{"title":"Promotional role of methanol and CO2 in carbon dioxide-rich syngas hydrogenation over slurry reactor utilizing combustion induced Cu-based catalysts","authors":"Vaibhav Pandey , Priyanshu Pratap Singh , Kamal Kishore Pant , Sreedevi Upadhyayula , Siddhartha Sengupta","doi":"10.1016/j.mtsust.2025.101082","DOIUrl":null,"url":null,"abstract":"<div><div>Converting CO<sub>2</sub> to methanol directly remains a hurdle due to catalyst and thermodynamic limitations. This study proposes a solution: using Cu–MgO–CeO<sub>2</sub> (CuMgCe) catalysts (synthesized by solvent combustion) in slurry reactors for methanol formation through methanol-assisted CO<sub>2</sub>-rich syngas hydrogenation. The key innovation lies in the catalyst design by focusing on CO<sub>2</sub>-rich syngas mixtures, we establish a crucial link between catalyst structure and its activity (structure-activity relationship). Our CuMgCe catalyst achieves a space-time yield of 646 g<sub>MeOH</sub>/kg<sub>cat</sub>-h<sup>−1</sup>, exceeding lab-made industrial catalysts (608.5 g<sub>MeOH</sub>/kg<sub>cat</sub>-h<sup>−1</sup>). This yield is further boosted by 5% through an ingenious method - adding initial methanol, which promotes formate intermediates for enhanced productivity. In-depth analysis reveals CO<sub>2</sub> formation during CO-TPD-MS and CO-TPR-MS, generating highly active surface species (CO<sub>2</sub><sup>δ−</sup>) ideal for forming formate intermediates. In-situ DRIFTS confirms the dominance of this formate pathway on CuMgCe for selective methanol synthesis. A mechanistic study sheds light on the synergistic effect of MgO and CeO<sub>2</sub> in the lab-prepared CuMgCe catalyst. This synergy promotes methanol formation during CO<sub>2</sub>-cofed syngas conversion. This research paves the way for highly efficient and selective catalysts for CO<sub>2</sub> utilization in slurry reactor technology, offering a significant step towards cleaner fuel production.</div></div>","PeriodicalId":18322,"journal":{"name":"Materials Today Sustainability","volume":"29 ","pages":"Article 101082"},"PeriodicalIF":7.1000,"publicationDate":"2025-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Materials Today Sustainability","FirstCategoryId":"88","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S2589234725000119","RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"GREEN & SUSTAINABLE SCIENCE & TECHNOLOGY","Score":null,"Total":0}
引用次数: 0
Abstract
Converting CO2 to methanol directly remains a hurdle due to catalyst and thermodynamic limitations. This study proposes a solution: using Cu–MgO–CeO2 (CuMgCe) catalysts (synthesized by solvent combustion) in slurry reactors for methanol formation through methanol-assisted CO2-rich syngas hydrogenation. The key innovation lies in the catalyst design by focusing on CO2-rich syngas mixtures, we establish a crucial link between catalyst structure and its activity (structure-activity relationship). Our CuMgCe catalyst achieves a space-time yield of 646 gMeOH/kgcat-h−1, exceeding lab-made industrial catalysts (608.5 gMeOH/kgcat-h−1). This yield is further boosted by 5% through an ingenious method - adding initial methanol, which promotes formate intermediates for enhanced productivity. In-depth analysis reveals CO2 formation during CO-TPD-MS and CO-TPR-MS, generating highly active surface species (CO2δ−) ideal for forming formate intermediates. In-situ DRIFTS confirms the dominance of this formate pathway on CuMgCe for selective methanol synthesis. A mechanistic study sheds light on the synergistic effect of MgO and CeO2 in the lab-prepared CuMgCe catalyst. This synergy promotes methanol formation during CO2-cofed syngas conversion. This research paves the way for highly efficient and selective catalysts for CO2 utilization in slurry reactor technology, offering a significant step towards cleaner fuel production.
期刊介绍:
Materials Today Sustainability is a multi-disciplinary journal covering all aspects of sustainability through materials science.
With a rapidly increasing population with growing demands, materials science has emerged as a critical discipline toward protecting of the environment and ensuring the long term survival of future generations.