MoP Nanoparticles Supported on Indium‐Doped Porous Carbon: Outstanding Catalysts for Highly Efficient CO<sub>2</sub> Electroreduction

Sun, Xiaofu; Lu, Lu; Zhu, Qinggong; Wu, Congyi; Yang, Dexin; Chen, Chunjun; Han, Buxing

doi:10.1002/ange.201712221

Cited by 44 publications

(5 citation statements)

References 56 publications

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“…This pathway is calculated to have a barrier as high as 2.3 eV, which is inconsistent with the low experimentally applied potentials. 46 In addition to nickel phosphides 40 and FeP, 46 other phosphides shown to catalyze CO 2 RR are MoP 47 and Cu 3 P 48 producing formic acid, BP 49 producing methanol, and CuP 2 , 50 which generates 1-butanol.…”

Section: ■ Introductionmentioning

confidence: 99%

Surface Hydrides on Fe₂P Electrocatalyst Reduce CO₂ at Low Overpotential: Steering Selectivity to Ethylene Glycol

et al. 2021

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Development of efficient electrocatalysts for the CO2 reduction reaction (CO2RR) to multicarbon products has been constrained by high overpotentials and poor selectivity. Here, we introduce iron phosphide (Fe2P) as an earth-abundant catalyst for the CO2RR to mainly C2–C4 products with a total CO2RR Faradaic efficiency of 53% at 0 V vs RHE. Carbon product selectivity is tuned in favor of ethylene glycol formation with increasing negative bias at the expense of C3–C4 products. Both Grand Canonical-DFT (GC-DFT) calculations and experiments reveal that *formate, not *CO, is the initial intermediate formed from surface phosphino-hydrides and that the latter form ionic hydrides at both surface phosphorus atoms (H@Ps) and P-reconstructed Fe3 hollow sites (H@P*). Binding of these surface hydrides weakens with negative bias (reactivity increases), which accounts for both the shift to C2 products over higher C–C coupling products and the increase in the H2 evolution reaction (HER) rate. GC-DFT predicts that phosphino-hydrides convert *formate to *formaldehyde, the key intermediate for C–C coupling, whereas hydrogen atoms on Fe generate tightly bound *CO via sequential PCET reactions to H2O. GC-DFT predicts the peak in CO2RR current density near −0.1 V is due to a local maximum in the binding affinity of *formate and *formaldehyde at this bias, which together with the more labile C2 product affinity, accounts for the shift to ethylene glycol and away from C3–C4 products. Consistent with these predictions, addition of exogenous CO is shown to block all carbon product formation and lower the HER rate. These results demonstrate that the formation of ionic hydrides and their binding affinity, as modulated by the applied potential, controls the carbon product distribution. This knowledge provides new insight into the influence of hydride speciation and applied bias on the chemical reaction mechanism of CO2RR that is relevant to all transition metal phosphides.

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Section: ■ Introductionmentioning

confidence: 99%

Surface Hydrides on Fe₂P Electrocatalyst Reduce CO₂ at Low Overpotential: Steering Selectivity to Ethylene Glycol

et al. 2021

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“…Moreover, In 3d peaks of Cu/In 2 O 3 NPs/C at 445.3 and 452.7 eV correspond to 3d 5/2 and 3d 3/2 of In 3+ in In 2 O 3 , respectively (Figure 4b) [40] . An obvious shift of In 3d peaks can be observed compared to Cu/In 2 O 3 NPs/C, where the peaks of In 3d 3/2 and 3d 5/2 are negatively shifted by 0.5 eV for Cu/In 2 O 3 NPs/C−H 2 , caused by the electron transfer between Cu\In 2 O 3 two phases [41] . No In signal can be detected for Cu NPs/C−H 2 , demonstrating that no contamination occurred for the prepared catalysts.…”

Section: Resultsmentioning

confidence: 94%

Amorphization‐Activated Copper Indium Core‐Shell Nanoparticles for Stable Syngas Production from Electrochemical CO₂ Reduction

Shen

Wang

et al. 2022

ChemSusChem

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Electrochemical carbon dioxide reduction reaction (CO2RR) refers to the conversion of carbon dioxide into compounds with added value through electrolysis. It is still a great challenge to design and manufacture efficient CO2RR catalysts for desired products. Producing syngas via CO2RR is an environmentally friendly way to reduce CO2 in the atmosphere and the dependence on fossil fuels. Herein, a new class of Cu/In2O3 nanoparticles (NPs) with controlled phases and structures were successfully prepared as superior electrocatalysts for CO2RR, where the CO/H2 ratios in syngas on Cu/In2O3 NPs/C−H2 remained about 1 : 2 at a broad potential range and the total faradaic efficiency of H2 and CO always remained about 90 %. Electronic structural analysis revealed that the excellent performance was attributed to the electronic interaction between amorphous In2O3 and Cu. This work broadens the horizons for designing and preparing fascinating electrocatalysts for CO2RR.

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“…In-SAs/NC exhibited a much lower Tafel slope (111.9 mV dec À1 ) than that of the two references, which was in favor of the improvement of kinetic activity. [11] Moreover, In-SAs/NC displayed excellent stability (Figure 3 d and Figure S28). The monodispersion of In species could be maintained as confirmed by the EDS maps, EXAFS and HAADF-STEM image ( Figures S29-S32).…”

Section: Chemiementioning

confidence: 96%

Design of a Single‐Atom Indium^δ+–N₄Interface for Efficient Electroreduction of CO₂to Formate

et al. 2020

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Main‐group element indium (In) is a promising electrocatalyst which triggers CO2 reduction to formate, while the high overpotential and low Faradaic efficiency (FE) hinder its practical application. Herein, we rationally design a new In single‐atom catalyst containing exclusive isolated Inδ+–N4 atomic interface sites for CO2 electroreduction to formate with high efficiency. This catalyst exhibits an extremely large turnover frequency (TOF) up to 12500 h−1 at −0.95 V versus the reversible hydrogen electrode (RHE), with a FE for formate of 96 % and current density of 8.87 mA cm−2 at low potential of −0.65 V versus RHE. Our findings present a feasible strategy for the accurate regulation of main‐group indium catalysts for CO2 reduction at atomic scale.

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MoP Nanoparticles Supported on Indium‐Doped Porous Carbon: Outstanding Catalysts for Highly Efficient CO₂ Electroreduction

Abstract: Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.

Cited by 44 publications

References 56 publications

Surface Hydrides on Fe₂P Electrocatalyst Reduce CO₂ at Low Overpotential: Steering Selectivity to Ethylene Glycol

Surface Hydrides on Fe₂P Electrocatalyst Reduce CO₂ at Low Overpotential: Steering Selectivity to Ethylene Glycol

Amorphization‐Activated Copper Indium Core‐Shell Nanoparticles for Stable Syngas Production from Electrochemical CO₂ Reduction

Design of a Single‐Atom Indium^δ+–N₄Interface for Efficient Electroreduction of CO₂to Formate

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MoP Nanoparticles Supported on Indium‐Doped Porous Carbon: Outstanding Catalysts for Highly Efficient CO2 Electroreduction

Abstract: Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.

Cited by 44 publications

References 56 publications

Surface Hydrides on Fe2P Electrocatalyst Reduce CO2 at Low Overpotential: Steering Selectivity to Ethylene Glycol

Surface Hydrides on Fe2P Electrocatalyst Reduce CO2 at Low Overpotential: Steering Selectivity to Ethylene Glycol

Amorphization‐Activated Copper Indium Core‐Shell Nanoparticles for Stable Syngas Production from Electrochemical CO2 Reduction

Design of a Single‐Atom Indiumδ+–N4Interface for Efficient Electroreduction of CO2to Formate

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MoP Nanoparticles Supported on Indium‐Doped Porous Carbon: Outstanding Catalysts for Highly Efficient CO₂ Electroreduction

Surface Hydrides on Fe₂P Electrocatalyst Reduce CO₂ at Low Overpotential: Steering Selectivity to Ethylene Glycol

Surface Hydrides on Fe₂P Electrocatalyst Reduce CO₂ at Low Overpotential: Steering Selectivity to Ethylene Glycol

Amorphization‐Activated Copper Indium Core‐Shell Nanoparticles for Stable Syngas Production from Electrochemical CO₂ Reduction

Design of a Single‐Atom Indium^δ+–N₄Interface for Efficient Electroreduction of CO₂to Formate