Density Functional Theory Study of Methanol Steam Reforming on Pt<sub>3</sub>Sn(111) and the Promotion Effect of a Surface Hydroxy Group
Methanol steam reforming (MSR) is studied on a Pt<sub>3</sub>Sn surface using the density functional theory (DFT). An MSR network is mapped out, including several reaction pathways. The main pathway proposed is CH<sub>3</sub>OH + OH → CH<sub>3</sub>O → CH<sub&g...
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MDPI AG
2024-02-01
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| Series: | Nanomaterials |
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| Online Access: | https://www.mdpi.com/2079-4991/14/3/318 |
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| author | Ping He Houyu Zhu Qianyao Sun Ming Li Dongyuan Liu Rui Li Xiaoqing Lu Wen Zhao Yuhua Chi Hao Ren Wenyue Guo |
| author_facet | Ping He Houyu Zhu Qianyao Sun Ming Li Dongyuan Liu Rui Li Xiaoqing Lu Wen Zhao Yuhua Chi Hao Ren Wenyue Guo |
| author_sort | Ping He |
| collection | DOAJ |
| description | Methanol steam reforming (MSR) is studied on a Pt<sub>3</sub>Sn surface using the density functional theory (DFT). An MSR network is mapped out, including several reaction pathways. The main pathway proposed is CH<sub>3</sub>OH + OH → CH<sub>3</sub>O → CH<sub>2</sub>O → CH<sub>2</sub>O + OH → CH<sub>2</sub>OOH → CHOOH → COOH → COOH + OH → CO<sub>2</sub> + H<sub>2</sub>O. The adsorption strengths of CH<sub>3</sub>OH, CH<sub>2</sub>O, CHOOH, H<sub>2</sub>O and CO<sub>2</sub> are relatively weak, while other intermediates are strongly adsorbed on Pt<sub>3</sub>Sn(111). H<sub>2</sub>O decomposition to OH is the rate-determining step on Pt<sub>3</sub>Sn(111). The promotion effect of the OH group is remarkable on the conversions of CH<sub>3</sub>OH, CH<sub>2</sub>O and <i>trans</i>-COOH. In particular, the activation barriers of the O–H bond cleavage (e.g., CH<sub>3</sub>OH → CH<sub>3</sub>O and <i>trans</i>-COOH → CO<sub>2</sub>) decrease substantially by ~1 eV because of the involvement of OH. Compared with the case of MSR on Pt(111), the generation of OH from H<sub>2</sub>O decomposition is more competitive on Pt<sub>3</sub>Sn(111), and the presence of abundant OH facilitates the combination of CO with OH to generate COOH, which accounts for the improved CO tolerance of the PtSn alloy over pure Pt. |
| first_indexed | 2024-03-08T03:51:25Z |
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| institution | Directory Open Access Journal |
| issn | 2079-4991 |
| language | English |
| last_indexed | 2024-03-08T03:51:25Z |
| publishDate | 2024-02-01 |
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| series | Nanomaterials |
| spelling | doaj.art-161b0772e12e4807b971a9ca3021c3d22024-02-09T15:19:34ZengMDPI AGNanomaterials2079-49912024-02-0114331810.3390/nano14030318Density Functional Theory Study of Methanol Steam Reforming on Pt<sub>3</sub>Sn(111) and the Promotion Effect of a Surface Hydroxy GroupPing He0Houyu Zhu1Qianyao Sun2Ming Li3Dongyuan Liu4Rui Li5Xiaoqing Lu6Wen Zhao7Yuhua Chi8Hao Ren9Wenyue Guo10College of Science, China University of Petroleum (East China), Qingdao 266580, ChinaSchool of Materials Science and Engineering, China University of Petroleum (East China), Qingdao 266580, ChinaSINOPEC Dalian Research Institute of Petroleum and Petrochemicals Co., Ltd., Dalian 116045, ChinaSINOPEC Dalian Research Institute of Petroleum and Petrochemicals Co., Ltd., Dalian 116045, ChinaSchool of Materials Science and Engineering, China University of Petroleum (East China), Qingdao 266580, ChinaSchool of Materials Science and Engineering, China University of Petroleum (East China), Qingdao 266580, ChinaSchool of Materials Science and Engineering, China University of Petroleum (East China), Qingdao 266580, ChinaSchool of Materials Science and Engineering, China University of Petroleum (East China), Qingdao 266580, ChinaSchool of Materials Science and Engineering, China University of Petroleum (East China), Qingdao 266580, ChinaSchool of Materials Science and Engineering, China University of Petroleum (East China), Qingdao 266580, ChinaCollege of Science, China University of Petroleum (East China), Qingdao 266580, ChinaMethanol steam reforming (MSR) is studied on a Pt<sub>3</sub>Sn surface using the density functional theory (DFT). An MSR network is mapped out, including several reaction pathways. The main pathway proposed is CH<sub>3</sub>OH + OH → CH<sub>3</sub>O → CH<sub>2</sub>O → CH<sub>2</sub>O + OH → CH<sub>2</sub>OOH → CHOOH → COOH → COOH + OH → CO<sub>2</sub> + H<sub>2</sub>O. The adsorption strengths of CH<sub>3</sub>OH, CH<sub>2</sub>O, CHOOH, H<sub>2</sub>O and CO<sub>2</sub> are relatively weak, while other intermediates are strongly adsorbed on Pt<sub>3</sub>Sn(111). H<sub>2</sub>O decomposition to OH is the rate-determining step on Pt<sub>3</sub>Sn(111). The promotion effect of the OH group is remarkable on the conversions of CH<sub>3</sub>OH, CH<sub>2</sub>O and <i>trans</i>-COOH. In particular, the activation barriers of the O–H bond cleavage (e.g., CH<sub>3</sub>OH → CH<sub>3</sub>O and <i>trans</i>-COOH → CO<sub>2</sub>) decrease substantially by ~1 eV because of the involvement of OH. Compared with the case of MSR on Pt(111), the generation of OH from H<sub>2</sub>O decomposition is more competitive on Pt<sub>3</sub>Sn(111), and the presence of abundant OH facilitates the combination of CO with OH to generate COOH, which accounts for the improved CO tolerance of the PtSn alloy over pure Pt.https://www.mdpi.com/2079-4991/14/3/318methanolsteam reformingPtSn alloyhydroxy groupdensity functional theory |
| spellingShingle | Ping He Houyu Zhu Qianyao Sun Ming Li Dongyuan Liu Rui Li Xiaoqing Lu Wen Zhao Yuhua Chi Hao Ren Wenyue Guo Density Functional Theory Study of Methanol Steam Reforming on Pt<sub>3</sub>Sn(111) and the Promotion Effect of a Surface Hydroxy Group Nanomaterials methanol steam reforming PtSn alloy hydroxy group density functional theory |
| title | Density Functional Theory Study of Methanol Steam Reforming on Pt<sub>3</sub>Sn(111) and the Promotion Effect of a Surface Hydroxy Group |
| title_full | Density Functional Theory Study of Methanol Steam Reforming on Pt<sub>3</sub>Sn(111) and the Promotion Effect of a Surface Hydroxy Group |
| title_fullStr | Density Functional Theory Study of Methanol Steam Reforming on Pt<sub>3</sub>Sn(111) and the Promotion Effect of a Surface Hydroxy Group |
| title_full_unstemmed | Density Functional Theory Study of Methanol Steam Reforming on Pt<sub>3</sub>Sn(111) and the Promotion Effect of a Surface Hydroxy Group |
| title_short | Density Functional Theory Study of Methanol Steam Reforming on Pt<sub>3</sub>Sn(111) and the Promotion Effect of a Surface Hydroxy Group |
| title_sort | density functional theory study of methanol steam reforming on pt sub 3 sub sn 111 and the promotion effect of a surface hydroxy group |
| topic | methanol steam reforming PtSn alloy hydroxy group density functional theory |
| url | https://www.mdpi.com/2079-4991/14/3/318 |
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