精确可控串联策略触发高效的氧还原活性

doi:10.1016/S1872-2067(21)63966-9

催化学报 ›› 2022, Vol. 43 ›› Issue (4): 1042-1048.DOI: 10.1016/S1872-2067(21)63966-9

精确可控串联策略触发高效的氧还原活性

蒋国星^†, 张龙海^†, 邹文午, 张伟锋, 王秀军, 宋慧宇, 崔志明, 杜丽^*()

华南理工大学化学与化工学院, 广东省燃料电池技术重点实验室, 广东广州510641

收稿日期:2021-09-25 接受日期:2021-09-25 出版日期:2022-03-05 发布日期:2022-03-01
通讯作者: 杜丽
作者简介:第一联系人：
^†共同第一作者
基金资助:
国家自然科学基金(21975080);国家自然科学基金(21776104);广东省自然科学基金-杰出青年基金(2021B1515020025);广州市应用基础研究基金(202102080460)

Precise and controllable tandem strategy triggering boosted oxygen reduction activity

Guoxing Jiang^†, Longhai Zhang^†, Wenwu Zou, Weifeng Zhang, Xiujun Wang, Huiyu Song, Zhiming Cui, Li Du*^*()

The Key Laboratory of Fuel Cell Technology of Guangdong Province, School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou 510641, Guangdong, China

Received:2021-09-25 Accepted:2021-09-25 Online:2022-03-05 Published:2022-03-01
Contact: Li Du*
About author:First author contact:
^†Contributed equally to this work.
Supported by:
National Natural Science Foundation of China(21975080);National Natural Science Foundation of China(21776104);Guangdong Basic and Applied Basic Research Foundation for Distinguished Young Scholar(2021B1515020025);Guangzhou Applied Basic Research Foundation(202102080460)

摘要/Abstract

摘要：

探索高效、经济的非金属氧还原(ORR)电催化剂已成为电化学能源体系的关键. 科学界最具挑战性的目标之一是通过合理地验证和精确地调节活性位点来设计结构明确、性能优异的催化剂材料.
本文提出一种精确和可控的串联协同作用的活性位点策略, 以提高MFCOFs的ORR催化活性. 以亚胺-N、噻吩-S和三嗪-N等作为结构单元, 通过精确的串联策略合成了三种MFCOFs, 分别为亚胺-N构建的TFPB-TAPB-COF、亚胺-N和噻吩-S构建的BTT-TAPB-COF以及亚胺-N、噻吩-S和三嗪-N三种活性中心构建的BTT-TAT-COF. 将三种MFCOFs置于超临界二氧化碳中活化处理后, 采用傅里叶变换红外光谱仪、X射线衍射、交叉极化结合魔角旋转技术¹³C核磁共振法和热重分析法、氮气吸脱附曲线等表征手段对其进行了测试, 并在含有0.1 mol/L KOH的电解液中测试其ORR催化活性.
结果表明, 与BTT-TAPB-COF相比, BTT-TAT-COF展现出更优异的ORR催化性能; 而BTT-TAPB-COF的催化性能优于TFPB-TAPB-COF. 具体表现为, BTT-TAT-COF的半波电位(0.77 V)和起始电位(0.87 V)均高于BTT-TAPB-COF (0.71 V, 0.80 V)和TFPB-TAPB-COF (0.65, 0.73 V). 此外, BTT-TAT-COF表现出较低的塔菲尔斜率和接近于4电子的ORR过程, 说明其具有较高的反应速率. DFT计算结果表明, 在费米能级附近, BTT-TAPB-COF比TFPB-TAPB-COF具有更窄的带隙, 而BTT-TAT-COF具有最窄的带隙. 因此, 与TFPB-TAPB-COF和BTT-TAPB-COF相比, BTT-TAT-COF可以更有效地激发电子转移, 增强ORR活性. 此外, 利用三种结构的吉布斯自由能图分析了ORR的过电位, 发现当亚胺-N、噻吩-S和三嗪-N结构被引入骨架后, 相同位点的过电势降低. 由此可见, 亚胺-N、噻吩-S和三嗪-N作为催化活性位点诱导了正的ORR过程. 此外, BTT-TAT-COF中部分碳原子(BTT-TAT-5, 9, 10)的过电势均低于BTT-TAPB-COF和TFPB-TAPB-COF中所有位点的过电势, 表明多活性位点发挥了协同催化的作用. 本文证明了精确串联协同催化的多活性位点策略提高ORR性能的可行性, 并为构建高效的COF基非金属ORR催化剂提供新的见解.

关键词: 共价有机框架材料, 非金属催化剂, 串联策略, 协同催化, 氧还原反应

Abstract:

The development of efficient and cost-effective metal-free electrocatalysts for oxygen reduction reaction (ORR) has become crucial for electrochemical energy systems. However, reasonably validating and precisely regulating the active sites for designing optimized materials are still challenging. Herein, we report a precise and controllable tandem strategy to boost the ORR activity based on metal-free covalent organic frameworks (MFCOFs) comprising imine-N, thiophene-S, or triazine-N. Among these MFCOFs, post-tandem BTT-TAT-COF structure displayed a more positive catalytic capability and excellent electrochemical stability, indicating that the synergistic catalysis of multiple active sites induced the ORR catalytic activity through the conjugated skeleton of the structure. Density-functional theory calculations suggest that the series-connected backbone contained highly effective electrocatalytic active centers and provided synergistic catalysis. More importantly, this strategy highlights new opportunities for the advancement of efficient COF-based metal-free ORR catalysts.

Key words: Covalent organic frameworks, Metal-free electrocatalyst, Tandem strategy, Synergistic catalysis, Oxygen reduction reaction

蒋国星, 张龙海, 邹文午, 张伟锋, 王秀军, 宋慧宇, 崔志明, 杜丽. 精确可控串联策略触发高效的氧还原活性[J]. 催化学报, 2022, 43(4): 1042-1048.

Guoxing Jiang, Longhai Zhang, Wenwu Zou, Weifeng Zhang, Xiujun Wang, Huiyu Song, Zhiming Cui, Li Du*. Precise and controllable tandem strategy triggering boosted oxygen reduction activity[J]. Chinese Journal of Catalysis, 2022, 43(4): 1042-1048.

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图/表 5

Scheme 1. Schematic of the (a) tandem synthetic procedure of the MFCOFs and (b) ORR process induced by BTT-TAT-COF.

Fig. 1. Probable chemical structures (left) and reconstructed structures of one hexagonal macrocycle (right) for TFPB-TAPB-COF (a), BTT-TAPB-COF (b), and BTT-TAT-COF (c) (gray, blue, and red spheres represent C, N, and S atoms, respectively); PXRD patterns of TFPB-TAPB-COF (d), BTT-TAPB-COF (e), and BTT-TAT-COF (f).

Fig. 2. (a) N2 adsorption-desorption isotherms of TFPB-TAPB-COF (pink), BTT-TAPB-COF (blue), and BTT-TAT-COF (red); (b) PXRD spectra of BTT-TAT-COF after treatment under different conditions; SEM images of TFPB-TAPB-COF (c), BTT-TAPB-COF (d), and BTT-TAT-COF (e); (f) TEM image and EDS maps for C, N, and S of BTT-TAT-COF.

Fig. 3. Electrochemical ORR performance. Comparison of LSV curves in O2-saturated 0.1 mol/L aqueous KOH at 1600 r min-1(a), Tafel plots (b), electron transfer number (n) and H2O2 yield (c), and mass activities and TOFs (d) for TFPB-TAPB-COF, BTT-TAPB-COF, and BTT-TAT-COF; Long-term stability test (e) and methanol tolerance (f) of BTT-TAT-COF; (g) Galvanostatic discharge curve when BTT-TAT-COF was used as electrodes in 6 mol/L KOH at a current density of 5 mA cm-2(without iR correction) and images of a “SCUT” LED panel powered by three series-connected ZABs.

Fig. 4. Optimized structures of TFPB-TAPB-COF (a), BTT-TAPB-COF (b), and BTT-TAT-COF (c). Gray, blue, red, and white balls represent C, N, S, and H atoms, respectively. Calculated density of states (d) and Kohn-Sham LUMOs, HOMOs, and LUMO-HOMO gaps based on the DFT methods with B3LYP/6-31G* (e) for TFPB-TAPB-COF, BTT-TAPB-COF, and BTT-TAT-COF; (f) Calculated free energy diagrams for TFPB-TAPB-COF (at site 1), BTT-TAPB-COF (at site 4), and BTT-TAT-COF (at site 5).

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精确可控串联策略触发高效的氧还原活性

Precise and controllable tandem strategy triggering boosted oxygen reduction activity

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