Accelerated Dinitrogen Electroreduction to Ammonia via Interfacial Polarization Triggered by Single-Atom Protrusions

Li, Jie; Shang, Chen; Quan, Fengjiao; Zhan, Guangming; Jia, Falong; Ai, Zhihui; Zhang, Lizhi

doi:10.1016/j.chempr.2020.01.013

Cited by 250 publications

(175 citation statements)

References 37 publications

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“…[ 11 ] Note that the basal plane of most available 2D electrocatalysts is chemically inert for the N 2 activation, thus is not efficient toward NRR in their pristine form, and the origin of activity and selectivity is primarily associated with their exposed edge sites or defective sites. [ 12 ] Several strategies, such as doping, [ 13 ] interfacial engineering, [ 14 ] and defect modifications, [ 15 ] have been employed to improve the specific activity of materials. However, such tactics typically require strict optimization of the conditions to produce suitable doping or defects (e.g., the solvents, dopants, as well as doping concentrations), and the resulting catalysts suffer from the limited active sites.…”

Section: Introductionmentioning

confidence: 99%

Establishing a Theoretical Landscape for Identifying Basal Plane Active 2D Metal Borides (MBenes) toward Nitrogen Electroreduction

Guo

Lin

et al. 2020

Adv Funct Materials

121

114

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To achieve efficient ammonia synthesis via electrochemical nitrogen reduction reaction (NRR), a qualified catalyst should have both high specific activity and large active surface area. However, integrating these two merits into one single material remains a big challenge due to the difficulty in balancing multiple reaction intermediates. Here, it is demonstrated that the boron‐analogues of MXenes, namely “MBenes”, could cope with the challenge and achieve the high activity and large reaction region simultaneously toward NRR. Using extensive density functional theory computations and taking 16 MBenes as representatives, it is identified that seven MBenes (CrB, MoB, WB, Mo2B, V3B4, CrMnB2, and CrFeB2) not only have intrinsic basal plane activity for NRR with limiting potentials ranging from −0.22 to −0.82 V, but also possess superior capability of suppressing the competitive hydrogen evolution reaction. Particularly, different from the MXenes whose surface oxidation may block the active sites, once oxidized, these MBenes can catalyze NRR via the self‐activating process, reducing O*/OH* into H2O* under reaction conditions, and favoring the N2 electroreduction. As a result, the exceptional activity and selectivity, high active area (≈1019 m−2), and antioxidation nature render these MBenes as pH‐universal catalysts for NH3 production without introducing any dopants and defects.

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Section: Introductionmentioning

confidence: 99%

Establishing a Theoretical Landscape for Identifying Basal Plane Active 2D Metal Borides (MBenes) toward Nitrogen Electroreduction

Guo

Lin

et al. 2020

Adv Funct Materials

121

114

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“…Single-atom catalysts (SACs) are expected to have great potential to improve the NRR performance due to the lowest site size,n early 100 %a tomic efficiency and unique lowcoordinated features. [8][9][10][11] Many SACs such as Ru, [12,13] Mo, [14] Fe, [15][16][17] Au, [18] Cu, [19] Y, [20] Ag, [20] and B [21] have been applied for the NRR in aqueous electrolytes.…”

Section: Introductionmentioning

confidence: 99%

Modulating Single‐Atom Palladium Sites with Copper for Enhanced Ambient Ammonia Electrosynthesis

Han

Ren

et al. 2020

Angewandte Chemie

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The electrochemical reduction of N 2 to NH 3 is emerging as ap romising alternative for sustainable and distributed production of NH 3 .H owever,t he development has been impeded by difficulties in N 2 adsorption, protonation of *NN,a nd inhibition of competing hydrogen evolution. To address the issues,w ed esign ac atalyst with diatomic Pd-Cu sites on N-doped carbon by modulation of single-atom Pd sites with Cu. The introduction of Cu not only shifts the partial density of states of Pd toward the Fermi level but also promotes the d-2p*c oupling between Pd and adsorbed N 2 ,l eading to enhanced chemisorption and activated protonation of N 2 ,and suppressed hydrogen evolution. As ar esult, the catalyst achieves ah igh Faradaic efficiency of 24.8 AE 0.8 %a nd ad esirable NH 3 yield rate of 69.2 AE 2.5 mgh À1 mg cat. À1 ,f ar outperforming the individual single-atom Pd catalyst. This work paves ap athway of engineering single-atom-based electrocatalysts for enhanced ammonia electrosynthesis.

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“…[35] Compared with the bulk Cu 2 O, the onset potential for N 2 reduction over ultrafine Cu 2 Ow as shifted to positive potentials,a long with am arkedly enhanced current density.R esults suggested that the supported ultrafine Cu 2 Oe nhanced pNRR activity by lowering the energy barrier for N 2 reduction. [36]…”

Section: Methodsmentioning

confidence: 99%

Sub‐3 nm Ultrafine Cu₂O for Visible Light Driven Nitrogen Fixation

et al. 2020

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Cu2O, a low‐cost, visible light responsive semiconductor photocatalyst represents an ideal candidate for visible light driven photocatalytic reduction of N2 to NH3 from the viewpoint of thermodynamics, but it remains unexplored. Reported here is the successful synthesis of uniformly sized and ultrafine Cu2O platelets, with a lateral size of <3 nm, by the in situ topotactic reduction of a CuII‐containing layered double hydroxide with ascorbic acid. The supported ultrafine Cu2O offered excellent performance and stability for the visible light driven photocatalytic reduction of N2 to NH3 (the Cu2O‐mass‐normalized rate as high as 4.10 mmol gCu2normalO −1 h−1 at λ>400 nm), with the origin of the high activity being long‐lived photoexcited electrons in trap states, an abundance of exposed active sites, and the underlying support structure. This work guides the future design of ultrafine catalysts for NH3 synthesis and other applications.

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Accelerated Dinitrogen Electroreduction to Ammonia via Interfacial Polarization Triggered by Single-Atom Protrusions

Cited by 250 publications

References 37 publications

Establishing a Theoretical Landscape for Identifying Basal Plane Active 2D Metal Borides (MBenes) toward Nitrogen Electroreduction

Establishing a Theoretical Landscape for Identifying Basal Plane Active 2D Metal Borides (MBenes) toward Nitrogen Electroreduction

Modulating Single‐Atom Palladium Sites with Copper for Enhanced Ambient Ammonia Electrosynthesis

Sub‐3 nm Ultrafine Cu₂O for Visible Light Driven Nitrogen Fixation

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Accelerated Dinitrogen Electroreduction to Ammonia via Interfacial Polarization Triggered by Single-Atom Protrusions

Cited by 250 publications

References 37 publications

Establishing a Theoretical Landscape for Identifying Basal Plane Active 2D Metal Borides (MBenes) toward Nitrogen Electroreduction

Establishing a Theoretical Landscape for Identifying Basal Plane Active 2D Metal Borides (MBenes) toward Nitrogen Electroreduction

Modulating Single‐Atom Palladium Sites with Copper for Enhanced Ambient Ammonia Electrosynthesis

Sub‐3 nm Ultrafine Cu2O for Visible Light Driven Nitrogen Fixation

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Sub‐3 nm Ultrafine Cu₂O for Visible Light Driven Nitrogen Fixation