期刊
CHEMISTRY-A EUROPEAN JOURNAL
卷 26, 期 7, 页码 1604-1611出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201904072
关键词
CO2 electrochemical reduction; cobalt porphyrins; high-performance electrocatalysts; post-modification; two-dimensional metal-organic framework nanosheets
资金
- NSFC [21922407]
- Young Elite Scholar Support (YESS) Program from CAST
- NSF of Jiangsu Province of China [BK20190086]
- Innovation Team Program of Jiangsu Province of China
- Priority Academic Program Development of Jiangsu Higher Education Institutions
- Program of Jiangsu Specially Appointed Professor
The electrochemical reduction of CO2 presents a promising strategy to mitigate the greenhouse effect and reduce excess carbon dioxide emission to realize a carbon-neutral energy cycle, but it suffers from the lack of high-performance electrocatalysts. In this work, catalytic active cobalt porphyrin [TCPP(Co)=(5,10,15,20)-tetrakis(4-carboxyphenyl)porphyrin-Co-II] was precisely anchored onto water-stable 2D metal-organic framework (MOF) nanosheets (Zr-BTB) to obtain ultrathin 2D MOF nanosheets [TCPP(Co)/Zr-BTB] with accessible catalytic sites for the CO2 reduction reaction. Compared with molecular cobalt porphyrin, the TCPP(Co)/Zr-BTB exhibits an ultrahigh turnover frequency (TOF=4768 h(-1) at -0.919 V vs. reversible hydrogen electrode, RHE) owing to high active-site utilization. In addition, three post-modified 2D MOF nanosheets [TCPP(Co)/Zr-BTB-PABA, TCPP(Co)/Zr-BTB-PSBA, TCPP(Co)/Zr-BTB-PSABA] were obtained, with the modifiers of p-(aminomethyl)benzoic acid (PABA), p-sulfobenzoic acid potassium (PSBA), and p-sulfamidobenzoic acid (PSABA), to change the micro-environments around TCPP(Co) through the tuning of steric effects. Among them, the TCPP(Co)/Zr-BTB-PSABA exhibited the best performance with a faradaic efficiency (FECO) of 85.1 %, TOF of 5315 h(-1), and j(total) of 6 mA cm(-2) at -0.769 V (vs. RHE). In addition, the long-term durability of the electrocatalysts is evaluated and the role of pH buffer is revealed.
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