothermal/photoacoustic conversion performance of anthracene-fused porphyrin via paramagnetic ion coordination strategy . Sci. China Chem. , 2023 , 66 ( 1 ), 164 - 173 . doi: 10.1007/s11426-022-1409-3 http://dx.doi.org/10.1007/s11426-022-1409-3

Zhou H. ; Liu S. J. ; Chen P. ; Yang L. H. ; Zhuo C. W. ; Gao F. X. ; Pang X. ; Chen X. S. ; Wang X. H. Polymeric catalyst with discrete distributed active centers for regulating backbone structure of poly(propylene carbonate) . Chin. J. Chem. , 2024 , 42 ( 21 ), 2599 - 2606 . doi: 10.1002/cjoc.202400398 http://dx.doi.org/10.1002/cjoc.202400398

Zhuo C. W. ; You H. ; Gao F. X. ; Liu S. J. ; Wang X. H. ; Wang F. S. Bottlebrush polymeric catalyst: boosting activity for CO 2 /epoxide copolymerization . Fuel , 2023 , 333 , 126434 . doi: 10.1016/j.fuel.2022.126434 http://dx.doi.org/10.1016/j.fuel.2022.126434

刘克共 , 刘顺杰 , 范培鑫 , 张若禹 , 陈学思 , 王献红 . 双功能卟啉铝催化二氧化碳与长链末端环氧化物共聚 . 高分子学报 , 2025 , 56 ( 2 ), 242 - 252 .

Zhuo C. W. ; Qin Y. S. ; Wang X. H. ; Wang F. S. Temperature-responsive catalyst for the coupling reaction of carbon dioxide and propylene oxide . Chin. J. Chem. , 2018 , 36 ( 4 ), 299 - 305 . doi: 10.1002/cjoc.201800019 http://dx.doi.org/10.1002/cjoc.201800019

Wang K. J. ; Si H. ; Wan Q. ; Wang Z. M. ; Qin A. J. ; Tang B. Z. Luminescent two-way reversible shape memory polymers prepared by hydroxyl-yne click polymerization . J. Mater. Chem. C , 2020 , 8 ( 45 ), 16121 - 16128 . doi: 10.1039/d0tc03888a http://dx.doi.org/10.1039/d0tc03888a

Wang E. H. ; Liu S. J. ; Cao H. ; Zhuo C. W. ; Wang X. H. ; Wang F. S. Chain-transfer-catalyst: strategy for construction of site-specific functional CO 2 -based polycarbonates . Sci. China Chem. , 2022 , 65 ( 1 ), 162 - 169 . doi: 10.1007/s11426-021-1098-4 http://dx.doi.org/10.1007/s11426-021-1098-4

Cao H. ; Qin Y. S. ; Zhuo C. W. ; Wang X. H. ; Wang F. S. Homogeneous metallic oligomer catalyst with multisite intramolecular cooperativity for the synthesis of CO 2 -based polymers . ACS Catal. , 2019 , 9 ( 9 ), 8669 - 8676 . doi: 10.1021/acscatal.9b02741 http://dx.doi.org/10.1021/acscatal.9b02741

Yang L. H. ; Liu S. J. ; Zhou Z. Z. ; Zhang R. Y. ; Zhou H. ; Zhuo C. W. ; Wang X. H. Aggregate catalysts: regulating multimetal cooperativity for CO 2 /epoxide copolymerization . Macromolecules , 2024 , 57 ( 1 ), 150 - 161 . doi: 10.1021/acs.macromol.3c02222 http://dx.doi.org/10.1021/acs.macromol.3c02222

Si H. ; Wang K. J. ; Song B. ; Qin A. J. ; Tang B. Z. Organobase-catalysed hydroxyl-yne click polymerization . Polym. Chem. , 2020 , 11 ( 14 ), 2568 - 2575 . doi: 10.1039/d0py00095g http://dx.doi.org/10.1039/d0py00095g

Song B. ; Lu D. ; Qin A. J. ; Tang B. Z. Combining hydroxyl-yne and thiol-ene click reactions to facilely access sequence-defined macromolecules for high-density data storage . J. Am. Chem. Soc. , 2022 , 144 ( 4 ), 1672 - 1680 . doi: 10.1021/jacs.1c10612 http://dx.doi.org/10.1021/jacs.1c10612

Abraham R. J. The proton magnetic resonance spectra of porphyrins . Mol. Phys. , 1961 , 4 ( 2 ), 145 - 152 . doi: 10.1080/00268976100100191 http://dx.doi.org/10.1080/00268976100100191

Zheng W. Q. ; Shan N. ; Yu L. X. ; Wang X. Q. UV-visible, fluorescence and EPR properties of porphyrins and metalloporphyrins . Dyes Pigm. , 2008 , 77 ( 1 ), 153 - 157 . doi: 10.1016/j.dyepig.2007.04.007 http://dx.doi.org/10.1016/j.dyepig.2007.04.007

Choi M. S. One-dimensional porphyrin H-aggregates induced by solvent polarity . Tetrahedron Lett. , 2008 , 49 ( 49 ), 7050 - 7053 . doi: 10.1016/j.tetlet.2008.09.140 http://dx.doi.org/10.1016/j.tetlet.2008.09.140

Egawa Y. ; Hayashida R. ; Anzai J. I. pH-induced interconversion between J-aggregates and H-aggregates of 5 , 10 , 15 , 20-tetrakis( 4 -sulfonatophenyl)porphyrin in polyelectrolyte multilayer films . Langmuir , 2007, 23 ( 26 ), 13146 - 13150 . doi: 10.1021/la701957b http://dx.doi.org/10.1021/la701957b

Kuttassery F. ; Sagawa S. ; Mathew S. ; Nabetani Y. ; Iwase A. ; Kudo A. ; Tachibana H. ; Inoue H. Water splitting on aluminum porphyrins to form hydrogen and hydrogen peroxide by one photon of visible light . ACS Appl. Energy Mater. , 2019 , 2 ( 11 ), 8045 - 8051 . doi: 10.1021/acsaem.9b01552 http://dx.doi.org/10.1021/acsaem.9b01552

Lyu Y. ; Xie C. ; Chechetka S. A. ; Miyako E. ; Pu K. Y. Semiconducting polymer nanobioconjugates for targeted photothermal activation of neurons . J. Am. Chem. Soc. , 2016 , 138 ( 29 ), 9049 - 9052 . doi: 10.1021/jacs.6b05192 http://dx.doi.org/10.1021/jacs.6b05192

Zhao Y. W. ; Cai X. ; Zhang Y. ; Chen C. C. ; Wang J. E. ; Pei R. J. Porphyrin-based metal-organic frameworks: protonation induced Q band absorption . Nanoscale , 2019 , 11 ( 25 ), 12250 - 12258 . doi: 10.1039/c9nr02463h http://dx.doi.org/10.1039/c9nr02463h

Li Y. Y. ; Li G. C. ; Zhang Q. ; Li Y. X. ; Jia Q. F. ; Zhang W. Y. ; Feng X. X. ; Xu W. B. ; Liu J. C. Heavy atom effect on water-soluble porphyrin photosensitizers for photodynamic therapy . Chem. Phys. Lett. , 2021 , 784 , 139091 . doi: 10.1016/j.cplett.2021.139091 http://dx.doi.org/10.1016/j.cplett.2021.139091

Cao H. ; Zhang R. Y. ; Zhou Z. Z. ; Liu S. J. ; Tao Y. H. ; Wang F. S. ; Wang X. H. On-demand transformation of carbon dioxide into polymers enabled by a comb-shaped metallic oligomer catalyst . ACS Catal. , 2022 , 12 ( 1 ), 481 - 490 . doi: 10.1021/acscatal.1c04431 http://dx.doi.org/10.1021/acscatal.1c04431

Eisenhardt K. H. S. ; Fiorentini F. ; Lindeboom W. ; Williams C. K. Quantifying CO 2 insertion equilibria for low-pressure propene oxide and carbon dioxide ring opening copolymerization catalysts . J. Am. Chem. Soc. , 2024 , 146 ( 15 ), 10451 - 10464 . doi: 10.1021/jacs.3c13959 http://dx.doi.org/10.1021/jacs.3c13959

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