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NEW JOURNAL OF CHEMISTRY · 2024 ·Vol. 48 ·期 17 ·7639-7645 · IF 2.7

Facile preparation of Co/C catalysts encapsulated in carbon and selective hydrogenation in nitroaromatic hydrocarbons

Qianxi Wang,Yuyu Dai,Xueli Hong,Yunyang Hong,Rui Zhang,Xinhuan Yan

Non-precious metal catalysts play a significant role in the field of hydrogenation. This study synthesized Co-BTC from cobalt nitrate hexahydrate and 1,3,5-tricarboxylic acid benzene. By changing the calcination temperature of Co-BTC in an inert atmosphere, a series of novel non-precious metal Co/C microsphere catalysts were successfully prepared. The composition and structure of the Co/C-n catalysts were characterised by FESEM, TEM, XRD, IR, XPS and BET. These results confirm that 1,3,5-benzenetricarboxylic acid provides a rich carbon matrix and metallic Co nanoparticles are generated by self-reduction on the carbon matrix. The graphite matrix formed during the calcination process has a rich pore structure and good dispersion of active components on the catalyst surface, which is very favourable for the catalytic reaction. In the hydrogenation of o-chloronitrobenzene (o-CNB) to o-chloroaniline (o-CAN), the Co/C-500 catalyst showed the best catalytic performance. At 80 °C and 2 MPa H2 for 60 minutes, the conversion rate of o-CNB reached 99% and the selectivity reached 99%. When the reaction takes 5 minutes, the conversion rate reaches 10.5%, and the TOF value reaches 36.3 h−1. The Co/C-500 catalyst can be easily recycled and reused after reaction with the help of a magnetic field. Moreover, this catalyst is also effective in the selective hydrogenation of other nitroaromatic hydrocarbons containing halogen or unsaturated groups to corresponding aniline. This simple and direct synthesis method may lead to the economic production of large-scale Co/C catalysts, which is an attractive prospect for the industrial trial production of corresponding aniline.

研究领域: 催化化学 · 材料科学
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CHINESE JOURNAL OF CHEMICAL ENGINEERING · 2023 · IF 3.8

Metal-organic framework-derived Co-C catalyst for the selective hydrogenation of cinnamaldehyde to cinnamic alcohol

Fuping Tian,Xinchi Zhang,Yingying Sheng,Xiao Chen,Xiang Wang,Changhai Liang

The liquid phase selective hydrogenation of cinnamaldehyde has been investigated over the catalysts Co-C- T ( T  = 400–700 °C), which were derived from the carbonization of the MOF precursor Co-BTC at different temperatures in inert atmosphere. Co-C-500 exhibited a higher conversion (85.3%) than those carbonized at other temperatures, with 51.5% selectivity to cinnamyl alcohol, under a mild condition (90 °C, 4 h, 2 MPa H 2 , solvent: 9 ml ethanol and 1 ml water). The high catalytic activity of Co-C-500 can be ascribed to the large specific surface area of the catalyst, the uniformly dispersed metallic cobalt nanoparticles , and the more defect sites on the carbon support. Moreover, Co-C-500 showed excellent reusability in 5 successive cycles, mainly related to the uniformly dispersed cobalt nanoparticles embedded in carbon support.

研究领域: 化学工程 · 催化材料
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FUEL · 2016 · IF 3.611

Catalytic transfer hydrogenation/hydrogenolysis of 5-hydroxymethylfurfural to 2,5-dimethylfuran over Ni-Co/C catalyst

Panpan Yang,Qineng Xia,Xiaohui Liu,Yanqin Wang

Catalytic transfer hydrogenation/hydrogenolysis of 5-hydroxymethylfurfural (HMF) to valuable chemicals, 2,5-dimethylfuran (DMF), is realized over a carbon supported nickel-cobalt catalyst with formic acid as hydrogen donor. The highest DMF yield, 90.0%, is achieved at 210   °C under self-generated pressure. A reaction route involving 5-methylfurfural (5-MF) instead of 2,5-bis(hydromethyl)furan (BHMF) as an intermediate has been investigated, which is different from that when H 2 is used as hydrogen source in previous reports. The influence of the amount of formic acid is investigated on the conversion of HMF and the yield of DMF. The effectiveness of this strategy has also been used for the conversion of furfural to 2-methylfuran, another valuable chemicals.

CAS / MDL: 7440-44-0 64365-11-3
研究领域: 催化 · 化学工程 · 可再生能源
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Sustainable Energy & Fuels · 2022 ·Vol. 6 ·期 10 ·2602-2612 · IF 6.813

Efficient production of ethylene glycol from cellulose over Co@C catalysts combined with tungstic acid

Haosheng Xin,Haiyong Wang,Song Li,Xiaohong Hu,Chenguang Wang,Longlong Ma,Qiying Liu

Catalytic conversion of renewable cellulose, instead of fossil resources, to high-value ethylene glycol (EG) is of great significance for reducing considerable worries regarding the energy problem. However, the EG production from cellulose is dependent on Ni and Ru based catalysts. Herein, encapsulated Co@C catalyst was firstly applied for EG production from cellulose combined with tungstic acid (TA). The mixing of the two catalysts in different ratios was compared and well-controlled, and the highest 67.3% yield of EG can be achieved. TA is used mainly to promote both the cellulose hydrolysis and the retro-aldol reaction of glucose to glycolaldehyde. Co@C catalysts are responsible for the hydrogenation of glycolaldehyde to EG. Compared with traditional noble metals and composite catalysts, the inexpensive and easily synthesized Co@C catalysts could greatly reduce the cost of production of EG. The Co@C catalysts encapsulated with outside graphene layers can keep high stability for at least 6 runs.

研究领域: 化学工程 · 催化 · 可再生能源 · 材料科学
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Reaction Chemistry & Engineering · 2022 ·Vol. 8 ·期 1 ·64-76 · IF 5.2

Cellulose hydrogenolysis to alcohol and ketone products using Co@C catalysts in the phosphoric acid aqueous solution

Haosheng Xin,Haiyong Wang,Xiaohong Hu,Xiuzheng Zhuang,Long Yan,Chenguang Wang,Longlong Ma,Qiying Liu

Cellulose hydrolysis and further conversion to diketones and alcohols was performed with graphene layer encapsulated cobalt catalysts (Co@C) in phosphoric acid aqueous solution. A total of 60.5% yield of the products mainly including ethanol, 2,5-hexanedione (2,5-HD) and diols could be achieved in 0.06 M H3PO4 solution. A series of characterization methods such as XRD, XPS, TEM, TG-MS, BET, ICP, H2-TPD, NH3-TPD, and Raman were carried out to explore the catalyst formation mechanism and reaction activity. The results of the analysis indicated that the calcination temperature had a deep influence on the structure formation of the Co@C catalysts, thus leading to differences in the reaction activity. While the calcination temperature was determined at 700 °C, the Co@C catalyst meets with the requirements of optimal reaction activity, appropriate particle size, suitable surface area, and pore size. Besides, it was found that H3PO4 is not only favorable in cellulose hydrolysis but also cooperates with the Co@C catalyst in the hydrogenolysis of C–O bond and C–C bonds for the formation of products. This work provides a possible way for renewable cellulose conversion to diketone and alcohols over encapsulated non-noble metal catalyst combined with phosphoric acid aqueous solution.

研究领域: 化学工程 · 催化 · 可再生能源
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JOURNAL OF ELECTROANALYTICAL CHEMISTRY · 2023 · IF 4.5

Electrocatalysis Cα–Cβ and Cβ–O bond cleavage of lignin model compound using Ni-Co/C as catalyst electrode in deep eutectic solventx

Jifang Zhang,Chengcheng Suo,Jinde Sun,Wei Li,Sha Luo,Chunhui Ma,Shouxin Liu

In this study, C α –C β and C β –O bond cleavage of β-O-4 model compound (2-phenoxy-1-phenylethanol) were accomplished by electrocatalysis depolymerization process in deep eutectic solvents (DES) systems. We have investigated the application of Ni-Co/C catalysts on working electrode, which were synthesized with impregnation method. The Ni-Co/C with porous structure and abundant active sites, was shown an excellent electrocatalysis activity. Specific structure of Ni-Co/C could provide greatly efficient adsorption and desorption capacity to promote C α –C β and C β –O bond cleavage. Therefore, in this electrocatalysis depolymerization process, the highest depolymerization rate exceeded 90%. And the yields (and conversion rates) of products (including benzaldehyde, acetophenone, benzoic acid, phenol) can reach to 124.08 mg/g (25.05%), 23.29 mg/g (4.15%), 44.64 mg/g (7.83%), 30.3 mg/g (6.9%). Furthermore, the electrocatalysis mechanism of C α –C β and C β –O bond was investigated. The cleavage of C α –C β and C β –O bond was initiated by in situ generated free radicals through Ni-Co/C. Then, the cleavage of C α –C β and C β –O bond were occurred by ·OH and ·O 2 − . The results were showed that the C α –C β bond cleavage was more in line with the β-C elimination and free radical pathways, and C β –O bond cleavage was consistent with direct oxidative addition. The enhanced electrocatalytic efficiency of the low-cost Ni-Co/C electrocatalyst combined with its good chemical stability and selectivity, which offer a promising route for developing an efficient lignin depolymerization technology.

研究领域: 化学工程 · 材料科学 · 环境化学 · 电化学
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