A trifunctional Ni–N/P–O-codoped graphene electrocatalyst enables dual-model rechargeable Zn–CO<sub>2</sub>/Zn–O<sub>2</sub> batteries

Yang, Rui; Xie, Jiafang; Liu, Qin; Huang, Yiyin; Lv, Jiangquan; Ghausi, Muhammad Arsalan; Wang, Xueyuan; Peng, Zhen; Wu, Maoxiang; Wang, Yaobing

doi:10.1039/c8ta10958c

Cited by 55 publications

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“…In addition, the Faradaic efficiency (FE) for CO 2 RR in Zn–CO 2 batteries, particularly for CO 2 ‐to‐CO conversion, is typically below 50% at relatively high discharge currents (e.g., 5 mA cm −2 ). [ 4 ]…”

Section: Figurementioning

confidence: 99%

“…[ 5 ] Among various M–N–C catalysts, Fe–N–C presents a low onset potential for CO production, whereas its CO Faradaic efficiency (FE CO ) and partial current density ( J CO ) are not high, particularly for concentrated electrolytes, [ 6 ] owing to the strong binding of *CO on the single Fe–N x site. [ 7 ] Strategies such as modifying the morphology and pore structure of the carbon substrate, [ 6a,8 ] and adjusting the coordination structure as well as the local environment of the metal center, [ 4b,5f,9 ] were employed to enhance CO 2 RR performance. In addition to the single Fe–N x sites, nonmetal moieties in the carbon plane of M–N–C, such as N‐doped sites and intrinsic defects, may additionally contribute to CO 2 RR (Figure S1, Supporting Information).…”

Section: Figurementioning

confidence: 99%

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Electroreduction of Carbon Dioxide Driven by the Intrinsic Defects in the Carbon Plane of a Single Fe–N₄ Site

et al. 2020

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various noble metal catalysts, such as Au, Ag, and Pd have demonstrated impressive potential for yielding CO through CO 2 RR. [2] Furthermore, Ir/Au [1a] and 3D Pd nanosheets [3] offer sufficient performances for Zn-CO 2 batteries. These electrocatalysts are, however, expensive and often require high overpotentials to generate desired products. In addition, the Faradaic efficiency (FE) for CO 2 RR in Zn-CO 2 batteries, particularly for CO 2-to-CO conversion, is typically below 50% at relatively high discharge currents (e.g., 5 mA cm −2). [4] As an alternative to noble metal catalysts, nitrogen-coordinated single-metal active sites anchored within porous carbon (M-N-C) have been recently identified as a new class of efficient CO 2 RR catalysts to enable CO 2-to-CO conversion, because of their abundance, high electrical conductivity, and good durability. [5] Among various M-N-C catalysts, Fe-N-C presents a low onset potential for CO production, whereas its CO Faradaic efficiency (FE CO) and partial current density (J CO) are not high, particularly for concentrated electrolytes, [6] owing to the strong binding of *CO on the single Fe-N x site. [7] Strategies such as modifying the morphology and pore structure of the carbon substrate, [6a,8] and adjusting the coordination structure as well as the local environment of the metal center, [4b,5f,9] were employed to enhance CO 2 RR performance. In addition to the single Fe-N x sites, nonmetal moieties in the carbon plane of M-N-C, such as N-doped sites and intrinsic defects, may additionally contribute to CO 2 RR (Figure S1, Supporting Information). Pyridinic and hydrogenated nitrogen species in Fe-N-C was demonstrated to exhibit preferential adsorption for CO 2 and acted as active sites for CO 2 RR. [5h,10] Moreover, the intrinsic carbon defects could also act as sole metal-free active sites for CO 2 RR, stemming from the electron redistribution around the defects, and consequently, form partially positive C atoms, as demonstrated very recently in certain studies. [11] For example, defectrich and metal-free mesoporous carbon materials exhibited enhanced CO generation from CO 2 RR, whereas the competing HER was suppressed. When an overpotential of 490 mV was applied, the FE CO was ≈80%, with a J CO of −2.9 mA cm −2. [11b] A positive correlation was also observed between the content of intrinsic carbon defects and the CO 2 RR performance of carbon-based catalysts. [11a] Despite these achievements, the J CO for the reported carbon catalysts containing intrinsic defects remained below 7 mA cm −2. [11] Considering that such catalysts Manipulating the in-plane defects of metal-nitrogen-carbon catalysts to regulate the electroreduction reaction of CO 2 (CO 2 RR) remains a challenging task. Here, it is demonstrated that the activity of the intrinsic carbon defects can be dramatically improved through coupling with single-atom Fe-N 4 sites. The resulting catalyst delivers a maximum CO Faradaic efficiency of 90% and a CO partial current density of 33 mA cm −2 in 0.1 m KHCO 3. The ...

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Section: Figurementioning

confidence: 99%

Section: Figurementioning

confidence: 99%

Electroreduction of Carbon Dioxide Driven by the Intrinsic Defects in the Carbon Plane of a Single Fe–N₄ Site

et al. 2020

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“…Great achievements have been made in ECDRR especially in last five years, however, high overpotential and low selectivity still challenge metal‐free carbon‐based catalysts, especially compared to benchmark noble metals. Specifically, there were two reports that benefited from P doping, as far as we know, including that P doping enabled onion‐like carbon to catalyze ECDRR with 81 % CO FE at −0.9 V and that P doping induced the suppression of competitive hydrogen evolution during ECDRR on Ni modified carbon material . However, how the dopant and dopants enhance ECDRR on metal‐free carbon‐based catalysts is still unclear.…”

Section: Introductionmentioning

confidence: 92%

Low‐Energy CO₂ Reduction on a Metal‐Free Carbon Material

et al. 2020

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Electrochemical CO 2 reduction to value-added chemicals on carbon-based catalysts is a potential approach for low-cost value-added CO 2 recycling. However, high overpotential and limited understanding of the mechanism remain challenging. Herein, a nitrogen and phosphorus co-doped carbon (NPC) material, which is synthesized through a simple pyrolysis, promoted low-energy electrochemical CO 2 reduction. The NPC electrocatalyst combines the advantages of active sites cooptimized by N and P, faster electrokinetics with bicarbonate providing proton, and more accessible active sites exposed by soft-template precursors. The NPC electrocatalyst exhibited more than ten-and fourfold enhancement of the partial current density of CO production compared to N-doped and P-doped carbon materials, respectively, with high selectivity (86 % faradaic efficiency) at only À 0.45 V. Experimental data coupled with density function theory calculations revealed that N and P dopants cooperated to enhance CO 2 adsorption, first electron transfer to CO 2 and then *COOH intermediate stabilization, leading to active and selective CO 2 -to-CO conversion. This work extends the design and understanding of metal-free carbonbased electrocatalysts for electrochemical CO 2 reduction.[a] Dr.adsorbates. The entropies of the free molecules were taken from the NIST database. [34][35][36] The solvent effect for stabilizing COOH* and CO* was 0.25 and 0.10 eV, respectively. [33] Due to the use of PBE functional, a further À 0.21 eV correction for the non-adsorbed gasphase CO molecule has been derived to accurately describe reaction free energy for CO 2 reduction to CO.

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“…d) CO generation in Zn–CO 2 batteries with NiPG cathode. Reproduced with permission . The Royal Society of Chemistry.…”

Section: Individual Development: Energy Storage or Chemical Productionmentioning

confidence: 99%

Metal–CO₂ Batteries at the Crossroad to Practical Energy Storage and CO₂ Recycle

Xie

Zhou

Wang

2019

Adv Funct Materials

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Metal–CO2 batteries show great promise in meeting the growing energy, chemical, and environmental demands of daily life and industry, because of their advantages of high flexibility and efficiency in both energy storage and CO2 recycle applications. It has been a trend that Li/Na‐CO2 and Zn/Al‐CO2 systems show different developments to achieve practical energy storage (e.g., high electricity supply) and CO2 recycling (e.g., flexible chemical production), respectively, which is often neglected. This inhibits the application of metal–CO2 batteries in maximizing energy supply and value‐added CO2 conversion. This progress report presents a critically selected overview of the individual developments of metal–CO2 batteries with emphasis on diverse fundamental origins, performance advantages, and the future of these two systems. Furthermore, the reaction pathways, particularly for catalytic materials, for the Li/Na‐CO2 and Zn/Al‐CO2 systems are discussed. Finally, the challenges of these two systems along with a hybrid Li/Na‐CO2 battery design that may simultaneously provide high operating voltages and flexible chemicals are outlined.

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A trifunctional Ni–N/P–O-codoped graphene electrocatalyst enables dual-model rechargeable Zn–CO₂/Zn–O₂ batteries

Abstract: Novel dual-model Zn–CO2/Zn–O2 batteries were proposed and realized with trifunctional NiPG catalysts and variable supply gases.

Cited by 55 publications

References 32 publications

Electroreduction of Carbon Dioxide Driven by the Intrinsic Defects in the Carbon Plane of a Single Fe–N₄ Site

Electroreduction of Carbon Dioxide Driven by the Intrinsic Defects in the Carbon Plane of a Single Fe–N₄ Site

Low‐Energy CO₂ Reduction on a Metal‐Free Carbon Material

Metal–CO₂ Batteries at the Crossroad to Practical Energy Storage and CO₂ Recycle

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A trifunctional Ni–N/P–O-codoped graphene electrocatalyst enables dual-model rechargeable Zn–CO2/Zn–O2 batteries

Abstract: Novel dual-model Zn–CO2/Zn–O2 batteries were proposed and realized with trifunctional NiPG catalysts and variable supply gases.

Cited by 55 publications

References 32 publications

Electroreduction of Carbon Dioxide Driven by the Intrinsic Defects in the Carbon Plane of a Single Fe–N4 Site

Electroreduction of Carbon Dioxide Driven by the Intrinsic Defects in the Carbon Plane of a Single Fe–N4 Site

Low‐Energy CO2 Reduction on a Metal‐Free Carbon Material

Metal–CO2 Batteries at the Crossroad to Practical Energy Storage and CO2 Recycle

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A trifunctional Ni–N/P–O-codoped graphene electrocatalyst enables dual-model rechargeable Zn–CO₂/Zn–O₂ batteries

Electroreduction of Carbon Dioxide Driven by the Intrinsic Defects in the Carbon Plane of a Single Fe–N₄ Site

Electroreduction of Carbon Dioxide Driven by the Intrinsic Defects in the Carbon Plane of a Single Fe–N₄ Site

Low‐Energy CO₂ Reduction on a Metal‐Free Carbon Material

Metal–CO₂ Batteries at the Crossroad to Practical Energy Storage and CO₂ Recycle