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Frontiers of Chemical Science and Engineering

ISSN 2095-0179

ISSN 2095-0187(Online)

CN 11-5981/TQ

邮发代号 80-969

2019 Impact Factor: 3.552

Frontiers of Chemical Science and Engineering  2021, Vol. 15 Issue (3): 666-678   https://doi.org/10.1007/s11705-020-1982-1
  本期目录
Enhanced synergy between Cu0 and Cu+ on nickel doped copper catalyst for gaseous acetic acid hydrogenation
Jingwei Zhang, Lingxin Kong, Yao Chen, Huijiang Huang, Huanhuan Zhang, Yaqi Yao, Yuxi Xu, Yan Xu, Shengping Wang, Xinbin Ma, Yujun Zhao()
Key Laboratory for Green Chemical Technology of Ministry of Education, Collaborative Innovation Center of Chemical Science and Engineering, School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072, China
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Abstract

As the substitution of common noble catalysts in the hydrogenation of carboxylic acid, a highly effective Cu-Ni/SiO2 catalyst was prepared by a novel stepwise ammonia evaporation method. Its performance in the gas-phase hydrogenation of acetic acid was further examined. With the introduction of Ni dopant, more stable Cuδ+ sites, which can adsorb more acetic acid, were formed due to the electron transfer from Cu to Ni. This makes more Cu0 sites available for hydrogen adsorption, which was suggested as the rate-determining step in acetic acid hydrogenation. A conversion of 99.6% was successfully achieved on this new Cu/SiO2-0.5Ni catalyst, accompanied by the ethanol selectivity of 90%. The incorporation of nickel between copper nanoparticles enhances the synergistic effect between Cu0 and Cu+. It also helps mitigate the aggregation of copper nanoparticles due to the Ostwald ripening effect induced by acetic acid and enhance the stability of copper catalyst in the conversion of carboxylic acid.

Key wordscarboxylic acid    hydrogenation    copper    nickel    stability
收稿日期: 2020-04-15      出版日期: 2021-05-10
Corresponding Author(s): Yujun Zhao   
 引用本文:   
. [J]. Frontiers of Chemical Science and Engineering, 2021, 15(3): 666-678.
Jingwei Zhang, Lingxin Kong, Yao Chen, Huijiang Huang, Huanhuan Zhang, Yaqi Yao, Yuxi Xu, Yan Xu, Shengping Wang, Xinbin Ma, Yujun Zhao. Enhanced synergy between Cu0 and Cu+ on nickel doped copper catalyst for gaseous acetic acid hydrogenation. Front. Chem. Sci. Eng., 2021, 15(3): 666-678.
 链接本文:  
https://academic.hep.com.cn/fcse/CN/10.1007/s11705-020-1982-1
https://academic.hep.com.cn/fcse/CN/Y2021/V15/I3/666
Catalysts Metal loading a)/wt-% SBETb)/(m2·g?1) Dpore/nm Vpore/(m3·g?1) dMc)/nm
Cu Ni
Cu/SiO2-AE Reduced 21.5 0 355 8.32 0.86 -
Used 21.5 0 302 10.68 0.85 10.6
Cu/SiO2-0.3Ni Reduced 21.4 0.2 368 8.44 0.92 -
Used 19.4 0.2 313 10.68 0.88 9.5
Cu/SiO2-0.5Ni Reduced 21.4 0.4 418 8.37 0.98 -
Used 20.1 0.3 366 10.42 1.03 7.9
Cu/SiO2-1Ni Reduced 22.4 0.8 419 8.29 0.99 -
Used 22.1 0.7 343 10.37 0.79 9.5
Cu/SiO2-3Ni Reduced 21.9 2.4 419 7.69 0.92 -
Used 21.5 2.3 323 10.05 0.71 11.2
Tab.1  
Fig.1  
Fig.2  
Fig.3  
Fig.4  
Fig.5  
Catalyst Kinetics energy/eV XCu0a) /% XCud+a)/% XCux+a) /% SCu0b)
/(m2·gcat?1)
SCux+c)
/(m2·gcat?1)
Cu0 Cu+ Cud+
Cu/SiO2-AE 916.0 913.5 ? 89.7 ? 10.3 21.7 2.6
Cu/SiO2-0.3 Ni 916.0 913.5 910.9 84.2 6.6 15.8 23.9 4.5
Cu/SiO2-0.5 Ni 915.9 913.4 909.9 72.6 9.6 27.4 27.8 10.5
Cu/SiO2-1.5 Ni 915.9 913.5 909.0 75.6 13.2 24.3 24.4 7.9
Tab.2  
Fig.6  
Catalysts Conv./% SEtOH/% SAcOEt/% SAlde/%
Cu/SiO2-AE 62.4 64.0 34.9 1.1
Cu/SiO2-0.3 Ni 73.7 57.6 41.2 1.0
Cu/SiO2-0.5 Ni 81.2 57.8 40.6 1.1
Cu/SiO2-1.5 Ni 75.3 57.9 40.7 1.0
Cu/SiO2-3 Ni 55.6 62.2 40.9 1.2
Tab.3  
Fig.7  
Fig.8  
Treatments XRD TEM
dCu/nm dCu2O/nm dparticle/nm
Cu-SiO2-AE 0.5Ni Cu-SiO2-AE 0.5Ni Cu-SiO2-AE 0.5Ni
Reduced ND ND ND ND 3.7 4.0
H2O+ N2 9.6 6.0 11.9 3.6 10.8 8.2
HAC+ N2 26.0 22.8 23 ND 24.5 21.8
HAC+ H2O+ N2 28.9 24.8 24.7 ND 31.8 26.2
H2O+ H2 4.7 4.5 ND ND 5.4 5.2
Tab.4  
Fig.9  
Fig.10  
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