Systematic study of transition-metal (Fe, Co, Ni, Cu) phthalocyanines as electrocatalysts for oxygen reduction and their evaluation by DFT

Zhang, Zhengping; Yang, Shaoxuan; Dou, Meiling; Liu, Haijing; Gu, Lin; Wang, Rui

doi:10.1039/c6ra12426g

Cited by 90 publications

(66 citation statements)

References 40 publications

(54 reference statements)

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“…[15,[21][22][23] Although the original Fe-N 4 moieties (e.g., the central part of iron phthalocyanine) have been proven to be the highly active sites for ORR, the coordination environment of Fe still needs to be optimized. [24,25] Considering that the high-temperature heat-treatment may make the Fe atoms aggregate and break the N-contained functional groups, [26] choosing an appropriate support material or tuning the coordination environment for Fe may be the important step to prepare high-performance SACs of Fe. [24,27] As one of the appropriate support materials, porous carbon with numerous functional groups can offer large surface area, which could favor the fine dispersion of Fe species and prevent the Fe aggregation for a long-term operation.…”

Section: Introductionmentioning

confidence: 99%

Biomass Derived N-Doped Porous Carbon Supported Single Fe Atoms as Superior Electrocatalysts for Oxygen Reduction

Zhang

Gao

Dou

et al. 2017

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Exploring sustainable and high-performance electrocatalysts for the oxygen reduction reaction (ORR) is the crucial issue for the large-scale application of fuel cell technology. A new strategy is demonstrated to utilize the biomass resource for the synthesis of N-doped hierarchically porous carbon supported single-atomic Fe (SA-Fe/NHPC) electrocatalyst toward the ORR. Based on the confinement effect of porous carbon and high-coordination natural iron source, SA-Fe/NHPC, derived from the hemin-adsorbed bio-porphyra-carbon by rapid heat-treatment up to 800 °C, presents the atomic dispersion of Fe atoms in the N-doped porous carbon. Compared with the molecular hemin and nanoparticle Fe samples, the as-prepared SA-Fe/NHPC exhibits a superior catalytic activity (E = 0.87 V and J = 4.1 mA cm , at 0.88 V), remarkable catalytic stability (≈1 mV negative shift of E , after 3000 potential cycles), and outstanding methanol-tolerance, even much better than the state-of-the-art Pt/C catalyst. The sustainable and effective strategy for utilizing biomass to achieve high-performance single-atom catalysts can also provide an opportunity for other catalytic applications in the atomic scale.

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Section: Introductionmentioning

confidence: 99%

Biomass Derived N-Doped Porous Carbon Supported Single Fe Atoms as Superior Electrocatalysts for Oxygen Reduction

Zhang

Gao

Dou

et al. 2017

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“…[21,22] Considering the requirements for forming saturated and unsaturated CuÀN 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 structures, a post treatment of MOF-derived N/C with much high nitrogen content is beneficial for generation of abundant unsaturated CuÀN structures for high-efficiency ORR electrocatalysis. [21,22] Considering the requirements for forming saturated and unsaturated CuÀN 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 structures, a post treatment of MOF-derived N/C with much high nitrogen content is beneficial for generation of abundant unsaturated CuÀN structures for high-efficie...…”

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confidence: 99%

Directly Anchoring Highly Dispersed Copper Sites on Nitrogen‐Doped Carbon for Enhanced Oxygen Reduction Electrocatalysis

et al. 2018

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A simple but efficient post-treatment strategy was developed to directly anchor highly active and dispersed copper sites on N/C for enhanced oxygen reduction reaction (ORR) electrocatalysis. The ORR activity and selectivity of the prepared CuÀN/C catalyst were significantly enhanced due to efficient binding of copper ions with nitrogen groups on the carbon skeleton to form highly active CuÀN sites. Moreover, the prepared CuÀN/C catalyst also exhibited excellent stability in alkaline electrolytes and Zn-air batteries, indicating great potential for energy applications.Developing cheap and efficient non-platinum group metal (non-PGM) electrocatalysts for oxygen reduction reaction (ORR) is highly desired for large-scale fabrication and application of next-generation ORR-involved sustainable energy devices, including fuel cell, metal-air battery, and chlor-alkali industry. [1,2] In the last decade, transition metal and nitrogen-co-doped nanocarbon (TMÀN/C) materials have been fabricated successfully and thus are promising candidates for replacing PGM materials toward efficient oxygen reduction electrocatalysis. [3][4][5][6] Doping nitrogen atoms into a carbon skeleton can change its intrinsic electronic structures, which then activates the inert conjugated p electrons to be active for ORR. [7,8] Furthermore, when transition metal and nitrogen atoms exist simultaneously during synthesis, highly active metal sites coordinated with nitrogen atoms (TM-N x ) on carbon matrix can be formed and thus significantly boost the ORR electrocatalytic performance of the derived catalyst through strong synergetic effects with nitrogen-doped sites. [9][10][11] However, conventional synthesis paths inevitably generate large-sized metal nanoparticles (NPs), making it difficult to distinguish the contributions from different types of metal sites as well as maximize the use of metal atoms.Recently, highly dispersed metal catalysts, especially singleatom catalysts (SACs) with singly dispersed and isolated metal sites on a support, has drawn much attention. [12,13] SACs not only can maximize the utilization of metal atoms, but also minimize the side reaction due to the homogeneity of metal active sites. Such unique catalysts with highly dispersed metal sites offer great potential for achieving high activity and selectivity, as well as identifying the active sites and revealing the catalytic mechanism for ORR on non-PGM materials. [14] Therefore, the controllable construction of TMÀN/C materials with highly dispersed TM-based sites on carbon matrix is a promising way to significantly improve their electrocatalytic properties for ORR. Y. Li et al. reported a metal-organic-framework (MOF)-based synthesis strategy for Co-based ORR SACs, in which Co-N 2 sites with a strong interaction with peroxide showed superior activity to Co-N 4 sites and Co NPs. [15] Furthermore, an MOF-based cage-encapsulated-precursor pyrolysis strategy was developed to fabricate Fe-based ORR SACs, the electrocatalytic performance of which outperformed commercial Pt/C a...

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“…design a bio‐inspired composite ORR electrocatalyst using pyridine functionalized single walled carbon nanotubes (CNT) to anchor FePc molecules, FePc with an axial ligand anchored on CNT (Figure a) . The Fe, Co, Ni and Cu phthalocyanine macrocycle supported on graphitized carbon black (TMPc/GCB) were prepared respectively by π‐π interaction self‐assembly (Figure b) and used in ORR …”

Section: Origin Configuration Characterization and Catalytic Mechanmentioning

confidence: 99%

“… Figure Caption. Schematic illustration of (a) the structure of FePc−Py−CNT and (b) the preparation process of the TMPc/GCB (TM=Fe, Co, Ni, Cu) electrocatalysts . Reprinted with permission from , , Copyright (2013) Springer Nature.…”

Section: Origin Configuration Characterization and Catalytic Mechanmentioning

confidence: 99%

Transition Metal‐Nitrogen‐Carbon Active Site for Oxygen Reduction Electrocatalysis: Beyond the Fascinations of TM‐N₄

Zhang

Zheng

2018

ChemCatChem

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Low cost transition metal‐nitrogen‐carbon (TM‐N‐C) catalysts hold excellent electrocatalytic activity and stability for oxygen reduction reaction (ORR), and have been considered as the most promising alternative to commercial Pt/C. TM‐N4, once identified as one potential active site for ORR, are brought to the spotlight by several single atom TM‐N‐C catalysts recently. However, it remains ambiguous whether this active site exists and is active for ORR because of the controversial analysis about similar TM‐N‐C catalysts by different groups. Herein, we elucidated the origin, architecture, characterization methods and possible catalytic mechanism of TM‐N4 active site. Some recent cases about single atom TM‐N‐C catalysts with TM‐N4 active site were comprehensively reviewed. Thus, some derived perspectives were presented. Undoubtedly, TM‐N4 enables being qualified as one possible type of active site for ORR. However, a general acceptance may mislead for clarifying, as confirmation of the metal‐centered coordination environment requires for more advanced technologies and strategies.

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Systematic study of transition-metal (Fe, Co, Ni, Cu) phthalocyanines as electrocatalysts for oxygen reduction and their evaluation by DFT

Abstract: A facile approach is reported to prepare a series of transition-metal phthalocyanines supported on graphitized carbon black (TMPc/GCB, TM: Fe, Co, Ni and Cu) as oxygen reduction reaction electrocatalysts,viaπ–π interaction self-assembly.

Cited by 90 publications

References 40 publications

Biomass Derived N-Doped Porous Carbon Supported Single Fe Atoms as Superior Electrocatalysts for Oxygen Reduction

Biomass Derived N-Doped Porous Carbon Supported Single Fe Atoms as Superior Electrocatalysts for Oxygen Reduction

Directly Anchoring Highly Dispersed Copper Sites on Nitrogen‐Doped Carbon for Enhanced Oxygen Reduction Electrocatalysis

Transition Metal‐Nitrogen‐Carbon Active Site for Oxygen Reduction Electrocatalysis: Beyond the Fascinations of TM‐N₄

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Systematic study of transition-metal (Fe, Co, Ni, Cu) phthalocyanines as electrocatalysts for oxygen reduction and their evaluation by DFT

Abstract: A facile approach is reported to prepare a series of transition-metal phthalocyanines supported on graphitized carbon black (TMPc/GCB, TM: Fe, Co, Ni and Cu) as oxygen reduction reaction electrocatalysts,viaπ–π interaction self-assembly.

Cited by 90 publications

References 40 publications

Biomass Derived N-Doped Porous Carbon Supported Single Fe Atoms as Superior Electrocatalysts for Oxygen Reduction

Biomass Derived N-Doped Porous Carbon Supported Single Fe Atoms as Superior Electrocatalysts for Oxygen Reduction

Directly Anchoring Highly Dispersed Copper Sites on Nitrogen‐Doped Carbon for Enhanced Oxygen Reduction Electrocatalysis

Transition Metal‐Nitrogen‐Carbon Active Site for Oxygen Reduction Electrocatalysis: Beyond the Fascinations of TM‐N4

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Transition Metal‐Nitrogen‐Carbon Active Site for Oxygen Reduction Electrocatalysis: Beyond the Fascinations of TM‐N₄