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NEW JOURNAL OF CHEMISTRY · 2023 ·Vol. 47 ·期 23 ·11318-11324 · IF 3.3

A general and selective Ni-catalysed reductive amination using hydrazine hydrate as facile hydrogen and nitrogen sources

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.

CAS / MDL: 1344-28-1 10026-12-7
研究领域: 有机化学 · 催化化学
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JOURNAL OF ORGANIC CHEMISTRY · 2022 · IF 4.198

Nickel-Catalyzed Decarbonylative Thioetherification of Carboxylic Acids with Thiols

Tianhao Xu,Xingyu Zhou,Xiong Xiao,Yan Yuan,Long Liu,Tianzeng Huang,Chunya Li,Zhi Tang,Tieqiao Chen

A nickel-catalyzed decarbonylative thioetherification of carboxylic acids with thiols was developed. Under the reaction conditions, benzoic acids, cinnamic acids, and benzyl carboxylic acids coupled with various thiols including both aromatic and aliphatic ones produce the corresponding thioethers in up to 99% yields. Moreover, this reaction was applicable to the modification of bioactive molecules such as 3-methylflavone-8-carboxylic acid, probenecid, and flufenamic acid, and the synthesis of acaricide chlorbenside. These results well demonstrated the potential synthetic value of this new reaction in organic synthesis.

研究领域: 有机化学 · 合成化学
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INTERNATIONAL JOURNAL OF HYDROGEN ENERGY · 2018 · IF 4.229

Hydrothermal gasification of microalgae over nickel catalysts for production of hydrogen-rich fuel gas: Effect of zeolite supports

Long-Fei Xie,Pei-Gao Duan,Jia-Li Jiao,Yu-Ping Xu

A series of Ni catalysts with different zeolites were prepared by wet impregnation method and used to catalyze supercritical water gasification (SCWG) of microalgae for production of hydrogen-rich fuel gas under conditions of 430 °C, 60 min, ρ H₂O  = 0.162 g/cm 3 , 2 g/g Ni/zeolites. Compared with noncatalytic SCWG, the presence of Ni/zeolite could increase the hydrogen gasification efficiency and carbon gasification efficiency by promoting water–gas shift and steam reforming reactions which are mainly affected by the amount of strong acid sites and Ni, respectively. The highest carbon gasification efficiency (CGE) and hydrogen gasification efficiency (HGE) of 23.61% and 23.55% were achieved with Ni/HY (Na 2 O, 0.8%). The gaseous produced mainly consisted of H 2 and CO 2 . The H 2 content in the gaseous products varied from 27.15 to 40.51% depending on the Ni/zeolites and increased with increasing the SiO 2 /Al 2 O 3 molar ratio of HZSM-5, which is 2.3–3.6 times higher than that of produced without catalyst. The H 2 yield varied between 2.57 and 3.61 mmol/g depending on the Ni/zeolites and increased from 2.19 to 5.61 mmol/g with increasing the SiO 2 /Al 2 O 3 molar ratio from 50:1 to 170:1, which is 3.6–7.8 times higher than that of produced without catalyst. Coke formation, surface area loss, and sintering of Ni could decrease the activity of the Ni/zeolites.

CAS / MDL: 13478-00-7
研究领域: 能源生物学 · 催化化学
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GREEN CHEMISTRY · 2021 ·Vol. 23 ·期 18 ·7065-7073 · IF 10.182

A nitrogen-doped carbon modified nickel catalyst for the hydrogenation of levulinic acid under mild conditions

Liang Jiang,Guangyue Xu,Yao Fu

The conversion of levulinic acid (LA) to γ-valerolactone (GVL) is one of the most important reactions from biomass-derived platform chemicals to value-added chemicals. In this work, nitrogen-doped carbon was introduced into a Ni/Al2O3 catalyst and was employed for the hydrogenation of LA to GVL with a full conversion and equivalent yield under mild conditions, at as low as ambient hydrogen pressure and 130 °C for 6 h. The doping of nitrogen introduced NiNx species and the imperfection of modified nitrogen-doped carbon were beneficial for the selective hydrogenation of carbonyl groups. This catalyst showed excellent activity and selectivity in various solvents and could be recycled for at least 6 runs with little deactivation. In addition to LA, various substrates with both carbonyl and carboxyl groups could also be selectively hydrogenated to the corresponding lactones. This study offers both theoretical foundation and practical instructions for the high-efficiency conversion of LA to GVL over non-noble metal catalysts under mild conditions, especially ambient H2 pressure.

研究领域: 催化化学 · 生物质能转化
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ChemCatChem · 2023 ·Vol. 15 ·期 8 ·e202300136 · IF 4.5

Nickel-Catalyzed Dry Reforming of Methane via Modulating the Zirconia Shapes

Ruifan Tan,Ping Wang,Luyao Guo,Zupeng Chen,Ronghe Lin,Xiaoling Mou,Yunjie Ding

Graphical The shape of zirconia hosts can tune the nature of active nickel species and the number of lattice oxygen species, which strongly influences the reaction and coking rates in the dry reforming of methane. The shape of the carriers has a profound impact on the catalytic performance of metal-supported catalysts. Herein, ZrO 2 of different shapes (nanorods-like, spherical or irregular nanoparticles, demoted as RZ, SPZ, and IPZ, respectively) are adopted to disperse Ni species to assess the shape effects on the catalytic performance in dry reforming of methane. To this end, the fresh and spent catalysts are thoroughly characterized by multiple techniques including N 2 sorption, powder X-ray diffraction, temperature-programmed reduction with H 2 , thermogravimetric analyses, transmission electron microscopy, Raman and X-ray photoelectron spectroscopies. It is revealed that the reducibility of NiO species follows the orders of Ni/RZ

CAS / MDL: 1314-23-4
研究领域: 催化化学 · 材料科学
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INTERNATIONAL JOURNAL OF HYDROGEN ENERGY · 2021 · IF 5.816

Catalyst support effect on ammonia decomposition over Ni/MgAl2O4 towards hydrogen production

Yu Qiu,Enkang Fu,Feng Gong,Rui Xiao

Ammonia is a prospective fuel for hydrogen storage and production, but its application is limited by the high cost of the catalysts (Ru, etc. ) to decompose NH 3 . Decomposing ammonia using non-precious Ni as catalysts can therefore improve its prospects to produce hydrogen. This work proposes several Ni/MgAl 2 O 4 with the support properties tuned and investigates the support effect on the catalytic performance. Ni/MgAl 2 O 4 -LDH shows high NH 3 conversion (∼88.7%) and H 2 production rate (∼1782.6 mmol g −1  h −1 ) at 30,000 L. kg −1  h −1 and 600 °C, which is 1.68 times as large as that of Ni/MgAl 2 O 4 -MM. The performance remains stable over 30 h. The characterizations manifest that the high specific surface area of Ni/MgAl 2 O 4 -LDH can introduce highly dispersed Ni on the surface. Kinetics analysis implies promoted NH 3 decomposition reaction and alleviated H 2 poisoning for Ni/MgAl 2 O 4 -LDH. A roughly linear relationship is obtained by fitting the curves of dispersed Ni on the surface vs the reaction orders regarding H 2 and NH 3 . This indicates that enhanced NH 3 decomposition performance can be ascribed to the strengthened NH 3 decomposition reaction and weakened H 2 poisoning by the highly dispersed Ni on the MgAl 2 O 4 -LDH surface. This work provides an opportunity to develop highly active and cost-effective catalysts to produce hydrogen via NH 3 decomposition.

研究领域: 化学工程 · 能源科学
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SYNTHESIS-STUTTGART · 2013 ·Vol. 45 ·期 16 ·2234-2240 · IF 2.5

Gram-Scale Ketone Synthesis by Direct Reductive Coupling of Alkyl Iodides with Acid Chlorides

Wenbin Lu,Zhuye Liang,Yuwei Zhang,Fan Wu,Qun Qian,Hegui Gong

Alkyl aryl ketones were prepared on a gram scale by the nickel-catalyzed reductive coupling of alkyl iodides with aroyl chlorides. When scaled up 30-fold, this reaction shows a comparable coupling efficiency to the previously reported reaction performed under small-scale conditions. The mild and convenient reaction conditions show excellent tolerance to a range of functional groups and provide the ketones in good to excellent yields.

研究领域: 有机化学 · 合成化学
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FUEL · 2021 · IF 6.609

Selective production of alkanes and fatty alcohol via hydrodeoxygenation of palmitic acid over red mud-supported nickel catalysts

Jinlei Chen,Dechao Wang,Fenqiang Luo,Xinyu Yang,Xingyong Li,Shuirong Li,Yueyuan Ye,Duo Wang,Zhifeng Zheng

Production of valuable chemicals and fuels from waste animal fat and vegetable oils can serve as alternatives to fossil energy. In this study, the selective production of alkanes and higher fatty alcohol via hydrodeoxygenation (HDO) of palmitic acid over red mud-supported nickel catalysts (Ni/RM) was reported. Meanwhile, the study has investigated the effect of Ni loading, reaction temperature, hydrogen pressure on the HDO of palmitic acid, analyzed the reusability of Ni/RM and explored the possible reaction mechanism. The results show that palmitic acid is completely converted over 7%Ni/RM. The selectivity of fatty alcohol and alkanes are 92.54% (260 °C) and 100% (300 °C), respectively. Ni/RM has shown the highest catalytic performance as compared to commercial Ni/SiO 2 and Ni/γ-Al 2 O 3 catalysts. The 7%Ni/RM also demonstrates stable catalytic performance after multiple times of reuse. Moreover, hexadecanol plays an important role in hydrodeoxygenation, decarbonylation, and decarboxylation routes.

研究领域: 化学工程 · 能源科学
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GREEN CHEMISTRY · 2019 ·Vol. 21 ·期 21 ·5828-5840 · IF 9.405

Nickel-catalyzed intelligent reductive transformation of the aldehyde group using hydrogen

Xinli Tong,Pengfei Guo,Shengyun Liao,Song Xue,Haigang Zhang

The selective transformation of the aldehyde group (–CHO) in multifunctional oxygenates is a key challenge in the development of sustainable biomass feedstock. Herein, a smart Ni-MFC catalyst was developed from a 2D Ni-based metal–organic framework (MOF), which efficiently promoted the transformation of –CHO in the presence of H2 to a methyl group (–CH3) via the reductive etherification and hydrogenolysis of the C–O ether bond in methanol. Moreover, the catalytic process could be controlled to directionally produce methyl ether (–CH2OR) using the reductive etherification protocol. For the catalytic reduction of vanillin, the Ni-MFC-700 catalyst guaranteed the full conversion of vanillin and 96.5% yield of the desired 2-methoxy-4-methylphenol (MMP), while the Ni-MFC-500 catalyst afforded about 82.7% yield of 4-(methoxymethyl)-2-methoxyphenol in methanol solvent. This is a novel and promising approach for the valorization of multifunctional oxygenates and biomass-derived platform compounds.

研究领域: 化学催化 · 生物质转化 · 有机合成
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FUEL PROCESSING TECHNOLOGY · 2020 · IF 4.982

Impact of pore structure on hydroxyapatite supported nickel catalysts (Ni/HAP) for dry reforming of methane

Bin Li,Xiaoqing Yuan,Baitao Li,Xiujun Wang

The hierarchical supports have motivated intensive research interests of chemists in the catalytic field because of the rational combination of mass transport property and large surface area. In this work, hydroxyapatite (HAP) supported nickel catalysts were prepared and employed to promote the dry reforming of methane (DRM). The proportion of mesopore/macropore in HAP was adjusted by the heating temperature (20, 50, 80, 120 °C) during the preparation process. The pore structure played an important role in regulating the physiochemical properties and thus affecting the catalytic performance in DRM. With increasing the proportion of mesopore on HAP, Ni preferentially dispersed on mesopore channel to form small-size particles. All catalysts possessed weak interaction between Ni nanoparticles and HAP; however, the interaction enhanced gradually with decreasing the Ni particles diameter. High proportion of macropore led to large-size Ni nanoparticle, while high proportion of small-size mesopore at 2–5 nm resulted in the complete blockage of these pore structures. These two boundary situations led to relatively weak interaction between nickel particles and the support, low metal dispersion and hence low activity as well as rapid deactivation in the DRM evaluation. Ni nanoparticles on HAP-80 and HAP-120 supports possessed relatively higher dispersion, which imparted these two catalysts with the function of strong anti-sintering ability and carbon resistance, thereby exhibiting better catalytic activity and stability in DRM evaluation. The deactivation of all catalysts during the reforming reaction was mainly ascribed to the sintering as well as encapsulation of Ni nanoparticles by graphitic carbon .

CAS / MDL: 7783-28-0 13477-34-4
研究领域: 催化化学 · 材料科学
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INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH · 2020 · IF 3.573

Green Synthesis of Highly Dispersed Ni/SiO2 Catalysts Using Natural Biomass of Sesbania Powder

Yong Bai,Xinran Qiu,Qian Zhang,Songbai Qiu,Yanlin Qin,Tiejun Wang

Recently, the ecofriendly techniques for production of nanohybrids using natural biomass have aroused great attention. This study reported a green and facile synthesis of highly dispersed supported metal catalysts using sesbania powder (SP) extracted from the natural sesbania plant. Well-dispersed Ni/SiO2 catalysts were effectively fabricated by an SP-assisted sol–gel method. The influencing factors including the additive amounts of SP, metal loadings, and metal types on the physicochemical properties of supported catalysts were primarily investigated. The testing results revealed that the additive SP significantly facilitated the uniform distribution of metal species during heat treatment, leading to the existence of ultrasmall nanoparticles (<4 nm) and high dispersion of supported metal. The as-prepared Ni/SiO2 catalysts were applied to the dry reforming of methane and demonstrated excellent catalytic performance due to the prevention of the agglomeration of Ni species and fabrication of Ni embedded in the silica framework through the introduction of SP.

研究领域: 催化化学 · 环境科学 · 材料科学
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INTERNATIONAL JOURNAL OF HYDROGEN ENERGY · 2025 · IF 8.3

Nickel phyllosilicate derived RuNi catalyst for ammonia decomposition to hydrogen

Qing Zhang,Boyun Gao,Fan Sun,Huijiang Huang,Yan Xu,Feng Gao,Yan Wang,Yujun Zhao

This study reports a stable catalyst for NH 3 decomposition to hydrogen. The precursor of SiO 2 @NP was prepared by hydrothermal method, and the hydrothermal treatment of spherical SiO 2 results in etching of SiO 2 and the formation of nickel phyllosilicate, which greatly increase specific surface area of the catalyst. Ru is loaded onto the SiO 2 @NP by incipient wetness impregnation, forming the catalyst 1Ru/SiO 2 @NP. At a gas hourly space velocity (GHSV) of 30,000 mL NH3 (g × h) −1 and 650 °C, the conversion of ammonia over 1Ru/SiO 2 @NP reaches 98%. Furthermore, the catalyst maintains excellent stability during a period of 210 h at 600 °C. To investigate the origination of activity and stability, various characterizations have been used. In its reduced form, Ni and Ru stay metallic, and Ru–Ni interactions are realized. Both high specific surface area and Ru–Ni interactions allow the generation of small metallic particles that are resistant to sintering during reaction process, thus improving the activity and stability of the catalyst. This study provides new insights and references for the preparation of efficient and stable catalysts for NH 3 decomposition.

CAS / MDL: 13478-00-7
研究领域: 催化化学 · 材料科学
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