Substrate augmented catalytic activity towards NRR: A case study of Li doped Al clusters on defective graphene

Samal, Pragnya Paramita; Poonam, .; Krishnamurty, Saïlaja

doi:10.1016/j.apsusc.2021.150586

Cited by 9 publications

(11 citation statements)

References 60 publications

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“…Samal et al reported a graphene-based catalyst with metal Li doped to Al clusters. [59] As shown in Figure 5, the 3-13 Al nanoclusters anchored on metal Li are more likely to generate active sites and activate N 2 molecules due to their quantum confinement of electrons, higher surface-volume ratio, and tunable catalytic activity anchored on the carrier. Considering the instability of nanoclusters, graphene with good electrical conductivity was selected as the substrate to support the Li-doped Al clusters.…”

Section: P-block Boron Group Metal-based Catalystsmentioning

confidence: 99%

“…This electron density distribution leads to charge transfer from N 2 to Al 12 Li@graphene and increases the N 2 bond activation. [59] Ga could be an active NRR catalyst due to its sp 3 hybrid orbitals for better N 2 capturing. Moreover, surface engineering strategy can further improve the electrochemical NRR performance of Ga.…”

Section: P-block Boron Group Metal-based Catalystsmentioning

confidence: 99%

“…a) Al 2 Li, b) Al 3 Li, c) Al 4 Li, d) Al 5 Li, e) Al 6 Li, f) Al 2 Li, g) Al 8 Li, h) Al 9 Li, i) Al 10 Li, j) Al 11 Li, k) Al 12Li, l) DOS plot of dinitrogen adsorbed Al12 Li @graphene complex, m) CDD plot of dinitrogen adsorbed Al12 Li @graphene complex. Reproduced with permission [59]. Copyright 2021, Elsevier.…”

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P‐Block Metal‐Based Electrocatalysts for Nitrogen Reduction to Ammonia: A Minireview

Wang

et al. 2023

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limited total amount and the advancement of mining technology have triggered a booming decline of fossil fuel reserves, resulting in a severe energy depletion crisis. [2][3][4] NH 3 is an essential primary raw material for synthesizing chemicals and fertilizers in the chemical industry. [5,6] Currently, NH 3 production relies on the traditional Haber-Bosch process. [7,8] However, the reaction conditions are very harsh, which entail thermocatalytic conversion of N 2 and H 2 (N 2 + 3H 2 → 2NH 3 , ΔG = −16.48 kJ mol −1 ) under high temperature (≈300-600 °C) and intense pressure (≈15-40 MPa). [9,10] Moreover, the Haber-Bosch process requires complex and extensive production equipment. Recently, the electrochemical nitrogen reduction reaction (NRR) to NH 3 has received tremendous attention due to its merits of energy saving and environmental friendliness, aiming to achieve clean and sustainable production of NH 3 using renewable energy. [11][12][13] Unfortunately, electrochemical NRR is seriously limited by the lack of effective catalysts that can both greatly activate N 2 and suppress the hydrogen evolution reaction (HER). Currently, strategies to solve these problems mainly focus on the design of catalysts to achieve effective activation of N 2 and inhibit the occurrence of HER side reaction. [14,15] Maingroup elements play an essential role in NRR due to various electronic structures. That N 2 molecule can be effectively activated through Lewis acid-based interaction, p electron reverse contribution, heteroatomic doping, and defect engineering. [16] In addition, intrinsically poor proton binding, hydrophobic electrode surface engineering, and alkali metal cation effect can effectively inhibit HER. [17] However, the main-group elements have poor NRR activity. Because of the empty d-orbitals for electron donation and back-donation for N 2 capture and activation, transition metal-based catalysts have been extensively studied for NRR. But the d-orbitals of transition metal-based catalysts and H-s orbital coupling resulted in fierce HER-competition on the catalytic surface, which would not only hindered the active sites of N 2 adsorption but also significantly reduced the Faradaic efficiency (FEs) of the catalyst. [18] Noble metal catalysts have high NH 3 yield and FEs, [19][20][21] but their high price limit applications. In contrast, metal-free electrocatalysts have been explored by more researchers. [22][23][24] Porous metal-free Electrochemical nitrogen reduction reaction (NRR) to ammonia (NH 3 ) using renewable electricity provides a promising approach towards carbon neutral. What's more, it has been regarded as the most promising alternative to the traditional Haber-Bosch route in current context of developing sustainable technologies. The development of a class of highly efficient electrocatalysts with high selectivity and stability is the key to electrochemical NRR. Among them, P-block metal-based electrocatalysts have significant application potential in NRR for which possessing a strong interaction with the N ...

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Section: P-block Boron Group Metal-based Catalystsmentioning

confidence: 99%

Section: P-block Boron Group Metal-based Catalystsmentioning

confidence: 99%

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P‐Block Metal‐Based Electrocatalysts for Nitrogen Reduction to Ammonia: A Minireview

Wang

et al. 2023

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“…107–109 To improve their catalytic activity of them, Samal et al presented a new catalyst, which was constructed by Li-doped Al clusters anchored on the defective graphene. 110 By comparing the binding energy of N 2 on Al n , Al n −1 Li ( n = 3–13), and Al n −1 Li@graphene, the outstanding N 2 activation ability of the supporting nanocluster catalyst was illuminated. Furthermore, the DOS analysis for Al n −1 Li@graphene described the interaction between the p orbitals of the Al atom and the p orbitals of the N atom, which revealed the mechanism of N 2 activation.…”

Section: Nrr On Metal Nanoclustersmentioning

confidence: 99%

“…There have been several studies on the Al based NCs (Al 6 Si, Al 6 P) and Lin (2 o n o 8), which are demonstrated as promising candidates for catalysing the NRR [107][108][109]. To improve their catalytic activity of them, Samal et al presented a new catalyst, which was constructed by Li-doped Al clusters anchored on the defective graphene 110. By comparing the binding energy of N 2 on Al n , Al nÀ1 Li (n = 3-13), and Al nÀ1 Li@graphene, the outstanding N 2 activation ability of the supporting nanocluster catalyst was illuminated.…”

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confidence: 99%

Theoretical and experimental progress of metal electrocatalysts for the nitrogen reduction reaction

Zhang

Liu

et al. 2023

Mater. Chem. Front.

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Can Li Atoms Anchored on Boron‐ and Nitrogen‐Doped Graphene Catalyze Dinitrogen Molecules to Ammonia? A DFT Study

et al. 2023

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The most successful electrochemical conversion of ammonia from dinitrogen molecule reported to date is through a Li mediated mechanism. In the framework of the above fact and that Li anchored graphene is an experimentally feasible system, the present work is a computational experiment to identify the potential of Li anchored graphene as a catalyst for N2 to NH3 conversion as a function of (a) minimum number of Li atoms needed for anchoring on graphene sheets and (b) the role of chemical modification of graphene surfaces. The studies bring forth an understanding that Li anchored graphene sheets are potential catalysts for ammonia conversion with preferential adsorption of N2 through end‐on configuration on Li atoms anchored on doped and pristine graphene surfaces. This mode of adsorption being characteristic of Nitrogen Reduction Reaction (NRR) through enzymatic pathway, examination of the same followed by analysis of electronic properties demonstrates that tri‐Li atoms (Tri Atom Catalysts, TACs) are more efficient as catalysts for NRR as compared to two Li atoms (Di Atom Catalysts, DACs). Either way, the rate determining step was found to be *NH2→*NH3 step (mixed pathway) with ΔGmax=1.02 eV and *NH2−*NH3→*NH2 step (enzymatic pathway) with ΔGmax=1.11 eV for 1B doped TAC and DAC on graphene sheet, respectively. Consequently, this work identifies the viability of Li anchored graphene based 2‐D sheets as hetero‐atom catalyst for NRR.

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Substrate augmented catalytic activity towards NRR: A case study of Li doped Al clusters on defective graphene

Cited by 9 publications

References 60 publications

P‐Block Metal‐Based Electrocatalysts for Nitrogen Reduction to Ammonia: A Minireview

P‐Block Metal‐Based Electrocatalysts for Nitrogen Reduction to Ammonia: A Minireview

Theoretical and experimental progress of metal electrocatalysts for the nitrogen reduction reaction

Can Li Atoms Anchored on Boron‐ and Nitrogen‐Doped Graphene Catalyze Dinitrogen Molecules to Ammonia? A DFT Study

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