Understanding activity origin for the oxygen reduction reaction on bi-atom catalysts by DFT studies and machine-learning

Deng, Chaofang; Su, Yang; Li, Fuhua; Shen, Weifeng; Chen, Zhongfang; Tang, Qing

doi:10.1039/d0ta08004g

Cited by 78 publications

(73 citation statements)

References 52 publications

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“…Although further studies are needed to understand the structural details on active sites of (Cu,Fe)–N–CNT, binuclear active sites of FeN 4 and CuN x might exist in the catalyst and exclusively catalyze the ORR to H 2 O. One of the proposed active site structures is a binuclear metal active site placed in the same N-doped graphene sheets (Figure S10a), ,, where the ORR activity can be governed by simple geometric parameters such as metal–metal distances . Heterobimetallic complexes with similar coordination environments have been reported .…”

Section: Resultsmentioning

confidence: 76%

Impact of Heterometallic Cooperativity of Iron and Copper Active Sites on Electrocatalytic Oxygen Reduction Kinetics

et al. 2021

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The oxygen reduction reaction (ORR) is a key reaction in polymer electrolyte fuel cells and metal-air batteries. In these electrochemical systems, platinum group metals (PGMs) have been widely used as ORR electrocatalysts. Because of material costs and scarcity of platinum group metals, non-PGM electrocatalysts are an ideal alternative for mass production with low material costs. Many non-PGM electrocatalysts have been intensively studied such as pyrolyzed Fe-, N-doped carbon (Fe-N-C) catalysts. However, many non-PGM electrocatalysts including Fe-N-C still suffer from product selectivity: the production of H2O2 as the byproduct. In this work, we synthesized an ORR electrocatalyst of Cu-, Fe-and N-doped carbon nanotubes, (Cu,Fe)-N-CNT. This heterobimetallic catalyst showed the selective 4ereduction of O2 to H2O with ca. 99%. Kinetic analysis of the electrocatalytic ORR and hydrogen peroxide reduction reaction (HPRR) in acidic media revealed that (Cu,Fe)-N-CNT showed two orders of magnitude higher rate constants for the direct 4ereduction of O2 to H2O than those for the 2ereduction of O2 to H2O2 whereas a monometallic Fe-N-CNT showed the same order of magnitude, indicating that the heterometallic cooperativity gave the drastic impact on the ORR kinetics. Our findings would open up possibilities to develop non-PGM ORR electrocatalysts with heterobimetallic active sites for the selective ORR. KEYWORDS. Non-PGM, oxygen reduction reaction, electrocatalysis, polymer electrolyte fuel cell, oxygen reduction kinetics, bio-inspired approach, heterobimetallic active sites.

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Section: Resultsmentioning

confidence: 76%

Impact of Heterometallic Cooperativity of Iron and Copper Active Sites on Electrocatalytic Oxygen Reduction Kinetics

et al. 2021

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“…A proton exchange membrane fuel cell (PEMFC) is a promising power generation device that can convert the chemical energy directly into electricity through electrochemical reactions. − However, the slow kinetics of the cathode oxygen reduction reaction (ORR) and the substantial dependence of Pt-based catalysts hamper the industrial application of the PEMFC. , In the past decades, certain strategies like preparing single-atom Pt catalysts or small-sized core/Pt-shell particles were developed to reduce the Pt loading while maintaining the high catalytic performance. − Unfortunately, the fabrication of high-Pt-loading single-atom catalysts remains a challenge, and the high-surface-energy, small-sized catalysts are easily aggregated under fuel-cell operation environments. − Therefore, alternative materials with high activity and long-term durability are highly sought for fuel cells. − …”

Section: Introductionmentioning

confidence: 99%

NiTe Monolayer: Two-Dimensional Metal with Superior Basal-Plane Activity for the Oxygen Reduction Reaction

Liu

Wang

2021

J. Phys. Chem. C

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Developing high-performance oxygen reduction reaction (ORR) catalysts has become a key scientific issue in the field of fuel cells. In this work, we proposed a promising non-Pt catalyst for the ORR, namely the two-dimensional (2D) NiTe monolayer, by means of comprehensive density functional theory (DFT) computations and microkinetic simulations. The NiTe monolayer is a stable 2D metallic crystal, and it can be flexibly exfoliated from its experimentally known layered bulk phase. Remarkably, the NiTe monolayer shows an outstanding basal-plane ORR activity with a half-wave potential of ∼0.86 V, which is higher than that of Pt(111) computed at the same theoretical level. More interestingly, the ORR activity of the NiTe monolayer can be greatly enhanced by applying the external tensile strain. In particular, when subjected to a biaxial tensile strain of 7%, the ORR activity of the monolayer can reach to the top of the activity volcano. Our results open new ways to design effective inexpensive ORR catalysts for fuel cells.

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“…[ 180 ] Theoretically, Co, Ni, and Cu‐based bi‐atom catalysts (BACs) have been predicted to have much higher activity toward O 2 reduction, as compared with their single‐atom counterparts. [ 181 ] Several metal dimers, including Mo 2 and Mn 2 , supported by 2D C 2 N monolayers, were predicted to have better catalytic activity than the corresponding SACs. Each metal atom combined with two pyrrole nitrogen atoms and two amino nitrogen atoms of the macrocycle to form the M 2 N 6 moiety.…”

Section: Rational Design Strategies For Electrocatalystsmentioning

confidence: 99%

Recent Advances and Perspective on Electrochemical Ammonia Synthesis under Ambient Conditions

Zhang

Mei

et al. 2021

Small Methods

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Ammonia is an essential chemical for agriculture and industry. To date, NH3 is mainly supplied by the traditional Haber–Bosch process, which is operated under high‐temperature and high‐pressure in a centralized way. To achieve ammonia production in an environmentally benign way, electrochemical NH3 synthesis under ambient conditions has become the frontier of energy and chemical conversion schemes, as it can be powered by renewable energy and operates in a decentralized way. The recent progress on developing different strategies for NH3 production, including 1) classic NH3 synthesis pathways over nanomaterials; 2) the Mars‐van Krevelen (MvK) mechanism over metal nitrides (MNx); 3) reducing the nitrate into NH3 over Cu‐based nanomaterial; and 4) metal–N2 battery release of NH3 from LixM. Moreover, the most recent advances in engineering strategies for developing highly active materials and the design of the reaction systems for NH3 synthesis are covered.

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Understanding activity origin for the oxygen reduction reaction on bi-atom catalysts by DFT studies and machine-learning

Abstract: The bi-atom catalysts (BACs) have attracted increasing attention in important electrocatalytic reactions such as oxygen reduction reaction (ORR). Here, by means of density functional theory simulations coupled with machine-learning technology,...

Cited by 78 publications

References 52 publications

Impact of Heterometallic Cooperativity of Iron and Copper Active Sites on Electrocatalytic Oxygen Reduction Kinetics

Impact of Heterometallic Cooperativity of Iron and Copper Active Sites on Electrocatalytic Oxygen Reduction Kinetics

NiTe Monolayer: Two-Dimensional Metal with Superior Basal-Plane Activity for the Oxygen Reduction Reaction

Recent Advances and Perspective on Electrochemical Ammonia Synthesis under Ambient Conditions

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