Heterometal‐Embedded Organic Conjugate Frameworks from Alternating Monomeric Iron and Cobalt Metalloporphyrins and Their Application in Design of Porous Carbon Catalysts

Lin, Qipu; Bu, Xianhui; Kong, Aiguo; Mao, Chengyu; Bu, Fei; Feng, Pingyun

doi:10.1002/adma.201500727

Cited by 242 publications

(144 citation statements)

References 52 publications

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“…Previously, phthalocyanine/porphyrin-like macrocycles have been widely studied as prospective scaffolds for the construction of nonprecious electrocatalysts for the oxygen reduction reaction (ORR), [26,27] whereas their application in the synthesis of high-performance OER catalysts is rarely reported. Previously, phthalocyanine/porphyrin-like macrocycles have been widely studied as prospective scaffolds for the construction of nonprecious electrocatalysts for the oxygen reduction reaction (ORR), [26,27] whereas their application in the synthesis of high-performance OER catalysts is rarely reported.…”

Section: Wwwadvmatde Wwwadvancedsciencenewscommentioning

confidence: 99%

“…[8,30] These characteristic peaks are more obvious in the carbon material prepared without NH 3 -treatment (Figure 1a). Compared to conventional Co-based electrocatalysts prepared using phthalocyanine-like rings as templates, [26,27] high-temperature pyrolysis may play a crucial role in formatting of Co 4 N, rather than other Co-based materials. In addition, to confirm the successful production of Co 4 N, we further prepared an analogue phthalocyanine-linked framework (Pc-POF-Co) in the absence of FeCl 2.…”

Section: Wwwadvmatde Wwwadvancedsciencenewscommentioning

confidence: 99%

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In Situ Coupling Strategy for the Preparation of FeCo Alloys and Co₄N Hybrid for Highly Efficient Oxygen Evolution

et al. 2017

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An in situ coupling approach is developed to create a new highly efficient and durable cobalt-based electrocatalyst for the oxygen evolution reaction (OER). Using a novel cyclotetramerization, a task-specific bimetallic phthalocyanine-based nanoporous organic framework is successfully built as a precursor for the carbonization synthesis of a nonprecious OER electrocatalyst. The resultant material exhibits an excellent OER activity with a low overpotential of 280 mV at a current density of 10 mA cm and high durability in an alkaline medium. This impressive result ranks among the best from known Co-based OER catalysts under the same conditions. The simultaneous installation of multiple diverse cobalt-based active sites, including FeCo alloys and Co N nanoparticles, plays a critical role in achieving this promising OER performance. This innovative approach not only enables high-performance OER activity to be achieved but simultaneously provides a means to control the surface features, thereby tuning the catalytic property of the material.

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Section: Wwwadvmatde Wwwadvancedsciencenewscommentioning

confidence: 99%

Section: Wwwadvmatde Wwwadvancedsciencenewscommentioning

confidence: 99%

In Situ Coupling Strategy for the Preparation of FeCo Alloys and Co₄N Hybrid for Highly Efficient Oxygen Evolution

et al. 2017

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“…However, low abundance, high cost and methanol-sensitivity of Pt has limited its application in ORR catalysis. [26][27][28] It has been reported that polymeric metallated porphyrins with multiple interconnected catalytic centers can directly reduce oxygen to water in high efficiency through 4e pathway. [3][4][5][6][7][8][9][10][11][12][13][14][15] Various ORR electrocatalysts containing non-precious metals (e.g.…”

Section: Introductionmentioning

confidence: 99%

“…Consequently, great efforts have been devoted to the search for durable and costeffective replacement of Pt-based catalysts. 24,[29][30][31][32] The advantages of POPs include large specific surface area, tunable pore size and high physiochemical stability. Fe and Co) have been extensively investigated for over 50 years, [16][17][18][19][20][21][22][23][24] such as transition metal oxides, 8,15,25 chalcogenides, 9,10 and bio-inspired organometallic complexes.…”

Section: Introductionmentioning

confidence: 99%

Metallated porphyrin based porous organic polymers as efficient electrocatalysts

Zhu

et al. 2015

Nanoscale

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Developing efficient, stable and low-cost catalysts for Oxygen Reduction Reaction (ORR) is of great significance to many emerging technologies including fuel cells and metal-air batteries. Herein, we report the development of a cobalt(II) porphyrin based porous organic polymer (CoPOP) and its pyrolyzed derivatives as highly active ORR catalysts. The as-synthesized CoPOP exhibits high porosity and excellent catalytic performance stability, retaining ∼100% constant ORR current over 50,000 s in both alkaline and acidic media. Pyrolysis of CoPOP at various temperatures (600 °C, 800 °C, and 1000 °C) yields the materials consisting of graphitic carbon layers and cobalt nanoparticles, which show greatly enhanced catalytic activity compared to the as-synthesized CoPOP. Among them, CoPOP-800/C pyrolyzed at 800 °C shows the highest specific surface area and ORR activity, displaying the most positive half-wave potential (0.825 V vs. RHE) and the largest limited diffusion current density (5.35 mA cm(-2)) in an alkaline medium, which are comparable to those of commercial Pt/C (20 wt%) (half-wave potential 0.829 V vs. RHE, limited diffusion current density 5.10 mA cm(-2)). RDE and RRDE experiments indicate that CoPOP-800/C directly reduces molecular oxygen to water through a 4-e(-) pathway in both alkaline and acidic media. More importantly, CoPOP-800/C exhibits excellent durability and methanol-tolerance under acidic and alkaline conditions, which surpass the Pt/C (20 wt%) system.

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“…IR spectra of porphyrin monomer and the polymer film are almost the same, indicating the existence of NH (3315 and 965 cm À1 ), sp 2 -CÀ H(3046 and 2918 cm À1 ), C=C(1560 and 1475 cm À1 ), porphyrin C = N(1388 cm À1 ), porphyrin skeleton (1005 cm À1 ), and psubstituted phenyl C À H( 799 cm À1 ). [21] Furthermore,t he high-resolution XPS spectrum of N1si sc omposed of two peaks (399.7 and 399.1 eV) with an intensity ratio of 1:1, which can be assigned to NH and N = C, respectively (Fig-ure 7e). TheXPS survey spectrum of the film has C1sand N1swith an intensity ratio of 13:1, which is close to the predicted value of 14:1 (Figure 7c;s ame as the EDX spectrum, iodine,p hosphorus,a nd palladium can also be observed).…”

Section: Angewandte Chemiementioning

confidence: 98%

Synthesis of C−C Bonded Two‐Dimensional Conjugated Covalent Organic Framework Films by Suzuki Polymerization on a Liquid–Liquid Interface

Deng

Tan

et al. 2019

Angewandte Chemie

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Synthesis of free-standing two-dimensional (2D) conjugated covalent organic framework (COF) films linked by CÀCb onds is highly desirable.N ow av ery simple and mild strategy has been developed to synthesize them by Suzuki polymerization on aw ater-toluene interface in ar efrigerator. The versatility of this strategy was confirmed by the successful synthesis of two different 2D-COF films:ap orous graphene and aporphyrin-contained 2D-COF.Both 2D-COF films have large lateral sizeand their crystalline domains were visualized by high resolution TEM. Based on the wide compatibility of Suzuki reaction, our breakthrough work opened adoor for the synthesis of various 2D conjugated COF films.For application studies,t he porous graphene exhibits ag ood carrier mobility, which is muchh igher than À C = N À linked 2D COF films and agood catalytic activity for hydrogen evolution reaction, which is comparable with nitrogen-or phosphorus-doped graphene. Angewandte Chemie Communications

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Heterometal‐Embedded Organic Conjugate Frameworks from Alternating Monomeric Iron and Cobalt Metalloporphyrins and Their Application in Design of Porous Carbon Catalysts

Cited by 242 publications

References 52 publications

In Situ Coupling Strategy for the Preparation of FeCo Alloys and Co₄N Hybrid for Highly Efficient Oxygen Evolution

In Situ Coupling Strategy for the Preparation of FeCo Alloys and Co₄N Hybrid for Highly Efficient Oxygen Evolution

Metallated porphyrin based porous organic polymers as efficient electrocatalysts

Synthesis of C−C Bonded Two‐Dimensional Conjugated Covalent Organic Framework Films by Suzuki Polymerization on a Liquid–Liquid Interface

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Heterometal‐Embedded Organic Conjugate Frameworks from Alternating Monomeric Iron and Cobalt Metalloporphyrins and Their Application in Design of Porous Carbon Catalysts

Cited by 242 publications

References 52 publications

In Situ Coupling Strategy for the Preparation of FeCo Alloys and Co4N Hybrid for Highly Efficient Oxygen Evolution

In Situ Coupling Strategy for the Preparation of FeCo Alloys and Co4N Hybrid for Highly Efficient Oxygen Evolution

Metallated porphyrin based porous organic polymers as efficient electrocatalysts

Synthesis of C−C Bonded Two‐Dimensional Conjugated Covalent Organic Framework Films by Suzuki Polymerization on a Liquid–Liquid Interface

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Product

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In Situ Coupling Strategy for the Preparation of FeCo Alloys and Co₄N Hybrid for Highly Efficient Oxygen Evolution

In Situ Coupling Strategy for the Preparation of FeCo Alloys and Co₄N Hybrid for Highly Efficient Oxygen Evolution