ACS Catalysis
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2025
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IF 13.1
Xiaorui Du,Chongshuai Gao,Jiaxin Huang,Yanbin Cui,Shijun Liu,Chenguang Wang
Controlling both the hydrogenation performance and the activation of Schiff base intermediate in catalysts is crucial for attaining high slectivity toward primary amine in the reduction amination of furfural. However, it remains pending for Pt-based catalysts, on which the reduction amination reactions rarely generate primary amines so far. In this work, we developed a Pt/TiO2 nanocluster (NC) catalyst with a size distribution independent of the reduction temperature and loading amount. The reductive amination performance was investigated by regulating the surface electronic state and the distance between Pt NCs, and the results, attractively, revealed that the catalyst with a lower loading amount exhibited a higher furfurylamine (FAM) yield. Further studies unraveled that the catalyst with a larger Pt NC proximity had more abundant effective adsorption sites for the key intermediate Schiff base, i.e., the surface Ti4+ sites adjacent to the Pt NC, promoting the transformation of the Schiff base. Meanwhile, reducing the surface density of Pt NCs helped control the intensity of hydrogen spillover, thereby inhibiting the occurrence of overhydrogenation reactions. Optimal activity for primary amine generation from furfural reductive amination was achieved with a Pt NC catalyst reduced at 500 °C and with a loading amount of only 0.1 wt %, resulting in a FAM yield exceeding 93% and a production rate of 297.9 gFAM gPt h–1. The reaction mechanism, involving the competitive relationship between NH3 and H2, was elucidated through kinetic studies and theoretical calculations. This work provides insights for the designation of catalysts with controllable hydrogenation activity and adsorption selectivity and contributes to the understanding of the mechanism of the reductive amination reaction.
研究领域:
催化化学
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绿色化学
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材料科学
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF CHEMICAL AND ENGINEERING DATA
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2013
·
IF 2.004
Fuxin Yang,Xiaopo Wang,Wei Wang,Zhigang Liu
In the present work, experimental values for the densities of primary amines (monoethanolamine and diglycolamine) in alcoholic solutions were studied at atmospheric pressure (97.57 kPa) using an Anton Paar digital vibrating U-tube densimeter (model DMA 5000 M) over the entire composition range from (283.15 to 343.15) K, along with the pure components. The alcoholic solutions investigated included methanol, ethylene glycol, and isopropanol. Excess molar volumes, thermal expansion coefficients, and excess thermal expansion coefficients were calculated using the experimental values. A Redlich–Kister type equation as a function of concentration was fitted with the excess molar volumes for representing the density values of the mixture solutions.
研究领域:
化学
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物理化学
✓ 已验证
产品关联
DOI
高影响因子
AICHE JOURNAL
·
2024
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IF 3.5
Yang Zhao,Qian Wang,Huifang Wu,Lirong Zheng,Zhexi Gao,Xuanlin Guo,Xingzhong Cao,Dianqing Li,Junting Feng
Reductive amination of biomass aldehydes is a vital process to synthesize chemical intermediates primary amine, but the selectivity is severely compromised by the self-condensation of highly reactive imine intermediates. Herein, we proposed a solution by manipulating the adsorption configuration of secondary imine via defect engineering. Specifically, a gradient reduction strategy was used to adjust the driving force of NiCo alloy crystallization, thus motivating the formation of metal vacancy clusters. The primary amine selectivity was raised from 70.9% to 95.1% with defect concentration increased from 36.1% to 42.5% on catalysts. In situ fourier transform infrared spectroscopy (FTIR) and density functional theory demonstrated metal vacancy clusters induced remarkable Ni Co electron transfer, which strengthened electronic coupling between secondary imine with catalyst, resulting in a flat configuration that was conducive to CN bond breakage to guarantee smooth conversion into primary amines. This catalyst exhibited potential real-life application prospects for its low cost, universality in reductive amination of various aldehydes, and long-life reusability.
研究领域:
化学工程
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催化材料科学
✓ 已验证
产品关联
DOI
高影响因子
CHINESE JOURNAL OF CATALYSIS
·
2015
·Vol. 36
·期 2
·204-208
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IF 1.964
Zhongkui Zhao,Renzhi Li,Yu Li,Guiru Wang
A clean and highly efficient catalytic aerobic reductive ring-cleavage of 3–methylanthra[1,2- c ]isoxazole-6,11-dione to 1-amino-2-acetylanthraquinone was performed using simple organic amines as organocatalysts and water as a green reaction medium. This method provides a new clean transformation of isoxazole-containing compounds to the corresponding ortho -amino ketones . The catalytic performance of various organic amines was carefully screened, and simple organic primary amines were found to be promising practical catalysts with outstanding catalytic performance. Isopropylamine as the organocatalyst gave 97.2% conversion of 3–methylanthra[1,2- c ]isoxazole-6,11-dione, with 97.2% selectivity to 1-amino-2–acetylanthraquinone, in the presence of oxygen only, using 1 equiv. of hydrazine hydrate at room temperature for 3 h. A possible mechanism is also proposed.
研究领域:
有机化学
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催化化学
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绿色化学
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药物化学
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合成方法学
✓ 已验证
DOI
高影响因子
MICROPOROUS AND MESOPOROUS MATERIALS
·
2022
·
IF 5.876
Qiqi Lu,Xiu-Zhi Wei,Jianguo Liu,Longlong Ma
Zeolite-tailored encapsulation of metal nanoparticles exhibits prominent catalytic performance in many fields especially for selective hydrogenation reaction due to the modulation effect of the zeolite microenvironment. Here, Pd nanoparticles encapsulated in MFI zeolite by an in-situ encapsulation method were first used in the selective hydrogenation of nitrile into a primary amine. After introducing KOH for mediating the acid-base property of zeolite microenvironment, the as-synthesized [email protected] manifested an improved selectivity in the synthesis of primary amine from nitrile, while outperformed both commercial catalysts and conventional Pd supported on zeolite catalyst. The remarkable performance of [email protected] could be attributed to both the basic property of the S-1-K zeolite for inhibiting the side reactions and the highly dispersed and ultrasmall Pd clusters for superior catalytic activity. Besides, the best yield of 81% was achieved at 80 °C, 5 bar H 2 , 2 h in ammonia solution via optimization experiments, and the moderate applicability of [email protected] catalyst was obtained by substrate scope test.
研究领域:
催化化学
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材料科学
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有机合成
✓ 已验证
产品关联
DOI
高影响因子
RSC Advances
·
2023
·Vol. 13
·期 43
·30243-30251
·
IF 3.9
Lan Wu,Yang Liu,Zhenhua Li,Jinhua Liang,Lei Geng,Li Chen,Zhengping Dong
Supported nano-catalysts with environmental sustainability and high catalytic performance are of great research interest for sustainable catalysis. In this article, a supported nano-catalyst, FeA-NC, with high catalytic performance was prepared by anchoring the transition metal iron onto nitrogen-doped porous carbon materials using chitosan as a raw material. Scanning electron microscopy (SEM), X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FT-IR) measurement results demonstrated that the obtained catalyst has an excellent mesoporous structure, and that the element Fe is evenly distributed. The support contains abundant N atoms, which can provide sufficient anchoring points for Fe and form Fe–Nx groups with Fe, improving the catalytic activity of the catalyst. Additionally, the FeA-NC with a porous structure can also enhance the mass transfer of reactants to improve the reaction efficiency. In addition, the prepared catalyst was used to catalyze the conversion of primary amines to the corresponding imines. The results showed that the direct oxidation of primary amines to the corresponding imines can be catalyzed by using air as an oxygen source and distilled H2O as a solvent under atmospheric pressure at 90 °C. Finally, the selectivity and stability of the as-prepared catalyst were also verified.
研究领域:
催化化学
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环境科学
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材料科学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
CHEMICAL ENGINEERING SCIENCE
·
2024
·
IF 4.1
Yan Ouyang,Qi Liu,Tong Luo,Qinlan Luo,Min Xiao,Hongxia Gao,Zhiwu Liang
CO 2 loaded amine polymerizes during solvent regeneration at temperatures above 100 °C, resulting in the deterioration of solvent performance. Herein, five primary amines were heated to 120, 135 and 150 °C with CO 2 loading of 0.4C/N to study thermal degradation. It was found that 2-amine-1-butanol showed the greatest amine loss of 38.5 % after heating to 135 °C for 672 hrs while 2-amino-2-methyl-1-propanol was most stable with amine loss of 17.4 % under the same conditions. The degradation products were identified and the reaction pathway was studied through density functional theory (DFT) calculation. Furthermore, the transition state for ring closure and opening reactions was analyzed. The ring closure reaction to form oxazolidinones had a higher energy barrier, showing that it was the limiting step. This is further supported by the good agreement with experimental results. The structure–activity relationship showed the strong steric hindrance effect and the methyl group at β-carbon improved the amine stability.
研究领域:
化学工程
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环境科学
·
计算化学
✓ 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）