Advancements in rationally designed PGM-free fuel cell catalysts derived from metal–organic frameworks

Barkholtz, Heather M.; Liu, Di Jia

doi:10.1039/c6mh00344c

Cited by 151 publications

(87 citation statements)

References 168 publications

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“…ZIFs are porous crystalline materials tailored with homogeneous M‐N 4 ligations throughout porous frameworks. Upon thermolysis, M‐N 4 ligations transform into density populated and uniformly distributed M–N–C, while five‐member imidazole rings transform into six‐member aromatic rings of graphitic structures without any need of carbon support . Particularly in Zn‐ZIFs, volatile Zn vapors under high temperatures (above 907 °C), creating more voids and higher surface areas than other metal ZIFs .…”

Section: Introductionmentioning

confidence: 99%

Engineering Fe–Fe₃C@Fe–N–C Active Sites and Hybrid Structures from Dual Metal–Organic Frameworks for Oxygen Reduction Reaction in H₂–O₂ Fuel Cell and Li–O₂ Battery

Wang

Yin

Liu

et al. 2019

Adv Funct Materials

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173

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Dual metal-organic frameworks (MOFs, i.e., MIL-100(Fe) and ZIF-8) are thermally converted into Fe-Fe 3 C-embedded Fe-N-codoped carbon as platinum group metal (PGM)-free oxygen reduction reaction (ORR) electrocatalysts. Pyrolysis enables imidazolate in ZIF-8 rearranged into highly N-doped carbon, while Fe from MIL-100(Fe) into N-ligated atomic sites concurrently with a few Fe-Fe 3 C nanoparticles. Upon precise control of MOF compositions, the optimal catalyst is highly active for the ORR in half-cells (0.88 V in base and 0.79 V versus RHE in acid in half-wave potential), a proton exchange membrane fuel cell (0.76 W cm −2 in peak power density) and an aprotic Li-O 2 battery (8749 mAh g −1 in discharge capacity), representing a state-of-the-art PGM-free ORR catalyst. In the material, amorphous carbon with partial graphitization ensures high active site exposure and fast charge transfer simultaneously. Macropores facilitate mass transport to the catalyst surface, followed by oxygen penetration in micropores to reach the infiltrated active sites. Further modeling simulations shed light on the true Fe-Fe 3 C contribution to the catalyst performance, suggesting Fe 3 C enhances oxygen affinity, while metallic Fe promotes *OH desorption as the rate-determining step at the nearby Fe-N-C sites. These findings demonstrate MOFs as model system for rational design of electrocatalyst for energy-based functional applications.

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Section: Introductionmentioning

confidence: 99%

Engineering Fe–Fe₃C@Fe–N–C Active Sites and Hybrid Structures from Dual Metal–Organic Frameworks for Oxygen Reduction Reaction in H₂–O₂ Fuel Cell and Li–O₂ Battery

Wang

Yin

Liu

et al. 2019

Adv Funct Materials

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173

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“…[41][42][43][44] Compared with the traditional synthesis of NPMNs, MOFs are optimal precursors that contain carbon and metal precursors together into one framework. [46] The earliest reported works for the utilization of MOFs as electrocatalysts for ORR date from 2012. In addition, the surface area and pore structure of MOFs can propagate to NPMNs in different degrees via controlled pyroly sis and post treatment, thus providing tailored surface properties and microstructures.…”

Section: Introductionmentioning

confidence: 99%

“…In addition, the surface area and pore structure of MOFs can propagate to NPMNs in different degrees via controlled pyroly sis and post treatment, thus providing tailored surface properties and microstructures. [46] The earliest reported works for the utilization of MOFs as electrocatalysts for ORR date from 2012. [47,48] Loh's group successfully synthesized the hybrid graphene-Fe-MOFs, which were employed as ORR electrocatalyst in alkaline media.…”

Section: Introductionmentioning

confidence: 99%

Metal‐Organic Framework‐Derived Non‐Precious Metal Nanocatalysts for Oxygen Reduction Reaction

Zhu

Song

et al. 2017

Advanced Energy Materials

326

167

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By virtue of diverse structures and tunable properties, metal‐organic frameworks (MOFs) have presented extensive applications including gas capture, energy storage, and catalysis. Recently, synthesis of MOFs and their derived nanomaterials provide an opportunity to obtain competent oxygen reduction reaction (ORR) electrocatalysts due to their large surface area, controllable composition and pore structure. This review starts with the introduction of MOFs and current challenges of ORR, followed by the discussion of MOF‐based non‐precious metal nanocatalysts (metal‐free and metal/metal oxide‐based carbonaceous materials) and their application in ORR electrocatalysis. Current issues in MOF‐derived ORR catalysts and some corresponding strategies in terms of composition and morphology to enhance their electrocatalytic performance are highlighted. In the last section, a perspective for future development of MOFs and their derivatives as catalysts for ORR is discussed.

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“…In addition, ZIFs act as sacrificial templates for heteroatom(s) doped hierarchical porous carbon synthesized through a simple pyrolysis process ,. Carbonaceous materials derived from ZIFs exhibit high graphitic character and electrical conductivity and, most importantly, highly interconnected porous structures; thus, anticipating their contribution towards enhancing ORR activity ,. The ORR active sites in ZIF derived catalysts are predicted to be the heteroatom(s) (mainly nitrogen) at defect sites and transition metal−nitrogen coordinated carbon sites for the predominant 4e − ORR process in acidic as well as in alkaline electrolytes …”

Section: Introductionmentioning

confidence: 99%

Insights Into the Effect of Nickel Doping on ZIF‐Derived Oxygen Reduction Catalysts for Zinc−Air Batteries

et al. 2019

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The advancement of cost-effective, efficient, and durable catalysts to replace high cost Pt-based electrocatalysts are of recent interest, especially to enhance the sluggish oxygen reduction reaction (ORR) in fuel cells and metalÀ air batteries. Herein, we report self-assembled CoÀ Ni based nitrogen doped carbon structures (CoÀ Ni/NC) derived from zeolitic imidazolate frameworks as a highly efficient and durable ORR catalyst for rechargeable zincÀ air batteries (ZAB). An effective three-phase boundary is recognised with a well-organized interconnected porous carbon framework of the CoÀ Ni/NC catalyst. The developed catalyst exhibited much improved onset and halfwave potentials (0.93 V and 0.86 V vs. RHE, respectively) in alkaline electrolyte, especially in the limiting current region, which was credited to the porous structure. Furthermore, excellent durability was found for the catalyst operated using continuous potential cycles for 5,000 times and chronoamperometric measurements for 50 h. Finally, the optimised CoÀ Ni/NC catalyst was successfully utilised as a cathode catalyst and delivered substantial power density in ZAB configuration under ambient operating conditions. Substantial battery durability was also observed over 1000 h by periodically replacing the anodic zinc electrode. Hence, the present investigation offers the prospect of the development of new non-precious, highly active, and durable oxygen reduction catalysts for zinc air battery applications.

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Advancements in rationally designed PGM-free fuel cell catalysts derived from metal–organic frameworks

Abstract: A comprehensive review revealed metal–organic frameworks as promising precursors for preparing highly active PGM-free electro-catalysts for oxygen reduction reaction.

Cited by 151 publications

References 168 publications

Engineering Fe–Fe₃C@Fe–N–C Active Sites and Hybrid Structures from Dual Metal–Organic Frameworks for Oxygen Reduction Reaction in H₂–O₂ Fuel Cell and Li–O₂ Battery

Engineering Fe–Fe₃C@Fe–N–C Active Sites and Hybrid Structures from Dual Metal–Organic Frameworks for Oxygen Reduction Reaction in H₂–O₂ Fuel Cell and Li–O₂ Battery

Metal‐Organic Framework‐Derived Non‐Precious Metal Nanocatalysts for Oxygen Reduction Reaction

Insights Into the Effect of Nickel Doping on ZIF‐Derived Oxygen Reduction Catalysts for Zinc−Air Batteries

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Advancements in rationally designed PGM-free fuel cell catalysts derived from metal–organic frameworks

Abstract: A comprehensive review revealed metal–organic frameworks as promising precursors for preparing highly active PGM-free electro-catalysts for oxygen reduction reaction.

Cited by 151 publications

References 168 publications

Engineering Fe–Fe3C@Fe–N–C Active Sites and Hybrid Structures from Dual Metal–Organic Frameworks for Oxygen Reduction Reaction in H2–O2 Fuel Cell and Li–O2 Battery

Engineering Fe–Fe3C@Fe–N–C Active Sites and Hybrid Structures from Dual Metal–Organic Frameworks for Oxygen Reduction Reaction in H2–O2 Fuel Cell and Li–O2 Battery

Metal‐Organic Framework‐Derived Non‐Precious Metal Nanocatalysts for Oxygen Reduction Reaction

Insights Into the Effect of Nickel Doping on ZIF‐Derived Oxygen Reduction Catalysts for Zinc−Air Batteries

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Resources

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Engineering Fe–Fe₃C@Fe–N–C Active Sites and Hybrid Structures from Dual Metal–Organic Frameworks for Oxygen Reduction Reaction in H₂–O₂ Fuel Cell and Li–O₂ Battery

Engineering Fe–Fe₃C@Fe–N–C Active Sites and Hybrid Structures from Dual Metal–Organic Frameworks for Oxygen Reduction Reaction in H₂–O₂ Fuel Cell and Li–O₂ Battery