A Co Porphyrin with Electron-Withdrawing and Hydrophilic Substituents for Improved Electrocatalytic Oxygen Reduction

Authors

Hong-Bo Guo, Key Laboratory for Colloid and Interface Chemistry Ministry of Education, School of Chemistry and Chemical Engineering, Shandong University, Jinan 250100, Shandong, China;
Ya-Ni Wang, Key Laboratory of Applied Surface and Colloid Chemistry, Ministry of Education, School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi’an 710119, China;
Kai Guo, Key Laboratory of Applied Surface and Colloid Chemistry, Ministry of Education, School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi’an 710119, China;
Hai-Tao Lei, Key Laboratory of Applied Surface and Colloid Chemistry, Ministry of Education, School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi’an 710119, China;
Zuo-Zhong Liang, Key Laboratory of Applied Surface and Colloid Chemistry, Ministry of Education, School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi’an 710119, China;Follow
Xue-Peng Zhang, Key Laboratory of Applied Surface and Colloid Chemistry, Ministry of Education, School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi’an 710119, China;Follow
Rui Cao, Key Laboratory of Applied Surface and Colloid Chemistry, Ministry of Education, School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi’an 710119, China;Follow

Corresponding Author

Zuo-Zhong Liang(liangzuozhong@snnu.edu.cn);
Xue-Peng Zhang(zhangxp@snnu.edu.cn);
Rui Cao(ruicao@snnu.edu.cn)

Abstract

Understanding factors that influence the catalyst activity for oxygen reduction reaction (ORR) is essential for the rational design of efficient ORR catalysts. Regulating catalyst electronic structure is commonly used to fine-tune electrocatalytic ORR activity. However, modifying the hydrophilicity of catalysts has been rarely reported to improve ORR, which happens at the liquid/gas/solid interface. Herein, we report on two Co porphyrins, namely, NO₂-CoP (Co complex of 5,10,15,20-tetrakis(4-nitrophenyl)porphyrin) and 5F-CoP (Co complex of 5,10,15,20-tetrakis(pentafluorophenyl)porphyrin), and their electrocatalytic ORR features. By simultaneously controlling the electronic structure and hydrophilic property of the meso-substituents, the NO₂-CoP showed higher electrocatalytic activity than the 5F-CoP by shifting the ORR half-wave potential to the anodic direction by 60 mV. Compared with the 5F-CoP, the complex NO₂-CoP was more hydrophilic. Theoretical calculations suggest that NO₂-CoP is also more efficient than 5F-CoP to bind with an O₂ molecule to form Co^III-O₂^·-. This work provides a simple but an effective strategy to improve ORR activity of Co porphyrins by using electron-withdrawing and hydrophilic substituents. This strategy will be also valuable for the design of other ORR molecular electrocatalysts.

Graphical Abstract

Keywords

molecular electrocatalysis, oxygen reduction, Co porphyrin, hydrophilicity, electronic structure

DOI Link

https://doi.org/10.13208/j.electrochem.2214002

Publication Date

2022-09-28

Online Available Date

2022-05-25

Revised Date

2022-05-17

Received Date

2022-04-13

Recommended Citation

Hong-Bo Guo, Ya-Ni Wang, Kai Guo, Hai-Tao Lei, Zuo-Zhong Liang, Xue-Peng Zhang, Rui Cao. A Co Porphyrin with Electron-Withdrawing and Hydrophilic Substituents for Improved Electrocatalytic Oxygen Reduction[J]. Journal of Electrochemistry, 2022 , 28(9): 2214002.
DOI: 10.13208/j.electrochem.2214002
Available at: https://jelectrochem.xmu.edu.cn/journal/vol28/iss9/7

References

[1] Zaman S, Huang L, Douka A I, Yang H, You B, Xia B Y. Oxygen reduction electrocatalysts toward practical fuel cells: Progress and perspectives[J]. Angew. Chem. Int. Ed., 2021, 60(33): 17832-17852.
doi: 10.1002/anie.202016977 pmid: 33533165

[2] Zhao C X, Liu J N, Wang J, Ren D, Li B Q, Zhang Q. Recent advances of noble-metal-free bifunctional oxygen reduction and evolution electrocatalysts[J]. Chem. Soc. Rev., 2021, 50(13): 7745-7778.
doi: 10.1039/D1CS00135C URL

[3] Amanullah S, Das P K, Samanta S, Dey A. Tuning the thermodynamic onset potential of electrocatalytic O₂ reduction reaction by synthetic iron-porphyrin complexes[J]. Chem. Commun., 2015, 51(49): 10010-10013.
doi: 10.1039/C5CC01938A URL

[4] Kong J F, Cheng W L. Recent advances in the rational design of electrocatalysts towards the oxygen reduction reaction[J]. Chin. J. Catal., 2017, 38(6): 951-969.
doi: 10.1016/S1872-2067(17)62801-8 URL

[5] Song P, Ruan M B, Liu J, Ran G J, Xu W L. Recent research progress for non-Pt-based oxygen reduction reaction electrocatalysts in fuel cell[J]. J. Electrochem., 2015, 21(2): 130-137.
doi: 10.13208/j.electrochem.141041 URL

[6] Wang D, Pan X N, Yang P X, Li R P, Xu H, Li Y, Meng F, Zhang J Q, An M Z. Transition metal and nitrogen Co-doped carbon-based electrocatalysts for the oxygen reduction reaction: From active site insights to the rational design of precursors and structures[J]. ChemSusChem, 2021, 14(1): 33-55.
doi: 10.1002/cssc.202002137 pmid: 33078564

[7] Zhao T, Luo E G, Wang X, Ge J J, Liu C P, Xing W. Challenges in the activity and stability of Pt-based catalysts toward ORR[J]. J. Electrochem., 2020, 26(1): 84-95.
doi: 10.13208/j.electrochem.181205 URL

[8] Kumar A, Zhang Y, Jia Y, Liu W, Sun X M. Redox chemistry of N₄-Fe²⁺ in iron phthalocyanines for oxygen reduction reaction[J]. Chin. J. Catal., 2021, 42(8): 1404-1412.
doi: 10.1016/S1872-2067(20)63731-7 URL

[9] Fukuzumi S, Lee Y M, Nam W. Recent progress in production and usage of hydrogen peroxide[J]. Chin. J Catal., 2021, 42(8): 1241-1252.
doi: 10.1016/S1872-2067(20)63767-6 URL

[10] Dey S, Mondal B, Chatterjee S, Rana A, Amanullah S K, Dey A. Molecular electrocatalysts for the oxygen reduction reaction[J]. Nat. Rev. Chem., 2017, 1(12): 0098.
doi: 10.1038/s41570-017-0098 URL

[11] Pegis M L, Wise C F, Martin D J, Mayer J M. Oxygen reduction by homogeneous molecular catalysts and electrocatalysts[J]. Chem. Rev., 2018, 118(5): 2340-2391.
doi: 10.1021/acs.chemrev.7b00542 pmid: 29406708

[12] Zhang W, Lai W Z, Cao R. Energy-related small molecule activation reactions: Oxygen reduction and hydrogen and oxygen evolution reactions catalyzed by porphyrin- and corrole-based systems[J]. Chem. Rev., 2017, 117(4): 3717-3797.
doi: 10.1021/acs.chemrev.6b00299 pmid: 28222601

[13] Passard G, Dogutan D K, Qiu M T, Costentin C, Nocera D G. Oxygen reduction reaction promoted by manganese porphyrins[J]. ACS Catal., 2018, 8(9): 8671-8679.
doi: 10.1021/acscatal.8b01944 URL

[14] Zhao Y M, Yu G Q, Wang F F, Wei P J, Liu J G. Bioinspired transition-metal complexes as electrocatalysts for the oxygen reduction reaction[J]. Chem. Eur. J., 2019, 25(15): 3726-3739.
doi: 10.1002/chem.201803764 URL

[15] Zhou Y, Xing Y F, Wen J, Ma H B, Wang F B, Xia X H. Axial ligands tailoring the ORR activity of cobalt porphyrin[J]. Sci. Bull., 2019, 64(16): 1158-1166.
doi: 10.1016/j.scib.2019.07.003 URL

[16] Xie L S, Zhang X P, Zhao B, Li P, Qi J, Guo X N, Wang B, Lei H T, Zhang W, Apfel U P, Cao R. Enzyme-inspired iron porphyrins for improved electrocatalytic oxygen reduction and evolution reactions[J]. Angew. Chem. Int. Ed., 2021, 60(14): 7576-7581.
doi: 10.1002/anie.202015478 pmid: 33462971

[17] Lv H Y, Guo H B, Guo K, Lei H T, Zhang W, Zheng H Q, Liang Z Z, Cao R. Substituent position effect of Co porphyrin on oxygen electrocatalysis[J]. Chin. Chem. Lett., 2021, 32(9): 2841-2845.
doi: 10.1016/j.cclet.2021.02.032 URL

[18] Lv B, Li X L, Guo K, Ma J, Wang Y Z, Lei H T, Wang F, Jin X T, Zhang Q X, Zhang W, Long R, Xiong Y J, Apfel U P, Cao R. Controlling oxygen reduction selectivity through steric effects: Electrocatalytic two-electron and four-electron oxygen reduction with cobalt porphyrin atropisomers[J]. Angew. Chem. Int. Ed., 2021, 60(23): 12742-12746.
doi: 10.1002/anie.202102523 pmid: 33742485

[19] Hong Y H, Han J W, Jung J, Nakagawa T, Lee Y M, Nam W, Fukuzumi S. Photocatalytic oxygenation reactions with a cobalt porphyrin complex using water as an oxygen source and dioxygen as an oxidant[J]. J. Am. Chem. Soc., 2019, 141(23): 9155-9159.
doi: 10.1021/jacs.9b02864 pmid: 31145595

[20] Li X L, Lei H T, Xie L S, Wang N, Zhang W, Cao R. Metalloporphyrins as catalytic models for studying hydrogen and oxygen evolution and oxygen reduction reactions[J]. Acc. Chem. Res., 2022, 55(6): 878-892.
doi: 10.1021/acs.accounts.1c00753 URL

[21] Zhang R, Warren J J. Recent developments in metallopo-rphyrin electrocatalysts for reduction of small molecules: Strategies for managing electron and proton transfer reactions[J]. ChemSusChem, 2021, 14(1): 293-302.
doi: 10.1002/cssc.202001914 pmid: 33064354

[22] Mondal B, Sen P, Dey A. Proton reduction in the presence of oxygen by iron porphyrin enabled with 2nd sphere redox active ferrocenes[J]. Chin. J. Catal., 2021, 42(8): 1327-1331.
doi: 10.1016/S1872-2067(20)63761-5 URL

[23] Grinstaff M W, Hill M G, Labinger J A, Gray H B. Mech-anism of catalytic oxygenation of alkanes by halogenated iron porphyrins[J]. Science, 1994, 264(5163): 1311-1313.
pmid: 8191283

[24] Zagal J H, Recio F J, Gutierrez C A, Zuniga C, Paez M A, Caro C A. Towards a unified way of comparing the electrocatalytic activity MN₄ macrocyclic metal catalysts for O₂ reduction on the basis of the reversible potential of the reaction[J]. Electrochem. Commun., 2014, 41: 24-26.
doi: 10.1016/j.elecom.2014.01.009 URL

[25] Li Y L, Wang N, Lei H T, Li X L, Zheng H Q, Wang H Y, Zhang W, Cao R. Bioinspired N₄-metallomacrocycles for electrocatalytic oxygen reduction reaction[J]. Coord. Chem. Rev., 2021, 442: 213996.
doi: 10.1016/j.ccr.2021.213996 URL

[26] Masa J, Schuhmann W. Systematic selection of metalloporphyrin-based catalysts for oxygen reduction by modulation of the donor-acceptor intermolecular hardness[J]. Chem. Eur. J., 2013, 19(29): 9644-9654.
doi: 10.1002/chem.201203846 URL

[27] Zhao C X, Li B Q, Liu J N, Huang J Q, Zhang Q. Transition metal coordinated framework porphyrin for electrocatalytic oxygen reduction[J]. Chin. Chem. Lett., 2019, 30(4): 911-914.
doi: 10.1016/j.cclet.2019.03.026 URL

[28] Wang Y H, Mondal B, Stahl S S. Molecular cobalt catalysts for O₂ reduction to H₂O₂: Benchmarking catalyst performance via rate-overpotential correlations[J]. ACS Catal., 2020, 10(20): 12031-12039.
doi: 10.1021/acscatal.0c02197 URL

[29] Lei H T, Zhang Q X, Wang Y B, Gao Y M, Wang Y Z, Liang Z Z, Zhang W, Cao R. Significantly boosted oxygen electrocatalysis with cooperation between cobalt and iron porphyrins dagger[J]. Dalton Trans., 2021, 50(15): 5120-5123.
doi: 10.1039/d1dt00441g pmid: 33881086

[30] Liu Y J, Zhou G J, Zhang Z Y, Lei H T, Yao Z, Li J F, Lin J, Cao R. Significantly improved electrocatalytic oxygen reduction by an asymmetrical pacman dinuclear cobalt(II) porphyrin-porphyrin dyad[J]. Chem. Sci., 2020, 11(1): 87-96.
doi: 10.1039/c9sc05041h pmid: 32110360

[31] Oldacre A N, Friedman A E, Cook T R. A self-assembled cofacial cobalt porphyrin prism for oxygen reduction catalysis[J]. J. Am. Chem. Soc., 2017, 139(4): 1424-1427.
doi: 10.1021/jacs.6b12404 pmid: 28102678

[32] Zhang W, Shaikh A U, Tsui E Y, Swager T M. Cobalt porphyrin functionalized carbon nanotubes for oxygen reduction[J]. Chem. Mater., 2009, 21(14): 3234-3241.

[33] Liang Z Z, Guo H B, Zhou G J, Guo K, Wang B, Lei H T, Zhang W, Zheng H Q, Apfel U P, Cao R. Metal-organic-framework-supported molecular electrocatalysis for the oxygen reduction reaction[J]. Angew. Chem. Int. Ed., 2021, 60(15): 8472-8476.
doi: 10.1002/anie.202016024 pmid: 33484092

[34] Crawley M R, Zhang D Y, Oldacre A N, Beavers C M, Friedman A E, Cook T R. Tuning the reactivity of cofacial porphyrin prisms for oxygen reduction using modular building blocks[J]. J. Am. Chem. Soc., 2021, 143(2): 1098-1106.
doi: 10.1021/jacs.0c11895 pmid: 33377787

[35] Wan H, Jensen A W, Escudero-Escribano M, Rossmeisl J. Insights in the oxygen reduction reaction: From metallic electrocatalysts to diporphyrins[J]. ACS Catal., 2020, 10(11): 5979-5989.
doi: 10.1021/acscatal.0c01085 URL

[36] Sun B, Ou Z P, Meng D Y, Fang Y Y, Song Y, Zhu W H, Solntsev P V, Nemykin V N, Kadish K M. Electrochemistry and catalytic properties for dioxygen reduction using ferrocene-substituted cobalt porphyrins[J]. Inorg. Chem., 2014, 53(16): 8600-8609.
doi: 10.1021/ic501210t pmid: 25068447

[37] Zhang Q X, Wang Y B, Wang Y Z, Yang S J, Wu X, Lv B, Wang N, Gao Y M, Xu X R, Lei H T, Cao R. Electropolymerization of cobalt porphyrins and corroles for the oxygen evolution reaction[J]. Chin. Chem. Lett., 2021, 32(12): 3807-3810.
doi: 10.1016/j.cclet.2021.04.048 URL

[38] Song E H, Shi C N, Anson F C. Comparison of the behavior of several cobalt porphyrins as electrocatalysts for the reduction of O₂ at graphite electrodes[J]. Langmuir, 1998, 14(15): 4315-4321.
doi: 10.1021/la980084d URL

[39] Xie L S, Li X L, Wang B, Meng J, Lei H T, Zhang W, Cao R. Molecular engineering of a 3D self-supported electrode for oxygen electrocatalysis in neutral media[J]. Angew. Chem. Int. Ed., 2019, 58(52): 18883-18887.
doi: 10.1002/anie.201911441 pmid: 31626385

[40] Han J X, Wang N, Li X L, Zhang W, Cao R. Improving electrocatalytic oxygen reduction activity and selectivity with a cobalt corrole appended with multiple positively charged proton relay sites[J]. J. Phys. Chem. C, 2021, 125(45): 24805-24813.
doi: 10.1021/acs.jpcc.1c07578 URL

[41] Sonkar P K, Prakash K, Yadav M, Ganesan V, Sankar M, Gupta R, Yadav D K. Co(II)-porphyrin-decorated carbon nanotubes as catalysts for oxygen reduction reactions: An approach for fuel cell improvement[J]. J. Mater. Chem. A, 2017, 5(13): 6263-6276.
doi: 10.1039/C6TA10482G URL

[42] McGuire R, Dogutan D K, Teets T S, Suntivich J, Shao-Horn Y, Nocera D G. Oxygen reduction reactivity of cobalt(II) hangman porphyrins[J]. Chem. Sci., 2010, 1(3): 411-414.
doi: 10.1039/c0sc00281j URL

[43] Liang Z, Wang H Y, Zheng H Q, Zhang W, Cao R. Porphyrin-based frameworks for oxygen electrocatalysis and catalytic reduction of carbon dioxide[J]. Chem. Soc. Rev., 2021, 50(4): 2540-2581.
doi: 10.1039/d0cs01482f pmid: 33475099

[44] Qin H N, Wang Y Z, Wang B, Duan X G, Lei H T, Zhang X P, Zheng H Q, Zhang W, Cao R. Cobalt porphyrins supported on carbon nanotubes as model catalysts of metal-N₄/C sites for oxygen electrocatalysis[J]. J. Energy Chem., 2021, 53: 77-81.
doi: 10.1016/j.jechem.2020.05.015 URL

[45] Xu W W, Lu Z Y, Sun X M, Jiang L, Duan X. Superwetting electrodes for gas-involving electrocatalysis[J]. Acc. Chem. Res., 2018, 51(7): 1590-1598.
doi: 10.1021/acs.accounts.8b00070 URL

[46] Longhi M, Cova C, Pargoletti E, Coduri M, Santangelo S, Patanè S, Ditaranto N, Cioffi N, Facibeni A, Scavini M. Synergistic effects of active sites’ nature and hydrophilicity on the oxygen reduction reaction activity of Pt-free catalysts[J]. Nanomaterials, 2018, 8(9): 643.
doi: 10.3390/nano8090643 URL

[47] Lei H T, Wang Y B, Zhang Q X, Cao R. First-row transition metal porphyrins for electrocatalytic hydrogen evolution — a SPP/JPP Young Investigator Award paper[J]. J. Porphyr. Phthalocyanines, 2020, 24(11-12): 1361-1371.
doi: 10.1142/S1088424620500157 URL

[48] Brüker AXS. APEX2 V2009.

[49] Sheldrick G. SADABS—Brüker AXS area detector scaling and absorption, version 2008/1. University of Göttingen, Germany, 2008.

[50] Sheldrick G M. Phase annealing in SHELX-90: Direct methods for larger structures[J]. Acta Cryst., 1990, 46: 467-473.
doi: 10.1107/S0108767390000277 URL

[51] Sheldrick G M. Crystal structure refinement with SHELXL[J]. Acta Cryst., 2015, 71: 3-8.

[52] Xia B Y, Yan Y, Li N, Wu H B, Lou X W, Wang X. A metal-organic framework-derived bifunctional oxygen electrocatalyst[J]. Nat. Energy, 2016, 1: 15006.
doi: 10.1038/nenergy.2015.6 URL

[53] Frisch M J, Trucks G W, Schlegel H B, Scuseria G E, Robb M A, Cheeseman J R, Fox D J. Gaussian16 Revision A. 03 (Wallingford, Ct: Gaussian Inc.), 2016.

[54] Grimme S, Ehrlich S, Goerigk L. Effect of the damping function in dispersion corrected density functional theory[J]. J. Comp. Chem., 2011, 32(7): 1456-1465.
doi: 10.1002/jcc.21759 URL

[55] Becke A D. Density-functional exchange-energy approximation with correct asymptotic behavior[J]. Phys. Rev. A, 1988, 38(6): 3098-3100.
doi: 10.1103/PhysRevA.38.3098 URL

[56] Lee C T, Yang W T, Parr R G. Development of the colle-salvetti correlation-energy formula into a functional of the electron density[J]. Phys. Rev. B, 1988, 37(2): 785-789.
pmid: 9944570

[57] Becke A D. Density-functional thermochemistry. III. The role of exact exchange[J]. J. Chem. Phys., 1993, 98(7): 5648-5652.
doi: 10.1063/1.464913 URL

[58] Weigend F, Ahlrichs R. Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy[J]. Phys. Chem. Chem. Phys., 2005, 7(18): 3297-3305.
pmid: 16240044[

59] Tomasi J, Mennucci B, Cammi R. Quantum mechanical continuum solvation models[J]. Chem. Rev., 2005, 105(8): 2999-3093.
doi: 10.1021/cr9904009 pmid: 16092826

[60] Reed A E, Curtiss L A, Weinhold F. Intermolecular interactions from a natural bond orbital, donor-acceptor viewpoint[J]. Chem. Rev., 1988, 88(6): 899-926.
doi: 10.1021/cr00088a005 URL