Electrocatalytic N<sub>2</sub>-to-NH<sub>3</sub> conversion with high faradaic efficiency enabled using a Bi nanosheet array

Zhang, Rong; Ji, Lei; Kong, Wenhan; Wang, Huanbo; Zhao, Runbo; Chen, Hongyu; Li, Tingshuai; Li, Baihai; Luo, Yonglan; Sun, Xuping

doi:10.1039/c9cc01703h

Cited by 102 publications

(53 citation statements)

References 38 publications

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“…Among the various reported NRR electrocatalysts (e.g., noble metals, transition metal compounds, heteroatom‐doped carbon, and single‐atom catalysts), [ 10,12–21 ] bismuth (Bi)‐based materials are very attractive for both electrochemical and photocatalytic nitrogen reduction due to their unique electronic structures. [ 22–24 ] These materials include: amorphous Bi 4 V 2 O 11 /CeO 2 hybrid, [ 25 ] vacancy‐rich BiVO 4 , [ 26 ] Bi nanosheets, [ 27,28 ] defect‐rich Bi (110) nanoplates, [ 29 ] Bi nanodendrites, [ 30 ] and ultrathin porous Bi 5 O 7 I nanotubes. [ 31 ] The Bi 6p band can provide localized electrons for back‐donation to the π* antibonding orbitals of adsorbed N 2 molecules, enabling efficient activation and reduction.…”

Section: Figurementioning

confidence: 99%

“…As shown in Figure 2b and Figure S10d (Supporting Information), the in situ synthesized Bi NPs achieve a maximum NH 3 yield of 3.25 ± 0.08 µg cm −2 h −1 at −0.7 V versus RHE and maximum faradaic efficiency (FE) of 12.11 ± 0.84% at −0.6 V versus RHE, which are comparable with previously reported bismuth catalysts (Table S1, Supporting Information). [ 25–31,51–53 ] N 2 H 4 cannot be detected in the electrolytes after 1 h electrolysis by the Watt and Chrisp method (Figures S11 and S12, Supporting Information). The electrocatalytic stability of the Bi NPs was evaluated by consecutive cycling tests at −0.7 V versus RHE without changing the electrode and Nafion membrane.…”

Section: Figurementioning

confidence: 99%

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In Situ Fragmented Bismuth Nanoparticles for Electrocatalytic Nitrogen Reduction

Yao

Tang

et al. 2020

Advanced Energy Materials

216

135

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The electrochemical nitrogen reduction reaction (NRR) is a promising alternative to the energy‐intensive Haber–Bosch process for ammonia synthesis. Among the possible electrocatalysts, bismuth‐based materials have shown unique NRR properties due to their electronic structures and poor hydrogen evolution activity. However, identification of the active sites and reaction mechanism is still difficult due to structural and chemical changes under reaction potentials. Herein, in situ Raman spectroscopy, complemented by electron microscopy, is employed to investigate the structural and chemical transformation of the Bi species during the NRR. Nanorod‐like bismuth‐based metal–organic frameworks are reduced in situ and fragment into densely contacted Bi0 nanoparticles under the applied potentials. The fragmented Bi0 nanoparticles exhibit excellent NRR performance in both neutral and acidic electrolytes, with an ammonia yield of 3.25 ± 0 .08 µg cm−2 h−1 at −0.7 V versus reversible hydrogen electrode and a Faradaic efficiency of 12.11 ± 0.84% at −0.6 V in 0.10 m Na2SO4. Online differential electrochemical mass spectrometry detects the production of NH3 and N2H2 during NRR, suggesting a possible pathway through two‐step reduction and decomposition. This work highlights the importance of monitoring and optimizing the electronic and geometric structures of the electrocatalysts under NRR conditions.

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Section: Figurementioning

confidence: 99%

Section: Figurementioning

confidence: 99%

In Situ Fragmented Bismuth Nanoparticles for Electrocatalytic Nitrogen Reduction

Yao

Tang

et al. 2020

Advanced Energy Materials

216

135

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“…Recently, the main‐group metals, especially Bi, have been investigated as promising candidates for NRR electrocatalysts, attracting increased attention because of their weak binding with hydrogen to suppress the HER . For instance, the Bi nanosheet array on Cu foil can realize a NH 3 yield of 6.89 × 10 −11 mol s −1 cm −2 with an FE of 10.26% at −0.5 V (vs RHE) in 0.1 m HCl . We envisage that further exploration of 2D materials with an intrinsic NRR activity will be of an important path to discover new 2D NRR electrocatalyst.…”

Section: D Nrr Electrocatalystsmentioning

confidence: 99%

“…The NRR electrocatalytic activities of other B‐containing 2D NRR materials such as B nanosheets, and BN nanosheets have also been explored. Recently, the main‐group metals, especially Bi, have been investigated as promising candidates for NRR electrocatalysts, attracting increased attention because of their weak binding with hydrogen to suppress the HER . For instance, the Bi nanosheet array on Cu foil can realize a NH 3 yield of 6.89 × 10 −11 mol s −1 cm −2 with an FE of 10.26% at −0.5 V (vs RHE) in 0.1 m HCl .…”

Section: D Nrr Electrocatalystsmentioning

confidence: 99%

2D Electrocatalysts for Converting Earth‐Abundant Simple Molecules into Value‐Added Commodity Chemicals: Recent Progress and Perspectives

et al. 2019

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those emerging electrocatalytic redox reactions involving water, oxygen, and carbon dioxide as reactants. [7][8][9] The excellent progress achieved over the past decade has placed 2D electrocatalysts as one of the most important classes of nanostructured electrocatalysts. More significantly, 2D nanostructures are particularly useful for developing nonprecious-material-based electrocatalysts. For example, transition metal (TM) dichalcogenide (TMD)-based 2D nanomaterials have been used for water reduction to generate hydrogen via the hydrogen evolution reaction (HER). [10] In addition, 2D layered metal hydroxides (LMHs), [8d,11] layered metal oxides (LMO), [12] and 2D metal-organic frameworks (MOFs) [9c] have been developed for water oxidation to produce oxygen via the oxygen evolution reaction (OER). Graphene-based electrocatalysts have been used to achieve the 4-electron oxygen reduction reaction (ORR) [13] for fuel cells and the 2-electron oxygen reduction reaction (2e-ORR) [14] to produce hydrogen peroxide. Furthermore, ultrathin metal oxides [9b,15] or metal nanosheets, [16] TMDs, [9d,17] MXenes, [18] and 2D MOFs [19] have successfully been applied to convert nitrogen and carbon dioxide into ammonia and carbon fuels via the nitrogen reduction reaction (NRR) and carbon dioxide reduction reaction (CO 2 RR). The great success of nonprecious 2D electrocatalysts in a short time is due mainly to the unique 2D features that allow for the easy manipulation and engineering 2D nanostructures into catalytically active structures. As an emerging class of electrocatalysts, there are still several unexplored scientific domains and unrealized application potentials for 2D electrocatalysts. This aspect added to their unique 2D features and their advantages in creating catalytically active structures will continuously attract and motivate further research activities in the catalysis field. Meanwhile, a timely review on 2D electrocatalysts would undoubtedly facilitate this future research.The design, controllable synthesis, and applications of various types of 2D nanomaterials have been comprehensively covered by numerous excellent reviews. [2d,e,5] A number of excellent reviews on 2D electrocatalysts can also be found in the literature. [10a,20-23] However, these reviews focused on the development of 2D electrocatalysts for extensively reported energy-related applications such as the HER, OER, and ORR. In recent years, 2D electrocatalysts have increasingly been usedThe electrocatalytic conversion of earth-abundant simple molecules into value-added commodity chemicals can transform current chemical production regimes with enormous socioeconomic and environmental benefits. For these applications, 2D electrocatalysts have emerged as a new class of high-performance electrocatalyst with massive forward-looking potential. Recent advances in 2D electrocatalysts are reviewed for emerging applications that utilize naturally existing H 2 O, N 2 , O 2 , Cl − (seawater) and CH 4 (natural gas) as reactants for nitrogen reduction...

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“…For example, surface reconstruction occurs during reactions, and certain metal catalysts would form surface oxide layers under reduction potentials. Nanosized catalysts also have more complexed exposed faces and defects than their bulk counterparts [74][75][76][77][78][79]. In recent years, various electrocatalysts have been explored for NH 3 synthesis from N 2 and H 2 O in liquid or aqueous media [80].…”

Section: Reaction Mechanismsmentioning

confidence: 99%

Alternative Strategies Toward Sustainable Ammonia Synthesis

Wang

Gong

2020

Trans. Tianjin Univ.

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As one of the world's most produced chemicals, ammonia (NH 3 ) is synthesized by Haber-Bosch process. This century-old industry nourishes billions of people and promotes social and economic development. In the meantime, 3%-5% of the world's natural gas and 1%-2% of the world's energy reserves are consumed, releasing millions of tons of carbon dioxide annually to the atmosphere. The urgency of replacing fossil fuels and mitigating climate change motivates us to progress toward more sustainable methods for N 2 reduction reaction based on clean energy. Herein, we overview the emerging advancement for sustainable N 2 fixation under mild conditions, which include electrochemical, photo-, plasma-enabled and homogeneous molecular NH 3 productions. We focus on NH 3 generation by electrocatalysts and photocatalysts. We clarify the features and progress of each kind of NH 3 synthesis process and provide promising strategies to further promote sustainable ammonia production and construct state-of-the-art catalytic systems.

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Electrocatalytic N₂-to-NH₃ conversion with high faradaic efficiency enabled using a Bi nanosheet array

Abstract: A Bi nanosheet array on Cu foil (Bi NS/CF) is efficient and stable for electrocatalytic N2 reduction. In 0.1 M HCl, it shows a high faradaic efficiency of 10.26% at −0.50 V vs. the reversible hydrogen electrode.

Cited by 102 publications

References 38 publications

In Situ Fragmented Bismuth Nanoparticles for Electrocatalytic Nitrogen Reduction

In Situ Fragmented Bismuth Nanoparticles for Electrocatalytic Nitrogen Reduction

2D Electrocatalysts for Converting Earth‐Abundant Simple Molecules into Value‐Added Commodity Chemicals: Recent Progress and Perspectives

Alternative Strategies Toward Sustainable Ammonia Synthesis

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Electrocatalytic N2-to-NH3 conversion with high faradaic efficiency enabled using a Bi nanosheet array

Abstract: A Bi nanosheet array on Cu foil (Bi NS/CF) is efficient and stable for electrocatalytic N2 reduction. In 0.1 M HCl, it shows a high faradaic efficiency of 10.26% at −0.50 V vs. the reversible hydrogen electrode.

Cited by 102 publications

References 38 publications

In Situ Fragmented Bismuth Nanoparticles for Electrocatalytic Nitrogen Reduction

In Situ Fragmented Bismuth Nanoparticles for Electrocatalytic Nitrogen Reduction

2D Electrocatalysts for Converting Earth‐Abundant Simple Molecules into Value‐Added Commodity Chemicals: Recent Progress and Perspectives

Alternative Strategies Toward Sustainable Ammonia Synthesis

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Electrocatalytic N₂-to-NH₃ conversion with high faradaic efficiency enabled using a Bi nanosheet array