Confined Polyhydroxylated C60 in Porphyrin COF Nanopore as Nanoreactor for CO2 Photoreduction

Shengzhong Hao; Xudong Yan; Haochun Yin; Hongqi Wang; Jiaxin Yu; Linlu Bai

doi:10.1007/s12209-026-00494-0

Transactions of Tianjin University ›› :1 -13. DOI: 10.1007/s12209-026-00494-0

Research Article

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Confined Polyhydroxylated C₆₀ in Porphyrin COF Nanopore as Nanoreactor for CO₂ Photoreduction

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¹Key Laboratory of Functional Inorganic Materials Chemistry (Ministry of Education), School of Chemistry and Materials Science, Heilongjiang University, 150080, Harbin, China

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^a 2025093@hlju.edu.cn

^b llbai@hlju.edu.cn

Haochun Yin

Haochun Yin is a postdoctoral researcher and assistant research fellow at Heilongjiang University. In recent years, his research has mainly focused on the design, synthesis, and performance investigation of photocatalytic nanoreactors based on covalent organic frameworks (COFs). By constructing two-dimensional COF nanosheets containing N-heterocyclic units and functionally confining ionic liquids through hydrogen-bonding, covalent-bonding, and ionic-bonding interactions, he has successfully developed a series of photocatalytic nanoreactors, enabling the selective conversion of CO₂ reduction products from C1 to C2 products. His related research achievements have been published as first-author or co-first-author papers in important international SCI journals, including Angewandte Chemie International Edition, Applied Catalysis B: Environmental, Advanced Energy Materials, and ACS Sustainable Chemistry & Engineering.

Linlu Bai

Linlu Bai is a professor in the School of Chemistry and Materials Science at Heilongjiang University and is affiliated with the Key Laboratory of Functional Inorganic Materials Chemistry (Heilongjiang University), Ministry of Education. She received his Ph.D. from the School of Chemical and Biomedical Engineering (SCBE) at Nanyang Technological University (NTU), Singapore. She has been selected for the High-Level Talent Program of Heilongjiang Province, the Outstanding Youth Project of the Heilongjiang Natural Science Foundation, and the High-Level Overseas Returnee Program of the Ministry of Human Resources and Social Security of China. His research focuses on the structure–activity relationship among the micro/nanostructure of photocatalysts, in situ dynamic photogenerated electron kinetics, and photocatalytic activity and selectivity. She aims to elucidate the dynamic mechanisms of photogenerated electrons and develop effective regulatory strategies to guide the design and synthesis of high-performance photocatalysts for chemical engineering applications. Over the past 5 yearsshe has led more than 10 research projects, including the General and Youth Programs of the National Natural Science Foundation of China, a sub-project of the National Key R&D Program in Engineering Science and Cross-discipline, the High-Level Overseas Returnee Program of the Ministry of Human Resources and Social Security, the Heilongjiang Natural Science Foundation, and the General Project of the China Postdoctoral Science Foundation. She has published 60 SCI-indexed papers, of which over 30 are first- or corresponding-author papers in prestigious journals such as Nature Communications, Angewandte Chemie International Edition, and Advanced Materials. She also serves as a young editorial board member for Transactions of Tianjin University, Acta Physico-Chimica Sinica, and Rare Metals.

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Abstract

The topological nanopores of covalent organic frameworks (COFs) are promising platforms for constructing photocatalytic nanoreactors for CO₂ conversion. However, simultaneously increasing electron density, promoting electron transfer, and enhancing CO₂ adsorption and activation within confined nanopore spaces remain critical challenges for boosting photocatalytic performance. Herein, polyhydroxylated fullerene (C₆₀OH) molecules were assembled within the nanopores of a two-dimensional porphyrin-based COF (pCOF) through hydrogen-bonding interactions with the hydroxyl-functionalized 2,5-dihydroxyterephthalaldehyde (DHTA) acceptor units in the pCOF, thereby constructing a C₆₀OH@pCOF photocatalytic nanoreactor featuring DHTA–C₆₀OH molecular heterojunctions. Under full-light irradiation, the optimized C₆₀OH@pCOF achieves a CO production rate of 40.47 μmol/(g·h) in pure water, approximately four times higher than that of pristine pCOF, along with a CO selectivity of 99%. This remarkable enhancement is mainly attributable to the introduction of C₆₀OH molecules into the pCOF, which facilitates the directional transfer of photogenerated electrons from the porphyrin donor to the DHTA moieties and then to the C₆₀OH acceptor. Moreover, the abundant surface hydroxyl groups on C₆₀OH serve as metal-free catalytic sites that effectively activate pre-accumulated CO₂ within the nanopore-based reactor and promote the formation and conversion of key intermediates. This study provides new insights into the design and construction of porous crystalline framework-based photocatalytic nanoreactors.

Keywords

Porphyrin COF / C₆₀OH / Nanoreactor / CO₂ Photoreduction

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Shengzhong Hao, Xudong Yan, Haochun Yin, Hongqi Wang, Jiaxin Yu, Linlu Bai. Confined Polyhydroxylated C₆₀ in Porphyrin COF Nanopore as Nanoreactor for CO₂ Photoreduction. Transactions of Tianjin University 1-13 DOI:10.1007/s12209-026-00494-0

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