氮化碳启发的共价有机框架光催化剂用于高效过氧化氢光合成

doi:10.1016/S1872-2067(22)64205-0

催化学报 ›› 2023, Vol. 46: 28-35.DOI: 10.1016/S1872-2067(22)64205-0

氮化碳启发的共价有机框架光催化剂用于高效过氧化氢光合成

邵潮晨^a^,^b, 何晴^a^,^b, 张默淳^a^,^b, 贾麟^a^,^b, 纪玉金^a^,^b, 胡永攀^a^,^b, 李有勇^a^,^b, 黄伟^a^,^b^,^*(), 李彦光^a^,^b^,^*()

^a苏州大学功能纳米与软物质研究院, 江苏苏州 215123
^b江苏省先进负碳技术重点实验室, 江苏苏州 215123

收稿日期:2022-10-05 接受日期:2022-12-05 出版日期:2023-03-18 发布日期:2023-02-21
通讯作者: *电子信箱: yanguang@suda.edu.cn (李彦光),weihuang@suda.edu.cn (黄伟)
作者简介:
¹共同第一作者
基金资助:
国家自然科学基金(22002100);国家自然科学基金(U2002213);江苏省自然科学基金(BK20220027);碳基功能材料和器件联合国际研究实验室

A covalent organic framework inspired by C₃N₄ for photosynthesis of hydrogen peroxide with high quantum efficiency

Chaochen Shao^a^,^b, Qing He^a^,^b, Mochun Zhang^a^,^b, Lin Jia^a^,^b, Yujin Ji^a^,^b, Yongpan Hu^a^,^b, Youyong Li^a^,^b, Wei Huang^a^,^b^,^*(), Yanguang Li^a^,^b^,^*()

^aInstitute of Functional Nano & Soft Materials (FUNSOM), Soochow University, Suzhou 215123, Jiangsu, China
^bJiangsu Key Laboratory for Advanced Negative Carbon Technologies, Soochow University, Suzhou 215123, Jiangsu, China

Received:2022-10-05 Accepted:2022-12-05 Online:2023-03-18 Published:2023-02-21
Contact: *E-mail: yanguang@suda.edu.cn (Y. Li), weihuang@suda.edu.cn (W. Huang)
About author:
¹Contributed equally to this work.
Supported by:
National Natural Science Foundation of China(22002100);National Natural Science Foundation of China(U2002213);The Natural Science Foundation of Jiangsu Province(BK20220027);Collaborative Innovation Center of Suzhou Nano Science and Technology, the 111 Project and Joint International Research Laboratory of Carbon-Based Functional Materials and Devices

摘要/Abstract

摘要：

过氧化氢(H₂O₂)是一种绿色高效氧化剂, 广泛应用于医药、食品和造纸等领域. 传统制备方法为蒽醌氧化法, 但该法不仅耗能高, 工艺复杂, 而且会产生大量废水、废气和固体废物. 探索绿色温和条件下新的H₂O₂合成方法成为当前研究热点. 其中, 以太阳能为驱动力的光催化H₂O₂合成策略广受关注. 在光催化反应过程中, 半导体光催化剂扮演着至关重要的角色, 它们捕获光能、产生光生电荷并引发界面的氧化还原反应. 因此, 开发高效半导体催化剂是实现高效光催化H₂O₂合成的关键. 氮化碳(C₃N₄)是目前应用最为广泛的H₂O₂光合成催化剂. 研究表明, C₃N₄中的庚嗪基团能够和活性氧中间体形稳定加成产物, 有利于H₂O₂的选择性生成. 然而, 由于C₃N₄可见光吸收范围窄及光生电荷复合快等问题, 导致光催化效率较低, 严重限制了其光合成H₂O₂的实际应用. 基于对C₃N₄本征优势和固有缺陷的了解, 本文提出将C₃N₄的庚嗪构筑单元整合到具有宽光谱吸收的共价有机框架(COFs)骨架中, 以优化材料的电荷分离动力学和光吸收性能, 从而实现H₂O₂的高效合成.

采用一步希夫碱缩合反应制备含庚嗪基团的COFs催化剂(COF-TpHt). XRD测试和结构模拟结果表明, COF-TpHt具有共轭的二维平面分子结构且层间通过π-π相互作用有序排列, 这不仅有利于提高材料光吸收能力, 同时也为光生载流子的分离提供了层内和层间传输通道. 紫外可见漫反射吸收光谱结果表明, 该催化剂在400-800 nm的宽范围内具有较好的可见光吸收能力. 稳态和时间分辨荧光光谱结果表明, C₃N₄在λ = 488 nm处具有很强的荧光强度, 而COF-TpHt的荧光强度显著淬灭. 另外, COF-TpHt比C₃N₄ (8.53 ns)具有更长的荧光平均寿命(9.19 ns)和更大的光电流响应, 这表明COF-TpHt中的电荷复合被有效抑制, 有利于提高光催化反应活性. 在光催化反应中, 以苯甲醇为电子供体, 在可见光(λ > 420 nm)照射下, 该催化剂实现了高达11986 μmol h^-1 g^-1的H₂O₂生成速率, 在420 nm处的表观量子效率为38%, 超过了目前报道的大多数有机或无机半导体光催化剂性能. 除此之外, 该催化剂也展现出较好的稳定性, 在连续循环反应4圈(12 h)后仍保持原有的形貌与结构, 且在长达30 h的连续光照反应过程中, H₂O₂产量仍能保持线性增长, 最终达到2971 μmol, 浓度约为59.4 mmol L^-1, 可满足消毒和污水处理的实际应用要求. 综上, 本文材料对光催化的方式获得高浓度H₂O₂具有独特优势.

关键词: 过氧化氢合成, 光催化, 氧还原, 共价有机框架, 氮化碳

Abstract:

Carbon nitride (C₃N₄) has been the main research focus for photocatalytic H₂O₂ synthesis that may enable the on-site and on-demand H₂O₂ production under mild conditions. Its potential is unfortunately shadowed by the narrow light absorption and fast charge recombination. Building on the understanding of the inherent merits and pitfalls of C₃N₄, we here propose to assemble active heptazine motifs with functional linkers in ordered molecular frameworks for highly efficient photocatalytic H₂O₂ production. Herein, a heptazine-based covalent organic framework is synthesized via the Schiff-base reaction. It has enhanced light absorption and charge separation. When irradiated with visible light in the presence of sacrificial electron donors, the sample exhibits an excellent H₂O₂ production rate of 11986 μmol h^-1 g^-1 and an apparent quantum efficiency up to 38% at 420 nm, outperforming most organic or inorganic competitors in our best knowledge. Impressively, the catalyst can also endure long time operation that affords the linear H₂O₂ accumulation to a practically usable concentration.

Key words: H₂O₂ production, Photocatalysis, Oxygen reduction, Covalent organic frameworks, Carbon nitride

邵潮晨, 何晴, 张默淳, 贾麟, 纪玉金, 胡永攀, 李有勇, 黄伟, 李彦光. 氮化碳启发的共价有机框架光催化剂用于高效过氧化氢光合成[J]. 催化学报, 2023, 46: 28-35.

Chaochen Shao, Qing He, Mochun Zhang, Lin Jia, Yujin Ji, Yongpan Hu, Youyong Li, Wei Huang, Yanguang Li. A covalent organic framework inspired by C₃N₄ for photosynthesis of hydrogen peroxide with high quantum efficiency[J]. Chinese Journal of Catalysis, 2023, 46: 28-35.

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氮化碳启发的共价有机框架光催化剂用于高效过氧化氢光合成

A covalent organic framework inspired by C₃N₄ for photosynthesis of hydrogen peroxide with high quantum efficiency

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氮化碳启发的共价有机框架光催化剂用于高效过氧化氢光合成

A covalent organic framework inspired by C3N4 for photosynthesis of hydrogen peroxide with high quantum efficiency

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A covalent organic framework inspired by C₃N₄ for photosynthesis of hydrogen peroxide with high quantum efficiency