Recent Advances in Noble‐Metal‐Free Catalysts for Electrocatalytic Synthesis of Ammonia under Ambient Conditions

Xiang, Zhongyuan; Li, Lihong; Wang, Ying; Song, Yanlin

doi:10.1002/asia.202000310

Cited by 10 publications

(7 citation statements)

References 168 publications

(355 reference statements)

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“…Thus, increasing the nitrogen-vacancy concentration of MIL-100 (Al) is favorable for increasing chemical adsorption sites, promoting NRR activity. Moreover, other researches have confirmed that the chemisorption process in this structure occurs on the metal surfaces. ,, Therefore, we propose that the unsaturated Al with the unique MOF structure in the MIL-100 (Al) should play a synergistic role in facilitating the electrochemical nitrogen fixation.…”

Section: Resultsmentioning

confidence: 71%

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Unsaturated p-Metal-Based Metal–Organic Frameworks for Selective Nitrogen Reduction under Ambient Conditions

Yang

Batmunkh

et al. 2020

ACS Appl. Mater. Interfaces

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Electrochemical ammonia synthesis through the nitrogen reduction reaction (NRR) using renewable electricity has recently attracted significant attention. Of particular importance is the development of efficient electrocatalysts at low costs. Herein, highly selective nitrogen capture using porous aluminum-based metal-organic frameworks (MOFs) materials, MIL-100 (Al), is first designed for the electrochemical NRR in alkaline media under ambient conditions. Owing to the unique structure, MIL-100 (Al) exhibits remarkable electrocatalytic performances (NH3 yield: 10.6 µg h -1 cm -2 mgcat. -1 , Faradaic efficiency: 22.6%) at a low overpotential (177 mV). Investigation indicates that the catalyst shows excellent N2-selective captures due to the unsaturated metal sites binding with N2. More specifically, Al as a main-group metal shows a highly selective affinity to N2 due to the strong interaction between the Al 3p band and N 2p orbitals. The manipulation of multifunctional MOFs delivers both high N2 selectivity and abundant catalytic sites, leading to remarkable efficiency for NH3 production. TOC GRAPHICSAmmonia (NH3) is an important chemical for many applications including pharmaceutical, synthetic fibres, and fertilizer production, while also showing great promise for energy storage systems (i.e. hydrogen (H2) storage). [1][2][3][4] Importantly, it is the only currently known carbon-free energy carrier that does not release carbon dioxide (CO2). Therefore, it is expected to play a significant role in the future hydrogen economy. However, at present, the traditional energy-intensive Haber-Bosch process is used for ammonia production at high temperature and pressure (300-550 °C and 200-350 atm) with substantial greenhouse gas emission. 5 There is a growing interest in developing alternative and sustainable approaches for ammonia synthesis. Up to now, environmentally benign processes such as photocatalysis and electrocatalysis without using hydrogen as a reactant through nitrogen reduction reaction (NRR) process under ambient conditions is a rapidly expanding field of research. [6][7][8][9][10][11] The electrochemical synthesis of ammonia was first discovered in 1807 by Davy et al. who used only water and dissolved air between two gold electrodes. 12 The main challenge for electrochemical method is the slow kinetics of N2 adsorption and subsequent N≡N triple bond cleavage. In addition, due to the standard reduction potential for the hydrogen evolution reaction (HER) (0 V vs. Standard Hydrogen Electrode (SHE)) is close to that of NRR (0.057 V vs. Reversible Hydrogen Electrode (RHE)), the competing HER significantly reduces the Faradaic efficiency (FE) of the NRR. 5 The cell reactors are categorized as either alkaline or acidic systems, but the HER is more dominant in acids as evidenced by the two orders of magnitude higher current density in acidic medium than that in alkaline electrolytes. 13 In this regard, developing efficient electrochemical NRR catalyst in alkaline media is of great significance.A key considerati...

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Section: Resultsmentioning

confidence: 71%

“…Moreover, other researches have confirmed that the chemisorption process in this structure occurs on the metal surfaces. 25,43,62 Therefore, we propose that the unsaturated Al with the unique MOF structure in the MIL-100 (Al) should play a synergistic role in facilitating the electrochemical nitrogen fixation.…”

Section: −1mentioning

confidence: 99%

Unsaturated p-Metal-Based Metal–Organic Frameworks for Selective Nitrogen Reduction under Ambient Conditions

Yang

Batmunkh

et al. 2020

ACS Appl. Mater. Interfaces

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“…OVs can first efficaciously capture the metastable electrons and then deliver them into the antibond of N 2 to recognize the electron receptor–donor process. [ 74 ] OVs have been universally verified to be effective in activating catalysts, especially on the surfaces of metal oxides.…”

Section: Recent Advances In Npmo Electrocatalysts For the Nrrmentioning

confidence: 99%

Recent Advances in Nonprecious Metal Oxide Electrocatalysts and Photocatalysts for N₂ Reduction Reaction under Ambient Condition

Liang

et al. 2021

Small Science

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NH3 plays an indispensable role in agriculture, fertilizer production as well as in the chemical industry. However, its large‐scale production still relies deeply on the century‐old Haber–Bosch process under high temperature and pressure along with greenhouse gas emission and fossil fuel consumption. The electrocatalytic and photocatalytic N2 reduction reactions (NRRs) for NH3 production are favorable approaches to avoid these issues because they are carbon‐neutral and energy‐saving. Recently, the nonprecious metal oxides (NPMO) have gathered the most attention due to their ease of synthesis, controllable stability, lower cost, and environmental friendliness. Herein, the recent advances in NPMO electrocatalysts and photocatalysts for the NRR are narrated and the strategies to improve the poor NRR activity of pristine NPMOs by heteroatom doping to engineer their surface‐active sites and introduction of oxygen vacancies are highlighted. A brief summary of and the future perspective on this research field are also presented.

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“…44 As NRR catalysts, SACs have been investigated both experimentally and theoretically. 45 Choi et al performed density functional theory (DFT) calculations on SACs that indicate suppression of HER with increased selectivity toward NRR. 46 Niu et al screened SACs supported on graphitic carbon nitrides with DFT and predicted good catalytic activity and selectivity toward NRR of single atom Nb, Mo, Ta, and W. 47 Li et al demonstrated Fe-based SAC on MoS 2 sheets as promising candidate with NRR reaction rate close to 36 mmol g -1 h -1 , which they attributed to high polarization at single atom protrusions.…”

Section: Introductionmentioning

confidence: 99%

“…As NRR catalysts, SACs have been investigated both experimentally and theoretically 45 . Choi et al.…”

Section: Introductionmentioning

confidence: 99%

Demonstration of no catalytical activity of Fe‐N‐C and Nb‐N‐C electrocatalysts toward nitrogen reduction using in‐line quantification

Sveinbjörnsson¹,

Gunnarsdóttir

Creel

et al. 2022

SusMat

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Ammonia (NH3) production via the electrochemical nitrogen reduction reaction (NRR) is a promising method for sustainable generation of this important chemical. Efforts are ongoing in finding an efficient, stable, and selective catalyst that will enable the reaction. However, progress is hindered in the field due to lack of reproducibility, most likely a consequence of reports of false‐positive results due to improper measurement control and methods. In this study, we explore the NRR activity of a promising class of single atom catalysts, transition metal‐nitrogen‐carbon (M‐N‐C) electrocatalysts. Using a state‐of‐the‐art in‐line ammonia quantification methodology, with detection limit as low as 1 ppb for ammonia, we show that single atom Nb and Fe embedded in a stable carbon and nitrogen framework do not electrochemically reduce N2 to NH3. Critically, this demonstrates that our experimental setup with in‐line sequential injection analysis successfully excludes ammonia contamination from the gas supply and atmospheric sources, allowing for thorough and high‐throughput examination of potential NRR catalysts.

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Recent Advances in Noble‐Metal‐Free Catalysts for Electrocatalytic Synthesis of Ammonia under Ambient Conditions

Cited by 10 publications

References 168 publications

Unsaturated p-Metal-Based Metal–Organic Frameworks for Selective Nitrogen Reduction under Ambient Conditions

Unsaturated p-Metal-Based Metal–Organic Frameworks for Selective Nitrogen Reduction under Ambient Conditions

Recent Advances in Nonprecious Metal Oxide Electrocatalysts and Photocatalysts for N₂ Reduction Reaction under Ambient Condition

Demonstration of no catalytical activity of Fe‐N‐C and Nb‐N‐C electrocatalysts toward nitrogen reduction using in‐line quantification

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Recent Advances in Noble‐Metal‐Free Catalysts for Electrocatalytic Synthesis of Ammonia under Ambient Conditions

Cited by 10 publications

References 168 publications

Unsaturated p-Metal-Based Metal–Organic Frameworks for Selective Nitrogen Reduction under Ambient Conditions

Unsaturated p-Metal-Based Metal–Organic Frameworks for Selective Nitrogen Reduction under Ambient Conditions

Recent Advances in Nonprecious Metal Oxide Electrocatalysts and Photocatalysts for N2 Reduction Reaction under Ambient Condition

Demonstration of no catalytical activity of Fe‐N‐C and Nb‐N‐C electrocatalysts toward nitrogen reduction using in‐line quantification

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Recent Advances in Nonprecious Metal Oxide Electrocatalysts and Photocatalysts for N₂ Reduction Reaction under Ambient Condition