Nanoscale
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2021
·Vol. 13
·期 38
·16307-16315
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IF 7.79
Xiaojia He,Haoran Guo,Tianhao Liao,Yi Pu,Long Lai,Zihao Wang,Hui Tang
Electrochemical nitrogen reduction reaction (NRR) driven by a renewable energy source offers a sustainable and environmentally benign route to produce ammonia (NH3), but it is highly dependent on efficient and specific catalysts to reduce the high reaction barrier and improve the selectivity. Defect engineering is extensively used to regulate the surface properties of materials to improve their catalytic performance. Herein we synthesized SnO2 with different oxygen vacancy concentrations by a controllable electrochemical method for electrocatalytic nitrogen (N2) fixation. The prepared SnO2 was used as an electrocatalyst and exhibited excellent NRR performance with an optimal NH3 yield rate of 25.27 μg h−1 mgcat.−1 and faradaic efficiency of 11.48% at −0.6 V (vs. the reversible hydrogen electrode) in 0.1 M Na2SO4. Oxygen vacancies provide more active sites and greater electron transfer ability on the catalyst surface to facilitate N2 adsorption and activation. The electrocatalytic NRR performance of SnO2 was enhanced with the increase in oxygen vacancy concentration. The density functional theory calculations indicate that the oxygen vacancies in SnO2 promote the electrocatalytic NRR performance by increasing the number of valence electrons of Sn and decreasing the energy barrier of the potential-determining step, thus promoting the activation of the N–N bond to further achieve efficient N2 fixation.
研究领域:
材料科学
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环境科学
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化学工程
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DOI
PubMed
高影响因子
CHEMISTRY-A EUROPEAN JOURNAL
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2019
·Vol. 25
·期 23
·5904-5911
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IF 5.16
Guoqiang Liu,Zhiqing Cui,Miaomiao Han,Shengbo Zhang,Cuijiao Zhao,Chun Chen,Guozhong Wang,Haimin Zhang
Graphical Room at the active site : A room-temperature redox approach is used to prepare a composite core–shell-structured Au@CeO 2 electrocatalyst (see figure) composed of small gold nanoparticles (<10 nm) and rich oxygen vacancies in CeO 2 nanoparticles to synergistically boost the electrocatalytic activity toward the N 2 reduction reaction (NRR) to NH 3 . Electrosynthesis of NH 3 through the N 2 reduction reaction (NRR) under ambient conditions is regarded as promising technology to replace the industrial energy- and capital-intensive Haber–Bosch process. Herein, a room-temperature spontaneous redox approach to fabricate a core–shell-structured Au@CeO 2 composite, with Au nanoparticle sizes below about 10 nm and a loading amount of 3.6 wt %, is reported for the NRR. The results demonstrate that as-synthesized Au@CeO 2 possesses a surface area of 40.7 m 2 g −1 and a porous structure. As an electrocatalyst, it exhibits high NRR activity, with an NH 3 yield rate of 28.2 μg h −1 cm −2 (10.6 μg h −1 mg −1 cat. , 293.8 μg h −1 mg −1 Au ) and a faradaic efficiency of 9.50 % at −0.4 V versus a reversible hydrogen electrode in 0.01 m H 2 SO 4 electrolyte. The characterization results reveal the presence of rich oxygen vacancies in the CeO 2 nanoparticle shell of Au@CeO 2 ; these are favorable for N 2 adsorption and activation for the NRR. This has been further verified by theoretical calculations. The abundant oxygen vacancies in the CeO 2 nanoparticle shell, combined with the Au nanoparticle core of Au@CeO 2 , are electrocatalytically active sites for the NRR, and thus, synergistically enhance the conversion of N 2 into NH 3 .
研究领域:
化学
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材料科学
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环境科学
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DOI
PubMed
高影响因子
Advanced Energy and Sustainability Research
·
2023
·Vol. 4
·期 11
·2300056
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IF 5.8
Wei Zhang,Tianyi Wang,Chuangwei Liu,Chongxiong Duan,Wei Xiong,Hao Li
Gold-based electrocatalysts are potential candidates for electrocatalytic nitrogen reduction reaction (e-NRR) application due to their high conductivity and low hydrogen evolution tendency. However, the role of nonmetallic Au surfaces is not widely studied. Herein, the self-assembly of gold nanoparticles confined in carbon felts (Au NPs@CFs) containing two different states of Au is reported, showing effective e-NRR performance. The effects of surfactant concentration on the morphology and electrochemical performance of the Au NPs are analyzed. X-ray photoelectron spectroscopy indicates two valence states of Au (Au 0 and Au 3+ ) in Au NPs@CFs. Interestingly, it is found that the e-NRR properties of Au NPs@CFs enhance with the increase of Au 3+ content. A typical sample Au NPs@CF-1.0 with the highest Au 3+ content exhibits the best e-NRR performance (NH 3 yield of 66.1 μg h −1 mg −1 cat. and Faradaic efficiency of 24.9% at −0.3 V vs reversible hydrogen electrode), which, in part due to the presence of Au 3+ , is conducive to nitrogen adsorption. Theoretical calculation results find that a stable Au 3+ surface can adsorb N 2 strongly, which in turn can lead to energetically favorable formation of ammonia. This study provides new insights into the relation between oxidation states and performance of gold-based electrocatalyst with high e-NRR performance.
研究领域:
材料科学
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电化学
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DOI
高影响因子
ChemSusChem
·
2021
·Vol. 15
·期 1
·e202102234
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IF 8.928
Xiyang Cai,Fan Yang,Lu An,Cehuang Fu,Liuxuan Luo,Shuiyun Shen,Junliang Zhang
Graphical No ammonia? A rigorous procedure is adopted to systematically evaluated the performance of commercial noble metals nanocatalysts (including Pt/C, Pd/C, Au/C, Ru/C, and Rh/C) toward electrochemical nitrogen reduction reaction. No discernible amount of ammonia (<10 ppb) is detected within a wide current range in either acidic or alkaline aqueous solutions. Electrochemical nitrogen reduction reaction (NRR) is intensively investigated by researchers for its potential to be the next-generation technology to produce ammonia. Many attempts have been made to explore the possibility of electrochemical ammonia production catalyzed by noble metals. However, the produced ammonia in most reported cases is in ppm level or even lower, which is susceptible to potential contaminants in experiments, leading to fluctuating or even contradictory results. Herein, a rigorous procedure was adopted to systematically evaluated the performance of commercial noble metal nanocatalysts toward NRR. No discernible amount of ammonia was detected in either acidic or alkaline solutions. Further, nitrogen-containing contaminants in catalysts that might cause false positive results were detected and characterized. An effective way to remove pre-existing pollutants by consecutive cyclic voltammetry scan was proposed, helping to obtain reliable and reproducible results.
研究领域:
化学
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材料科学
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DOI
PubMed
高影响因子
APPLIED SURFACE SCIENCE
·
2022
·
IF 7.392
Xianwei Li,Shuangxiu Ma,Fang Luo,Zehui Yang
Electrochemical hydrogenerations of nitrogen and oxygen molecules are of significance for nitrogen reduction and oxygen reduction reactions. Strengthening the binding between active sites and gaseous molecules is beneficial for enhancing the catalytic performance, especially in NRR catalysis. In this work, we have engineered the oxygen vacancies in Co 3 O 4 nanoparticles to boost the catalytic activity towards NRR and ORR. Ascribing to the p-d hybridization between Co and N atoms, N 2 electrochemical adsorption is promoted and the related energy barrier of N 2 protonation is significantly decreased by 50%; as a consequence, Faradaic efficiency is 11.2% at −0.4 V vs. RHE, 3-fold higher than Co 3 O 4 /CNT; moreover, due to the oxygen vacancies in Co 3 O 4-x /CNT leading to a higher oxophilicity, Co 3 O 4-x /CNT showed a better selectivity in ORR catalysis and kinetic current density at 0.85 V vs. RHE is boosted by 2.4 times. Consequently, Co 3 O 4-x /CNT exhibits a better rechargeable zinc air battery performance than Pt/C-IrO 2 by a factor of 2.2.
研究领域:
材料科学
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电化学
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催化科学
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DOI
高影响因子
ACS Applied Nano Materials
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2024
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IF 5.3
Guanghui Yang,Hugang Zhang,Jiarong Li,Yile Wang,Kai Deng,Hongjie Yu,Hongjing Wang,Ziqiang Wang,Liang Wang
It is important to achieve sustainable ammonia production under mild conditions, and the electrocatalytic nitrogen reduction reaction (NRR) is a promising strategy. However, the precise construction of highly active NRR electrocatalysts for ammonia synthesis remains challenging. Here, we construct B-doped PdRh mesoporous nanotubes (B-PdRh MNTs) as efficient NRR electrocatalysts. The mesoporous nanotubular structure provides abundant active sites, and B doping enhances the adsorption energy of N2. As such, the NH3 yield and Faraday efficiency of B-PdRh MNTs reach 12.03 μg h–1 mgcat–1 and 16.28% under 0.1 M Na2SO4, respectively. This work provides strategies for B-doped catalysts for efficient electrocatalytic NRR applications.
研究领域:
材料科学
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电化学
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产品关联
DOI
高影响因子
Cell Reports Physical Science
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2020
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IF 0
Yi Han,Wenwen Cai,Xueke Wu,Wenjing Qi,Bin Li,Hongdong Li,Dan Zhang,Yue Pan,Zuochao Wang,Jianping Lai,Lei Wang
To date, the development of the nitrogen reduction reaction (NRR) electrocatalysts to achieve high ammonia production at low overpotentials is insufficient. Here, Sb 2 Te 3 displays notable electrochemical NRR performance at 0 V (versus RHE), with an ammonia yield rate of 13.8 μg h −1 cm −2 and a faradic efficiency of 27.7% (the highest yield rate at low overpotentials reported, to the best of our knowledge). Sb 2 Te 3 is also stable over 50 h. Density functional theory (DFT) calculations disclose that there are multiple promoted-synergetic effects in telluride. Tellurium sites can modulate the electronic structure of catalysts to drive nitrogen adsorption on antimony sites. Tellurium sites also allow surface hydrogenation to suppress hydrogen evolution, facilitate the reduction of nitrogen into ∗NNH (the rate-determining step) in NRR, and accelerate the desorption of NH 3 . The other tellurides (CoTe 2 , CdTe, and Bi 3 Te 4 ) also show high NRR performance at low overpotentials, implying that such multiple promoted-synergism may be generalized.
研究领域:
材料科学
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化学工程
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理论计算
✓ 已验证
DOI
APPLIED CATALYSIS A-GENERAL
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2024
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IF 4.7
Ge Li,Chunxiao Jin,Baodong Wang,Ziran Ma,Pan Gao,Shuwei Zhou,Renqin Chang,Yuxue Yue,Jia Zhao
The electrochemical NRR, which can be driven by renewable energy sources, is an emerging strategy for addressing the high energy consumption and CO 2 emission issues caused by the traditional Haber–Bosch ammonia synthesis technique. FePc catalyzes the electrochemical ammonia synthesis reaction well, but intermolecular π-stacking and multi-layer overlapping lead to low NH 3 yields. Here, [Bmim][Cl] and [Bmim][NTF 2 ] ILs were used to induce monolayer dispersion of FePc. Ionic-liquid-induced FePc electrocatalyst, namely FePc/C-700, which was constructed with ILs as the carbon source, gave an excellent NH 3 yield (24.25 μg mg cat −1 h −1 ) and Faradaic efficiency (30.59%) at − 0.1 V. The formation of a monolayer FePc structure was confirmed by HAADF-STEM and XANES. The results of DFT calculations and NRR experiments showed that the monolayer FePc structure promoted N 2 adsorption and inhibited the competitive HER. These results will be useful in the design of active sites of layered macromolecules to achieve efficient electrochemical NRR.
研究领域:
材料科学
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电化学
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催化化学
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产品关联
DOI
高影响因子
ChemElectroChem
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2019
·Vol. 6
·期 8
·2215-2218
·
IF 3.975
Jiali Yu,Jian Li,Xiaojuan Zhu,Xiaoxue Zhang,Kun Jia,Wenhan Kong,Peipei Wei,Hongyu Chen,Xifeng Shi,Abdullah M. Asiri,Quan Li,Xuping Sun
Graphical Fix it : structured PANI is an efficient metal-free catalyst for electrochemical N 2 fixation in aqueous solution at ambient conditions. In 0.1 M HCl, the catalyst achieves a NH 3 yield rate of 5.45×10 −11 mol s −1 cm −2 and a Faradaic efficiency of 3.76 % at −0.70 and −0.60 V vs. reversible hydrogen electrode, respectively. Furthermore, it also possesses high selectivity and stability. NH 3 production vastly relies on the Haber-Bosch process, causing high energy consumption and carbon dioxide emission. Electrochemical N 2 fixation is considered as an eco-friendly and sustainable process, but its efficiency depends greatly on the activity and stability of the catalyst used. Therefore, it is imperative to develop efficient electrocatalysts in the field of nitrogen reduction reaction (NRR). In this communication, we propose that structured polyaniline is an efficient metal-free NRR electrocatalyst in aqueous solution, achieving a NH 3 yield rate of 5.45×10 −11 mol s −1 cm −2 and a Faradaic efficiency of 3.76 % at −0.70 and −0.60 V vs. reversible hydrogen electrode in 0.1 M HCl, respectively. Furthermore, it also possesses high selectivity and stability.
研究领域:
材料科学
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电化学
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催化科学
✓ 已验证
产品关联
DOI
高影响因子
Materials Today Energy
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2021
·
IF 7.311
Changchang Dong,Feng Wei,Jiadong Li,Qiao Lu,Xiaojun Han
The electrochemical ammonia synthesis under ambient conditions is a promising process instead of the energy-intensity Haber-Bosch process with the release of huge greenhouse gases. But it still faces sluggish catalytic kinetics owing to difficulty of N 2 adsorption and N≡N bond cleavage. Herein, the uniform ZrO 2 @C with octahedral structure is synthesized via two-step annealing treatment of UiO-66. The formation of ZrO 2 originates from Zr and O elements in UiO-66, and the grain size is confined by the produced carbon matrix from the carbonization of the organic ligand, resulting in more exposure of the active sites. ZrO 2 @C obtained at 650 °C presents excellent electrocatalytic nitrogen reduction performance with a NH 3 yield rate of 6.72 μg h −1 mg cat. −1 and a Faradaic efficiency of 2.68% at −0.6 V versus reversible hydrogen electrode (RHE). This work provides a strategy to design metal oxide@C from metal-organic frameworks for nitrogen fixation.
研究领域:
材料科学
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电化学
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能源化学
✓ 已验证
产品关联
DOI
高影响因子
ACS Sustainable Chemistry & Engineering
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2019
·
IF 6.97
Hongjing Wang,Dandan Yang,Songliang Liu,Shuli Yin,Hongjie Yu,You Xu,Xiaonian Li,Ziqiang Wang,Liang Wang
The electrocatalytic nitrogen to ammonia has attracted intensive attention but suffers from severe bottlenecks of low Faradaic efficiency and NH3 yield. Herein, we report a two-step process to prepare amorphous sulfur multilayer decorated gold nanowires (S/Au NWs) as superior catalysts for electrochemical NH3 production. The chemisorbed sulfur multilayers are favorable for selective hydrogenation of nitrogen to ammonia and provide sufficient exposed active sites for nitrogen reduction reaction (NRR). The S/Au NWs show a high NH3 yield of 21.04 μg h–1 mg–1cat. and Faradaic efficiency of 15.34%, as well as excellent durability. The superior NRR performance of Au catalysts with S chemisorption would stimulate interest toward NRR catalyst design of sulfur bonding to metal surfaces.
研究领域:
材料科学
·
电化学
✓ 已验证
产品关联
DOI
高影响因子
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
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2020
·
IF 4.939
Hongwei Li,Ting-Ting Li,Jinjie Qian,Yan Mei,Yue-Qing Zheng
Ammonia synthesis based on electrocatalytic nitrogen reduction reaction (NRR) by using renewable sources of energy under ambient conditions has attracted wide research attentions. Herein, we report that the noble-metal-free CuCo 2 S 4 /multiwalled carbon nanotube nanocomposite , which is synthesized via a facile one-step hydrothermal and sulfuration approach, can work as the high active and durable catalyst for electrocatalytic NRR. This nanocomposite achieves a high NH 3 yield of 137.5 μg h −1 mg cat −1 and a high Faradaic efficiency of 8.7% at −0.5 V vs reversible hydrogen electrode (RHE) in 0.1 M Na 2 SO 4 solution, which outperforms CuCo 2 S 4 counterpart and most reported NRR catalysts. These results reveal that the MWCNT in nanocomposite not only suppresses the aggregation of CuCo 2 S 4 nanoparticles and maximizes the exposure of active sites, but also contributes to the synergistic effect between CuCo 2 S 4 nanoparticles and MWCNT, and facilitates the interfacial reaction kinetics.
研究领域:
材料科学
·
化学工程
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环境科学
✓ 已验证
产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）