Laura G. Graversen, Mikkel Juelsholt, Olivia Aalling-Frederiksen, Ulrik Friis-Jensen, Rebecca K. Pittkowski, Maria S. Thomsen, Andrea Kirsch, Nicolas P. L. Magnard and Kirsten M. Ø. Jensen
{"title":"溶剂热合成中MoO2纳米颗粒在溶剂引导下生长和结构的机理研究","authors":"Laura G. Graversen, Mikkel Juelsholt, Olivia Aalling-Frederiksen, Ulrik Friis-Jensen, Rebecca K. Pittkowski, Maria S. Thomsen, Andrea Kirsch, Nicolas P. L. Magnard and Kirsten M. Ø. Jensen","doi":"10.1039/D5SC03247D","DOIUrl":null,"url":null,"abstract":"<p >Understanding the processes involved in the nucleation and growth of nanoparticles is essential for the development of tailored nanomaterials. Here, we investigate the solvent effects on the atomic structure and size of nanocrystalline MoO<small><sub>2</sub></small> obtained from a solvothermal synthesis and deduce their reaction pathways. Detailed pair distribution function (PDF) analysis reveals the formation of distinct MoO<small><sub>2</sub></small> structures, depending on the alcohol used. We show that the atomic structure and crystallite size of the formed materials are directly related to their formation pathway. <em>In situ</em> PDF analysis together with X-ray absorption spectroscopy of the reaction between MoCl<small><sub>5</sub></small> and an alcohol solvent allows us to see that larger nanoparticles (<em>ca.</em> 30 nm) with the conventional MoO<small><sub>2</sub></small> distorted rutile structure form when the initial Cl/O-ligand exchange is fast, but the subsequent condensation and crystallization are slowed down in the synthesis process. On the other hand, when the Cl/O exchange is slowed down, a [M<small><sup>IV</sup></small>Cl<small><sub><em>x</em></sub></small>O<small><sub><em>y</em></sub></small>]-complex is formed, and we obtain very small nanoparticles (2–3 nm) with the MoO<small><sub>2</sub></small> high-pressure polymorph structure. The study shows how the chemistry of the reaction solvent affects the mechanistic pathways, and consequently the intermediate formed just prior to crystallization, which is directly applicable to the process of obtaining specific nanocrystalline materials.</p>","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":" 31","pages":" 14350-14365"},"PeriodicalIF":7.4000,"publicationDate":"2025-06-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/sc/d5sc03247d?page=search","citationCount":"0","resultStr":"{\"title\":\"Mechanistic insights into solvent-guided growth and structure of MoO2 nanoparticles in solvothermal synthesis†\",\"authors\":\"Laura G. Graversen, Mikkel Juelsholt, Olivia Aalling-Frederiksen, Ulrik Friis-Jensen, Rebecca K. Pittkowski, Maria S. Thomsen, Andrea Kirsch, Nicolas P. L. Magnard and Kirsten M. Ø. Jensen\",\"doi\":\"10.1039/D5SC03247D\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >Understanding the processes involved in the nucleation and growth of nanoparticles is essential for the development of tailored nanomaterials. Here, we investigate the solvent effects on the atomic structure and size of nanocrystalline MoO<small><sub>2</sub></small> obtained from a solvothermal synthesis and deduce their reaction pathways. Detailed pair distribution function (PDF) analysis reveals the formation of distinct MoO<small><sub>2</sub></small> structures, depending on the alcohol used. We show that the atomic structure and crystallite size of the formed materials are directly related to their formation pathway. <em>In situ</em> PDF analysis together with X-ray absorption spectroscopy of the reaction between MoCl<small><sub>5</sub></small> and an alcohol solvent allows us to see that larger nanoparticles (<em>ca.</em> 30 nm) with the conventional MoO<small><sub>2</sub></small> distorted rutile structure form when the initial Cl/O-ligand exchange is fast, but the subsequent condensation and crystallization are slowed down in the synthesis process. On the other hand, when the Cl/O exchange is slowed down, a [M<small><sup>IV</sup></small>Cl<small><sub><em>x</em></sub></small>O<small><sub><em>y</em></sub></small>]-complex is formed, and we obtain very small nanoparticles (2–3 nm) with the MoO<small><sub>2</sub></small> high-pressure polymorph structure. The study shows how the chemistry of the reaction solvent affects the mechanistic pathways, and consequently the intermediate formed just prior to crystallization, which is directly applicable to the process of obtaining specific nanocrystalline materials.</p>\",\"PeriodicalId\":9909,\"journal\":{\"name\":\"Chemical Science\",\"volume\":\" 31\",\"pages\":\" 14350-14365\"},\"PeriodicalIF\":7.4000,\"publicationDate\":\"2025-06-30\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://pubs.rsc.org/en/content/articlepdf/2025/sc/d5sc03247d?page=search\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Chemical Science\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://pubs.rsc.org/en/content/articlelanding/2025/sc/d5sc03247d\",\"RegionNum\":1,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Chemical Science","FirstCategoryId":"92","ListUrlMain":"https://pubs.rsc.org/en/content/articlelanding/2025/sc/d5sc03247d","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
Mechanistic insights into solvent-guided growth and structure of MoO2 nanoparticles in solvothermal synthesis†
Understanding the processes involved in the nucleation and growth of nanoparticles is essential for the development of tailored nanomaterials. Here, we investigate the solvent effects on the atomic structure and size of nanocrystalline MoO2 obtained from a solvothermal synthesis and deduce their reaction pathways. Detailed pair distribution function (PDF) analysis reveals the formation of distinct MoO2 structures, depending on the alcohol used. We show that the atomic structure and crystallite size of the formed materials are directly related to their formation pathway. In situ PDF analysis together with X-ray absorption spectroscopy of the reaction between MoCl5 and an alcohol solvent allows us to see that larger nanoparticles (ca. 30 nm) with the conventional MoO2 distorted rutile structure form when the initial Cl/O-ligand exchange is fast, but the subsequent condensation and crystallization are slowed down in the synthesis process. On the other hand, when the Cl/O exchange is slowed down, a [MIVClxOy]-complex is formed, and we obtain very small nanoparticles (2–3 nm) with the MoO2 high-pressure polymorph structure. The study shows how the chemistry of the reaction solvent affects the mechanistic pathways, and consequently the intermediate formed just prior to crystallization, which is directly applicable to the process of obtaining specific nanocrystalline materials.
期刊介绍:
Chemical Science is a journal that encompasses various disciplines within the chemical sciences. Its scope includes publishing ground-breaking research with significant implications for its respective field, as well as appealing to a wider audience in related areas. To be considered for publication, articles must showcase innovative and original advances in their field of study and be presented in a manner that is understandable to scientists from diverse backgrounds. However, the journal generally does not publish highly specialized research.