Science China-Materials
·
2024
·
IF 6.8
He Xun,Xie Ting,Dong Kai,Nan Jue,Sun Hang,Yao Yongchao,Fan Xiaoya,Zheng Dongdong,Luo Yongsong,Sun Shengjun,Liu Qian,Li Luming,Chu Wei,Xie Lisi,Kong Qingquan,Sun Xuping
Electrocatalytic reduction of nitrate (NO 3 − ) can efficiently transform NO 3 − into ammonia (NH 3 ), enabling the simultaneous removal of NO 3 − pollutant from wastewater and the production of NH 3 . Here, we report the use of rare-earth lanthanum-doped Co 3 O 4 nanowires array on carbon cloth (La-Co 3 O 4 /CC) as an efficient electrocatalyst for the conversion of NO 3 − to NH 3 . The as-synthesized La-Co 3 O 4 /CC demonstrates a remarkable NH 3 Faradaic efficiency (96.36%) and NH 3 yield (537.44 µmol h −1 cm −2 ), markedly surpassing its Co 3 O 4 counterpart (87.78%, 279.4 µmol h −1 cm −2 ). Theoretical computations unveil that the incorporation of La doping promotes NO 3 − adsorption and optimizes the hydrogenation process, thus enhancing the electroreduction activity of Co 3 O 4 in NO 3 − conversion and NH 3 selectivity. Furthermore, a Zn–NO 3 − battery incorporating La-Co 3 O 4 /CC achieved a peak power density of 9.86 mW cm −2 . This work advances the application of Co 3 O 4 -based electrodes in electrocatalysis and highlights the effectiveness of rare earth element doping in NO 3 − reduction reactions.
研究领域:
环境科学
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电化学
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材料科学
✓ 已验证
DOI
高影响因子
Catalysis Science & Technology
·
2021
·Vol. 11
·期 14
·4783-4792
·
IF 6.119
Yi Zhang,Shuo Gu,Xiaoyu Zhou,Kaiyue Gao,Kai Sun,Di Wu,Jingjing Xia,Xiufang Wang
Photocatalytic nitrogen fixation performance is mainly hampered by slow carrier transport and inefficient surface reaction, where surface oxygen vacancies have been proved to alleviate these limitations. However, there are a few reports on the introduction of metal vacancies into photocatalysts and the effect of metal vacancies on the N2 photofixing properties. Herein, we injected bismuth vacancies (VBi) into the surface of BiOBr nanospheres with oxygen vacancies (VO) via an ion exchange strategy to form hierarchical Bi2MoO6/BiOBr composite structures. The intentionally introduced VBi adjust the band structures of VO–BiOBr and act as charge separation centers in coordination with VO, which improves the separation efficiency of electron–hole pairs. The presence of VBi and the Bi2MoO6 phase enhances the light absorption of the composite materials. Additionally, the hierarchical nanosheet assembly structure facilitates the surface adsorption and activation of N2 on the catalyst. In particular, the optimal defect-rich Bi2MoO6/VBi+O–BiOBr exhibits the best photocatalytic ammonia production activity. After two hours, the NH3 yield was 412.18 mol L−1 without any noble metal cocatalyst and sacrificial agent, and was nearly 4 times higher than that of the original VO–BiOBr (96.08 mol L−1). This work provides a new inspiration for the design of efficient N2 immobilizing photocatalysts through synergistic metal and oxygen vacancy engineering.
研究领域:
材料科学
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环境科学
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化学工程
✓ 已验证
DOI
高影响因子
JOURNAL OF COLLOID AND INTERFACE SCIENCE
·
2023
·
IF 9.9
Peng Yang,Heng Guo,Haoran Wu,Fengying Zhang,Jiaxin Liu,Mengyue Li,Yuantao Yang,Yuehan Cao,Guidong Yang,Ying Zhou
The electrocatalytic nitrogen reduction reaction (eNRR) to ammonia (NH 3 ) has been recognized as an effective, carbon–neutral, and great-potential strategy for ammonia production. However, the conversion efficiency and selectivity of eNRR still face significant challenges due to the slow transfer kinetics and lack of effective N 2 adsorption and activation sites in this process. Herein, we designed and fabricated defect-rich TiO 2 nanosheets furnished with oxygen vacancies (OVs) and Au nanoparticles (Au/TiO 2-x ) as the electrocatalyst for efficient N 2 -fixing. The experimental results demonstrate that OVs act as active sites, which enable efficient chemisorption and activation of N 2 molecules. The Au nanoparticles loaded on the OVs-rich TiO 2 nanosheets not only accelerate charge transfer but also change the local electronic structure, thus enhancing N 2 adsorption and activation. In this work, the optimal Au/TiO 2-x electrocatalyst displays a considerable NH 3 yield activity of 12.5 μg h −1 mg cat. -1 and a faradaic efficiency (FE) of 10.2 % at −0.40 V vs reversible hydrogen electrode (RHE). More importantly, the Au/TiO 2-x exhibits a stable N 2 -fixing activity in cycling and it persists even after 80 h of consecutive electrolysis. Density functional theory (DFT) calculations reveal that the OVs serve as the active sites in TiO 2 , while Au nanoparticles are crucial for improving N 2 chemisorption and lowering the reaction energy barrier by facilitating the charge transfer for eNRR with a distal hydrogenation pathway. This research offers a rational catalytic site design for modulating charge transfer of active sites on metal-supported defective catalysts to boost N 2 electroreduction to NH 3 .
研究领域:
材料科学
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催化化学
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环境科学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
RARE METALS
·
2025
·
IF 11
Yang Hui-Ying,Zhao Yu,Huang Ke-Lei,Meng Xiang-Chao
Combining interfacial solar evaporation with a three-phase photocatalytic system can theoretically improve the production efficiency of ammonia. Herein, we designed a simple solar evaporator via in situ growth of TiO 2 onto hydrophilic carbon paper using a fast Joule heating method. This system had porous channels for high water evaporation rates, wide light-responsive wavelength range, effective light absorption, and potentially high catalytic activity. The lattice disorder and oxygen vacancies created by the rapid heating and cooling process could be reaction sites for nitrogen adsorption and activation. The ammonia yield in the three-phase system was up to 360.37 mol·g −1 ·h −1 , which was higher than the two-phase system (17.14 μmol·g −1 ·h −1 ). Additionally, the ammonia yield rate was 73.65 μmol·g −1 ·h −1 in an outdoor test, demonstrating the potential for large-scale solar nitrogen reduction reaction (NRR). As detected, the activation energy for N 2 reduction to NH 3 was reduced to 26.3 kJ·mol −1 , indicating that this process was facilitated by the design of the photothermal–photocatalytic system. Furthermore, density functional theory (DFT) calculations confirmed the roles of oxygen vacancies as active sites in promoting the NRR. This work provided a new approach to applying solar evaporators for the highly efficient ammonia production by the synergistic effects of photothermal and photocatalytic processes. Graphical abstract
研究领域:
化学
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环境科学
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材料科学
✓ 已验证
产品关联
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2021
·
IF 13.273
Fengcai Lei,Wenli Xu,Jing Yu,Kun Li,Junfeng Xie,Pin Hao,Guanwei Cui,Bo Tang
Nitrate contaminant in groundwater has become a global problem. As a nitrogen-containing source, catalyzing nitrate to ammonia by electrochemical conversion draws promising blueprint from the perspective of solving energy crisis and environment pollution. Here we report a sulfur doped graphene with indium confined for nitrate reduction . The catalyst exhibits an ammonia production of 220 mmol g cat -1 h −1 and a Faradaic efficiency of about 75% at −0.5 V vs reversible hydrogen electrode (RHE). The experimental results combined with density functional theory (DFT) calculations demonstrate that the abundant active sites afforded by S doped graphene and hybrid electronic structure of In species in catalyst account for predominant nitrate reduction and suppression of hydrogen evolution reaction. This work can offer an electronic structure design strategy for other energy related applications.
研究领域:
环境科学
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材料科学
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电化学
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF POROUS MATERIALS
·
2022
·Vol. 29
·期 5
·1431-1440
·
IF 2.523
Zhang Shixian,Rong Xinshan,Sun Ting,Gao Ping,Liu Jun,Qiu Xuchun,Zhou Xiangtong,Wu Zhiren
An energy-efficient and environmentally friendly nitrogen fixation process is urgently needed to solve problems of high energy consumption and high emissions in the traditional ammonia industry. In this work, a Z-scheme porous g-C 3 N 4 /ZnFe 2 O 4 photocatalyst was synthesized, characterized and employed for N 2 photofixation. Temperature programmed desorption characterization confirmed that the adsorption capacity of nitrogen was improved for the porous structure. From N 2 photofixation evaluation experiments, the highest ammonia production efficiency can reach 147.33 μmol/L within 120 min. Photocatalytic performance is greatly improved because of the increasing of specific surface areas, enhancement of N 2 adsorption ability and synergistic effect of Z-scheme photocatalytic system. In the ammonia production process of the research, visible light is used as energy; N 2 and H 2 O are used as raw materials, which possesses a good application potential due to the advantages of being energy-efficient, environmentally friendly and pollution-free.
研究领域:
环境科学
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材料科学
✓ 已验证
产品关联
DOI
高影响因子
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
·
2024
·
IF 8.1
Yuhao Qian,Jiabao Lv,Yunhao Zhong,Xuting Liu,Xiaodong Li,Yaqi Peng,Jianhua Yan,Angjian Wu
Electrocatalytic nitrate reduction reaction (NO 3 RR) provides a promising route for nitrate recycling and ammonia production. In this work, Co nanoparticle catalyst was developed on a copper foam substrate (CoNPs/CF) by electrodeposition. The CoNPs/CF catalysis exhibits a Faradaic efficiency (FE) of 92.0% at −0.2 V vs. RHE and an NH 3 yield rate of 14328.65 μg h −1 cm −2 at −0.5 V vs. RHE. In-suit Raman spectroscopy and theoretical calculations demonstrated that the 3D copper foam structure of the substrate enhances the electron exchange capacity, which promotes the adsorption of nitrate on the cobalt (Co) surface. Moreover, Membrane Electrode Assembly (MEA) is employed with CoNPs/CF, contributing to 98.43 mg h −1 with FE over 80%. Coupled with an air stripping process, this configuration has enabled the successful production of high-purity gaseous NH 3 products. This work suggests a practical and viable approach for the conversion of wastewater nitrate into valuable ammonia products.
研究领域:
环境科学
·
电化学
✓ 已验证
产品关联
DOI
高影响因子
Nature Communications
·
2025
·Vol. 16
·期 1
·1-12
·
IF 15.7
Guo Xiaotian,Gao Rui-Ting,Ren Shijie,Nguyen Nhat Truong,Chen Haojie,Wu Limin,Wang Lei
Photoelectrochemical production of ammonia usually suffers from a low solar-to-ammonia efficiency and a high overpotential, which influences the bias-free operation of sustainable photoelectrochemistry. Herein, we realize solar-driven ammonia production from waste nitrate by constructing copper-osmium catalysts deposited on the Sb 2 (S,Se) 3 semiconductor, enabling optimized photo-carrier transport pathways and a beneficial co-adsorption configuration of *NO 3 -H 2 O moieties. The photocathode reaches a photocurrent density of 5.6 mA cm −2 at 0 V RHE with a low onset potential of 0.86 V RHE and a Faradaic efficiency of 96.98% at 0.6 V RHE under AM 1.5 G illumination. We further employ glycerol oxidation reaction on ruthenium doped bismuth oxide catalyst decorated on titanium oxide photoanode, requiring an onset potential of 0.3 V RHE to enable bias-free operation. The unbiased photoelectrochemical system shows Faradaic efficiencies of over 97% for ammonia products and above 77% for glycerol oxidation product under AM 1.5 G illumination. The large-sized photoelectrodes maintain a stability for 24 h without noticeable degradation. Our works indicate that unassisted and stable PEC ammonia production is feasible with in situ glycerol valorization using the photoanode and photocathode.
研究领域:
材料科学
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化学工程
·
能源技术
✓ 已验证
产品关联
DOI
PubMed
高影响因子
ELECTROCHIMICA ACTA
·
2022
·
IF 7.336
Lifang Deng,Lufeng Wang,Guoqiang Wei,Haoran Yuan,Jun Xie,Yong Chen
Electrocatalytic reduction of N 2 to ammonia (NH 3 ) at ambient conditions has attracted widespread attention, and revealing the mechanism has been a remarkably challenging problem for decades. This work developed a low-cost and efficient multiple heteroatom codoped porous carbon catalyst from municipal sludge (MSB-P), which demonstrated excellent electrochemical stability and selectivity for the electrochemical N 2 reduction reaction (N 2 RR). In 0.1 mol/L HCl solution, a high NH 3 yield rate of 35.76 µg. h − 1 .mg −1 cat. and an excellent Faraday Efficiency (FE) of 7.79% at -0.7 V vs. RHE (reversible hydrogen electrode) were obtained under ambient conditions. Furthermore, the electrocatalytic mechanism of MSB-P for N 2 RR was also revealed by in situ Fourier transform infrared spectroscopy (FTIR) data, and an associative route was identified. These findings provide an exciting new method for fabricating inexpensive and efficient carbon-based catalysts for production of NH 3 at ambient conditions.
研究领域:
环境科学
·
材料科学
·
电化学
✓ 已验证
产品关联
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2025
·
IF 13.2
Yibo Xu,Long Cao,Hele Hua,Rui Li,Yunfang Wang,Jianxin Liu,Yawen Wang,Caimei Fan
Electrocatalytic nitrate reduction, as an emerging sustainable process for ammonia production, has garnered significant attention in recent years. In this study, mixed metal oxides CoMoO 4 microspheres was obtained by adding Mo 5+ to the preparation process of Co 3 O 4 . The obtained CoMoO 4 can effectively convert NO 3 – to NH 3 in neutral electrolytes (with a yield of up to 1481.49 μg h −1 mg -1 cat and a Faraday efficiency (FE) of 91.17 %), much better than Co 3 O 4 (with a yield of 785.56 μg h −1 mg -1 cat and a FE of 81.3 %). Subsequent characterization showed that compared to Co 3 O 4 , owing to the introduction of Mo, CoMoO 4 could increase production as well as consumption of *H, and showed enhanced adsorption capacity for reactants and intermediates. More interestingly, multiple characterizations and theoretical computations confirm that after adsorption key *NO intermediates on each catalyst, the change in electron aggregation position led to a different subsequent reaction pathway from *NO→*NOH→*N of Co 3 O 4 to *NO→*NHO of CoMoO 4 , the latter exhibits a lower reaction energy barrier, better facilitating the hydrogenation of *NO and ultimately improving NH 3 yield and selectivity.
研究领域:
材料科学
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电化学
·
催化反应
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF COLLOID AND INTERFACE SCIENCE
·
2024
·
IF 9.4
Siyu Qiang,Sijuan Zeng,Hualei Liu,Jin Dai,Shuyu Liu,Yihe Yin,Fei Wang,Jianyong Yu,Yi-Tao Liu,Bin Ding
In light of the high energy consumption and substantial carbon emissions associated with traditional NH 3 production based on the Haber–Bosch process, the aqueous electrochemical nitrogen reduction reaction (NRR) offers a clean and sustainable alternative production route. Nevertheless, activating the N N bonds at room temperature is challenging due to the high bond energy, severely hindering the development and commercialization of the electrochemical NRR. Herein, we report a synergistic strategy for achieving efficient N 2 activation at ambient conditions that combines electrolyte engineering with catalytic site-modulated TiO 2−x nanofiber electrocatalysts. The synthesized TiO 2−x nanofiber electrocatalysts contained abundant intrinsic oxygen vacancies and were further modified with hydroxyl groups to create electron-rich Lewis acidic Ti sites. Additionally, BF 3 was engineered into the electrolyte microenvironment, and it could form adducts with N 2 , serving as a dynamic carrier for N 2 transport. The electron-rich Lewis acidic sites and the dynamic carriers exerted a ‘pull–pull’ effect on N 2 , thereby weakening the N N bonds. Through electrochemical performance evaluation, the designed electrocatalytic scheme achieved an NH 3 yield of ∼57.15 μg h −1 mg −1 and a Faradaic efficiency of ∼15.14 %. We anticipate that this methodology will provide new insights into the development of electrochemical ammonia synthesis, particularly in relation to multifaceted design.
研究领域:
材料科学
·
催化化学
·
环境科学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Functional Materials Letters
·
2023
·
IF 1.3
Meiqi Zhai,Yajie Bai,Xia Li,Fengfeng Wang,Wei-Qiang Fan,Hongye Bai
Photoelectrochemical reduction of nitrate (PEC NRR) to ammonia (NH 3 ) is a promising means with water as hydrogen source under room temperature. The construction of photoelectrode with efficient light response and reaction kinetics is the core point to achieve high NH 3 yield efficiency. Herein, a cerium-based metal organic framework (Ce-MOF) was successfully decorated on the copper phthalocyanine (CuPc). The CuPc/Ce-MOF heterostructure exhibits the ideal nitrate catalytic reduction activity, and the NH 3 yield (−0.6 V versus RHE) increases to 1.58 μ g h − 1 cm − 2 from 0.67 μ g h − 1 cm − 2 (CuPc). Besides, the cycle experiments reveal that the CuPc/Ce-MOF heterostructure has maintained good catalytic stability. This work explores the PEC NRR process mechanism of CuPc/Ce-MOF samples and provides a new idea for green NH 3 production.
研究领域:
材料科学
·
电化学
·
光化学
·
催化
✓ 已验证
DOI
高影响因子
危险品化学品经营许可证（带存储）