高稳定二维联咔唑sp2碳共轭共价有机框架材料用于高效电催化氧还原★

doi:10.6023/A23040132

摘要/Abstract

化石燃料的过度消耗和环境污染已成为全球面临的主要问题, 如何合理开发利用新能源成为我国能源战略中的主要目标. 新型能量转换技术是促进新能源发展的关键. 目前, 以金属-空气电池、燃料电池等为主导的新型清洁电化学能量转换技术在转换效率、经济性等方面均取得了重大突破, 极具产业化应用前景. 开发高效、稳定、低成本的电化学催化剂是促进清洁能转换装置发展的关键. 在此, 报道了一种基于联咔唑构筑单元合成的高稳定sp²键型的共价有机框架材料(JUC-557)用于燃料电池阴极氧还原反应(ORR). 该材料具有高比表面积、高稳定性等优点, 同时也表现出高效的ORR催化性能和组装锌-空电池的应用潜力. 此外, 该材料相比于贵金属催化剂, 也具有低成本、低污染、结构明确、原子和结构精度可控等优势. 本研究为构建异质原子高效非金属电催化剂提供了一种新思路.

关键词: 多孔材料, 共价有机框架, 电催化, 氧化还原, 非金属催化剂

With the extensive utilization of fossil fuels in industrial development, the energy crisis and environmental issues have become crucial challenges for current scientific development. The development of sustainable and clean energy is of great importance for sustainable human progress. Fuel and metal-air batteries have emerged as promising alternatives to fossil fuels, providing environmentally friendly and sustainable clean energy. Improving the efficiency of the oxygen reduction reaction (ORR) is crucial for energy generation and storage processes of batteries. Therefore, the development of efficient and stable ORR electrocatalysts is a key task to improve battery performance. Noble metal-based materials are known for their excellent ORR catalytic performance, but their high cost and instability have limited their applications. Hence, it is essential to develop low-cost, low-pollution, and high-efficiency electrocatalysts as noble metal-based alternatives. Transition-metal (TM)-based materials, metal alloys, and metal-free carbon nanomaterials have been reported as alternatives, but their properties are not as good as those of noble metal-based materials. In addition, their complex processes and difficult-to-identify active sites make it challenging to elucidate the intrinsic mechanisms. Rational design and precise synthesis of electrochemical catalysts are critical strategies. Covalent organic frameworks (COFs) have several advantages, including high crystallinity, high specific surface area, high stability, and regular pore channels. Besides, the construction of COFs has the advantages of pre-design and precise synthesis. Reasonable design and construction unit is an important strategy to realize the functional application of COFs materials. Many new products with structural characteristics have been reported since the introduction of COFs, and they have demonstrated excellent performance in several fields. In this study, we investigated the application of a highly stable sp²-carbon-linked COF (JUC-557) based on a bicarbazole building block for electrocatalytic oxygen reduction. We performed various characterizations of JUC-557, which demonstrated its high crystallinity, high specific surface area (870.64 m²/g), and regular structure. Moreover, JUC-557 exhibited excellent thermal and chemical stability. In the ORR performance test, JUC-557 showed good ORR catalytic performance, with an onset potential of 0.80 V vs. RHE, a half-wave potential of 0.68 V vs. RHE, a Tafel slope of only 62.20 mA•cm^－2, and a C_dl of 5.79 mF•cm^－2. Moreover, the Zn-air battery assembled with JUC-557 as an air-cathode electrode catalyst has a stable open-circuit voltage of 1.29 V and can easily light up the “COF” LED board. In conclusion, the rational construction of COFs as ORR catalysts has great potential in energy device application.

Key words: porous materials, covalent organic frameworks, electrocatalyst, oxidation reduction, metal-free catalyst

引用此文

刘建川, 李翠艳, 刘耀祖, 王钰杰, 方千荣. 高稳定二维联咔唑sp²碳共轭共价有机框架材料用于高效电催化氧还原^★[J]. 化学学报, 2023, 81(8): 884-890.

Jianchuan Liu, Cuiyan Li, Yaozu Liu, Yujie Wang, Qianrong Fang. Highly-Stable Two-Dimensional Bicarbazole-based sp²-Carbon-conjugated Covalent Organic Framework for Efficient Electrocatalytic Oxygen Reduction^★[J]. Acta Chimica Sinica, 2023, 81(8): 884-890.

导出引用 EndNote|Reference Manager|ProCite|BibTeX|RefWorks

分享此文

图/表 7

图式1. JUC-557的合成策略

Scheme 1. Synthesis strategy of JUC-557

图1. JUC-557的PXRD (黑色: 实验值; 红色: Pawley精修数据; 蓝色: 模拟值; 绿色: 误差范围; 黄色插图: JUC-557的模拟结构)

Figure 1. PXRD of JUC-557 (Black: Experimental value; Red: Pawley refined value; Blue: Calculated value; green: Difference; Yellow illustration: Simulated structure of JUC-557)

图2. JUC-557的(a) FT-IR谱图和(b)固态13C NMR谱图

Figure 2. (a) FT-IR and (b) solid-state 13C NMR spectra of JUC-557

图3. JUC-557的(a) SEM图像和(b) TEM图像

Figure 3. (a) SEM image and (b) TEM image of JUC-557

图4. JUC-557的(a) 77 K条件下氮气吸附-脱附等温曲线; (b)孔径分布图; (c)热重曲线; (d)酸、碱和有机试剂处理后的PXRD对比图

Figure 4. (a) Nitrogen adsorption-desorption isotherm curves at 77 K; (b) the pore-size distribution of JUC-557; (c) TGA curve; (d) comparison of the PXRD patterns after treatment in different solvents of JUC-557

图5. JUC-557的(a) 1600 r/min下线性扫描伏安曲线; (b)不同转速下线性扫描伏安曲线; (c) H2O2产率和转移电子数; (d)塔菲尔斜率曲线

Figure 5. (a) LSV curve at 1600 r/min; (b) LSV curves at different speeds; (c) the H2O2 yield and the electron transfer numbers; (d) Tafel plots of JUC-557

图6. JUC-557的(a)不同扫速下的循环伏安曲线; (b)电化学双层电容; (c)翻转频率和质量活度; (d) JUC-557在0.7 V (vs. RHE)下的长期稳定性试验; (e)电流-时间曲线; (f)自制锌-空电池示意图; (g)开路电压和基于JUC-557的ZAB点亮“COF” LED显示屏的照片

Figure 6. (a) CV curves at different scanning speeds; (b) Cdl; (c) TOF and mass acitivity; (d) long-term stability test; (e) current-time curve of JUC-557 at 0.7 V (vs. RHE); (f) a schematic diagram of the homemade ZAB; (g) the open circuit voltage and the photograph of a “COF” LED screen powered by series JUC-557 ZAB

参考文献 43

[1]	Zou X.; Zhang Y. Chem. Soc. Rev. 2015, 44, 5148. doi: 10.1039/C4CS00448E
[2]	Bu R.; Lu Y.; Zhang B. Chem. Res. Chin. Univ. 2022, 38, 1151. doi: 10.1007/s40242-022-2219-2
[3]	Yang C.; Yang Z.-D.; Dong H.; Sun N.; Lu Y.; Zhang F.-M.; Zhang G. ACS Energy Lett. 2019, 4, 2251. doi: 10.1021/acsenergylett.9b01691
[4]	Tao S.; Jiang D. CCS Chem. 2021, 3, 2003. doi: 10.31635/ccschem.020.202000491
[5]	Debe M. K. Nature 2012, 486, 43. doi: 10.1038/nature11115
[6]	Zhang J.; Zhao Y.; Chen C.; Huang Y.-C.; Dong C.-L.; Chen C.-J.; Liu R.-S.; Wang C.; Yan K.; Li Y. J. Am. Chem. Soc. 2019, 141, 20118. doi: 10.1021/jacs.9b09352
[7]	Lee Y.; Suntivich J.; May K. J.; Perry E. E.; Shao-Horn Y. J. Phys. Chem. Lett. 2012, 3, 399.
[8]	Nørskov J. K.; Rossmeisl J.; Logadottir A.; Lindqvist L.; Kitchin J. R.; Bligaard T.; Jonsson H. J. Phys. Chem. B 2004, 108, 17886. doi: 10.1021/jp047349j
[9]	Miles M. Electrochim. Acta 1978, 23, 521. doi: 10.1016/0013-4686(78)85030-0
[10]	Gong K.; Du F.; Xia Z.; Durstock M.; Dai L. Science 2009, 323, 760. doi: 10.1126/science.1168049
[11]	Yang Z.; Xiang M.; Zhu Y.; Hui J.; Jiang Y.; Dong S.; Yu C.; Ou J.; Qin H. Chem. Eng. J. 2021, 426, 131347. doi: 10.1016/j.cej.2021.131347
[12]	Wang J.; Cui W.; Liu Q.; Xing Z.; Asiri A. M.; Sun X. Adv. Mater. 2016, 28, 215. doi: 10.1002/adma.201502696
[13]	Shao M.; Chang Q.; Dodelet J.-P.; Chenitz R. Chem. Rev. 2016, 116, 3594. doi: 10.1021/acs.chemrev.5b00462
[14]	Cote A. P.; Benin A. I.; Ockwig N. W.; O'keeffe M.; Matzger A. J.; Yaghi O. M. Science 2005, 310, 1166. doi: 10.1126/science.1120411
[15]	Feng X.; Liu L.; Honsho Y.; Saeki A.; Seki S.; Irle S.; Dong Y.; Nagai A.; Jiang D. Angew. Chem., Int. Ed. 2012, 51, 2618. doi: 10.1002/anie.201106203
[16]	Zhang Z.; Jiang F.; Wu K.; Shen P. Acta Chim. Sinica 2022, 80, 56. (in Chinese) doi: 10.6023/A21090440
	( 张竹涵, 蒋峰景, 吴珂科, 申鹏, 化学学报, 2022, 80, 56.)
[17]	Zhuang R.; Xu X.; Qu C.; Xu S.; Yu T.; Wang H.; Xu F. Acta Chim. Sinica 2021, 79, 378. (in Chinese) doi: 10.6023/A20100462
	( 庄容, 许潇洒, 曲昌镇, 徐顺奇, 于涛, 王洪强, 徐飞, 化学学报, 2021, 79, 378.)
[18]	Li J. L.; Xiao Y.; Shui F.; Yi M.; Zhang Z. Y.; Liu X. L.; Zhang L. Y.; You Z. F.; Yang R. F.; Yang S. Q.; Li B. Y.; Bu X. H. Chin. J. Chem. 2022, 40, 2445. doi: 10.1002/cjoc.v40.20
[19]	Yu C.; Li H.; Wang Y.; Suo J.; Guan X.; Wang R.; Valtchev V.; Yan Y.; Qiu S.; Fang Q. Angew. Chem., Int. Ed. 2022, 61, e202117101. doi: 10.1002/anie.v61.13
[20]	Song J.; Wang Z.; Liu Y.; Tuo C.; Wang Y.; Fang Q.; Qiu S.; Chem. Res. Chin. Univ. 2022, 38, 834. doi: 10.1007/s40242-022-2060-7
[21]	Fang Q.; Wang J.; Gu S.; Kaspar R. B.; Zhuang Z.; Zheng J.; Guo H.; Qiu S.; Yan Y. J. Am. Chem. Soc. 2015, 137, 8352. doi: 10.1021/jacs.5b04147
[22]	Wang T.; Zhao L.; Wang K.; Bai Y.; Feng F. Acta Chim. Sinica 2021, 79, 600. (in Chinese) doi: 10.6023/A20120578
	( 王涛, 赵璐, 王科伟, 白云峰, 冯锋, 化学学报, 2021, 79, 600.)
[23]	Liao L.; Zhang Z. R.; Guan X. Y.; Li H.; Liu Y. Z.; Zhang M. H.; Tang B.; Valtchev V.; Yan Y. S.; Qiu S. L.; Yao X. D.; Fang Q. R. Chin. J. Chem. 2022, 40, 2081. doi: 10.1002/cjoc.v40.17
[24]	Li Z.; Zhang Y.; Xia H.; Mu Y.; Liu X. Chem. Commun. 2016, 52, 6613. doi: 10.1039/C6CC01476C
[25]	Xian W.; Zhang P.; Zhu C.; Zuo X.; Ma S.; Sun Q. CCS Chem. 2021, 3, 2464.
[26]	Haotian R.; Zhu Z.; Cai Y.; Wang W.; Wang Z.; Liang A.; Luo A. Acta Chim. Sinica 2022, 80, 1524. (in Chinese) doi: 10.6023/A22070339
	( 浩天瑞霖, 朱子煜, 蔡艳慧, 王微, 王祯, 梁阿新, 罗爱芹, 化学学报, 2022, 80, 1524.)
[27]	Chandra S.; Kundu T.; Kandambeth S.; Babarao R.; Marathe Y.; Kunjir S. M.; Banerjee R. J. Am. Chem. Soc. 2014, 136, 6570. doi: 10.1021/ja502212v
[28]	Shao M. C.; Liu Y. Q.; Guo Y. L. Chin. J. Chem. 2023, 41, 1260. doi: 10.1002/cjoc.v41.10
[29]	Li D.; Li C.; Zhang L.; Li H.; Zhu L.; Yang D.; Fang Q.; Qiu S.; Yao X. J. Am. Chem. Soc. 2020, 142, 8104. doi: 10.1021/jacs.0c02225
[30]	Chang S.; Li C.; Li H.; Zhu L.; Fang Q. Chem. Res. Chin. Univ. 2022, 38, 396. doi: 10.1007/s40242-022-1465-7
[31]	Yu X.; Huang W.; Li Y. Acta Chim. Sinica 2022, 80, 1494. (in Chinese) doi: 10.6023/A22070303
	( 于潇涵, 黄伟, 李彦光, 化学学报, 2022, 80, 1494.)
[32]	Chen Q.; Kuang Q.; Xie Z. Acta Chim. Sinica 2021, 79, 10. (in Chinese) doi: 10.6023/A20080384
	( 陈钱, 匡勤, 谢兆雄, 化学学报, 2021, 79, 10.)
[33]	Chen Y.; Chen Q.; Zhang Z. Chin. J. Org. Chem. 2021, 41, 3826. (in Chinese) doi: 10.6023/cjoc202107030
	( 陈育萱, 陈奇, 张占辉, 有机化学, 2021, 41, 3826.)
[34]	Dong M.; Li W.; Zhou J.; You S. Q.; Sun C. Y.; Yao X. H.; Qin C.; Wang X. L.; Su Z. M. Chin. J. Chem. 2022, 40, 2678. doi: 10.1002/cjoc.v40.22
[35]	Ma L.; Wang S.; Feng X.; Wang B. Chin. Chem. Lett. 2016, 27, 1383. doi: 10.1016/j.cclet.2016.06.046
[36]	Tang X.; Chen Z.; Xu Q.; Su Y.; Xu H.; Horike S.; Zhang H.; Li Y.; Gu C. CCS Chem. 2022, 4, 2842. doi: 10.31635/ccschem.021.202101198
[37]	Nagai A.; Guo Z.; Feng X.; Jin S.; Chen X.; Ding X.; Jiang D. Nat. Commun. 2011, 2, 1.
[38]	Xiang Z.; Xue Y.; Cao D.; Huang L.; Chen J. F.; Dai L. Angew. Chem., Int. Ed. 2014, 53, 2433. doi: 10.1002/anie.201308896
[39]	Bunck D. N.; Dichtel W. R. Angew. Chem., Int. Ed. 2012, 51, 1885. doi: 10.1002/anie.v51.8
[40]	Yu X.; Ma Y.; Li C.; Guan X.; Fang Q.; Qiu S. Chem. Res. Chin. Univ. 2022, 38, 167. doi: 10.1007/s40242-021-1374-1
[41]	Liu Y.; Ren J.; Wang Y.; Zhu X.; Guan X.; Wang Z.; Zhou Y.; Zhu L.; Qiu S.; Xiao S.; Fang Q. CCS Chem. 2023, DOI: 10.31635/ccschem.022.202202352. doi: 10.31635/ccschem.022.202202352
[42]	Materials Studio ver.7.0, Diego, S. Accelrys Inc, 2013.
[43]	El-Mahdy A. F.; Lai M.-Y.; Kuo S.-W. J. Mater. Chem. C 2020, 8, 9520. doi: 10.1039/D0TC01872D

高稳定二维联咔唑sp²碳共轭共价有机框架材料用于高效电催化氧还原^★

Highly-Stable Two-Dimensional Bicarbazole-based sp²-Carbon-conjugated Covalent Organic Framework for Efficient Electrocatalytic Oxygen Reduction^★

RichHTML

PDF

可视化

摘要/Abstract

引用此文

分享此文

图/表 7

参考文献 43

相关文章 15

编辑推荐

相关统计

本文评价

[1]	李珊, 路俊欣, 刘杰, 蒋绿齐, 易文斌. 氟烷基亚磺酸钠盐电化学合成α-氟烷基酮[J]. 化学学报, 2024, 82(2): 110-114.
[2]	林航青, 马若茹, 江怡蓝, 许木榕, 林洋彭, 杜克钊. 用于卤素捕获的材料研究进展[J]. 化学学报, 2024, 82(1): 62-74.
[3]	魏颖, 王家成, 李玥, 汪涛, 马述威, 解令海. 碳碳键链接的二维共价有机框架研究进展[J]. 化学学报, 2024, 82(1): 75-102.
[4]	杨蓉婕, 周璘, 苏彬. 基于共价有机框架修饰电极的维生素A和C的选择性检测^★[J]. 化学学报, 2023, 81(8): 920-927.
[5]	何明慧, 叶子秋, 林桂庆, 尹晟, 黄心翊, 周旭, 尹颖, 桂波, 汪成. 卟啉基共价有机框架的光催化研究进展^★[J]. 化学学报, 2023, 81(7): 784-792.
[6]	陈俊畅, 张明星, 王殳凹. 晶态多孔材料合成方法的研究进展[J]. 化学学报, 2023, 81(2): 146-157.
[7]	杨镇鸿, 干晓娟, 王书哲, 段君元, 翟天佑, 刘友文. 金属性Ni₃N纳米粒子的制备与乙二醇电氧化性能^★[J]. 化学学报, 2023, 81(11): 1471-1477.
[8]	闫绍兵, 焦龙, 何传新, 江海龙. ZIF-67/石墨烯复合物衍生的氮掺杂碳限域Co纳米颗粒用于高效电催化氧还原[J]. 化学学报, 2022, 80(8): 1084-1090.
[9]	王振华, 马聪, 方萍, 徐海超, 梅天胜. 有机电化学合成的研究进展[J]. 化学学报, 2022, 80(8): 1115-1134.
[10]	何家伟, 焦柳, 程雪怡, 陈光海, 吴强, 王喜章, 杨立军, 胡征. 金属有机框架衍生的空心碳纳米笼的结构调控与锂硫电池性能研究[J]. 化学学报, 2022, 80(7): 896-902.
[11]	蒋银龙, 李国超, 陈青松, 徐忠宁, 林姗姗, 郭国聪. 富晶格位错的多孔铋纳米花高效电还原二氧化碳制甲酸盐^※[J]. 化学学报, 2022, 80(6): 703-707.
[12]	王丹, 封波, 张晓昕, 刘亚楠, 裴燕, 乔明华, 宗保宁. 基于热解ZIF-8的氮掺杂碳电化学氧还原合成过氧化氢催化剂[J]. 化学学报, 2022, 80(6): 772-780.
[13]	应霞薇, 浮建军, 曾敏, 刘文, 张天宇, 沈培康, 张信义. 基于BiOCl-Fe₂O₃@TiO₂介孔复合材料的光电化学合成氨性能研究[J]. 化学学报, 2022, 80(4): 503-509.
[14]	李泽洋, 杨宇森, 卫敏. 二氧化碳还原电催化剂的结构设计及性能研究进展[J]. 化学学报, 2022, 80(2): 199-213.
[15]	张蒙茜, 冯霄. 共轭微孔聚合物膜的制备策略及其分离应用[J]. 化学学报, 2022, 80(2): 168-179.