The vacancy, created by the removal or \u201ccleavage\u201d of an oxygen atom, makes it easier for the gaseous mixture to reach and bind with a redox-active vanadium cation, or positively charged ion.<\/p>\n \u201cTheoretical investigations in recent years have suggested that creation of an oxygen-atom vacancy at the surface of metal oxide materials is often a key step in facilitating a reaction,\u201d Matson says. \u201cBy extending this chemistry to polyoxometalates (a class of metal oxide clusters than can also include molybdenum or tungsten), we have demonstrated that our clusters can model the surface chemistry of extended solids. This idea has been tossed around for decades by chemists, and for the first time our lab is realizing these types of goals in cluster research!\u201d<\/p>\n \u201cWhat’s cool about modeling the surface chemistry with a discrete molecule like this is that we can monitor these types of complicated, multi-electron reactions spectroscopically. We can take CO2<\/sub> or another oxygenated substrate, add it to a reaction vessel that contains our reduced polyoxovanadate cluster, and watch, in real-time, how the two compounds react.\u201d<\/p>\n \u201cWhat we are hoping,\u201d she adds, \u201cis that our findings can influence the way materials chemists design their systems \u2013 how they pick the materials they\u2019re going to put into their solid-state reactors to see if they produce the reactions they\u2019re looking for. This is a new and exciting approach for testing some of the scientific hypotheses that have been promoted through theory. Understanding the surface chemistry through experiments will really change the scope of understanding of the reactivity of materials.\u201d<\/p>\n The discovery came about \u201calmost serendipitously,\u201d Matson says. The lab used a reducing agent to cleave an element-oxygen bond \u201cin work with our iron-functionalized polyoxovanadate clusters.\u201d When a gaseous substrate, like nitric oxide, is bound to iron in these clusters, exposure of the system to a reductant results in loss of an oxygen atom.<\/p>\n \u201cWe were super excited at first, thinking that we had cleaved the N=O bond of the substrate,\u201d Matson says. \u201cHowever, our results were pretty confusing, and we set aside the data for awhile.\u201d Later, in thoughtful control experiments involving all-vanadium versions of the cluster, Petel used the same reducing agent, and confirmed the loss of oxygen atoms at the surface through mass spectrometry and nuclear magnetic resonance spectroscopy.<\/p>\n Other research teams across the country are also exploring the synthesis and reactivity of multimetallic clusters, in particular their reactivity with small molecules. However, most research groups have focused on modelling the active sites of metalloenzymes, mimicking chemistry performed in nature, Matson says.<\/p>\n \u201cWhat makes our program so distinct is that we\u2019re studying these multi-metallic assemblies as models of extended solids, for materials applications. We\u2019re carving out a new area where we\u2019re digging into some really exciting mechanisms for small molecule activation. It\u2019s an incredibly exciting direction for our research group!\u201d<\/p>\n Polyoxovanadate clusters have provided a fruitful area of research for the Matson Laboratory. In 2017, Matson received a National Science Foundation CAREER award<\/a> study the formation of heterometallic polyoxovanadate clusters. The overarching goal of this research is to generate catalysts capable of storing multiple electrons, that more efficiently convert greenhouse gases to useful chemical fuels. The Matson Laboratory continues to push boundaries with these hexavanadate cluster, earlier this year reporting the modification of polyoxovanadate-alkoxide clusters for more efficient electrochemical energy storage in a redox flow battery<\/a>.<\/p>\n William Brennessel, an X-ray crystallographer and scientist with the Department of Chemistry, also contributed to the research for this paper.<\/p>\n","protected":false},"excerpt":{"rendered":" A new method of opening solid state materials to oxygenation, using metallic oxide clusters, can eliminate guesswork from discovery of new catalysts. The ultimate goal is to more efficiently convert greenhouse gases to useful fuels.<\/p>\n","protected":false},"author":286,"featured_media":331312,"comment_status":"closed","ping_status":"closed","sticky":false,"template":"","format":"standard","meta":{"_acf_changed":false,"footnotes":""},"categories":[116],"tags":[19862,34282,4626,37312,27132,18572,16072],"class_list":["post-331302","post","type-post","status-publish","format-standard","has-post-thumbnail","hentry","category-sci-tech","tag-department-of-chemistry","tag-ellen-matson","tag-featured-post","tag-materials-science-program","tag-natural-sciences","tag-research-finding","tag-school-of-arts-and-sciences"],"acf":[],"yoast_head":"\n![\"graphic](\"https:\/\/www.rochester.edu\/newscenter\/wp-content\/uploads\/2018\/08\/atom-vacancy.png\")
Serendipitous solutions<\/h2>\n