Regulating the coordination environment through doping N atoms for single-atom Mn electrocatalyst of N2 reduction with high catalytic activity and selectivity: A theoretical study

Gao, Zhengyang; Huang, Hanyu; Xu, Shaopeng; Li, Linlin; Gao, Yan; Zhao, Mingliang; Yang, Weijie; Zhao, Xiaojun

doi:10.1016/j.mcat.2020.111091

Cited by 16 publications

(12 citation statements)

References 43 publications

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“…The high electron conductivity benefits the electrocatalytic activity of HER. [333] Meanwhile, ELF can be adopted to estimate the interacting configurations. For instance, Gao et al [333] disclosed the selectivity of N 2 adsorption configuration through ELF.…”

Section: Electron Localization Function (Elf)mentioning

confidence: 99%

“…[333] Meanwhile, ELF can be adopted to estimate the interacting configurations. For instance, Gao et al [333] disclosed the selectivity of N 2 adsorption configuration through ELF. They found that the electron lone-pair of N 2 is easy to participate in the bonding process via the end-on configuration, resulting in greater adsorption energy than that in side-on mode.…”

Section: Electron Localization Function (Elf)mentioning

confidence: 99%

“…For the ORR reaction, the hydrogen peroxide production is a competitive reaction, which can convert O 2 to H 2 O 2 involving the intermediate (*OOH) with two‐electron transfer process as (Figure 10d): [ 333 ]

{normalO}_{2} + * + {normalH}^{+} + e^{‐} \to {OOH}^{*}

{OOH}^{*} + {normalH}^{+} + e^{‐} \to {normalH}_{2} {normalO}_{2} + *

…”

Section: Electrocatalytic Reactionsmentioning

confidence: 99%

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Density Functional Theory for Electrocatalysis

Liao

Xia

et al. 2021

Energy & Environ Materials

114

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With the increase in energy demand and worldwide natural environment crises, it is imperative to develop green and sustainable energy systems to produce clean fuels and chemicals, which can replace fossil fuels and reduce carbon dioxide emissions. [1][2][3] A promising strategy is to develop advanced electrochemical technologies that can convert some common molecules (e.g., water, carbon dioxide, and nitrogen) into high-value chemical products (e.g., hydrogen, hydrocarbons, oxygenates, ammonia, and carbonates). [4][5][6][7] The important energy-related electrocatalytic reactions, including hydrogen evolution reaction (HER), oxygen evolution reaction (OER), oxygen reduction reaction (ORR), nitrogen reduction reaction (NRR), carbon dioxide reduction reaction (CO 2 RR), are the key conversion routes. In the complex processes for the electrocatalytic reactions, an efficient, highly selective, and stable electrocatalyst plays a pivotal role in speeding up the reaction kinetics and decreasing the overpotential, [5,8,9] which can enhance the sustainable energy conversion efficiency. Over the past few decades, tremendous progresses have been made in the establishment of electrocatalysts preparation and fundamental catalytic mechanisms. [6,7,[9][10][11][12][13][14][15][16][17][18] Nevertheless, those breakthroughs still stay at the stage of experimental synthesis and lack of indepth understanding of fundamental principles of the active site on the catalyst surface and catalytic reactions mechanisms, which seriously limits the development of efficient catalysts. Researchers are full of enthusiasm about preparation of advanced catalysts with ideal properties, expecting to establish the composition-structure-function relationships. Density functional theory (DFT) calculations are based on quantum mechanics, which can calculate the electronic structure of the whole catalytic system. It is probably the most powerful computational approach to investigate the structure-activity relationships of electrocatalysts at atomic level. With the rapid advances of computer technology, DFT calculations have created tremendous opportunities in shedding light on the electrocatalytic mechanisms and predicting promising catalysts. [19,20] Identification of the active sites and understanding of the reaction mechanisms are the two key aspects for the study of electrocatalytic reactions. [21] For the former, the experimental approach for identifying active sites is indirect by prepared specified catalysts and establishing definite correlations between catalytic performances and controllable factors. [22,23] Actually, many intermediate states of electrocatalytic

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Section: Electron Localization Function (Elf)mentioning

confidence: 99%

Section: Electron Localization Function (Elf)mentioning

confidence: 99%

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Density Functional Theory for Electrocatalysis

Liao

Xia

et al. 2021

Energy & Environ Materials

114

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“…To elucidate the electronic properties of Fe SA -NO-C structure,w ef irst performed DFT calculations on the optimized Fe-N 2 O 2 and FeN 4 model structures ( Figure S1). As shown in Figure 1a, Figure 1b,more electrons tend to be transferred from the Fe atom to the N 2 molecule after the introduction of Os pecies,i ndicating that the extra charge might occupy the anti-bounding orbitals of the N 2 molecule leading the activation of N 2 .T he electron localization function (ELF) [5] was further employed to study the adsorption ability of FeN 4 ,F e-N 3 O 1 ,F e-N 2 O 2 and Fe-N 1 O 3 models ( Figure S2). As the coordination number of oxygen increased, the lone-pair of electrons was less likely to participate in the bonding process,r esulting in aw eakened adsorption of N 2 molecules.T hus,itcan be inferred that the Fe SA -NO-C holds favorable properties for electrocatalysis of NRR.…”

Section: Resultsmentioning

confidence: 98%

Boosting Electroreduction Kinetics of Nitrogen to Ammonia via Tuning Electron Distribution of Single‐Atomic Iron Sites

Huang

et al. 2021

Angewandte Chemie

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Electrocatalytic nitrogen reduction reaction (NRR) playsavital role for next-generation electrochemical energy conversion technologies.H owever,t he NRR kinetics is still limited by the sluggish hydrogenation process on noble-metalfree electrocatalyst. Herein, we report the rational design and synthesis of ah ybrid catalyst with atomic iron sites anchored on aN ,O-doped porous carbon (Fe SA-NO-C) matrix of an inverse opal structure,leading to aremarkably high NH 3 yield rate of 31.9 mg NH 3 h À1 mg À1 cat. and Faradaic efficiency of 11.8 % at À0.4 Vf or NRR electrocatalysis,o utperformed almost all previously reported atomically dispersed metal-nitrogen-carbon catalysts.T heoretical calculations revealed that the observed high NRR catalytic activity for the Fe SA-NO-C catalyst stemmed mainly from the optimizedc harge-transfer between the adjacent Oa nd Fe atoms homogenously distributed on the porous carbon support, which could not only significantly facilitate the transportation of N 2 and ions but also effectively decrease the binding energy between the isolated Fe atom and *N 2 intermediate and the thermodynamic Gibbsfree energy of the rate-determining step (*N 2 ! *NNH).

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“…For the associative mechanism, we compared the enzymatic (* [38] for NRR (Figure 3a), and the free energy change for each step is illustrated in Figure 3b,c. The difference between the two mechanisms is that in the enzymatic mechanism, the proton-electron pair (H + + e − ) alternately attacks two N atoms, while in the consecutive mechanism, the proton-electron pair first continuously approaches one N atom to generate the first NH 3 and then attacks the other N atom to generate the second NH 3 [39].…”

Section: N 2 Reaction On Fe 3 @C 2 Nmentioning

confidence: 99%

Fe3 Cluster Anchored on the C2N Monolayer for Efficient Electrochemical Nitrogen Fixation

Han

Meng

et al. 2020

Catalysts

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Under the current double challenge of energy and the environment, an effective nitrogen reduction reaction (NRR) has become a very urgent need. However, the largest production of ammonia gas today is carried out by the Haber–Bosch process, which has many disadvantages, among which energy consumption and air pollution are typical. As the best alternative procedure, electrochemistry has received extensive attention. In this paper, a catalyst loaded with Fe3 clusters on the two-dimensional material C2N (Fe3@C2N) is proposed to achieve effective electrochemical NRR, and our first-principles calculations reveal that the stable Fe3@C2N exhibits excellent catalytic performance for electrochemical nitrogen fixation with a limiting potential of 0.57 eV, while also suppressing the major competing hydrogen evolution reaction. Our findings will open a new door for the development of non-precious single-cluster catalysts for effective nitrogen reduction reactions.

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Regulating the coordination environment through doping N atoms for single-atom Mn electrocatalyst of N2 reduction with high catalytic activity and selectivity: A theoretical study

Cited by 16 publications

References 43 publications

Density Functional Theory for Electrocatalysis

Density Functional Theory for Electrocatalysis

Boosting Electroreduction Kinetics of Nitrogen to Ammonia via Tuning Electron Distribution of Single‐Atomic Iron Sites

Fe3 Cluster Anchored on the C2N Monolayer for Efficient Electrochemical Nitrogen Fixation

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