{"title":"利用高熵合金(Co-Cu-Fe-Mn-Ni)和支持物(CeO2)的相互作用将二氧化碳转化为合成气","authors":"Bhanu P. Gangwar, Rahul Mitra, Arko Parui, Pooja Gakhad, Pradeep Kumar Yadav, Abhishek Kumar Singh, Chandra Sekhar Tiwary, Krishanu Biswas, Sudhanshu Sharma","doi":"10.1002/adsu.202400219","DOIUrl":null,"url":null,"abstract":"<p>Here metal support interaction (MSI) is demonstrated in a high entropy alloy (HEA: CoCuFeMnNi) supported CeO<sub>2</sub>. The HEA behaves as an active dry reforming catalyst only when it is supported over CeO<sub>2</sub> oxide, clearly demonstrating MSI. Based on spectroscopic and microscopic observations, it is envisaged that the substitutional effect is the one that causes the lattice oxygen activation, an important active species during DRM reaction. Transient studies are performed to understand the surface chemistry of the interaction between methane and CO<sub>2</sub> in the presence of a catalyst, which results in a methane decomposition first to generate hydrogen and carbon and followed by a CO<sub>2</sub> reaction to give CO using deposited carbon. The experimental observations are further proven by mechanistic study with DFT calculations which show a major contribution of H-assisted CO<sub>2</sub> dissociation and pre-H<sub>2</sub> releasing carbon depositing CH<sub>4</sub> dissociation and a minor contribution of pre-CO releasing H<sub>2</sub> formation. This MSI moves the d-band center of the Co atoms of CoCuFeMnNi/CeO<sub>2</sub> to the closest position of the Fermi level as compared to the isolated nanoparticles. This study can be taken as a proof of concept to demonstrate that MSI can be generated in the HEA/CeO<sub>2</sub> catalysts for a generic heterogeneous gas phase reaction.</p>","PeriodicalId":7294,"journal":{"name":"Advanced Sustainable Systems","volume":"8 11","pages":""},"PeriodicalIF":6.5000,"publicationDate":"2024-07-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Utilization of High Entropy Alloy (Co–Cu–Fe–Mn–Ni) and Support (CeO2) Interaction for CO2 Conversion into Syngas\",\"authors\":\"Bhanu P. Gangwar, Rahul Mitra, Arko Parui, Pooja Gakhad, Pradeep Kumar Yadav, Abhishek Kumar Singh, Chandra Sekhar Tiwary, Krishanu Biswas, Sudhanshu Sharma\",\"doi\":\"10.1002/adsu.202400219\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p>Here metal support interaction (MSI) is demonstrated in a high entropy alloy (HEA: CoCuFeMnNi) supported CeO<sub>2</sub>. The HEA behaves as an active dry reforming catalyst only when it is supported over CeO<sub>2</sub> oxide, clearly demonstrating MSI. Based on spectroscopic and microscopic observations, it is envisaged that the substitutional effect is the one that causes the lattice oxygen activation, an important active species during DRM reaction. Transient studies are performed to understand the surface chemistry of the interaction between methane and CO<sub>2</sub> in the presence of a catalyst, which results in a methane decomposition first to generate hydrogen and carbon and followed by a CO<sub>2</sub> reaction to give CO using deposited carbon. The experimental observations are further proven by mechanistic study with DFT calculations which show a major contribution of H-assisted CO<sub>2</sub> dissociation and pre-H<sub>2</sub> releasing carbon depositing CH<sub>4</sub> dissociation and a minor contribution of pre-CO releasing H<sub>2</sub> formation. This MSI moves the d-band center of the Co atoms of CoCuFeMnNi/CeO<sub>2</sub> to the closest position of the Fermi level as compared to the isolated nanoparticles. 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引用次数: 0
摘要
在此,我们展示了以 CeO2 为载体的高熵合金(HEA:CoCuFeMnNi)中的金属载体相互作用(MSI)。只有当 HEA 被 CeO2 氧化物支撑时,它才表现为活性干重整催化剂,这清楚地证明了 MSI。根据光谱和显微镜观察,我们认为置换效应是导致晶格氧活化的原因,而晶格氧是 DRM 反应过程中的重要活性物种。瞬态研究旨在了解甲烷和二氧化碳在催化剂作用下的表面化学反应,其结果是甲烷首先分解生成氢和碳,然后与二氧化碳反应,利用沉积碳生成一氧化碳。通过 DFT 计算进行的机理研究进一步证实了实验观察结果,该计算显示,H 辅助 CO2 解离和 H2 释放前碳沉积 CH4 解离起主要作用,CO 释放前 H2 形成起次要作用。与孤立的纳米粒子相比,这种 MSI 将 CoCuFeMnNi/CeO2 中 Co 原子的 d 波段中心移到了费米级的最近位置。这项研究可以作为概念验证,证明在 HEA/CeO2 催化剂中可以产生 MSI,用于一般的异相气相反应。
Utilization of High Entropy Alloy (Co–Cu–Fe–Mn–Ni) and Support (CeO2) Interaction for CO2 Conversion into Syngas
Here metal support interaction (MSI) is demonstrated in a high entropy alloy (HEA: CoCuFeMnNi) supported CeO2. The HEA behaves as an active dry reforming catalyst only when it is supported over CeO2 oxide, clearly demonstrating MSI. Based on spectroscopic and microscopic observations, it is envisaged that the substitutional effect is the one that causes the lattice oxygen activation, an important active species during DRM reaction. Transient studies are performed to understand the surface chemistry of the interaction between methane and CO2 in the presence of a catalyst, which results in a methane decomposition first to generate hydrogen and carbon and followed by a CO2 reaction to give CO using deposited carbon. The experimental observations are further proven by mechanistic study with DFT calculations which show a major contribution of H-assisted CO2 dissociation and pre-H2 releasing carbon depositing CH4 dissociation and a minor contribution of pre-CO releasing H2 formation. This MSI moves the d-band center of the Co atoms of CoCuFeMnNi/CeO2 to the closest position of the Fermi level as compared to the isolated nanoparticles. This study can be taken as a proof of concept to demonstrate that MSI can be generated in the HEA/CeO2 catalysts for a generic heterogeneous gas phase reaction.
期刊介绍:
Advanced Sustainable Systems, a part of the esteemed Advanced portfolio, serves as an interdisciplinary sustainability science journal. It focuses on impactful research in the advancement of sustainable, efficient, and less wasteful systems and technologies. Aligned with the UN's Sustainable Development Goals, the journal bridges knowledge gaps between fundamental research, implementation, and policy-making. Covering diverse topics such as climate change, food sustainability, environmental science, renewable energy, water, urban development, and socio-economic challenges, it contributes to the understanding and promotion of sustainable systems.