ACS Applied Materials & Interfaces
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2020
·
IF 8.758
Xue Zhao,Ziqiong Yang,Artem V. Kuklin,Glib V. Baryshnikov,Hans Ågren,Wenjing Liu,Haibo Zhang,Xiaohai Zhou
The electricity provided by solar or wind power can drive nitrogen in the atmosphere, combining with ubiquitous water to form ammonia, and distributed production methods can alleviate the irreversible damage to the environment caused by the energy-intensive Haber–Bosch process. Here, we have designed a novel Ni-doped BCN heterojunction (S/M-BOPs-1) as a catalyst for the electrochemical nitrogen reduction reaction (NRR). The ammonia yield rate and Faraday efficiency in NRR driven by S/M-BOPs-1 reach up to 16.72 μg–1 h–1 cm–2 and 13.06%, respectively. Moreover, S/M-BOPs-1 still maintains high NRR activity and excellent stability after recycling for eight times and long-time operation of 12 h. Using density functional theory calculations, we reveal a possible NRR path for N2 to NH3 on Ni, BCN, and the S/M-BOPs-1 composite surfaces. The interaction between the BCN matrix and Ni nanoparticles promotes a synergetic effect for the electrochemical NRR efficiency due to the partial electron transfer from the Ni particles to BCN that inhibits hydrogen evolution reaction and decreases the rate-determining step on Ni surfaces toward NRR by ∼1.5 times. Therefore, efficient NRR performance can be achieved by tuning the electronic properties of non-noble metals via the formation of a heterointerface.
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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电化学
✓ 已验证
DOI
PubMed
高影响因子
Nature Communications
·
2023
·Vol. 14
·期 1
·1-10
·
IF 16.6
Zhang Shuo,Wu Jianghua,Zheng Mengting,Jin Xin,Shen Zihan,Li Zhonghua,Wang Yanjun,Wang Quan,Wang Xuebin,Wei Hui,Zhang Jiangwei,Wang Peng,Zhang Shanqing,Yu Liyan,Dong Lifeng,Zhu Qingshan,Zhang Huigang,Lu Jun
Electrochemical conversion of nitrate to ammonia offers an efficient approach to reducing nitrate pollutants and a potential technology for low-temperature and low-pressure ammonia synthesis. However, the process is limited by multiple competing reactions and NO 3 − adsorption on cathode surfaces. Here, we report a Fe/Cu diatomic catalyst on holey nitrogen-doped graphene which exhibits high catalytic activities and selectivity for ammonia production. The catalyst enables a maximum ammonia Faradaic efficiency of 92.51% (−0.3 V(RHE)) and a high NH 3 yield rate of 1.08 mmol h −1 mg −1 (at − 0.5 V(RHE)). Computational and theoretical analysis reveals that a relatively strong interaction between NO 3 − and Fe/Cu promotes the adsorption and discharge of NO 3 − anions. Nitrogen-oxygen bonds are also shown to be weakened due to the existence of hetero-atomic dual sites which lowers the overall reaction barriers. The dual-site and hetero-atom strategy in this work provides a flexible design for further catalyst development and expands the electrocatalytic techniques for nitrate reduction and ammonia synthesis.
研究领域:
催化
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电化学
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环境科学
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材料科学
✓ 已验证
DOI
高影响因子
Nano Energy
·
2021
·
IF 17.881
Cheng Du,Chenglong Qiu,Zhongying Fang,Ping Li,Yijing Gao,Jianguo Wang,Wei Chen
Electrocatalytic nitrogen reduction reaction (NRR), which can produce ammonia from N 2 and H 2 O under ambient conditions, has emerged as a promising sustainable alternative to the Haber-Bosch (H-B) process. However, their unsatisfied conversion efficiency and selectivity severely restrict the real utilization of NRR, owing to the stubborn triple bond in the N 2 molecule and the competitive hydrogen evolution reaction (HER). Here, inspired from the local microenvironment of the nitrogenase, we report for the first time a facile and general strategy to boost the NRR selectivity and activity through the self-assembled monolayer (SAM) of hexanethiol (HEX) on a series of metal electrocatalysts (Cu, Au, Pt, Pd and Ni). Molecular dynamics (MD) simulations suggest that the HEX SAM provides a hydrophobic microenvironment to impede the diffusion and adsorption of water molecules and promote that of N 2 molecules, thus inhibiting HER and simultaneously improving the NRR performance. Notably, among all the prepared samples, the highest Faradic efficiency (FE) of 50.5% is achieved on Cu-HEX with NH 3 formation rate (R) of 1.2 μg h −1 cm −2 . Remarkably, for the HER-favored Pt catalyst, the highest R of 26.4 μg h −1 cm −2 is also achieved on Pt-HEX with FE of 1.8% under 1 cm 2 of electrode area. The present strategy not only represents a general diffusion-controlled method to engineer high-performance NRR electrocatalysts, but also provides a new insight into the effect of surface chemistry of catalysts on the NRR process and kinetics.
研究领域:
电化学
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催化
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材料科学
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化学工程
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可持续化学
✓ 已验证
产品关联
DOI
高影响因子
Nano Research
·
2024
·Vol. 17
·期 6
·4898-4907
·
IF 9.5
Geng Jing,Ji Sihan
Electrocatalytic nitrate ( \({\rm{N}}{{\rm{O}}_3}^ -\) ) reduction to ammonia (NH 3 ) offers a viable approach for sustainable NH 3 production and environmental denitrification. Copper (Cu) possesses a distinctive electronic structure, which can augment the reaction kinetics of \({\rm{N}}{{\rm{O}}_3}^ -\) and impede hydrogen evolution reaction (HER), rendering it a promising contender for the electrosynthesis of NH 3 from \({\rm{N}}{{\rm{O}}_3}^ -\) . Nevertheless, the role of Cu 2 O in copper-based catalysts still requires further investigation for a more comprehensive understanding. Herein, the Cu 2 O/Cu(OH) 2 heterostructures are successfully fabricated through liquid laser irradiation using CuO nanoparticles as a precursor. Experimental and theoretical researches reveal that Cu 2 O/Cu(OH) 2 heterostructure exhibits enhanced electrocatalytic performance for \({\rm{N}}{{\rm{O}}_3}^ -\) to NH 3 because Cu(OH) 2 promotes electron transfer and reduces the valence state of Cu active site in Cu 2 O. At −0.6 V (vs. reversible hydrogen electrode (RHE)), the NH 3 yield reaches its maximum at 1630.66 ± 29.72 \({\rm{\mu g}} \cdot {{\rm{h}}^{ - 1}} \cdot {\rm{m}}{{\rm{g}}_{{\rm{cat}}}}^{ - 1}\) , while the maximum of Faraday efficiency (FE) is 76.95% ± 5.51%. This study expands the technical scope of copper-based catalyst preparation and enhances the understanding of the electrocatalytic mechanism of \({\rm{N}}{{\rm{O}}_3}^ -\) to NH 3 .
研究领域:
电化学
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催化
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环境科学
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纳米材料
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能量转换
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表面化学
✓ 已验证
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2025
·
IF 13.2
Yi Wang,Jiaxin Liu,Qixin Wang,Yuan Xu,Qianling Zhang
The electrocatalytic nitrate reduction reaction (NO 3 − RR) is a promising and economic green alternative to the traditional Haber-Bosch process for ammonia (NH 3 ) production. However, it suffers from high overpotential and poor NH 3 selectivity due to various competing reactions. In this study, we developed a CuO/Co 3 O 4 nanoneedle heterostructure catalyst grown on nickel foam. After electro-activation to Cu/Co 3 O 4 , it achieved nearly 100 % NH 3 selectivity in both alkaline and neutral electrolytes across a wide range of potentials. The catalyst showed a high NH 3 yield rate of 617.14 μmol h −1 cm −2 at −0.2 V vs. reversible hydrogen electrode along with an excellent stability over a 120-hour test. The mechanism involves CuO reducing to Cu, forming a heterostructure that modifies the electronic environment of Co sites, the synergistic Cu and Co 3 O 4 interfaces enhancing rapid *NO 3 adsorption and lowering the energy barriers for NH 3 production, thereby facilitating the overall efficiency even at low concentrations (0.01 M NO 3 − ).
研究领域:
电催化
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可持续能源
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材料科学
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环境修复
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氨生产
✓ 已验证
DOI
高影响因子
Nature Chemistry
·
2024
·
IF 19.2
Zhang Yangyu,Peng Xuanbei,Tian Han-Rui,Yang Bo,Chen Zuo-Chang,Li Jiejie,Zhang Tianhua,Zhang Mingyuan,Liang Xiaocong,Yu Zhiyang,Zhou Yanliang,Zheng Lirong,Wang Xiuyun,Zheng Jian-Wei,Tang Yu,Au Chak-tong,Jiang Lilong,Xie Su-Yuan
Developing highly effective catalysts for ammonia (NH 3 ) synthesis is a challenging task. Even the current, prevalent iron-derived catalysts used for industrial NH 3 synthesis require harsh reaction conditions and involve massive energy consumption. Here we show that anchoring buckminsterfullerene (C 60 ) onto non-iron transition metals yields cluster-matrix co-catalysts that are highly efficient for NH 3 synthesis. Such co-catalysts feature separate catalytic active sites for hydrogen and nitrogen. The ‘electron buffer’ behaviour of C 60 balances the electron density at catalytic transition metal sites and enables the synergistic activation of nitrogen on transition metals in addition to the activation and migration of hydrogen on C 60 sites. As demonstrated in long-term, continuous runs, the C 60 -promoting transition metal co-catalysts exhibit higher NH 3 synthesis rates than catalysts without C 60 . With the involvement of C 60 , the rate-determining step in the cluster-matrix co-catalysis is found to be the hydrogenation of *NH 2 . C 60 incorporation exemplifies a practical approach for solving hydrogen poisoning on a wide variety of oxide-supported Ru catalysts.
研究领域:
化学
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材料科学
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催化
·
氨生产
✓ 已验证
DOI
PubMed
高影响因子
危险品化学品经营许可证（带存储）