Heterogeneous Bimetallic Cu–Ni Nanoparticle-Supported Catalysts in the Selective Oxidation of Benzyl Alcohol to Benzaldehyde
Three bimetallic Cu−Ni nanoparticle-supported catalysts were synthesized by co-immobilization followed by H<sub>2</sub> reduction. A chromium(III) terephthalate metal organic framework (MIL-101), titanium dioxide (TiO<sub>2</sub>), and carbon (C) with different prop...
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MDPI AG
2019-06-01
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| Series: | Catalysts |
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| Online Access: | https://www.mdpi.com/2073-4344/9/6/538 |
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doaj-09b557c8a3d7433daf537da746c94a342020-11-25T01:17:03ZengMDPI AGCatalysts2073-43442019-06-019653810.3390/catal9060538catal9060538Heterogeneous Bimetallic Cu–Ni Nanoparticle-Supported Catalysts in the Selective Oxidation of Benzyl Alcohol to BenzaldehydeLili Liu0Xiaojing Zhou1Li Liu2Shuai Jiang3Yingjie Li4Luxia Guo5Shijuan Yan6Xishi Tai7School of Chemistry & Chemical Engineering and Environmental Engineering, Weifang University, Weifang 261061, ChinaSchool of Chemistry & Chemical Engineering and Environmental Engineering, Weifang University, Weifang 261061, ChinaSchool of Chemistry & Chemical Engineering and Environmental Engineering, Weifang University, Weifang 261061, ChinaSchool of Chemistry & Chemical Engineering and Environmental Engineering, Weifang University, Weifang 261061, ChinaSchool of Chemistry & Chemical Engineering and Environmental Engineering, Weifang University, Weifang 261061, ChinaSchool of Chemistry & Chemical Engineering and Environmental Engineering, Weifang University, Weifang 261061, ChinaSchool of Chemistry & Chemical Engineering and Environmental Engineering, Weifang University, Weifang 261061, ChinaSchool of Chemistry & Chemical Engineering and Environmental Engineering, Weifang University, Weifang 261061, ChinaThree bimetallic Cu−Ni nanoparticle-supported catalysts were synthesized by co-immobilization followed by H<sub>2</sub> reduction. A chromium(III) terephthalate metal organic framework (MIL-101), titanium dioxide (TiO<sub>2</sub>), and carbon (C) with different properties (acidity and Brunauer−Emmett−Teller surface area) were selected as supports for studying the effect of the support nature on the catalytic activity and selectivity in the oxidation of benzyl alcohol. The physicochemical properties of the Cu−Ni-supported catalysts were characterized by XRD, NH<sub>3</sub>-TPD, nitrogen adsorption/desorption, TEM, EDS, XPS, and ICP-OES. Bimetallic Cu−Ni nanoparticles were highly dispersed on the support. The catalytic activities of CuNi/MIL-101, CuNi/TiO<sub>2</sub>, and CuNi/C were tested in the selective oxidation of benzyl alcohol to benzaldehyde in the presence of molecular oxygen under mild reaction conditions. The highest benzaldehyde yields were achieved with CuNi/TiO<sub>2</sub>, CuNi/MIL-101, and CuNi/C catalysts at 100 °C within 4 h under 5, 3, and 3 bar of O<sub>2</sub>, respectively. The bimetallic Cu−Ni-supported catalysts possessed two types of catalytic active sites: acid sites and bimetallic Cu−Ni nanoparticles. The CuNi/MIL-101 catalyst possessed a high number of acid sites and exhibited high yield during selective benzyl alcohol oxidation to benzaldehyde. Importantly, the catalysts exhibited a high functional group (electron-donating and electron-withdrawing groups) tolerance. Cu−Ni-supported catalysts with an Cu:Ni mole ratio of 1:1 exhibited the highest yield of 47% for the selective oxidation of benzyl alcohol to benzaldehyde. Reusability and leaching experiment results exhibited that CuNi/MIL-101 showed better stability than CuNi/TiO<sub>2</sub> and CuNi/C catalysts due to the large porous cavities of MIL-101 support; these cavities can be used to trap bimetallic Cu−Ni nanoparticles and inhibit nanoparticle leaching.https://www.mdpi.com/2073-4344/9/6/538Cu–Ni nanoparticlesMIL-101TiO<sub>2</sub>carbonbenzyl alcohol oxidation |
| collection |
DOAJ |
| language |
English |
| format |
Article |
| sources |
DOAJ |
| author |
Lili Liu Xiaojing Zhou Li Liu Shuai Jiang Yingjie Li Luxia Guo Shijuan Yan Xishi Tai |
| spellingShingle |
Lili Liu Xiaojing Zhou Li Liu Shuai Jiang Yingjie Li Luxia Guo Shijuan Yan Xishi Tai Heterogeneous Bimetallic Cu–Ni Nanoparticle-Supported Catalysts in the Selective Oxidation of Benzyl Alcohol to Benzaldehyde Catalysts Cu–Ni nanoparticles MIL-101 TiO<sub>2</sub> carbon benzyl alcohol oxidation |
| author_facet |
Lili Liu Xiaojing Zhou Li Liu Shuai Jiang Yingjie Li Luxia Guo Shijuan Yan Xishi Tai |
| author_sort |
Lili Liu |
| title |
Heterogeneous Bimetallic Cu–Ni Nanoparticle-Supported Catalysts in the Selective Oxidation of Benzyl Alcohol to Benzaldehyde |
| title_short |
Heterogeneous Bimetallic Cu–Ni Nanoparticle-Supported Catalysts in the Selective Oxidation of Benzyl Alcohol to Benzaldehyde |
| title_full |
Heterogeneous Bimetallic Cu–Ni Nanoparticle-Supported Catalysts in the Selective Oxidation of Benzyl Alcohol to Benzaldehyde |
| title_fullStr |
Heterogeneous Bimetallic Cu–Ni Nanoparticle-Supported Catalysts in the Selective Oxidation of Benzyl Alcohol to Benzaldehyde |
| title_full_unstemmed |
Heterogeneous Bimetallic Cu–Ni Nanoparticle-Supported Catalysts in the Selective Oxidation of Benzyl Alcohol to Benzaldehyde |
| title_sort |
heterogeneous bimetallic cu–ni nanoparticle-supported catalysts in the selective oxidation of benzyl alcohol to benzaldehyde |
| publisher |
MDPI AG |
| series |
Catalysts |
| issn |
2073-4344 |
| publishDate |
2019-06-01 |
| description |
Three bimetallic Cu−Ni nanoparticle-supported catalysts were synthesized by co-immobilization followed by H<sub>2</sub> reduction. A chromium(III) terephthalate metal organic framework (MIL-101), titanium dioxide (TiO<sub>2</sub>), and carbon (C) with different properties (acidity and Brunauer−Emmett−Teller surface area) were selected as supports for studying the effect of the support nature on the catalytic activity and selectivity in the oxidation of benzyl alcohol. The physicochemical properties of the Cu−Ni-supported catalysts were characterized by XRD, NH<sub>3</sub>-TPD, nitrogen adsorption/desorption, TEM, EDS, XPS, and ICP-OES. Bimetallic Cu−Ni nanoparticles were highly dispersed on the support. The catalytic activities of CuNi/MIL-101, CuNi/TiO<sub>2</sub>, and CuNi/C were tested in the selective oxidation of benzyl alcohol to benzaldehyde in the presence of molecular oxygen under mild reaction conditions. The highest benzaldehyde yields were achieved with CuNi/TiO<sub>2</sub>, CuNi/MIL-101, and CuNi/C catalysts at 100 °C within 4 h under 5, 3, and 3 bar of O<sub>2</sub>, respectively. The bimetallic Cu−Ni-supported catalysts possessed two types of catalytic active sites: acid sites and bimetallic Cu−Ni nanoparticles. The CuNi/MIL-101 catalyst possessed a high number of acid sites and exhibited high yield during selective benzyl alcohol oxidation to benzaldehyde. Importantly, the catalysts exhibited a high functional group (electron-donating and electron-withdrawing groups) tolerance. Cu−Ni-supported catalysts with an Cu:Ni mole ratio of 1:1 exhibited the highest yield of 47% for the selective oxidation of benzyl alcohol to benzaldehyde. Reusability and leaching experiment results exhibited that CuNi/MIL-101 showed better stability than CuNi/TiO<sub>2</sub> and CuNi/C catalysts due to the large porous cavities of MIL-101 support; these cavities can be used to trap bimetallic Cu−Ni nanoparticles and inhibit nanoparticle leaching. |
| topic |
Cu–Ni nanoparticles MIL-101 TiO<sub>2</sub> carbon benzyl alcohol oxidation |
| url |
https://www.mdpi.com/2073-4344/9/6/538 |
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