Porphyrin-based frameworks for oxygen electrocatalysis and catalytic reduction of carbon dioxide

Liang, Zuozhong; Wang, Hong-Yan; Zheng, Haoquan; Zhang, Wei; Cao, Rui

doi:10.1039/d0cs01482f

Cited by 351 publications

(202 citation statements)

References 405 publications

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“…O 2 can be reduced by two electrons (2 e − ) to H 2 O 2 or by four electrons (4 e − ) to H 2 O [1–3] . The 4 e − ORR is required in many energy conversion techniques, [4–7] while the 2 e − ORR makes H 2 O 2 , which is a widely used industrial oxidant and also a promising fuel [8–10] . Recently, many molecular ORR catalysts have been reported [1–5, 11–28] .…”

Section: Methodsmentioning

confidence: 99%

Controlling Oxygen Reduction Selectivity through Steric Effects: Electrocatalytic Two‐Electron and Four‐Electron Oxygen Reduction with Cobalt Porphyrin Atropisomers

Guo

et al. 2021

Angewandte Chemie

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Achieving a selective 2 e À or 4 e À oxygen reduction reaction (ORR) is critical but challenging. Herein, we report controlling ORR selectivity of Co porphyrins by tuning only steric effects. We designed Co porphyrin 1 with meso-phenyls each bearing a bulky ortho-amido group. Due to the resulted steric hinderance, 1 has four atropisomers with similar electronic structures but dissimilar steric effects. Isomers abab and aaaa catalyze ORR with n = 2.10 and 3.75 (n is the electron number transferred per O 2 ), respectively, but aabb and aaab show poor selectivity with n = 2.89-3.10. Isomer abab catalyzes 2 e À ORR by preventing a bimolecular O 2 activation path, while aaaa improves 4 e À ORR selectivity by improving O 2 binding at its pocket, a feature confirmed by spectroscopy methods, including O K-edge near-edge X-ray absorption fine structure. This work represents an unparalleled example to improve 2 e À and 4 e À ORR by tuning only steric effects without changing molecular and electronic structures.

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Section: Methodsmentioning

confidence: 99%

Controlling Oxygen Reduction Selectivity through Steric Effects: Electrocatalytic Two‐Electron and Four‐Electron Oxygen Reduction with Cobalt Porphyrin Atropisomers

Guo

et al. 2021

Angewandte Chemie

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“…The zinc–air battery has been regarded as an ideal energy storage technology with attractive advantages of low cost, safety, and zero pollution [1–10] . For the rechargeable Zn‐air battery, bifunctional electrocatalysts on air electrode for oxygen reduction/evolution reaction (ORR/OER) are urgently needed due to current drawbacks.…”

Section: Figurementioning

confidence: 99%

“…The zinc-air battery has been regarded as an ideal energy storage technology with attractive advantages of low cost, safety, and zero pollution. [1][2][3][4][5][6][7][8][9][10] For the rechargeable Zn-air battery, bifunctional electrocatalysts on air electrode for oxygen reduction/evolution reaction (ORR/OER) are urgently needed due to current drawbacks. Precious metal based catalysts (such as Pt/C and RuO 2 ) are expensive, while low-cost transition-metal-based catalysts still does not meet commercial requirements.…”

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confidence: 99%

Highly Curved Nanostructure‐Coated Co, N‐Doped Carbon Materials for Oxygen Electrocatalysis

et al. 2021

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Nitrogen-doped graphene could catalyze the electrochemical reduction and evolution of oxygen, but unfortunately suffers from sluggish catalytic kinetics. Herein, for the first time, we report an onion-like carbon coated Co, N-doped carbon (OLC/Co-N-C) material, which possesses multilayers of highly curved nanostructures that form mesoporous architectures. These unique nanospheres are produced when surfactant micelles are introduced to synthesis precursors. Owing to the combined electronic effect and nanostructuring effect, our OLC/Co-N-C materials exhibit high bifunctional oxygen reduction/evolution reaction (ORR/OER) activity, showing a promising application in rechargeable Zn-air batteries. Experimental results are rationalized by theoretical calculations, showing that the curvature of graphitic carbon plays a vital role in promoting activities of meta-carbon atoms near graphitic N and ortho/meta carbon atoms close to pyridinic N.

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“…7,8 ). In addition, resulting from the interference of competitive hydrogen evolution reaction (HER) and the multiple electron transfer processes involved during the reaction, the ECR-tohydrocarbons suffers from low selectivity since different pathways occur under similar reduction potentials with various products [8][9][10] . To date, Cu-based electrocatalysts, including Cu oxides 11,12 , metallic Cu 13,14 , and Cu-containing molecules 15 , have been proved to be capable of promoting ECR toward hydrocarbons and alcohol products at acceptable FEs.…”

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confidence: 99%

Coordination environment dependent selectivity of single-site-Cu enriched crystalline porous catalysts in CO2 reduction to CH4

et al. 2021

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The electrochemical CO2 reduction to high-value-added chemicals is one of the most promising and challenging research in the energy conversion field. An efficient ECR catalyst based on a Cu-based conductive metal-organic framework (Cu-DBC) is dedicated to producing CH4 with superior activity and selectivity, showing a Faradaic efficiency of CH4 as high as ~80% and a large current density of −203 mA cm−2 at −0.9 V vs. RHE. The further investigation based on theoretical calculations and experimental results indicates the Cu-DBC with oxygen-coordinated Cu sites exhibits higher selectivity and activity over the other two crystalline ECR catalysts with nitrogen-coordinated Cu sites due to the lower energy barriers of Cu-O4 sites during ECR process. This work unravels the strong dependence of ECR selectivity on the Cu site coordination environment in crystalline porous catalysts, and provides a platform for constructing highly selective ECR catalysts.

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Porphyrin-based frameworks for oxygen electrocatalysis and catalytic reduction of carbon dioxide

Abstract: The recent progress made on porphyrin-based frameworks and their applications in energy-related conversion technologies (e.g., ORR, OER and CO2RR) and storage technologies (e.g., Zn–air batteries).

Cited by 351 publications

References 405 publications

Controlling Oxygen Reduction Selectivity through Steric Effects: Electrocatalytic Two‐Electron and Four‐Electron Oxygen Reduction with Cobalt Porphyrin Atropisomers

Controlling Oxygen Reduction Selectivity through Steric Effects: Electrocatalytic Two‐Electron and Four‐Electron Oxygen Reduction with Cobalt Porphyrin Atropisomers

Highly Curved Nanostructure‐Coated Co, N‐Doped Carbon Materials for Oxygen Electrocatalysis

Coordination environment dependent selectivity of single-site-Cu enriched crystalline porous catalysts in CO2 reduction to CH4

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