Ammonia (NH3) electrosynthesis gains significant attention as NH3is essentially important for fertilizer production and fuel utilization. However, electrochemical nitrogen reduction reaction (NRR) remains a great challenge because of low activity and poor selectivity. Herein, a new class of atomically dispersed Ni site electrocatalyst is reported, which exhibits the optimal NH3yield of 115 µg cm−2h−1at –0.8 V versus reversible hydrogen electrode (RHE) under neutral conditions. High faradic efficiency of 21 ± 1.9% is achieved at ‐0.2 V versus RHE under alkaline conditions, although the ammonia yield is lower. The Ni sites are stabilized with nitrogen, which is verified by advanced X‐ray absorption spectroscopy and electron microscopy. Density functional theory calculations provide insightful understanding on the possible structure of active sites, relevant reaction pathways, and confirm that the Ni‐N3sites are responsible for the experimentally observed activity and selectivity. Extensive controls strongly suggest that the atomically dispersed NiN3site‐rich catalyst provides more intrinsically active sites than those in N‐doped carbon, instead of possible environmental contamination. This work further indicates that single‐metal site catalysts with optimal nitrogen coordination is very promising for NRR and indeed improves the scaling relationship of transition metals.
Electro- and Photocatalytic Conversion of N 2 to NH 3 by Chemically Modified Transition Metal Dichalcogenides, MoS 2 , and WS 2
Electro- and photocatalytic reduction of N 2 to NH 3 —the nitrogen reduction reaction (NRR)—is an environmentally- and energy-friendly alternative to the Haber-Bosch process for ammonia production. There is a great demand for the development of novel semiconductor-based electrocatalysts with high efficiency and stability for the direct conversion of inert substrates—including N 2 to ammonia—using visible light irradiation under ambient conditions. Herein we report electro-, and photocatalytic NRR with transition metal dichalcogenides (TMDCs), viz MoS 2 and WS 2 . Improved acid treatment of bulk TMDCs yields exfoliated TMDCs (exTMDCs) only a few layers thick with ∼10% S vacancies. Linear scan voltammograms on exMoS 2 and exWS 2 electrodes reveal significant NRR activity for exTMDC-modified electrodes, which is greatly enhanced by visible light illumination. Spectral measurements confirm ammonia as the main reaction product of electrocatalytic and photocatalytic NRR, and the absence of hydrazine byproduct. Femtosecond-resolved transient absorption studies provide direct evidence of interaction between photo-generated excitons/trions with N 2 adsorbed at S vacancies. DFT calculations corroborate N 2 binding to exMoS 2 at S-vacancies, with substantial π -backbonding to activate dinitrogen. Our findings suggest that chemically functionalized exTMDC materials could fulfill the need for highly-desired, inexpensive catalysts for the sustainable production of NH 3 using Sunlight under neutral pH conditions without appreciable competing production of H 2 .
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- NSF-PAR ID:
- 10425289
- Date Published:
- Journal Name:
- Journal of The Electrochemical Society
- Volume:
- 170
- Issue:
- 5
- ISSN:
- 0013-4651
- Page Range / eLocation ID:
- 056501
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Abstract -
The electrocatalytic nitrogen reduction reaction (NRR) is of significant interest as an environmentally friendly method for NH 3 production for agricultural and clean energy applications. Selectivity of NRR vis-à-vis the hydrogen evolution reaction (HER), however, is thought to adversely impact many potential catalysts, including Earth-abundant transition metal oxynitrides. Relative HER/NRR selectivities are therefore directly compared for two transition metal oxynitrides with different metal oxophilicities—Co and V. Electrocatalytic current–potential measurements, operando fluorescence, absorption, and GC measurements of H 2 and NH 3 production, ex situ X-ray photoelectron spectroscopy (XPS), and density functional theory (DFT) calculations are combined to directly compare NRR and HER activities under identical reaction conditions. Results show that cobalt oxynitrides – with Co primarily in the Co( ii ) oxidation state – are NRR active at pH 10, with electrochemical reduction of both lattice nitrogen and dissolved N 2 , the latter occurring without N incorporation into the lattice. Removal of lattice N then yields Co( ii ) oxide, which is still NRR active. These results are complemented by calculations showing that N 2 binding at Co( ii ) sites is energetically favored over binding at Co( iii ) sites. GC analysis demonstrates that H 2 production occurs in concert with ammonia production but at a far greater rate. In contrast, vanadium oxynitride films are HER inactive under the same (pH 10) conditions, as well as at pH 7, but are NRR active at pH 7. DFT calculations indicate that a major difference in the two materials is hindered O–H dissociation of H 2 O adsorbed at O-ligated Co vs. V cation centers. The combined studies indicate significant variation in HER vs. NRR selectivity as a function of employed transition metal oxynitrides, as well as different HER mechanisms in V and Co oxynitrides.more » « less
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Atmospheric nitrogen fixation using a photocatalytic system is a promising approach to produce ammonia. However, most of the recently explored photocatalysts for N 2 fixation are in the powder form, suffering from agglomeration and difficulty in the collection and leading to unsatisfactory conversion efficiency. Developing efficient film catalysts for N 2 photofixation under ambient conditions remains challenging. Herein, we report the efficient photofixation of N 2 over a periodic WS 2 @TiO 2 nanoporous film, which is fabricated through a facile method that combines anodization, E-beam evaporation, and chemical vapor deposition (CVD). Oxygen vacancies are introduced into TiO 2 nanoporous films through Ar annealing treatment, which plays a vital role in N 2 adsorption and activation. The periodic WS 2 @TiO 2 nanoporous film with an optimized WS 2 content shows highly efficient photocatalytic performance for N 2 fixation with an NH 3 evolution rate of 1.39 mmol g −1 h −1 , representing one of the state-of-the-art catalysts.more » « less
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Abstract Photo‐responsive semiconductors can facilitate nitrogen activation and ammonia production, but the high recombination rate of photogenerated carriers represents a significant barrier. Ferroelectric photocatalysts show great promise in overcoming this challenge. Herein, by adopting a low‐temperature hydrothermal procedure with varying concentrations of glyoxal as the reducing agent, oxygen vacancies (Vo) are effectively produced on the surface of ferroelectric SrBi4Ti4O15(SBTO) nanosheets, which leads to a considerable increase in photocatalytic activity toward nitrogen fixation under simulated solar light with an ammonia production rate of 53.41 µmol g−1h−1, without the need of sacrificial agents or photosensitizers. This is ascribed to oxygen vacancies that markedly enhance the self‐polarization and internal electric field of ferroelectric SBTO, and hence, facilitate the separation of photogenerated charge carriers and light trapping as well as N2adsorption and activation, as compared to pristine SBTO. Consistent results are obtained in theoretical studies. Results from this study highlight the significance of surface oxygen vacancies in enhancing the performance of photocatalytic nitrogen fixation by ferroelectric catalysts.
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1149/1945-7111/acd02d
