{"title":"甲醇蒸汽转化过程中锆改性铜基催化剂的结构-活性关系","authors":"Qing Zhang, Didi Li, Zhaocong Jiang, Haoyuan Gu, Mengyuan Zhu, Shiqing Jin, Minghui Zhu","doi":"10.1016/j.jcat.2024.115584","DOIUrl":null,"url":null,"abstract":"<div><p>Acknowledged as an ideal method for <em>in situ</em> hydrogen generation, methanol steam reforming (MSR) requires high-performance catalysts to enhance production efficiency. Herein, we prepared a series of Zr-modified Cu-based catalysts by a coprecipitation method and conducted a systematic analysis of the impacts of structural variations on MSR performance. Extensive characterization reveals a strong dependence of the catalyst’s surface structure on Zr content. Introducing a moderate amount of Zr to the Cu/ZnO catalysts forms ZnZrO<sub>x</sub> solid solution and increases Cu dispersion, forming more Cu-ZnZrO<sub>x</sub> and Cu-ZnO interfacial sites with higher H<sub>2</sub> production rate. Further increases in Zr content enlarge Cu nanoparticles and multiply Cu-ZrO<sub>2</sub> interfacial sites. The optimal catalyst with a Zn/Zr molar ratio of 5, with the richest Cu-ZnO/Cu-ZnZrO<sub>x</sub> interfacial sites, achieves the highest H<sub>2</sub> production rate of 117.4 <span><math><mrow><msub><mtext>mmol</mtext><msub><mtext>H</mtext><mtext>2</mtext></msub></msub><mspace></mspace><msubsup><mtext>g</mtext><mrow><mtext>cat</mtext></mrow><mtext>-1</mtext></msubsup><mspace></mspace><msup><mrow><mtext>h</mtext></mrow><mtext>-1</mtext></msup></mrow></math></span> at 200 °C, which is 1.3 times and 6.8 times higher than those of Cu/ZnO and Cu/ZrO<sub>2</sub>, respectively.</p></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":null,"pages":null},"PeriodicalIF":6.5000,"publicationDate":"2024-06-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Structure-activity relationships of zirconium-modified copper-based catalysts during methanol steam reforming\",\"authors\":\"Qing Zhang, Didi Li, Zhaocong Jiang, Haoyuan Gu, Mengyuan Zhu, Shiqing Jin, Minghui Zhu\",\"doi\":\"10.1016/j.jcat.2024.115584\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p>Acknowledged as an ideal method for <em>in situ</em> hydrogen generation, methanol steam reforming (MSR) requires high-performance catalysts to enhance production efficiency. Herein, we prepared a series of Zr-modified Cu-based catalysts by a coprecipitation method and conducted a systematic analysis of the impacts of structural variations on MSR performance. Extensive characterization reveals a strong dependence of the catalyst’s surface structure on Zr content. Introducing a moderate amount of Zr to the Cu/ZnO catalysts forms ZnZrO<sub>x</sub> solid solution and increases Cu dispersion, forming more Cu-ZnZrO<sub>x</sub> and Cu-ZnO interfacial sites with higher H<sub>2</sub> production rate. Further increases in Zr content enlarge Cu nanoparticles and multiply Cu-ZrO<sub>2</sub> interfacial sites. The optimal catalyst with a Zn/Zr molar ratio of 5, with the richest Cu-ZnO/Cu-ZnZrO<sub>x</sub> interfacial sites, achieves the highest H<sub>2</sub> production rate of 117.4 <span><math><mrow><msub><mtext>mmol</mtext><msub><mtext>H</mtext><mtext>2</mtext></msub></msub><mspace></mspace><msubsup><mtext>g</mtext><mrow><mtext>cat</mtext></mrow><mtext>-1</mtext></msubsup><mspace></mspace><msup><mrow><mtext>h</mtext></mrow><mtext>-1</mtext></msup></mrow></math></span> at 200 °C, which is 1.3 times and 6.8 times higher than those of Cu/ZnO and Cu/ZrO<sub>2</sub>, respectively.</p></div>\",\"PeriodicalId\":346,\"journal\":{\"name\":\"Journal of Catalysis\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":6.5000,\"publicationDate\":\"2024-06-02\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Journal of Catalysis\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S0021951724002975\",\"RegionNum\":1,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Catalysis","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0021951724002975","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
Structure-activity relationships of zirconium-modified copper-based catalysts during methanol steam reforming
Acknowledged as an ideal method for in situ hydrogen generation, methanol steam reforming (MSR) requires high-performance catalysts to enhance production efficiency. Herein, we prepared a series of Zr-modified Cu-based catalysts by a coprecipitation method and conducted a systematic analysis of the impacts of structural variations on MSR performance. Extensive characterization reveals a strong dependence of the catalyst’s surface structure on Zr content. Introducing a moderate amount of Zr to the Cu/ZnO catalysts forms ZnZrOx solid solution and increases Cu dispersion, forming more Cu-ZnZrOx and Cu-ZnO interfacial sites with higher H2 production rate. Further increases in Zr content enlarge Cu nanoparticles and multiply Cu-ZrO2 interfacial sites. The optimal catalyst with a Zn/Zr molar ratio of 5, with the richest Cu-ZnO/Cu-ZnZrOx interfacial sites, achieves the highest H2 production rate of 117.4 at 200 °C, which is 1.3 times and 6.8 times higher than those of Cu/ZnO and Cu/ZrO2, respectively.
期刊介绍:
The Journal of Catalysis publishes scholarly articles on both heterogeneous and homogeneous catalysis, covering a wide range of chemical transformations. These include various types of catalysis, such as those mediated by photons, plasmons, and electrons. The focus of the studies is to understand the relationship between catalytic function and the underlying chemical properties of surfaces and metal complexes.
The articles in the journal offer innovative concepts and explore the synthesis and kinetics of inorganic solids and homogeneous complexes. Furthermore, they discuss spectroscopic techniques for characterizing catalysts, investigate the interaction of probes and reacting species with catalysts, and employ theoretical methods.
The research presented in the journal should have direct relevance to the field of catalytic processes, addressing either fundamental aspects or applications of catalysis.