Rare-earth metal-N<sub>6</sub> centers in porous carbon for electrocatalytic CO<sub>2</sub> reduction

Zeng, Xianshi; Liao, Luliang; Wang, Meishan; Wang, Hongming

doi:10.1039/d3cp02314a

Cited by 7 publications

(6 citation statements)

References 49 publications

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“…Theoretical predictions suggest that the monoatomic catalyzed CO 2 reduction process primarily produces C 1 products. The most commonly observed C 1 products in the electrocatalytic reduction of CO 2 include CH 3 OH, CH 4 , HCOOH, HCHO, and CO. Based on the electrocatalytic reduction scheme for obtaining C 1 products from CO 2 [ 52 , 53 , 54 , 55 , 56 , 57 ], the CO 2 reduction to CO and HCOOH is a process with two electrons (2e). The pathways for converting carbon dioxide into CO and HCOOH are CO 2 → *COOH → *CO → CO and CO 2 → *OCHO → *HCOOH → HCOOH, respectively.…”

Section: Resultsmentioning

confidence: 99%

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Exploring the CO2 Electrocatalysis Potential of 2D Metal–Organic Transition Metal–Hexahydroxytriquinoline Frameworks: A DFT Investigation

Wen,

Jiang,

Lai

et al. 2024

Molecules

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Metal–organic frameworks have demonstrated great capacity in catalytic CO2 reduction due to their versatile pore structures, diverse active sites, and functionalization capabilities. In this study, a novel electrocatalytic framework for CO2 reduction was designed and implemented using 2D coordination network-type transition metal–hexahydroxytricyclic quinazoline (TM–HHTQ) materials. Density functional theory calculations were carried out to examine the binding energies between the HHTQ substrate and 10 single TM atoms, ranging from Sc to Zn, which revealed a stable distribution of metal atoms on the HHTQ substrate. The majority of the catalysts exhibited high selectivity for CO2 reduction, except for the Mn–HHTQ catalysts, which only exhibited selectivity at pH values above 4.183. Specifically, Ti and Cr primarily produced HCOOH, with corresponding 0.606 V and 0.236 V overpotentials. Vanadium produced CH4 as the main product with an overpotential of 0.675 V, while Fe formed HCHO with an overpotential of 0.342 V. Therefore, V, Cr, Fe, and Ti exhibit promising potential as electrocatalysts for carbon dioxide reduction due to their favorable product selectivity and low overpotential. Cu mainly produces CH3OH as the primary product, with an overpotential of 0.96 V. Zn primarily produces CO with a relatively high overpotential of 1.046 V. In contrast, catalysts such as Sc, Mn, Ni, and Co, among others, produce multiple products simultaneously at the same rate-limiting step and potential threshold.

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Section: Resultsmentioning

confidence: 99%

“…For reactions involving transfer of electrons, energy can be determined using a standard hydrogen electrode model, as presented by Nørskov et al [ 52 , 54 ]. Equation ( 2 ) outlines the calculation of Gibbs free energy.…”

Section: Calculation Detailsmentioning

confidence: 99%

Exploring the CO2 Electrocatalysis Potential of 2D Metal–Organic Transition Metal–Hexahydroxytriquinoline Frameworks: A DFT Investigation

Wen,

Jiang,

Lai

et al. 2024

Molecules

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“…The most commonly observed C 1 products in electrocatalytic CO 2 reduction include CO, CH 4 , HCOOH, CH 3 OH, and HCHO. The intermediate steps and reaction paths corresponding to each electronic step of the catalytic process are shown in Figure S1 [41][42][43][44][45]. The structural models of the intermediates are shown in Table S12.…”

Section: Potential Pathways and Adsorption Energiesmentioning

confidence: 99%

“…According to the proposed scheme for electrocatalytic CO 2 reduction to obtain C 1 products [41][42][43][44][45], the reduction of CO 2 to CO and HCOOH involves a 2e process. The paths of reduction can be described as CO 2 → * COOH → * CO → CO and CO 2 → * OCHO → * HCOOH → HCOOH.…”

Section: Potential Pathways and Adsorption Energiesmentioning

confidence: 99%

“…Table S11: Rh-THQ electrocatalytic CO 2 reduction steps for each intermediate and Gibbs free energy variation; Table S12: Structural modelling of each intermediate in TM-THQ electrocatalytic carbon dioxide reduction; Figure S1: TM-THQ electrocatalytic CO 2 reduction for each electronic step and reaction pathway. The reaction starts with *+CO 2 , where * denotes the catalyst and the green box is the products [41][42][43][44][45].…”

Section: Supplementary Materialsmentioning

confidence: 99%

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Density Functional Study of Electrocatalytic Carbon Dioxide Reduction in Fourth-Period Transition Metal–Tetrahydroxyquinone Organic Framework

Wen,

Zeng,

Xiao

et al. 2024

Molecules

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This study investigates the utilisation of organometallic network frameworks composed of fourth-period transition metals and tetrahydroxyquinone (THQ) in electrocatalytic CO2 reduction. Density functional theory (DFT) calculations were employed in analysing binding energies, as well as the stabilities of metal atoms within the THQ frameworks, for transition metal TM-THQs ranging from Y to Cd. The findings demonstrate how metal atoms could be effectively dispersed and held within the THQ frameworks due to sufficiently high binding energies. Most TM-THQ frameworks exhibited favourable selectivity towards CO2 reduction, except for Tc and Ru, which experienced competition from hydrogen evolution reaction (HER) and required solution environments with pH values greater than 5.716 and 8.819, respectively, to exhibit CO2RR selectivity. Notably, the primary product of Y, Ag, and Cd was HCOOH; Mo produced HCHO; Pd yielded CO; and Zr, Nb, Tc, Ru, and Rh predominantly generated CH4. Among the studied frameworks, Zr-THQ displayed values of 1.212 V and 1.043 V, corresponding to the highest limiting potential and overpotential, respectively, while other metal–organic frameworks displayed relatively low ranges of overpotentials from 0.179 V to 0.949 V. Consequently, it is predicted that the TM-THQ framework constructed using a fourth-period transition metal and tetrahydroxyquinone exhibits robust electrocatalytic reduction of CO2 catalytic activity.

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Rare Earth Er‐Nd Dual Single‐Atomic Catalysts for Efficient Visible‐light Induced CO₂ Reduction to C_nH_2n+1OH (n=1, 2)

Li,

Qi,

Yan

2024

Angewandte Chemie

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Efficient synthesis of CnH2n+1OH (n=1, 2) via photochemical CO2 reduction holds promise for achieving carbon neutrality but remains challenging. Here, we present rare‐earth dual single atoms (SAs) catalysts containing ErN6 and NdN6 moieties, fabricated via an atom‐confinement and coordination method. The dual Er‐Nd SAs catalysts exhibit unprecedented generation rates of 1761.4 μmol g–1 h–1 and 987.7 μmol g–1 h–1 for CH3CH2OH and CH3OH, respectively. Through a combination of theoretical calculation, X‐ray absorption near edge structural analysis, aberration‐corrected transmission electron microscopy, and in‐situ FT‐IR spectroscopy, we demonstrate that the Er SAs facilitate charge transfer, serving as active centers for C−C bond formation, while Nd SAs provide the necessary *CO for C−C coupling in C2H5OH synthesis under visible light. Furthermore, the experiment and density functional theory calculation elucidate that the variety of electronic states induced by 4f orbitals of the Er SAs and the p−f orbital hybridization of Er−N moieties enable the formation of charge‐transfer channel. Therefore, this study sheds light on the pivotal role of *CO adsorption in achieving efficient conversion from CO2 to CnH2n+1OH (n=1, 2) via a novel rare‐earth‐based dual SAs photocatalysis approach.

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Rare-earth metal-N₆ centers in porous carbon for electrocatalytic CO₂ reduction

Abstract: Single-atom catalysts made from rare earths for electrocatalytic carbon dioxide reduction have emerged, but they need to be studied systematically and intensively. The usage of density functional theory is to...

Cited by 7 publications

References 49 publications

Exploring the CO2 Electrocatalysis Potential of 2D Metal–Organic Transition Metal–Hexahydroxytriquinoline Frameworks: A DFT Investigation

Exploring the CO2 Electrocatalysis Potential of 2D Metal–Organic Transition Metal–Hexahydroxytriquinoline Frameworks: A DFT Investigation

Density Functional Study of Electrocatalytic Carbon Dioxide Reduction in Fourth-Period Transition Metal–Tetrahydroxyquinone Organic Framework

Rare Earth Er‐Nd Dual Single‐Atomic Catalysts for Efficient Visible‐light Induced CO₂ Reduction to C_nH_2n+1OH (n=1, 2)

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Rare-earth metal-N6 centers in porous carbon for electrocatalytic CO2 reduction

Abstract: Single-atom catalysts made from rare earths for electrocatalytic carbon dioxide reduction have emerged, but they need to be studied systematically and intensively. The usage of density functional theory is to...

Cited by 7 publications

References 49 publications

Exploring the CO2 Electrocatalysis Potential of 2D Metal–Organic Transition Metal–Hexahydroxytriquinoline Frameworks: A DFT Investigation

Exploring the CO2 Electrocatalysis Potential of 2D Metal–Organic Transition Metal–Hexahydroxytriquinoline Frameworks: A DFT Investigation

Density Functional Study of Electrocatalytic Carbon Dioxide Reduction in Fourth-Period Transition Metal–Tetrahydroxyquinone Organic Framework

Rare Earth Er‐Nd Dual Single‐Atomic Catalysts for Efficient Visible‐light Induced CO2 Reduction to CnH2n+1OH (n=1, 2)

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Rare-earth metal-N₆ centers in porous carbon for electrocatalytic CO₂ reduction

Rare Earth Er‐Nd Dual Single‐Atomic Catalysts for Efficient Visible‐light Induced CO₂ Reduction to C_nH_2n+1OH (n=1, 2)