Recent advances in covalent organic frameworks （COFs） for electrocatalysis of oxygen electrodes

doi:10.19799/j.cnki.2095-4239.2021.0401

Abstract

Abstract:

Clean energy technologies such as fuel cells, water electrolysis, and metal-air batteries have improved energy efficiency and could become new energy consumption methods in the future to peak carbon dioxide emissions and achieve carbon neutrality. The sluggish kinetics of oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) hinder the development of these clean energy technologies. Although noble metal catalysts are considered superior, they have apparent disadvantages, such as poor durability, low selectivity, and high cost. The determination of noble metal-free catalysts has become a trend in related researches. As an emerging class of polymer materials linked by special covalent bonds, covalent organic frameworks (COFs) demonstrate advantages of tunable structure, low density, high stability, and large specific surface area. COFs are widely considered as promising electrocatalysts that can be gradually applied utilizing reasonable design strategies. Herein, this review aims to research 2D COFs suitable for ORR, OER, and bifunctional electrocatalysis in recent years and primarily introduces the strategies of pristine COF as an electrocatalyst, composite structure formation, and pyrolysis. The key factors for forming electrocatalytic active centers or improving electrocatalytic activity have been summarized from the molecular design and electronic tuning aspects, which are expected to serve as a reference in future works.

Key words: covalent organic frameworks (COFs), oxygen reduction reaction (ORR), oxygen evolution reaction (OER), electrocatalyst

CLC Number:

O 643.36

Wenwu ZOU, Guoxing JIANG, Li DU. Recent advances in covalent organic frameworks （COFs） for electrocatalysis of oxygen electrodes[J]. Energy Storage Science and Technology, 2021, 10(6): 1891-1905.

Figures/Tables 1

References 68

1	SHAO M, CHANG Q, DODELET J P, et al. Recent advances in electrocatalysts for oxygen reduction reaction[J]. Chemical Reviews, 2016, 116(6): 3594-3657.
2	SEH Z W, KIBSGAARD J, DICKENS C F, et al. Combining theory and experiment in electrocatalysis: Insights into materials design[J]. Science, 2017, 355(6321): eaad4998. DOI:10.1126/science.aad4998.
3	ZHENG J F, ZHANG W F, ZHANG J X, et al. Recent advances in nanostructured transition metal nitrides for fuel cells[J]. Journal of Materials Chemistry A, 2020, 8(40): 20803-20818.
4	ZHAO C X, LIU J N, WANG J, et al. Recent advances of noble-metal-free bifunctional oxygen reduction and evolution electrocatalysts[J]. Chemical Society Reviews, 2021, 50(13): 7745-7778.
5	PENG P, ZHOU Z H, GUO J N, et al. Well-defined 2D covalent organic polymers for energy electrocatalysis[J]. ACS Energy Letters, 2017, 2(6): 1308-1314.
6	GENG K, HE T, LIU R, et al. Covalent organic frameworks: Design, synthesis, and functions[J]. Chemical Reviews, 2020, 120(16): 8814-8933.
7	COTE A P. Porous, crystalline, covalent organic frameworks[J]. Science, 2005, 310(5751): 1166-1170.
8	CHEN X Y, GENG K Y, LIU R Y, et al. Covalent organic frameworks: Chemical approaches to designer structures and built-in functions[J]. Angewandte Chemie International Edition, 2020, 59(13): 5050-5091.
9	ZHAO X, PACHFULE P, THOMAS A. Covalent organic frameworks (COFs) for electrochemical applications[J]. Chemical Society Reviews, 2021, 50(12): 6871-6913.
10	DIERCKS C S, YAGHI O M. The atom, the molecule, and the covalent organic framework[J]. Science, 2017, 355(6328): eaal1585.
11	SHARMA R K, YADAV P, YADAV M, et al. Recent development of covalent organic frameworks (COFs): Synthesis and catalytic (organic-electro-photo) applications[J]. Materials Horizons, 2020, 7(2): 411-454.
12	HU C G, DAI L M. Doping of carbon materials for metal-free electrocatalysis[J]. Advanced Materials, 2019, 31(7): 1804672.
13	JIA Y, ZHANG L Z, DU A J, et al. Defect graphene as a trifunctional catalyst for electrochemical reactions[J]. Advanced Materials (Deerfield Beach, Fla), 2016, 28(43): 9532-9538.
14	TANG C, ZHANG Q. Nanocarbon for oxygen reduction electrocatalysis: Dopants, edges, and defects[J]. Advanced Materials (Deerfield Beach, Fla), 2017, 29(13): doi:10.1002/adma.201604103.
15	LI D H, JIA Y, CHANG G J, et al. A defect-driven metal-free electrocatalyst for oxygen reduction in acidic electrolyte[J]. Chem, 2018, 4(10): 2345-2356.
16	QUÍLEZ-BERMEJO J, MORALLÓN E, CAZORLA-AMORÓS D. Metal-free heteroatom-doped carbon-based catalysts for ORR: A critical assessment about the role of heteroatoms[J]. Carbon, 2020, 165: 434-454.
17	JI W Y, WANG T X, DING X S, et al. Porphyrin- and phthalocyanine-based porous organic polymers: From synthesis to application[J]. Coordination Chemistry Reviews, 2021, 439: 213875.
18	LIAO Z J, WANG Y L, WANG Q L, et al. Bimetal-phthalocyanine based covalent organic polymers for highly efficient oxygen electrode[J]. Applied Catalysis B: Environmental, 2019, 243: 204-211.
19	WANG M C, WANG M, LIN H H, et al. High-mobility semiconducting two-dimensional conjugated covalent organic frameworks with p-type doping[J]. Journal of the American Chemical Society, 2020, 142(52): 21622-21627.
20	JIA H X, SUN Z J, JIANG D C, et al. Covalent cobalt porphyrin framework on multiwalled carbon nanotubes for efficient water oxidation at low overpotential[J]. Chemistry of Materials, 2015, 27(13): 4586-4593.
21	SUN B, LIU J, CAO A, et al. Interfacial synthesis of ordered and stable covalent organic frameworks on amino-functionalized carbon nanotubes with enhanced electrochemical performance[J]. Chemical Communications, 2017, 53(47): 6303-6306.
22	JARIWALA D, MARKS T J, HERSAM M C. Mixed-dimensional van der Waals heterostructures[J]. Nature Materials, 2017, 16(2): 170-181.
23	CHEN X D, ZHANG H, CI C G, et al. Few-layered boronic ester based covalent organic frameworks/carbon nanotube composites for high-performance K-organic batteries[J]. ACS Nano, 2019, 13(3): 3600-3607.
24	IWASE K, NAKANISHI S, MIYAYAMA M, et al. Rational molecular design of electrocatalysts based on single-atom modified covalent organic frameworks for efficient oxygen reduction reaction[J]. ACS Applied Energy Materials, 2020, 3(2): 1644-1652.
25	WANG J, WANG J R, QI S Y, et al. Stable multifunctional single-atom catalysts resulting from the synergistic effect of anchored transition-metal atoms and host covalent-organic frameworks[J]. The Journal of Physical Chemistry C, 2020, 124(32): 17675-17683.
26	ZHAI L P, YANG S, YANG X B, et al. Conjugated covalent organic frameworks as platinum nanoparticle supports for catalyzing the oxygen reduction reaction[J]. Chemistry of Materials, 2020, 32(22): 9747-9752.
27	XIANG Z H, CAO D P, HUANG L, et al. Nitrogen-doped holey graphitic carbon from 2D covalent organic polymers for oxygen reduction[J]. Advanced Materials, 2014, 26(20): 3315-3320.
28	GE X M, SUMBOJA A, WUU D, et al. Oxygen reduction in alkaline media: From mechanisms to recent advances of catalysts[J]. ACS Catalysis, 2015, 5(8): 4643-4667.
29	ZHU X F, HU C G, AMAL R, et al. Heteroatom-doped carbon catalysts for zinc-air batteries: Progress, mechanism, and opportunities[J]. Energy & Environmental Science, 2020, 13(12): 4536-4563.
30	YU L, PAN X L, CAO X M, et al. Oxygen reduction reaction mechanism on nitrogen-doped graphene: A density functional theory study[J]. Journal of Catalysis, 2011, 282(1): 183-190.
31	WANG Y W, QIU W J, SONG E H, et al. Adsorption-energy-based activity descriptors for electrocatalysts in energy storage applications[J]. National Science Review, 2018, 5(3): 327-341.
32	LI D, LI C, ZHANG L, et al. Metal-free thiophene-sulfur covalent organic frameworks: Precise and controllable synthesis of catalytic active sites for oxygen reduction[J]. Journal of the American Chemical Society, 2020, 142(18): 8104-8108.
33	WU S, LI M, PHAN H, et al. Toward two-dimensional π-conjugated covalent organic radical frameworks[J]. Angewandte Chemie, 2018, 57(27): 8007-8011.
34	GUO J N, LIN C Y, XIA Z H, et al. A pyrolysis-free covalent organic polymer for oxygen reduction[J]. Angewandte Chemie International Edition, 2018, 57(38): 12567-12572.
35	CHEN S, ZHENG Y, ZHANG B, et al. Cobalt, nitrogen-doped porous carbon nanosheet-assembled flowers from metal-coordinated covalent organic polymers for efficient oxygen reduction[J]. ACS Applied Materials & Interfaces, 2019, 11(1): 1384-1393.
36	ZHANG S H, XIA W, YANG Q, et al. Core-shell motif construction: Highly graphitic nitrogen-doped porous carbon electrocatalysts using MOF-derived carbon@COF heterostructures as sacrificial templates[J]. Chemical Engineering Journal, 2020, 396: 125154.
37	LIN Q P, BU X H, KONG A G, et al. Heterometal-embedded organic conjugate frameworks from alternating monomeric iron and cobalt metalloporphyrins and their application in design of porous carbon catalysts[J]. Advanced Materials, 2015, 27(22): 3431-3436.
38	PACHFULE P, DHAVALE V M, KANDAMBETH S, et al. Porous-organic-framework-templated nitrogen-rich porous carbon as a more proficient electrocatalyst than Pt/C for the electrochemical reduction of oxygen[J]. Chemistry (Weinheim an Der Bergstrasse, Germany), 2013, 19(3): 974-980.
39	ZHAO X J, PACHFULE P, LI S, et al. Silica-templated covalent organic framework-derived Fe-N-doped mesoporous carbon as oxygen reduction electrocatalyst[J]. Chemistry of Materials, 2019, 31(9): 3274-3280.
40	LI Z, ZHAO W, YIN C, et al. Synergistic effects between doped nitrogen and phosphorus in metal-free cathode for zinc-air battery from covalent organic frameworks coated CNT[J]. ACS Applied Materials & Interfaces, 2017, 9(51): 44519-44528.
41	WEI S, WANG Y, CHEN W, et al. Atomically dispersed Fe atoms anchored on COF-derived N-doped carbon nanospheres as efficient multi-functional catalysts[J]. Chemical Science, 2019, 11(3): 786-790.
42	XU Q, TANG Y, ZHANG X, et al. Template conversion of covalent organic frameworks into 2D conducting nanocarbons for catalyzing oxygen reduction reaction[J]. Advanced Materials, 2018, 30(15): e1706330.
43	KAMIYA K, KAMAI R, HASHIMOTO K, et al. Platinum-modified covalent triazine frameworks hybridized with carbon nanoparticles as methanol-tolerant oxygen reduction electrocatalysts[J]. Nature Communications, 2014, 5: 5040.
44	BIAN G, YIN J, ZHU J. Recent advances on conductive 2D covalent organic frameworks[J]. Small, 2021, 17(22): 2006043.
45	WANG J, ZHONG H X, QIN Y L, et al. An efficient three-dimensional oxygen evolution electrode[J]. Angewandte Chemie, 2013, 52(20): 5248-5253.
46	SONG J J, WEI C, HUANG Z F, et al. A review on fundamentals for designing oxygen evolution electrocatalysts[J]. Chemical Society Reviews, 2020, 49(7): 2196-2214.
47	SUEN N T, HUNG S F, QUAN Q, et al. Electrocatalysis for the oxygen evolution reaction: Recent development and future perspectives[J]. Chemical Society Reviews, 2017, 46(2): 337-365.
48	GOPI S, KATHIRESAN M. 1, 4-Phenylenediamine based covalent triazine framework as an electro catalyst[J]. Polymer, 2017, 109: 315-320.
49	MONDAL S, MOHANTY B, NURHUDA M, et al. A thiadiazole-based covalent organic framework: A metal-free electrocatalyst toward oxygen evolution reaction[J]. ACS Catalysis, 2020, 10(10): 5623-5630.
50	AIYAPPA H B, THOTE J, SHINDE D B, et al. Cobalt-modified covalent organic framework as a robust water oxidation electrocatalyst[J]. Chemistry of Materials, 2016, 28(12): 4375-4379.
51	MULLANGI D, DHAVALE V, SHALINI S, et al. Low-overpotential electrocatalytic water splitting with noble-metal-free nanoparticles supported in a sp3N-rich flexible COF[J]. Advanced Energy Materials, 2016, 6(13): 1600110.
52	ZHAO X, PACHFULE P, LI S, et al. Macro/microporous covalent organic frameworks for efficient electrocatalysis[J]. Journal of the American Chemical Society, 2019, 141(16): 6623-6630.
53	NANDI S, SINGH S K, MULLANGI D, et al. Low band gap benzimidazole COF supported Ni3N as highly active OER catalyst[J]. Advanced Energy Materials, 2016, 6(24): 1601189.
54	ZHUANG G L, GAO Y F, ZHOU X, et al. ZIF-67/COF-derived highly dispersed Co₃O₄/N-doped porous carbon with excellent performance for oxygen evolution reaction and Li-ion batteries[J]. Chemical Engineering Journal, 2017, 330: 1255-1264.
55	FAN X H, KONG F T, KONG A G, et al. Covalent porphyrin framework-derived Fe₂P@Fe4N-coupled nanoparticles embedded in N-doped carbons as efficient trifunctional electrocatalysts[J]. ACS Applied Materials & Interfaces, 2017, 9(38): 32840-32850.
56	GAO Z, YU Z W, HUANG Y X, et al. Flexible and robust bimetallic covalent organic frameworks for the reversible switching of electrocatalytic oxygen evolution activity[J]. Journal of Materials Chemistry A, 2020, 8(12): 5907-5912.
57	GAO Z, GONG L L, HE X Q, et al. General strategy to fabricate metal-incorporated pyrolysis-free covalent organic framework for efficient oxygen evolution reaction[J]. Inorganic Chemistry, 2020, 59(7): 4995-5003.
58	YANG C, YANG Z-D, DONG H, et al. Theory-driven design and targeting synthesis of a highly-conjugated basal-plane 2D covalent organic framework for metal-free electrocatalytic OER[J]. ACS Energy Letters, 2019, 4(9): 2251-2258.
59	JIA H X, YAO Y C, GAO Y Y, et al. Pyrolyzed cobalt porphyrin-based conjugated mesoporous polymers as bifunctional catalysts for hydrogen production and oxygen evolution in water[J]. Chemical Communications (Cambridge, England), 2016, 52(92): 13483-13486.
60	DEY S, MONDAL B, CHATTERJEE S, et al. Molecular electrocatalysts for the oxygen reduction reaction[J]. Nature Reviews Chemistry, 2017, 1: 0098.
61	FU J, LIANG R, LIU G, et al. Recent progress in electrically rechargeable zinc-air batteries[J]. Advanced Materials, 2019, 31(31): e1805230.
62	APPEL A M, HELM M L. Determining the overpotential for a molecular electrocatalyst[J]. ACS Catalysis, 2014, 4(2): 630-633.
63	KONG F T, FAN X H, KONG A G, et al. Covalent phenanthroline framework derived FeS@Fe₃C composite nanoparticles embedding in N-S-codoped carbons as highly efficient trifunctional electrocatalysts[J]. Advanced Functional Materials, 2018, 28(51): 1803973.
64	PARK J H, LEE C H, JU J M, et al. Bifunctional covalent organic framework-derived electrocatalysts with modulated p-band centers for rechargeable Zn-air batteries[J]. Advanced Functional Materials, 2021, 31(25): 2101727.
65	LIU C, LIU F, LI H, et al. One-dimensional van der waals heterostructures as efficient metal-free oxygen electrocatalysts[J]. ACS Nano, 2021, 15(2): 3309-3319.
66	ZHANG H, QU Z, TANG H M, et al. On-chip integration of a covalent organic framework-based catalyst into a miniaturized Zn-air battery with high energy density[J]. ACS Energy Letters, 2021, 6(7): 2491-2498.
67	LIN X X, PENG P, GUO J N, et al. Reaction milling for scalable synthesis of N, P-codoped covalent organic polymers for metal-free bifunctional electrocatalysts[J]. Chemical Engineering Journal, 2019, 358: 427-434.
68	LI B Q, ZHANG S Y, CHEN X, et al. Framework porphyrins: One-pot synthesis of framework porphyrin materials and their applications in bifunctional oxygen electrocatalysis[J]. Advanced Functional Materials, 2019, 29(29): 1970198.

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