INORGANIC CHEMISTRY
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2025
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IF 4.7
Jing Xu,Kangle Wan,Jianjie Wu,Yunchao Wu,Wei Yan,Lichuan Zhang,Yuanping Chen,Yingcong Wei
During the piezoelectric photocatalytic process, the surface curvature of the piezoelectric photocatalyst undergoes dynamic changes under the influence of external mechanical forces. However, the correlation between the surface curvature and catalytic performance remains largely unexplored. Here, we demonstrate that decreasing the radius of curvature of MoSe2 significantly enhances its piezoelectric-photocatalytic activity for C–N coupling reactions, enabling imine synthesis from benzylamine. Comprehensive characterization and DFT calculations together show that the piezoelectric effect in the curved MoSe2 structure inhibits photogenerated charge carriers from recombination, improving carrier utilization efficiency. Additionally, the surface curvature effect induced by ultrasonic driving reduces the band gap. It promotes the effective transfer of electrons from Mo atoms in MoSe2 to −NH2 in benzylamine, thereby facilitating the activation of the benzylamine molecule. As a result, the synergistic effects of the piezoelectric and curvature characteristics significantly enhance the photocatalytic performance of MoSe2 toward the C–N coupling of benzylamine. This study not only provides new insights into interfacial reaction mechanisms in piezoelectric photocatalysis but also offers a novel perspective for designing high-performance catalytic systems.
研究领域:
材料科学
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催化化学
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理论计算
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DOI
PubMed
高影响因子
Chem
·
2024
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IF 19.1
Xiaoran Zhang,Xiaorong Zhu,Shuowen Bo,Chen Chen,Qingfeng Zhai,Shuang Li,Xiaojin Tu,Jianyun Zheng,Dongdong Wang,Xiaoxiao Wei,Wei Chen,Tehua Wang,Yafei Li,Qinghua Liu,San Ping Jiang,Liming Dai,Shuangyin Wang
Electrocatalysis offers a sustainable approach to artificial nitrogen fixation yet faces numerous challenges. Selective synthesis of nitrogen-containing compounds shows promise but needs significant improvement. Herein, we demonstrate selective ammonia and urea synthesis via co-electrolysis with CO 2 . High CO binding energy on Re-Mn catalysts leads to the formation of ∗C species, which serve as electron reservoirs to enhance N 2 activation for C-N coupling (N 2 + ∗C → ∗CN 2 ), followed by C-N dissociation. This results in ammonia production with a yield rate of 48.9 ± 2.4 mg g −1 h −1 and an N-selectivity of 98.4%. In contrast, Zn-Mn sites, characterized by low CO binding, facilitate the migration of CO and its coupling with adsorbed N 2 (CO + ∗N=N∗ → ∗NCON∗). Subsequent hydrogenations of ∗NCON∗ promote urea synthesis with an N-selectivity of 89.1%. Utilizing Janus coupling with two C-N pathways aims to meet energy, agriculture, and chemical industry demands. We realized the selective synthesis of ammonia and urea, respectively, in one electrocatalytic system for the first time by Janus coupling with two distinguishable C-N coupling paths from N 2 and CO 2 .
研究领域:
化学工程
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能源科学
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农业科学
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DOI
高影响因子
APPLIED SURFACE SCIENCE
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2024
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IF 6.3
Songhao Yu,Guifen Tian,Liduan Li,Fei Wang,Kefeng Wang,Junyu Lei,Haijun Hao,Qinghong Xu
TpFO-PA, a novel spherical hollow mesoporous polyamide, was firstly synthesized by the reaction among 1,3,5-tris(4-aminophenyl)benzene (TAPB), furylamine and oxalyl chloride in using silica-gel nanoparticle as hard template, and the composite Cu(I)@TpFO-PA with high catalytic activities in C-N coupling reactions between (hetero)aryl bromide and (hetero)aryl amines under mild conditions was prepared basing on presence of N in the framework. A maximum activity of the catalyst with yield of C-N coupling product were about 311.9 g (product) /mol Cu(I) ·h and 95 % respectively, and the activity could be maintained at least 5 times after the catalyst was reused. The composite Cu(I)@TpFO-PA is a few heterogeneous catalysts reported in catalyzing coupling reaction between aromatic amines and brominated aromatic compounds.
研究领域:
化学
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材料科学
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产品关联
DOI
高影响因子
Nature Communications
·
2022
·Vol. 13
·期 1
·1-9
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IF 17.694
Zhang Xiaoran,Zhu Xiaorong,Bo Shuowen,Chen Chen,Qiu Mengyi,Wei Xiaoxiao,He Nihan,Xie Chao,Chen Wei,Zheng Jianyun,Chen Pinsong,Jiang San Ping,Li Yafei,Liu Qinghua,Wang Shuangyin
Electrocatalytic urea synthesis emerged as the promising alternative of Haber–Bosch process and industrial urea synthetic protocol. Here, we report that a diatomic catalyst with bonded Fe–Ni pairs can significantly improve the efficiency of electrochemical urea synthesis. Compared with isolated diatomic and single-atom catalysts, the bonded Fe–Ni pairs act as the efficient sites for coordinated adsorption and activation of multiple reactants, enhancing the crucial C–N coupling thermodynamically and kinetically. The performance for urea synthesis up to an order of magnitude higher than those of single-atom and isolated diatomic electrocatalysts, a high urea yield rate of 20.2 mmol h −1 g −1 with corresponding Faradaic efficiency of 17.8% has been successfully achieved. A total Faradaic efficiency of about 100% for the formation of value-added urea, CO, and NH 3 was realized. This work presents an insight into synergistic catalysis towards sustainable urea synthesis via identifying and tailoring the atomic site configurations.
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
Catalysis Science & Technology
·
2023
·Vol. 13
·期 6
·1855-1865
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IF 5
Shuyi Yang,Jiayi Deng,Jiaying Chen,Qingmei Tan,Tianren Liu,Ke Chen,Dongxue Han,Yingming Ma,Mengjiao Dai,Li Niu
The conversion of N2 and CO2 into urea through a photocatalytic C–N coupling reaction under ambient conditions serves as a novel green avenue for urea synthesis. However, the poor adsorption and C–N coupling capability of inert gas molecules hinder the efficient catalytic activity. Herein, palladium-decorated CeO2 (Pd–CeO2) was demonstrated as an efficient photocatalyst for C–N coupling reaction and delivered a remarkable urea yield rate of 9.2 μmol h−1 g−1, which was superior to that of pristine CeO2 (2.5 μmol h−1 g−1). Comprehensive investigations further endorsed that the emerged space-charge region in the CeO2(111)/Pd(111) interface not only effectively facilitates the targeted capture and activation of inert CO2 and N2 but also stabilizes the formation of key intermediates (*NCON). Besides, the effective inhibition of the endothermic *NNH intermediate is conducive to the subsequent C–N coupling process and the improvement of reaction selectivity. The reaction mechanism was studied in detail by density functional theory (DFT) with the formation of a C–N bond via a thermodynamically spontaneous reaction between *NN* and CO. This work provides novel insights into the conversion of CO2 and N2 into urea.
研究领域:
化学工程
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材料科学
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环境科学
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产品关联
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
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2025
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IF 13.2
Ying Chen,Zhiliang Cheng,Shujie Hu,Mengyue Zhang,Di Wu,Xuan Zhao,Haoran Yang,Linjiang Zhong,Xinjie Chai,Hong Liu,Facheng Qiu,Yuan Liu
Electrochemical carbon dioxide synergistic nitrate for urea synthesis is essential for mitigating greenhouse effects and recycling resources. Limited ion migration in traditional H-type electrolysis cells has led to a growing preference for flow cells to enhance mass transfer, but mechanisms of their impact on synthesis of value-added product urea remain unclear. Herein, this study was devoted to revealing the differences in ion transport among different electrolysis cells and their effect on C-N coupling, providing insights into optimizing urea synthesis. Simulation of the multi-physics fields in flow-through, flow-by, and H-type electrolytic cells systematically investigated these effects. The simulations revealed that the flow-through cell significantly enriched NO 3 − on the cathode surface and within its pore structures under hydrodynamic conditions, facilitating intermediate interactions. Experimental validation using KHCO 3 and KNO 3 demonstrated that the flow-through cell achieved a urea yield of 3182.7 μg h −1 mg cat. −1 and an electricity consumption of 95.7 kWh kg urea −1 . Additionally, the urea Faradaic efficiency reached 24.9 %, which was 12.7 % and 27 % higher than those of the flow-by and H-type cells, respectively, underscoring the superior urea selectivity of the flow-through cell. Mechanistic analysis through electrochemical tests further demonstrated the flow-through cell exhibited a faster reaction rate, enhanced charge transfer, and lower NO 3 − diffusion resistance. These results highlight the critical role of flow-through electrolysis in promoting ion-to-intermediate conversion and suggest that targeted modifications of porous electrodes to enhance NO 3 − enrichment could further improve the efficiency of electrochemical C-N coupling for urea synthesis.
研究领域:
化学工程
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环境科学
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电化学
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DOI
高影响因子
JOURNAL OF LUMINESCENCE
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2024
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IF 3.3
Ziting Yuan,Zhiping Shi,Xi Nian,Bingbing Li,Kai Li,Liqiong Liao
Ellagic acid (EA), a natural polyphenol, features a highly organized planar structure with an extensive sp 2 carbon-conjugated area, making it favorable for light energy absorption and fluorescent emission. However, this planar structure can easily aggregate through π-π stacking, leading to aggregation-caused quenching of fluorescence. In this research, aniline-doped ellagic acid (EAAn 2 ) was successfully synthesized via a C-N coupling reaction to address this issue. The fluorescence properties of EAAn 2 in various organic solvents were thoroughly investigated. Compared to EA, EAAn 2 exhibited a red shift in fluorescence emission, primarily revealing yellow fluorescence instead of the green fluorescence of EA. Moreover, the fluorescence intensity and the concentration at which aggregation-caused quenching occurs for EAAn 2 were substantially improved due to the two grafted aniline molecules. EAAn 2 was utilized as a molecular fluorescent probe in DMSO to detect three kinds of metal ions: alkali and alkaline-earth metal ions, transition metal ions, and post-transition metal ions, using EA as a control. It was found that the combination of EAAn 2 with these metal ions exhibited stronger fluorescence intensity than EA and effectively resisted the blue shift in fluorescence emission due to aniline doping. Based on these results, Mg 2 ⁺ ions could be clearly distinguished from other alkali and alkaline-earth metal ions by differences in their fluorescence emission, as could Cr 2 ⁺ ions among transition metals. This research effectively enhances the fluorescence properties of EA through C-N coupling and demonstrates its greater potential in the detection of metal ions, providing fundamental and valuable information for future fluorescent applications.
研究领域:
化学
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材料科学
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分析化学
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DOI
高影响因子
Journal of Energy Chemistry
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2024
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IF 14
Yinuo Wang,Yian Wang,Qinglan Zhao,Hongming Xu,Shangqian Zhu,Fei Yang,Ernest P. Delmo,Xiaoyi Qiu,Chi Song,Juhee Jang,Tiehuai Li,Ping Gao,M. Danny Gu,Minhua Shao
Urea generation through electrochemical CO 2 and NO 3 − co-reduction reaction (CO 2 NO 3 RR) is still limited by either the low selectivity or yield rate of urea. Herein, we report copper carbonate hydroxide (Cu 2 (OH) 2 CO 3 ) as an efficient CO 2 NO 3 RR electrocatalyst with an impressive urea Faradaic efficiency of 45.2% ± 2.1% and a high yield rate of 1564.5 ± 145.2 μg h −1 mg cat −1 . More importantly, H 2 evolution is fully inhibited on this electrocatalyst over a wide potential range between −0.3 and −0.8 V versus reversible hydrogen electrode. Our thermodynamic simulation reveals that the first C-N coupling follows a unique pathway on Cu 2 (OH) 2 CO 3 by combining the two intermediates, *COOH and *NHO. This work demonstrates that high selectivity and yield rate of urea can be simultaneously achieved on simple Cu-based electrocatalysts in CO 2 NO 3 RR, and provide guidance for rational design of more advanced catalysts.
研究领域:
电化学
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材料科学
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产品关联
DOI
高影响因子
AICHE JOURNAL
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2024
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IF 3.5
Sibo Chen,Guangtong Hai,Hui Cheng,Dan Xie,Gao-Feng Chen,Liang-Xin Ding,Haihui Wang
The electrochemical co-reduction of CO 2 and NO 3 − to urea is an alternative to traditional urea synthesis. However, the significant difference in the energy barriers and reaction rates for CO 2 and NO 3 − reduction restricts the efficiency of the C N coupling. Herein, we report a strategy to coordinate the C N coupling intermediates by unilaterally increasing the efficiency of CO 2 reduction to match that of facile NO 3 − reduction. We demonstrate this strategy using an electrochemical reaction system consisting of a Cu 2 O-loaded ordered gas-diffusion electrode, which offers a high urea yield rate of 1373.5 μg h −1 mg cat. −1 at a low applied potential of −0.6 V versus RHE. This work not only provides a feasible strategy to coordinate the reductive coupling of CO 2 and NO 3 − , but also brings new insight into the reaction mechanism of urea electrosynthesis.
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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产品关联
DOI
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
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2023
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IF 22.1
Yini Mao,Yong Jiang,Qiao Gou,Shengmei Lv,Zuyou Song,Yimin Jiang,Wenbin Wang,Ming Li,Lirong Zheng,Wei Su,Rongxing He
Urea is of great importance for the survival and development of mankind because of its advantages in effectively increasing crop yields. A novel carbon-supported indium-doped bismuth nanoparticles (Bi: 10 %In/C NPs) was prepared for the synthesis of urea via the co-activated reduction of nitrate and CO 2 with an average Faraday efficiency (FE) of 20.31 % and urea yield (R urea ) of 606.38 μg mg −1 h −1 . Interestingly, the In doped here not only serves as the active site, but also acts as an activator to stimulate the activity of Bi through electronic interaction, thus making Bi also the active site for the electrocatalytic C-N coupling reaction. Simultaneously, the key intermediates of the reaction are revealed to be *NH 2 and *CO. This work provides further insight into the role of indium in the electrocatalytic C-N coupling for the synthesis of urea, which gives a direction for thinking about the design and construction of subsequent highly efficient electrocatalysts.
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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产品关联
DOI
高影响因子
Journal of the American Chemical Society
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2024
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IF 14.4
Weihang Li,Haoyang Jiang,Xiang Zhang,Bo Lei,Le Li,Haoshen Zhou,Miao Zhong
Electrified synthesis of high-value organonitrogen chemicals from low-cost carbon- and nitrogen-based feedstocks offers an economically and environmentally appealing alternative to traditional thermocatalytic methods. However, the intricate electrochemical reactions at electrode surfaces pose significant challenges in controlling selectivity and activity, especially for producing complex substances such as N,N-dimethylformamide (DMF). Herein, we tackle this challenge by developing relay catalysis for efficient DMF production using a composite WO2–NiOOH/Ni catalyst with two distinctive active sites. Specifically, WO2 selectively promotes dimethylamine (DMA) electrooxidation to produce strongly surface-bound (CH3)2N*, while nearby NiOOH facilitates methanol electrooxidation to yield more weakly bound *CHO. The disparity in binding energetics of the key C- and N-intermediates expedites C–N coupling at the WO2–NiOOH interface. In situ infrared spectroscopy with isotope-labeling experiments, quasi-in situ electron paramagnetic resonance trapping experiments, and electrochemical operating experiments revealed the C–N coupling mechanism and enhanced DMF-synthesis selectivity and activity. In situ X-ray absorption spectroscopy (XAS) and postreaction transmission electron microscopy (TEM) studies verified the stability of WO2–NiOOH/Ni during extended electrochemical operation. A Faradaic efficiency of ∼50% and a production rate of 438 μmol cm–2 h–1 were achieved at an industrially relevant current density of 100 mA cm–2 over an 80 h DMF production period. This study introduces a new paradigm for developing electrothermo relay catalysis for the sustainable and efficient synthesis of valuable organic chemicals with industrial potential.
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
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产品关联
DOI
PubMed
高影响因子
危险品化学品经营许可证（带存储）