CHEMICAL RECORD
·
2022
·Vol. 22
·期 11
·e202200139
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IF 6.935
Suchi Smita Biswas,Soumita Chakraborty,Arunava Saha,Muthusamy Eswaramoorthy
Aqueous electrochemical nitrogen reduction (ENR) to ammonia (NH 3 ) under ambient conditions is considered as an alternative to the energy-intensive Haber-Bosch process for ammonia production. Many metal, non-metal, carbon-based materials along with metal-chalcogenides, metal-nitrides have been explored for their ENR activity. The reported NH 3 production through ENR is still in the micro-gram level and often falls in the range of NH 3 and NO x contaminations from the surrounding. The quantification of NH 3 at very low concentration possess enormous challenge in this field and thus many reported ENR electrocatalysts suffer from reproducibility issue. This review highlights in detail the challenges associated with ENR in aqueous medium and necessitates standardization of protocols to quantify the low concentration of NH 3 free of false-positives. It concludes the prospects of electrochemical NH 3 production through lithium-mediated N 2 reduction.
研究领域:
化学工程
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材料科学
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环境科学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
NEW JOURNAL OF CHEMISTRY
·
2025
·
IF 2.5
Yang Yang,Mengyao Tan,Xiaoman Li,Min Luo
The photocatalytic nitrogen reduction reaction provides an alternative process for nitrogen cycling and ammonia (NH3) production under mild conditions. Herein, we have synthesized Ag-loaded In2O3 (Ag@In2O3-X) by solvothermal and photoreduction methods. The introduction of Ag significantly alters the band structure of In2O3, resulting in a slight reduction in the band gap and a more negative conduction band position, thereby facilitating the generation of reductive electrons in In2O3. Moreover, the synergistic interaction between loaded Ag nanoparticles and In2O3 forms a Schottky barrier, which widens the light absorption range and promotes charge separation. Under simulated sunlight, the photocatalytic nitrogen fixation performance of Ag@In2O3-5 reaches 35.56 μmol h−1 gcat−1, which is higher than other composites and 3.58 times that of pure In2O3. At the same time, the catalyst has good structural stability and cycle life. Density functional theory (DFT) calculations demonstrate that Ag exhibits a stronger interaction with N2 and lowers the potential barrier of the N2 hydrogenation reaction. The synergistic effect between precious metals and semiconductors offers novel insights and presents challenges for the photocatalytic N2 fixation process. This work provides new insights and challenges for designing and synthesizing nanomaterials for photocatalytic nitrogen fixation.
研究领域:
材料科学
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环境科学
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化学
✓ 已验证
产品关联
DOI
高影响因子
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
·
2024
·
IF 8.1
Yu Tan,Yike Wei,Gaigai Liu,Yuhang Cai,Siyu Liu,Shijie Wang,Shenghan Zhang,Kexin Liang
The mild reaction conditions, simple process, and clean raw materials make electrochemical nitrogen reduction reaction to ammonia (NRR) a promising method for producing this crucial substance for human life. The proposed catalysts have been shown to reduce the reaction barrier and improve catalytic efficiency, making them an excellent choice for this process. Carbon nanotubes coated FeMoO 4 (FeMoO 4 @CNTs) nanorods are a highly efficient catalyst for fixing N 2 to NH 3 . Carbon nanotubes doped FeMoO 4 improve the efficiency of electrocatalytic NRR by increasing their active surface. A superior ammonia yield of 18.49 μg h −1 ·mg·cat −1 at −0.65 V was obtained in a 0.1 mol L −1 Na 2 SO 4 solution, with a corresponding Faraday efficiency of 16.14%. The response of the experimental system to environmental factors was also investigated. The data clearly indicates that raising the temperature does not enhance the yield of ammonia. This reaction system is optimal for neutral or alkaline environments.
研究领域:
化学
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材料科学
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环境科学
✓ 已验证
DOI
高影响因子
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
·
2025
·
IF 3.9
Cuilian Sun,Huhu Yin,Xiujing Xing,Yaokang Lv,Wei Xiong,Hao Li
In recent years, a variety of catalysts have been applied to electrocatalytic nitrogen reduction (NRR). Previous research has shown that in bimetallic catalysis the synergistic effect between the bimetals results in catalytic properties superior to those of monometallic catalysts. In this work, bimetallic oxide MnMoO4 nanomaterials with different particle sizes were prepared by a solvothermal method, and the effects of different ratios of the solvents (water/ethylene glycol) on the particle sizes of MnMoO4 and their influence on the NRR performance were systematically investigated. The results showed that as the proportion of ethylene glycol solvent increased, scanning electron microscopy (SEM) characterization showed a transformation of morphology from micrometer-scale rods to nanoscale particles, and the smallest MnMoO4 particle size was obtained at a water/ethylene glycol ratio of 0:1. Under this condition, the formed MnMoO4 exhibited excellent NRR properties at −0.40 V vs RHE with an NH3 yield as high as 21.89 μg h–1 mgcat–1 and a Faraday efficiency (FE) of 15.12%, with the best stability among all catalysts synthesized in this work. This may be attributed to the increased viscosity of the ethylene glycol environment, leading to a deceleration of the precursor reactions. This leads to the production of materials with smaller particle sizes, exposing more active sites and improving catalytic performance. In addition, we explored the effect of other solvents (n-butanol and glycerol) on the morphology of the materials. This work indicates that changing the solvent to regulate the morphology and size of the bimetallic oxide MnMoO4 can improve the catalytic efficiency of the catalyst, providing a promising electrocatalyst for nitrogen reduction reactions.
研究领域:
材料科学
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催化化学
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能源化学
✓ 已验证
产品关联
DOI
高影响因子
DALTON TRANSACTIONS
·
2023
·Vol. 52
·期 45
·16670-16679
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IF 4
Huhu Yin,Xiujing Xing,Wei Zhang,Jin Li,Wei Xiong,Hao Li
Electrocatalytic nitrogen reduction (NRR) for artificial ammonia synthesis under ambient conditions is considered a promising alternative to the traditional Haber–Bosch process. However, it still faces multiple challenges such as the difficulty of N2 adsorption and activation and limited Faraday efficiency. In this work, a bimetallic oxide MnMoO4 was prepared by a hydrothermal method and low temperature calcination. The influence of the sintering temperature on the microstructure (crystallinity and oxygen vacancies) of the oxide and its NRR properties were systematically explored. The results showed that MnMoO4 sintered at 500 °C had the highest concentration of OVs and showed excellent NRR performance, with the highest NH3 yield (up to 12.28 μg h−1 mgcat−1), high Faraday efficiency (23.04% at −0.30 V vs. RHE), and good stability at −0.40 V vs. RHE, and the catalytic performance was about two times higher than that of Mn2O3 and MoO3. It is also superior to other bimetallic oxide NRR electrocatalysts reported in some cases. In addition, we also explored the ratio between Mn and Mo metals, and the catalytic effect was the best when Mn : Mo = 1 : 1. Due to the synergistic effect between Mn and Mo metals and the large number of OVs present internally, the catalytic activity for the NRR was largely improved. This study suggests that the bimetallic oxide MnMoO4 may be a promising NRR electrocatalyst.
研究领域:
材料科学
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电化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
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2019
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IF 14.229
Zishan Han,Changhyeok Choi,Song Hong,Tai-Sing Wu,Yun-Liang Soo,Yousung Jung,Jieshan Qiu,Zhenyu Sun
Renewable energy-driven electrochemical N 2 reduction reaction (NRR) provides a green and sustainable route for NH 3 synthesis under ambient conditions but is plagued by a high reaction barrier and low selectivity. To promote NRR, modification of the catalyst surface to increase N 2 adsorption and activation is key. Here, we show that engineering surface oxygen vacancies of TiO 2 permits significantly enhanced NRR activity with an NH 3 yield rate of about 3.0 μg NH3 h −1 mg cat. −1 and a faradaic efficiency (FE) of 6.5% at -0.12 V ( vs . the reversible hydrogen electrode, RHE). Efficient conversion of N 2 to NH 3 is achieved in a wide applied potential range from -0.07 to -0.22 V ( vs . RHE) with NH 3 production rates ≥ 2.0 μg NH3 h −1 mg cat. -1 and NH 3 FEs ≥ 4.9%, respectively. An NH 3 FE as high as 9.8% is obtained at a low overpotential of 80 mV. Density functional theory calculations reveal that the surface oxygen vacancies in TiO 2 play a vital role in facilitating electrochemical N 2 reduction by activating the first protonation step and also increasing N 2 chemisorption (relative to *H).
研究领域:
材料科学
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电化学
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能源科学
✓ 已验证
产品关联
DOI
高影响因子
Journal of Materials Chemistry A
·
2019
·Vol. 7
·期 28
·16969-16978
·
IF 10.733
Tianxing Wu,Miaomiao Han,Xiaoguang Zhu,Guozhong Wang,Yunxia Zhang,Haimin Zhang,Huijun Zhao
Deeply understanding the electrochemical activation and inactivation processes of an electrocatalyst is critically important for establishing a high-efficiency nitrogen reduction reaction (NRR) to synthesize an NH3 system. Here we report the utilization of a facile vapor-phase hydrothermal (VPH) method to directly grow ultrafine Nb3O7(OH) nanoparticles on commercial carbon fiber cloth (Nb3O7(OH)/CFC) for the NRR. The results demonstrate that the Nb3O7(OH)/CFC can afford an average NH3 yield rate of 622 μg h−1 mgcat.−1 with a high faradaic efficiency (FE) of 39.9% at −0.4 V versus the reversible hydrogen electrode (RHE) in 0.1 M Na2SO4 electrolyte (pH = 6.1) within 30 min of the NRR, surpassing the performance of most recently reported aqueous-based NRR electrocatalysts. The experimental and theoretical calculation results reveal that the in situ electrochemically converted NbO from Nb3O7(OH) during the NRR is the catalytic active phase with a N2 adsorption free energy of −0.97 eV; however with a reaction time over 30 min, the generated active *N atoms in the *N–NH3 → *N + NH3 hydrogenation step during the NRR are thermodynamically favourable for binding to the oxygen vacancies of NbO to form oxygen-containing NbN0.64 with reduced N2 adsorption free energy (−0.32 eV), resulting in significantly decreased NRR activity. Our studies suggest that although NbO possesses high NRR activity, it may not be a suitable NRR electrocatalyst, owing to easy formation of low active niobium oxynitride during the NRR.
研究领域:
材料科学
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电化学
✓ 已验证
产品关联
DOI
高影响因子
ELECTROCHIMICA ACTA
·
2021
·
IF 6.901
Chaoqun Ma,Naihua Zhai,Bingping Liu,Shihai Yan
Although the electrochemical N 2 reduction reaction (NRR) to NH 3 provides a promising avenue for artificial N 2 fixation, building of efficient NRR electrocatalysts with high activity and stability remains a tremendous challenge. The combined experimental results and theoretical calculation reveal that MoS 2 with sulfur-vacancy defect (V S -MoS 2 ) is an admirable NRR catalyst. Electrochemical results demonstrate that V S -MoS 2 (5:2) possesses outstanding NRR performances, including a superior NH 3 average yield rate (46.1 × 10 −11 mol s −1 cm −2 at -0.5 V vs reversible hydrogen electrode (RHE)), an excellent faraday efficiency (FE: 4.58% at -0.4 V vs RHE), good electrochemical stability (at least 24 h), and high selectivity (no by-product of N 2 H 4 ). Density functional theory (DFT) calculations demonstrate that the rate determining steps (RDSs) of all V S -MoS 2 (010)-2, V S -MoS 2 (010)-1, and MoS 2 (010) are the first hydrogenation step to form *NNH intermediate, as reflected by the energy barriers of 0.06 eV, 0.20 eV, and 0.93 eV, the significantly charge transfer (1.02 e , 0.45 e vs. 0.41 e ) from two Mo atoms to N 2 , as well as the stretching of N N bond (1.200 Å, 1.140 Å vs. 0.970 Å), respectively. These results reveal that V S -MoS 2 (010)-2 can effectively activate inert N 2 molecule and have the potential application in nitrogen fixation under mild conditions.
研究领域:
材料科学
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电化学
·
理论计算
✓ 已验证
产品关联
DOI
高影响因子
NEW JOURNAL OF CHEMISTRY
·
2021
·Vol. 45
·期 5
·2488-2495
·
IF 3.591
Bin Fang,Junjie Yao,Xiaojun Zhang,Liang Ma,Yaqi Ye,Jiayi Tang,Guifu Zou,Junchang Zhang,Lin Jiang,Yinghui Sun
Electrochemical nitrogen fixation provides an environmentally friendly strategy for producing ammonia (NH3) under ambient conditions. However, an inexpensive and efficient electrocatalyst for the electrocatalytic nitrogen reduction reaction (NRR) under ambient conditions is still needed. Herein, we report an efficient non-noble-metal electrocatalyst consisting of large scaled-up monocrystalline 3R MoS2, which is first utilized as an electrocatalyst for the NRR under ambient conditions. The NRR performance can be optimized via improving the electrochemically active surface area (ECSA) of MoS2. The NH3 yield rate and FE of MoS2-700 reach 8.8 μg h−1 mgcat−1 and 1.9%, respectively. Notably, 3R MoS2-700 shows excellent stability, with the negligible fluctuation of electrocatalytic activity after being recycled seven times. This study may provide a new strategy for structuring efficient electrocatalysts for the NRR.
研究领域:
材料科学
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环境科学
✓ 已验证
产品关联
DOI
高影响因子
Journal of Energy Chemistry
·
2020
·
IF 7.216
Huimin Liu,Yidan Zhang,Jingshan Luo
Ammonia synthesis by electrocatalytic nitrogen reduction reaction (NRR) is considered as a promising alternative to the Haber−Bosch process. However, due to the extremely low ammonia yield and easily accessible extraneous contamination in the laboratory, NRR study always suffers from fluctuation and variability. Finding and eliminating all kinds of possible extraneous contamination is crucial to evaluate the performance of electrocatalytic ammonia synthesis accurately. In this work, we systematically explored two factors that affect NRR results but are easy to be ignored: the selection of membrane for NRR and the unconscious N-source in NRR catalysts. After series of experiments, we proposed a low-cost and almost pollution-free Celgard 3501 membrane as the separator for NRR to avoid the adsorption and release of ammonia by the membrane. In addition, we proposed a pre-reduction strategy to remove residual or adsorbed NO x contaminants in catalysts. These two solutions will help the community to evaluate the NRR activity more accurately.
研究领域:
化学工程
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
Solar RRL
·
2022
·Vol. 6
·期 12
·2200869
·
IF 9.173
Kaiyue Gao,Haibao Zhu,Chengming Zhang,Xiaojie Song,Li Lao,Liping Ni,Jianli Chen,Congliang Cheng,Xiufang Wang
The main obstacles to the photocatalytic reduction of nitrogen are the low separation efficiency of photogenerated charges and the few activation sites for nitrogen. It is highly desirable to explore new strategies for improving the nitrogen fixation performance of catalysts. Herein, the Bi metal active sites are constructed on the surface of BiOBr/BiOI heterojunction by in situ reaction, which promote the absorption, activation, and dissociation of nitrogen molecules. Moreover, the existence of Bi metal and BiOBr/BiOI heterojunction enhances the light absorption ability and facilitates the separation and transfer of photogenerated charges. The theoretical calculation also demonstrates that the BiOBr/BiOI/Bi composite has excellent electron structure and electron transfer efficiency. So, the ternary BiOBr/BiOI/Bi catalyst shows excellent performance of photocatalytic reduction of nitrogen to ammonia. The nitrogen reduction rate is 221.9 μmol g −1 h −1 , which is 7.6 and 5 times higher than that of pure BiOBr and BiOBr/BiOI. The mechanism of photocatalytic nitrogen fixation of the BiOBr/BiOI/Bi is proposed based on the experimental and theoretical results. This study provides a novel method for improving the photocatalytic nitrogen reduction performance of catalysts.
研究领域:
材料科学
·
环境科学
✓ 已验证
产品关联
DOI
高影响因子
Materials Today Energy
·
2021
·
IF 7.311
Songliang Liu,Shuli Yin,Shiqian Jiao,Hugang Zhang,Ziqiang Wang,You Xu,Xiaonian Li,Liang Wang,Hongjing Wang
Electrochemical N 2 reduction reaction (NRR) under ambient conditions provides sustainable and green pathways; meanwhile, efficient electrocatalysts are strongly required. In this work, we report an interfacial active site strategy to improve the electrocatalytic NRR performance by modification of Au nanowire (Au NW) surface with oxygen-rich tannic acid (TA). Benefiting from their ultrafine one-dimensional nanowire architecture and the TA-modified metallic interface, the TA-Au NWs effectively facilitate the adsorption and activation of reactants. The TA-Au NWs exhibit a large NH 3 yield rate (15.71 μg h −1 mg −1 cat. ) and a high Faraday efficiency of 14.83% at −0.3 V (vs. the reversible hydrogen electrode) in a N 2 -saturated 0.1 M Na 2 SO 4 with an excellent electrochemical durability. This work provides a general surface modification strategy to fabricate highly active NRR electrocatalysts.
研究领域:
材料科学
·
电化学
✓ 已验证
DOI
高影响因子
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