NEW JOURNAL OF CHEMISTRY
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2023
·Vol. 47
·期 23
·11318-11324
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IF 3.3
Jiazheng Zhu,Chengjie Duan,Sen Ye,Qizhong Zhang,Kun Li,Guangke He,Xiang Liu,Zhiguo Zhang
Exploring synthetic methods and catalysts that are easy to handle, highly active, and low-cost for producing industrially important chemicals is a long-term goal in both science and industry. Herein, we present a general and facile Ni-catalyzed reductive amination of aldehydes/ketones methodology using hydrazine as both nitrogen and hydrogen sources, instead of the traditionally used hydrogen gas and ammonia. The mesostructured alumina-supported Ni catalyst with a relatively high ratio of Ni0 and small-sized Ni nanoparticles plays a critical role in this transformation, resulting in 55 aldehydes/ketones successfully converting to their corresponding primary amines with 61–99% yields. This work outlines a low-cost yet robust catalytic methodology for the facile and general synthesis of primary amines for practical laboratory and industrial application.
研究领域:
有机化学
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催化化学
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产品关联
DOI
高影响因子
ChemCatChem
·
2019
·Vol. 11
·期 22
·5562-5569
·
IF 4.495
Kuo Zhou,Bixian Chen,Xiaoting Zhou,Shimin Kang,Yongjun Xu,Jinjia Wei
Graphical Rane drops keep fallin’ : Cobalt proved to be the most efficient metal for furfurylamine synthesis by reductive amination of furfural with NH 3 and H 2 . Effect of metal nature on reductive amination was investigated with biomass-based furfural as a typical substrate. Among the tested heterogeneous metal catalysts, cobalt proved to be the most effective metal for the synthesis of the corresponding primary amine. Under a relatively mild reaction condition, 98.9 % yield of furfurylamine was obtained over Raney Co and it can be reused more than eight times without a significant decrease in the catalytic performance. By extensively studying the catalytic pathways and reaction mechanism, it is found that the selectivity to primary amine and secondary amine was governed by the relative rate of hydrogenolysis and hydrogenation of the Schiff base intermediate. The superiority of Raney Co in furfurylamine synthesis can be ascribed to its high efficiency on hydrogenolysis of the Schiff base intermediate and its low performance in the hydrogenation of the Schiff base, carbonyl group and furan ring. Furthermore, ammonia greatly promoted the catalytic hydrogenolysis of the Schiff base intermediate over Raney Co without clear deactivation of the metal active sites.
研究领域:
化学工程
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生物质转化
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催化科学
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DOI
高影响因子
NEW JOURNAL OF CHEMISTRY
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2025
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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
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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
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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
Advanced Sustainable Systems
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2022
·Vol. 6
·期 3
·2100321
·
IF 6.737
Pei-dong Wu,Hu Li,Zhen Fang
Bimetallic synergy and carbon–nitrogen doping can contribute to enhanced catalytic activity due to the strong electronic state and unique geometrical structure. In this work, a series of biomass-derived Co-M bimetallic C N doped catalysts (Co-M@Chitosan-X; M = Zr, Ni, Fe, Cu, In; X denotes the molar percentage of M) are prepared via simple oil bath reflow and annealing. The Co-Zr@Chitosan-X catalysts are determined to contain alloys (Co-Zr), metal-carbon bonds (Co-C, Zr-C), metal-nitrogen bonds (Co-N, Zr-N), and metal oxides (Co 3 O 4 , ZrO 2 ) through a series of characterizations, in which graphite-coated alloys and metal oxides are found to be the catalytically active species. The doping of the second metal results in a significant enhancement for the number of active sites in the catalyst, and the d-band center is shifted toward a deviation from the Fermi energy level. Among the tested catalysts, Co-Zr@Chitosan-20 exhibits superior catalytic activity for the reductive amination of biobased levulinic acid to 5-methyl-2-pyrrolidone in 99.3% selectivity and 92.8% yield. This non-noble metal bimetallic synergistic catalytic protocol opens an avenue for efficiently producing biomass-derived nitrogenous chemicals.
研究领域:
化学工程
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催化科学
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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
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2024
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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
✓ 已验证
产品关联
DOI
高影响因子
CHEMICAL RESEARCH IN CHINESE UNIVERSITIES
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2019
·Vol. 35
·期 3
·457-462
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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
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2017
·Vol. 7
·期 18
·4129-4135
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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
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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
Green Energy & Environment
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2022
·
IF 12.781
Xiuzheng Zhuang,Jianguo Liu,Longlong Ma
Since the utilization of abundant biomass to develop advanced materials has become an utmost priority in recent years, we developed two sustainable routes (i.e., the impregnation method and the one-pot synthesis) to prepare the hydrochar-supported catalysts and tested its catalytic performance on the reductive amination. Several techniques, such as TEM, XRD and XPS, were adopted to characterize the structural and catalytic features of samples. Results indicated that the impregnation method favors the formation of outer-sphere surface complexes with porous structure as well as well-distributed metallic nanoparticles, while the one-pot synthesis tends to form the inner-sphere surface complexes with relatively smooth appearance and amorphous metals. This difference explains the better activity of catalysts prepared by the impregnation method which can selectively convert benzaldehyde to benzylamine with an excellent yield of 93.7% under the optimal reaction conditions; in contrast, the catalyst prepared by the one-pot synthesis only exhibits a low selectivity near to zero. Furthermore, the gram-scale test catalyzed by the same catalysts exhibits a similar yield of benzylamine in comparison to its smaller scale, which is comparable to the previously reported heterogeneous noble-based catalysts. More surprisingly, the prepared catalysts can be expediently recycled by a magnetic bar and remain the satisfying catalytic activity after reusing up to five times. In conclusion, these developed catalysts enable the synthesis of functional amines with excellent selectivity and carbon balance, proving cost-effective and sustainable access to the wide application of reductive amination.
研究领域:
催化化学
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生物质利用
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材料科学
✓ 已验证
产品关联
DOI
高影响因子
Analytical Methods
·
2023
·Vol. 15
·期 29
·3586-3591
·
IF 3.1
Li Zhang,Jiyan Huang,Mixue Chen,Hongmei Huang,Yi Xiao,Ronghua Yang,Youyu Zhang,Xiaoxiao He,Kemin Wang
Amphiphilic aggregation-induced emission (AIE) molecules show superior potential for fabricating novel ultrasmall nanoprobes. Here, an anionic dipyridyl tetraphenylethene (TPE) derivative is rationally designed and a super-small self-assembled AIEgen nanoprobe (TPE-2Py-SO3NaNPs, ca. 2.48 nm) is thus conveniently constructed for the supersensitive detection of protamine and trypsin. In HEPES/DMSO solution (8 : 2, v/v, pH = 7.4), negatively charged TPE-2Py-SO3NaNPs exhibited an AIE effect in the presence of positively charged protamine, presenting a fluorescence enhancement at 498 nm together with a large Stokes shift of 150 nm and a low detection limit of 8.0 ng mL−1. In addition, the in situ formed TPE-2Py-SO3Na/protamine nanocomposite can be dissociated by trypsin due to the highly selective degradation of protamine via enzymatic hydrolysis, achieving a detection limit for trypsin as low as 5.0 ng mL−1.
研究领域:
生物化学
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分析化学
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医学检测
✓ 已验证
DOI
PubMed
高影响因子
危险品化学品经营许可证（带存储）