NEW JOURNAL OF CHEMISTRY
·
2022
·Vol. 46
·期 35
·16743-16751
·
IF 3.925
Kun Jiang,Kai Li,Shuirong Li,Yan Li,Tao Li,Yun-Quan Liu,Duo Wang,Yueyuan Ye
Transition metal nitrogenous complexes have been extensively studied for electrochemical synthesis of ammonia due to their great capabilities in adsorbing and activating nitrogen molecules; yet the improvement of their catalytic performance is still a big challenge. Herein, a series of novel bimetallic Fe, Mo–N nanosheet arrays (FeMo–N) supported on nickel foam were fabricated through a facile hydrothermal–pyrolysis method, which were used as electrocatalysts for the nitrogen reduction reaction (NRR). It was discovered that the catalyst Fe1Mo1–N exhibited a promising performance with a NH3 yield rate of 46.64 μg mg−1cat. h−1 and a faradaic efficiency (FE) of 1.12% at −0.8 V vs. RHE, which also demonstrated excellent selectivity and thermal stability. The specific two-dimensional nanosheet morphology of the catalyst was believed to be the major reason contributing to the prominent electrochemical performance. The XPS characterization and NH3 yield study at different N contents in the M–N bond further revealed that FeMo–N species are the primary active centers for the NRR, and the N content forming the M–N bond is closely related to the catalytic activity.
研究领域:
材料科学
·
电化学
✓ 已验证
产品关联
DOI
高影响因子
ChemPlusChem
·
2023
·Vol. 88
·期 3
·e202300023
·
IF 3.4
Cheng Nan,Huimin Yang,Fanfan Gao,Nan Gao,Wenjing Zhou,Haiyan Du,Zhenhai Liang
Graphical A series of molybdenum - doped CeO 2 nanorod catalysts were successfully fabricated via a hydrothermal reaction coupled with high temperature calcination. The obtained 5 %-Mo-CeO 2 nanorods provide as a superior electrocatalyst in neutral electrolytes of 0.1 M Na 2 SO 4 . Such electrocatalyst significantly enhances nitrogen reduction reaction performance with an NH 3 yield of 10.9 μg h −1 mg −1 cat at −0.45 V vs reversible hydrogen electrode (RHE) and a Faradaic efficiency of 26.5 % at −0.25 V vs RHE, much higher 4 times than of CeO 2 nanorods (2.6 μg h −1 mg −1 cat ; 4.9 %). As a green and sustainable strategy, the electrocatalytic N 2 reduction reaction (NRR) has been considered the best potential approach to replace the traditional Haber-Bosch process under ambient conditions. The key is to exploit efficient and low-cost electrocatalysts according to the current situation. Herein, a series of Molybdenum (Mo) doped CeO 2 nanorods (NR) catalysts were successfully fabricated via a hydrothermal reaction coupled with high temperature calcination. The nanorod structures were not altered after Mo atom doping. The obtained 5 %-Mo-CeO 2 nanorods act as a superior electrocatalyst in neutral electrolytes of 0.1 M Na 2 SO 4 . Such electrocatalyst significantly enhances NRR performance with an NH 3 yield of 10.9 μg h −1 mg −1 cat at −0.45 V vs reversible hydrogen electrode (RHE) and a Faradaic efficiency (FE) of 26.5 % at −0.25 V vs RHE. That outcome is 4 times higher than that of CeO 2 nanorods (2.6 μg h −1 mg −1 cat ; 4.9 %). Meanwhile, density functional theory (DFT) calculation shows the characteristics after Mo doping: the band gap value lowers, the density of states increases, electrons are more easily excited, and N 2 molecules are more easily adsorbed, thereby enhancing the activity of the electrocatalytic NRR.
研究领域:
材料科学
·
电化学
·
理论计算
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Nanoscale
·
2019
·Vol. 12
·期 3
·1811-1816
·
IF 6.97
Yongqin Liu,Liang Huang,Xinyang Zhu,Youxing Fang,Shaojun Dong
The electrochemical nitrogen reduction reaction (NRR) under ambient conditions is currently attracting intense attention, but it still remains a great challenge to develop highly selective and active NRR electrocatalysts. Inspired by the intrinsic NRR activity of Au, we systematically studied the synergistic enhanced effect of incorporating other transition metals into Au on its NRR activity. A general strategy was used to synthesize a series of Au-based bimetallic nanocatalysts (AuCu, AuAg, AuPd and AuRu), and the NRR catalytic performance of the as-obtained electrocatalysts was investigated in detail. The experimental results indicate that the positive effect of Cu on NRR was the most remarkable in comparison with that of Ag, Ru and Pd, which can be ascribed to the synergy of the Au and Cu components via modulating the electronic structure and further changing the binding affinity of adsorbed N atoms on the catalyst. Finally, the optimized nanocatalyst with the atom ratio of Au1Cu1 achieved the highest faradaic efficiency (54.96%) and ammonia yield rate (154.91 μg h−1 mgcat−1) at −0.2 V vs. RHE, exceeding those of the previously reported Au nanocatalysts.
研究领域:
材料科学
·
电化学
✓ 已验证
DOI
高影响因子
ACS Nano
·
2024
·
IF 15.8
Jian-Jia Mu,Xuan-Wen Gao,Zhiwei Zhao,Zhao-Meng Liu,Qinfen Gu,Wen-Bin Luo
A dynamic-regulated Pd–Fe–N electrocatalyst was effectively constructed with electron-donating and back-donating effects, which serves as an efficient engineering strategy to optimize the electrocatalytic activity. The designed PdFe3/FeN features a comprehensive electrocatalytic performance toward the nitrogen reduction reaction (NRR, yield rate of 29.94 μg h–1 mgcat–1 and FE of 38.43% at −0.2 V vs RHE) and oxygen evolution reaction (OER, 308 mV at 100 mA cm–2). Combining in situ ATR-FTIR, XAS, and DFT results, the role of the interstitial-N-dopant-induced electron sponge effect has been significantly elucidated in strengthening the electrocatalytic NRR process. Specifically, the introduction of a N dopant, an electron acceptor, initiates the generation of robust Lewis-acidic Fe sites, facilitating free N2 capture and bonding. Simultaneously, after NH3 adsorption, the N dopant can back-donate electrons to Fe sites, strengthening the NH3 deportation through weakening the Lewis acidity of Fe centers. Besides, the electron-deficient Fe sites contribute to the reconstruction of FeOOH, the real active species during the OER, which accelerates the four-electron reaction kinetics. This research offers a perspective on electrocatalyst design, potentially facilitating the evolution of advanced material engineering for efficient electrocatalytic synthesis and energy storage.
研究领域:
材料科学
·
电化学
·
催化科学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
LANGMUIR
·
2024
·
IF 3.7
Zhuangzhi Sun,Jiawei Lin,Suwei Lu,Yuhang Li,Tingting Qi,Xiaobo Peng,Shijing Liang,Lilong Jiang
The electrochemical nitrogen reduction reaction (eNRR) has emerged as a promising strategy for green ammonia synthesis. However, it suffers unsatisfactory reaction performance owing to the low aqueous solubility of N2 in aqueous solution, the high dissociation energy of N≡N, and the unavoidable competing hydrogen evolution reaction (HER). Herein, a MIL-53(Fe)@TiO2 catalyst is designed and synthesized for highly efficient eNRR. Relative to simple MIL-53(Fe), MIL-53(Fe)@TiO2 achieves a 2-fold enhancement in the Faradaic efficiency (FE) with an improved ammonia yield rate by 76.5% at −0.1 V versus reversible hydrogen electrode (RHE). After four cycles of electrocatalysis, MIL-53(Fe)@TiO2 can maintain a good catalytic activity, while MIL-53(Fe) exhibits a significant decrease in the NH3 yield rate and FE by 79.8 and 82.3%, respectively. Benefiting from the synergetic effect between TiO2 and MIL-53(Fe) in the composites, Fe3+ ions can be greatly stabilized in MIL-53(Fe) during the eNRR process, which greatly hinders the catalyst deactivation caused by the electrochemical reduction of Fe3+ ions. Further, the charge transfer ability in the interface of composites can be improved, and thus, the eNRR activity is significantly boosted. These findings provide a promising insight into the preparation of efficient composite electrocatalysts.
研究领域:
材料科学
·
电化学
·
催化化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
·
2021
·
IF 5.816
Yangsen Xu,Xi Xu,Ning Cao,Xianfen Wang,Xuehua Liu,Marco Fronzi,Lei Bi
The electrochemical conversion of N 2 to NH 3 is an interesting research topic as it provided an alternative and energy-saving method compared with the traditional way of NH 3 production. Although different materials have been proposed for N 2 reduction, the use of defects in oxides was only reported recently and the relevant working mechanism was not fully revealed. In this study, Sr was used as the dopant for LaFeO 3 to create oxygen vacancies , forming the Sr-doped LFO (La 0.5 Sr 0.5 FeO 3-δ ) perovskite oxide. The La 0.5 Sr 0.5 FeO 3-δ ceramic oxide used as a catalyst achieves an NH 3 yield of 11.51 μgh −1 mg −1 and the desirable faradic efficiency (F.E.) of 0.54% at −0.6 V vs reversible hydrogen electrode (RHE), which surpassed that of LaFeO 3 nanoparticles . The 15 N isotope labeling method was employed to prove the La 0.5 Sr 0.5 FeO 3-δ catalyst had the function of converting N 2 into NH 3 under the electrolysis condition. The first principle calculations were used to investigate the mechanism at the atomistic level, revealing that the free energy barriers changed significantly with the introduction of oxygen vacancies that accelerated the overall nitrogen reduction reaction (NRR) procedure.
研究领域:
材料科学
·
电催化
·
化学工程
✓ 已验证
DOI
高影响因子
INORGANIC CHEMISTRY
·
2020
·
IF 4.825
Guoliang Zhao,Xin Wang,Chen Xu
NH3, as one of the most massively used chemical products in the world, not only serves as the main nitrogen source of chemical fertilizers but also is considered as a promising renewable energy source. Most ammonia in industry is produced by the Haber–Bosch process under extremely high temperature and pressure conditions, which is intensively energy consuming and environmentally unfriendly. Electrocatalytic nitrogen reduction reaction (NRR) has been regarded as a promising way to produce NH3 under ambient conditions in recent years, but the research for efficient earth-abundant electrocatalysts is still highly limited. In this work, different TiO2 phases (anatase and rutile)/carbon nanocomposites with a sandwich architecture are produced by annealing MXene at different temperatures, which shows excellent electrocatalytic NRR performance. In 0.1 M Na2SO4, anatase TiO2/C composites show better NRR performance than the rutile ones, which achieve a large NH3 yield of 14.0 μg h–1 cm–2, a high Faradaic efficiency of 13.3% at −0.2 V vs a reversible hydrogen electrode, and a high electrochemical stability. The sandwich architecture of anatase TiO2 nanoparticles well-dispersed on the surface of carbon layers could increase the conductivity of TiO2 and the exposure of active sites, which could explain the improved NRR activity of anatase TiO2/C composites compared with previous work. Density functional theory calculations suggest that the energy barrier of most steps for the surface of anatase TiO2 is relatively lower than that of rutile TiO2, which could explain the better electrocatalytic NRR performance for anatase TiO2/C composites compared with the rutile ones.
研究领域:
材料科学
·
电化学
·
催化化学
✓ 已验证
DOI
高影响因子
ChemSusChem
·
2021
·Vol. 14
·期 12
·2521-2528
·
IF 8.928
Huinan Guo,Weiqin Li,Kai Chen,Mengyuan Yue,Yike Huang,Yafei Liu,Huaxu Shao,Chengcheng Chen,Caiyun Wang,Yijing Wang
Graphical In the bag : An optimized one-step pyrolysis strategy is used to design yolk–shell microcages (YS Co@C/BLCNTs), consisting of Co nanocrystals encapsulated in N-doped carbon framework and bridged by bamboo-like carbon nanotubes (BLCNTs).The yolk–shell microcage catalyst integrates the advantages of “micro-bag” and “cage effect” to realize effective nitrogen fixation. The electrocatalytic nitrogen reduction reaction (ENRR) under ambient conditions is considered as a promising process to produce ammonia. Towards highly efficient catalysts, here an optimized one-step pyrolysis strategy was tailored to design yolk–shell microcages (YS Co@C/BLCNTs), consisting of Co nanocrystals encapsulated in N-doped carbon framework and bridged by bamboo-like carbon nanotubes (BLCNTs). The cavity created between yolk and shell not only served as a “micro-bag” to store the reactant N 2 and enhance its dissolution, but also induced a “cage effect” to confine the diffusion of reaction intermediate, hence making the reaction proceed in the direction of producing NH 3 . This catalyst displayed excellent catalytic activities for ENRR: a high NH 3 yield of 12.87 μg mg cat −1 h −1 at a high faradaic efficiency of 20.7 % at −0.45 V (vs. reversible hydrogen electrode, RHE). After 5 cycles of consecutive ENRR process, the NH 3 yield rate was 11.29 μg mg cat −1 h −1 , indicating the excellent electrocatalytic stability. These results provide a structural engineering for ENRR catalyst with doped N, cooperating with non-precious metal to activate the inert triple bond of N 2 and achieve NH 3 fixation.
研究领域:
材料科学
·
催化化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Sustainable Energy & Fuels
·
2020
·Vol. 4
·期 10
·5061-5071
·
IF 5.503
Anmin Liu,Qiyue Yang,Xuefeng Ren,Mengfan Gao,Yanan Yang,Liguo Gao,Yanqiang Li,Yingyuan Zhao,Xingyou Liang,Tingli Ma
The Haber–Bosch process is one of the most widely utilized approaches for the synthesis of ammonia, and has many disadvantages, such as the high energy consumption and generation of large amounts of greenhouse gases. Therefore, the electrochemical nitrogen reduction reaction (NRR) has received significant attention, as it is more sustainable and environmentally friendly. In this study, we report a CuAg/Ti3C2 MXene catalyst for the electrocatalytic NRR. This MXene-based composite material exhibits remarkable performance for electrochemical synthesis of ammonia under ambient conditions. When measured in a 0.1 M KOH solution at an applied potential of −0.5 V vs. reversible hydrogen electrode (RHE), the catalyst achieved an ammonia production rate and faradaic efficiency of 4.12 μmol cm−2 h−1 and 9.77%, respectively. These values indicate excellent stability and selectivity compared with the previously reported 2D NRR electrocatalysts. Moreover, the results of density functional theory calculations illustrate that with preferable adsorption of N2, desorption of NH3, and suppression of the HER, CuAg/Ti3C2 is a promising catalyst for the NRR. The excellent electrical conductivity and fast electron transport in the CuAg/Ti3C2 catalyst are favorable for the evaluated electrocatalytic reaction. Both experimental results and DFT calculations reveal that CuAg plays a crucial role in the catalytic activity and electrical conductivity enhancement for Ti3C2 based materials.
研究领域:
材料科学
·
催化化学
·
环境科学
✓ 已验证
产品关联
DOI
高影响因子
Journal of Materials Chemistry A
·
2020
·Vol. 9
·期 4
·2145-2151
·
IF 11.301
Jiaojiao Xia,Haoran Guo,Maozeng Cheng,Chuyan Chen,Minkang Wang,Yong Xiang,Tingshuai Li,Enrico Traversa
The electrocatalytic nitrogen reduction reaction (NRR) has been deemed a promising and reliable approach to massively produce ammonia under ambient conditions. A high-efficiency electrocatalyst with an excellent selectivity is highly required to reduce the multiple reaction barriers of N2 + 3H2O → 2NH3 + 1.5O2. Here, we report electrospun zirconia nanofibers as a non-noble NRR electrocatalyst to convert nitrogen to ammonia. Theoretical calculations predict that the Zr sites with oxygen vacancies are favorable for nitrogen adsorption and reduction. Experimentally, the larger concentration of oxygen defects in such an electrocatalyst allowed achieving a NH3 formation rate of 9.63 μg h−1 mgcat.−1 and an optimal faradaic efficiency of 12.1% at −0.7 V vs. the reversible hydrogen electrode in 0.1 M Na2SO4.
研究领域:
材料科学
·
电化学
·
催化反应
✓ 已验证
产品关联
DOI
高影响因子
CARBON
·
2021
·
IF 9.594
Nan Li,Yueyu Tong,Hao Li,Liqun Wang,Feng Hou,Shi Xue Dou,Ji Liang
Electrochemical reduction of dinitrogen (N 2 ) to ammonia (NH 3 ) at the ambient condition is a promising alternative to the traditional Haber-Bosch process due its energy-saving and eco-friendly natures. However, the extremely stable N N triple-bonds in N 2 molecules and the competitive hydrogen evolution reaction (HER) have been regarded as the two essential issues in the electrocatalytic nitrogen reduction reaction (eNRR), making the simultaneous achievement of a high NH 3 yield rate and a satisfactory Faradaic efficiency (FE) very difficult. To address this issue, we herein report a metal-free electrocatalyst , the boron-doped carbon nanosphere , to effectively activate the N N triple-bonds and suppress the HER during the eNRR process. In this protocol, the B–C configurations can be easily tailored by simply changing the boron precursor amount, and the one that is ( i.e. , BC 3 ) beneficial to the enhancement of eNRR can achieve the maximum relative content of ∼43% in the optimum sample. Under this boron-doping amount, the material simultaneously delivers a high NH 3 yield of 33.8 μg h −1 mg −1 cat and a high FE of 39.2% at −0.7 V vs. reversible hydrogen electrode , accompanied with a superior stability for a continuous eNRR. This study thus offers an efficient, stable, and low-cost carbon-based catalyst for eNRR.
研究领域:
材料科学
·
电化学
·
催化科学
✓ 已验证
产品关联
DOI
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
·
2021
·
IF 19.503
Ying Deng,Zhenyu Xiao,Zuochao Wang,Jianping Lai,Xiaobin Liu,Dan Zhang,Yi Han,Shaoxiang Li,Wei Sun,Lei Wang
Following the guidance of nitrogenase, the natural iron-based catalysts with remarkably high activity in nitrogen reduction reaction (NRR) may be a talent option to develop artificial molecular mimics. However, the electrochemical NRR process of iron-based catalysts still suffers from the high overpotential, poor lifespan, and slow reaction kinetics of the hydrogenation process. Through a controllable etching and in-situ carbonating process, a Pt-doped FeP/C hollow nanorod catalysts was fabricated. Driven by the doped Pt atom, the catalyst solves the key kinetic problem about insufficient proton feeding in the process of nitrogen reduction, and actively transfers protons to intermediates of the hydrogenation steps in NRR. Moreover, the as-prepared catalyst presents the highest NH 3 yield value of 10.22 μg h −1 cm −2 among multitudinous Fe based catalysts at lower potential of −0.05 V ( vs . RHE) with an excellent Faraday efficiency (FE) of 15.3 %, which is higher than FeP/C without the Pt-driven proton-feeding effect, and the cathodic current density presents no significant change within 50 h. In addition, the density functional theory (DFT) and Attenuated total reflection surface-enhanced infrared absorption spectrum (ATR-SEIRAS) results verify the reaction path and protons-feeding kinetic process.
研究领域:
材料科学
·
电化学
·
催化作用
✓ 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）