NEW JOURNAL OF CHEMISTRY
·
2025
·
IF 2.5
Yun Wang,Jiayang Wang,Zhiyang Zhang,Runsheng Xu,Shuang Wang
The reductive amination of biomass-derived furfural over non-noble metal catalysts represents a promising but challenging strategy for the sustainable synthesis of furfurylamine. Herein, we report mesoporous carbon supported CoZn bimetallic catalysts (CoxZny@MC) via a one-pot solvent evaporation induced self-assembly (EISA) method for high-efficiency reductive amination of furfural to furfurylamine with hydrous hydrazine (N2H4⋅H2O) as a nitrogen source. A complete conversion of furfural with a 97.5% yield of furfurylamine was achieved over bimetallic Co1Zn3@MC catalyst under mild conditions of 100 °C and 1.5 MPa H2 for 3 h. Furthermore, Co1Zn3@MC could be reused for at least five times with only a slight loss in activity. The excellent performance of the Co1Zn3@MC catalyst was mainly attributed to the introduction of moderate Zn species, which led to high dispersion of Co particles on the catalyst surface, as well as the abundant mesopores and high specific surface area of the catalyst. Moreover, a significant electron transfer from Zn species to Co centers occurs, which improves the inherent catalytic activity of the non-noble bimetallic catalyst by enhancing the electron density of Co particles.
研究领域:
催化化学
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材料科学
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绿色化学
✓ 已验证
产品关联
DOI
高影响因子
Molecular Catalysis
·
2024
·
IF 3.9
Meng Xu,Xiaoling Liu,Zhuo Xiong,Yue Wu,Zhen Meng,Yu Zhou,Jun Wang
Furfural is an abundant biomass-derived building block that can be converted into furan-based N-containing compounds through direct reductive amination by using dihydrogen (H 2 ). Nonetheless, the synthesis of furan-based tertiary amines is highly limited via this route. Herein, we reported the straightforward synthesis of MFI zeolite encapsulated Pt nanoparticles and finely modulated the surface electronic state by facilely controlling the reduction process. The constructed catalyst Pt@Z5 effectively catalyzed the amination of furfural with diethylamine for the synthesis of N-ethyl-N-(furan-2-ylmethyl)ethanamine, affording the high yield (>95 %), large turnover number (TON) of 2058, turnover frequency (TOF) of 1029 h −1 , and stable recyclability. Systematic investigations comprising in-situ Fourier transform infrared spectroscopy (FTIR) spectra and kinetic isotope effect (KIE) unraveled that the mild reduction condition allowed the catalyst with a superior affinity towards H atom and beneficial furfural adsorption behavior, accelerating the H 2 activation in the rate-determining step for the conversion of furfural into furan-based amine.
研究领域:
催化化学
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生物质转化
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材料科学
✓ 已验证
产品关联
DOI
高影响因子
ACS Catalysis
·
2025
·
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 Physical Chemistry C
·
2024
·
IF 3.3
Zhi-Qiang Wang,Wanjun Guo,Shengchao Jia,Yaxuan Jing,Shiting Li,Yong Guo,Xiaohui Liu,Xue-Qing Gong,Yanqin Wang
The selective production of primary amines through reductive amination has received increasing attention due to their extensive applications, while efficient reductive amination is still challenging. Herein, a novel strategy was developed to realize the efficient reductive amination of carbonyl compounds with NH3 via d–d orbital coupling strategies in RuCo alloys. The designed series of RuCo alloy catalysts not only exhibited excellent performance in conversion of various substrates but also demonstrated universal applicability across different supports. The key role of RuCo alloy is its unique ability to effectively catalyze the ammonolysis of a Schiff base, the rate-determining step in reductive amination. Theoretical studies reveal that the d–d orbital coupling strategies break the five d orbital equivalent contributions of metal (Co or Ru) atoms, and the d orbitals primarily contribute through the dz2 and dx2-y2 orbitals of Ru and the dz2 orbital of Co on the RuCo(001) surface, which significantly driving the homolytic NH3 dissociation during the ammonolysis of the Schiff base. Furthermore, stable Co–H covalent bond species and RuCo-NH2 half-ionic and half-covalent bond species on the RuCo(001) surface were generated with lower energy levels. This work not only achieves efficient reductive amination but also provides an atomic orbital-level understanding of the d–d orbital coupling strategies for heterogeneous catalysis.
研究领域:
催化化学
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材料科学
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理论化学
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产品关联
DOI
高影响因子
CHEMICAL RESEARCH IN CHINESE UNIVERSITIES
·
2019
·Vol. 35
·期 3
·457-462
·
IF 1.071
Liu Junmei,Guo Wanwan,Sun Hao,Li Ruyue,Feng Zhipeng,Zhou Xuyang,Huang Jun
Reductive amination of aldehydes/ketones with aqueous NH 3 and hydrogenation of nitriles to primary amines with Co catalysts were reported. Co@NC-700 exhibited remarkable activity and high selectivity for the reductive amination of aldehydes/ketones with aqueous NH 3 and the hydrogenation of nitriles to primary amines. Several primary amines can be obtained with good to excellent yields via the reductive amination of aldehydes/ketones and the hydrogenation of nitriles. The nitrogen-doped carbon(C)-supported Co@NC-700 metal catalyst was prepared via the pyrolysis of bioMOF Co/adenine in activated C. Co@NC-700 can be reused five times without evident loss of activity.
研究领域:
有机化学
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催化化学
✓ 已验证
DOI
高影响因子
Catalysis Science & Technology
·
2017
·Vol. 7
·期 18
·4129-4135
·
IF 5.773
Yingxin Liu,Kuo Zhou,Huimin Shu,Haiyan Liu,Jiongtao Lou,Dechao Guo,Zuojun Wei,Xiaonian Li
RANEY® Ni proved to be an effective heterogeneous catalyst for switchable reductive amination of furfuryl alcohol to tetrahydrofurfurylamine and furfurylamine with NH3 by simply adding or not adding 1.0 MPa H2 into the reaction bulk. After further optimization of the reaction conditions, we finally obtained 94.0% yield of tetrahydrofurfurylamine and 78.8% yield of furfurylamine with high selectivity. By extensively studying the catalytic pathways and mechanism of catalyst deactivation with XRD and XPS characterization, we have confirmed that an excess amount of H2 in the reaction bulk leads to the deep hydrogenation of the furan ring while an insufficient amount of H2 leads to the formation of Ni3N and the deactivation of the catalyst.
研究领域:
化学工程
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催化化学
✓ 已验证
DOI
高影响因子
CATALYSIS TODAY
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2016
·
IF 4.312
Ran Ma,Yue-Biao Zhou,Liang-Nian He
A mixture of iron powder and catalytic palladium on activated carbon has been developed for reductive amination of various aromatic aldehydes, including 2-pyridinecarboxaldehyde, in water under CO 2 atmosphere. The reversible reaction of CO 2 with water could form carbonic acid and hydrogen transfer from water to Pd(0) took place with the presence of iron powder, leading to formation of high-active Pd hydrides for the reductive amination process. On the other hand, the reaction system could be inherently neutralized by ready removal of CO 2 , thus resulting in facile post-processing.
研究领域:
有机化学
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催化化学
✓ 已验证
产品关联
DOI
高影响因子
FUEL
·
2024
·
IF 6.7
Yilin Wei,Zhiwei Sun,Qingqing Li,Dan Wu,Jianshe Wang,Yuexing Zhang,Chunbao Charles Xu,Renfeng Nie
Cost-effective and environmentally friendly production of biomass-derived amines under mild conditions is highly desirable but challenging. Herein, bifunctional Co@CoO x catalysts comprised of Co and CoO x were prepared by controllable precipitation-reduction and adopted for furfural (FAL) reductive amination with N 2 H 4 . The structure of Co species can be regulated gradually via tuning reduction temperature, resulting in a significant influence on reductive amination. The optimal CoO x -250 can achieve 96.4 % furfurylamine (FFA) yield at 60 °C, and even 95.8 % at 30 °C. The control experiments and DFT calculations suggest that the metal Co is responsible for H 2 dissociation and C N reduction, while the oxygen-vacant CoO x favors the hydrogen spillover and the C N bond activation, thus resulting in a collaborative effort for FAL reductive amination. The catalyst is stable and versatile for various aldehydes/ketones with amine yields around 95–99 %, showing great potential for industrial application.
研究领域:
催化化学
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生物质转化
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF CATALYSIS
·
2019
·
IF 7.723
Ziliang Yuan,Bing Liu,Peng Zhou,Zehui Zhang,Quan Chi
The use of non-noble metal catalysts with high activity is of great importance for organic transformations. Herein, nitrogen-doped carbon supported cobalt catalysts with high surface area up to 981.2 m 2 /g were prepared via the simple pyrolysis of cobalt coordinated organic polymers with silica as the hard template. The pyrolysis temperature showed a great effect on the structure and properties of the as-prepared catalysts. The Co@NC-800 catalyst with the pyrolysis temperature of 800 °C demonstrated a high activity for the selective reductive amination of carbonyl compounds to primary amines with ammonia and hydrogen. Structurally-diverse primary amines with yields in the range from 81.8% to 100% were attained under the optimal conditions. The Co@NC-800 catalyst could be reused without the loss of its activity. The Co@NC-800 catalyst demonstrated comparable activity as the reported heterogeneous noble metal catalysts.
研究领域:
化学
·
催化材料
✓ 已验证
DOI
高影响因子
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
·
2017
·
IF 2.843
Liang Jiang,Peng Zhou,Zehui Zhang,Shiwei Jin,Quan Chi
Developing new heterogeneous non-noble metal catalysts to replace noble-metal catalysts in organic transformations is of high importance in modern synthetic chemistry. Herein, nitrogen-doped carbon embedded Co catalysts (abbreviated as Co@CN-T-AT, in which T represents the pyrolysis temperature, AT represents the acid-leaching process) were prepared through the simple pyrolysis of graphene oxide-supported cobalt-based zeolitic imidazolate-frameworks, followed by the acid-leaching process. The Co@CN-600-AT catalyst demonstrated the highest catalytic activity among the synthesized Co catalyst toward the reductive amination of carbonyl compounds with nitro compounds by transfer hydrogenation with formic acid as the hydrogen donor, which integrated three consecutive steps into a one-pot reaction. By applying this catalyst, structurally diverse secondary amines were produced in good to excellent yields without the reduction of other functional groups. The transfer hydrogenation of the imines (C═N bonds) was the rate-determining step. Furthermore, the catalyst was highly stable and could be reused without decrease of the catalytic activity.
研究领域:
有机化学
·
催化化学
✓ 已验证
DOI
高影响因子
ChemCatChem
·
2022
·Vol. 14
·期 13
·e202200311
·
IF 5.497
Yuyao Zeng,Bowei Wang,Fanyong Yan,Wensheng Xu,Guoyi Bai,Yang Li,Xilong Yan,Ligong Chen
Graphical Through a convenient impregnation method, highly-distributed and stable Cu nanoparticles were dispersed on the boron doped γ-Al 2 O 3 support, which catalyzed continuous reductive amination of levulinic acid to corresponding N-substituted pyrrolidinones. The reductive amination of biomass-derived levulinic acid (LA) to value-added N-substituted pyrrolidinones with amine and molecular hydrogen over heterogeneous catalyst represents an atom-economical and scalable route. In this paper, a series of boron doped Cu/Al 2 O 3 catalysts via kneading and impregnation method are developed for the continuous reductive amination of LA. Compared with Cu/Al 2 O 3 , Cu 10 /AlB 3 O catalyst exhibits greatly improved catalytic performance for this reaction at low operation temperature. Structure-property correlation investigations were performed with diverse characterization methods, and the results revealed that the excellent catalytic performance of boron doped Cu/Al 2 O 3 catalysts was mainly attributed to the synergistic effect of its well-dispersed Cu nanoparticles, appropriate surface Cu electronic state and surface acidic sites nearby. Besides, Cu 10 /AlB 3 O shows great stability during the reaction over 200 h. This work provides a low-cost, efficient and environmentally friendly heterogeneous catalytic system for the continuous production of N-substituted pyrrolidinones.
研究领域:
催化化学
·
绿色化学
·
生物质转化
✓ 已验证
DOI
高影响因子
AICHE JOURNAL
·
2024
·
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
·
催化材料科学
✓ 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）