TY - JOUR
T1 - [2,1,3]-Benzothiadiazole-Spaced Co-Porphyrin-Based Covalent Organic Frameworks for O2 Reduction
AU - Bhunia, Subhajit
AU - Peña-Duarte, Armando
AU - Li, Huifang
AU - Li, Hong
AU - Sanad, Mohamed Fathi
AU - Saha, Pranay
AU - Addicoat, Matthew A.
AU - Sasaki, Kotaro
AU - Strom, T. Amanda
AU - Yacamán, Miguel José
AU - Cabrera, Carlos R.
AU - Seshadri, Ram
AU - Bhattacharya, Santanu
AU - Brédas, Jean Luc
AU - Echegoyen, Luis
N1 - Funding Information:
L.E. thanks the NSF for the generous support of this work under CHE-1801317. The Robert A. Welch Foundation is also acknowledged for an endowed chair to L.E. (grant AH-0033). The work at the University of Arizona was supported by the UA College of Science. H.F.L acknowledges financial support from the Natural Science Foundation of Shandong Province, China (No. ZR2020MB045). This work was also supported by Center for Alkaline Based Energy Solutions (CABES), an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, under award # DESC0019445. C.R.C. acknowledges the STARS Award (2021) of the University of Texas System. This research used beamline 7-BM (QAS) of the National Synchrotron Light Source II, a US DOE Office of Science User Facility operated for the DOE Office of Science by Brookhaven National Laboratory under Contract No. DE-SC0012704. Beamline operations were supported in part by the Synchrotron Catalysis Consortium (US DOE, Office of Basic Energy Sciences, Grant No. DE-SC0012335). The authors appreciate the discussions with S. Ehrlich, L. Ma, and, N. Marinkovic (BNL). The MRL Shared Experimental Facilities are supported by the MRSEC Program of the NSF under Award No. DMR 1720256; a member of the NSF-funded Materials Research Facilities Network ( www.mrfn.org ). The authors want to also thank J. Nolt (MRL, UC Santa Barbara) for BET analysis. HPC time was granted by the MMM Hub, which is partially funded by EPSRC (EP/T022213).
Funding Information:
L.E. thanks the NSF for the generous support of this work under CHE-1801317. The Robert A. Welch Foundation is also acknowledged for an endowed chair to L.E. (grant AH-0033). The work at the University of Arizona was supported by the UA College of Science. H.F.L acknowledges financial support from the Natural Science Foundation of Shandong Province, China (No. ZR2020MB045). This work was also supported by Center for Alkaline Based Energy Solutions (CABES), an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, under award # DESC0019445. C.R.C. acknowledges the STARS Award (2021) of the University of Texas System. This research used beamline 7-BM (QAS) of the National Synchrotron Light Source II, a US DOE Office of Science User Facility operated for the DOE Office of Science by Brookhaven National Laboratory under Contract No. DE-SC0012704. Beamline operations were supported in part by the Synchrotron Catalysis Consortium (US DOE, Office of Basic Energy Sciences, Grant No. DE-SC0012335). The authors appreciate the discussions with S. Ehrlich, L. Ma, and, N. Marinkovic (BNL). The MRL Shared Experimental Facilities are supported by the MRSEC Program of the NSF under Award No. DMR 1720256; a member of the NSF-funded Materials Research Facilities Network (www.mrfn.org). The authors want to also thank J. Nolt (MRL, UC Santa Barbara) for BET analysis. HPC time was granted by the MMM Hub, which is partially funded by EPSRC (EP/T022213).
Publisher Copyright:
© 2023 American Chemical Society.
PY - 2023/2/28
Y1 - 2023/2/28
N2 - Designing N-coordinated porous single-atom catalysts (SACs) for the oxygen reduction reaction (ORR) is a promising approach to achieve enhanced energy conversion due to maximized atom utilization and higher activity. Here, we report two Co(II)-porphyrin/ [2,1,3]-benzothiadiazole (BTD)-based covalent organic frameworks (COFs; Co@rhm-PorBTD and Co@sql-PorBTD), which are efficient SAC systems for O2 electrocatalysis (ORR). Experimental results demonstrate that these two COFs outperform the mass activity (at 0.85 V) of commercial Pt/C (20%) by 5.8 times (Co@rhm-PorBTD) and 1.3 times (Co@sql-PorBTD), respectively. The specific activities of Co@rhm-PorBTD and Co@sql-PorBTD were found to be 10 times and 2.5 times larger than that of Pt/C, respectively. These COFs also exhibit larger power density and recycling stability in Zn-air batteries compared with a Pt/C-based air cathode. A theoretical analysis demonstrates that the combination of Co-porphyrin with two different BTD ligands affords two crystalline porous electrocatalysts having different d-band center positions, which leads to reactivity differences toward alkaline ORR. The strategy, design, and electrochemical performance of these two COFs offer a pyrolysis-free bottom-up approach that avoids the creation of random atomic sites, significant metal aggregation, or unpredictable structural features.
AB - Designing N-coordinated porous single-atom catalysts (SACs) for the oxygen reduction reaction (ORR) is a promising approach to achieve enhanced energy conversion due to maximized atom utilization and higher activity. Here, we report two Co(II)-porphyrin/ [2,1,3]-benzothiadiazole (BTD)-based covalent organic frameworks (COFs; Co@rhm-PorBTD and Co@sql-PorBTD), which are efficient SAC systems for O2 electrocatalysis (ORR). Experimental results demonstrate that these two COFs outperform the mass activity (at 0.85 V) of commercial Pt/C (20%) by 5.8 times (Co@rhm-PorBTD) and 1.3 times (Co@sql-PorBTD), respectively. The specific activities of Co@rhm-PorBTD and Co@sql-PorBTD were found to be 10 times and 2.5 times larger than that of Pt/C, respectively. These COFs also exhibit larger power density and recycling stability in Zn-air batteries compared with a Pt/C-based air cathode. A theoretical analysis demonstrates that the combination of Co-porphyrin with two different BTD ligands affords two crystalline porous electrocatalysts having different d-band center positions, which leads to reactivity differences toward alkaline ORR. The strategy, design, and electrochemical performance of these two COFs offer a pyrolysis-free bottom-up approach that avoids the creation of random atomic sites, significant metal aggregation, or unpredictable structural features.
KW - alkaline oxygen reduction
KW - benzothiadiazole based
KW - covalent organic framework
KW - donor−acceptor
KW - porphyrin-benzothiadiazole
KW - porphyrinic framework
UR - http://www.scopus.com/inward/record.url?scp=85147828551&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=85147828551&partnerID=8YFLogxK
U2 - 10.1021/acsnano.2c09838
DO - 10.1021/acsnano.2c09838
M3 - Article
C2 - 36753696
AN - SCOPUS:85147828551
SN - 1936-0851
VL - 17
SP - 3492
EP - 3505
JO - ACS Nano
JF - ACS Nano
IS - 4
ER -