Jan Fingerhut, Jessalyn A. DeVine, Rongrong Yin, Mark E. Bernard, Alice Bremer, Dmitriy Borodin, Kai Golibrzuch, Theofanis N. Kitsopoulos, Daniel J. Auerbach, Hua Guo and Alec M. Wodtke*,
{"title":"","authors":"Jan Fingerhut, Jessalyn A. DeVine, Rongrong Yin, Mark E. Bernard, Alice Bremer, Dmitriy Borodin, Kai Golibrzuch, Theofanis N. Kitsopoulos, Daniel J. Auerbach, Hua Guo and Alec M. Wodtke*, ","doi":"","DOIUrl":"","url":null,"abstract":"","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"15 12","pages":"XXX-XXX XXX-XXX"},"PeriodicalIF":11.3,"publicationDate":"2025-06-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acscatal.5c01448","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144429059","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Francesco Falcioni*, Luke Humphreys*, Richard C. Lloyd*, Hao Wu, Isamir Martinez, Jonathan Jones, Shane McKenna, Katharina Neufeld, Ryan M. Phelan, Tay Rosenthal, Christophe J. Szczepaniak, Kumiko Yamamoto, Scott P. France and Anna Fryszkowska,
{"title":"","authors":"Francesco Falcioni*, Luke Humphreys*, Richard C. Lloyd*, Hao Wu, Isamir Martinez, Jonathan Jones, Shane McKenna, Katharina Neufeld, Ryan M. Phelan, Tay Rosenthal, Christophe J. Szczepaniak, Kumiko Yamamoto, Scott P. France and Anna Fryszkowska, ","doi":"","DOIUrl":"","url":null,"abstract":"","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"15 12","pages":"XXX-XXX XXX-XXX"},"PeriodicalIF":11.3,"publicationDate":"2025-06-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acscatal.5c01646","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144429077","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Antara Bhowmick, Sanjana Srinivas, Junyan Zhang, Jorge Moncada, Charles J. Titus, Bruce Ravel, Cherno Jaye, Daniel A. Fischer, Genevieve Yarema, Song Luo, Yuying Shu, Kewei Yu, Akash Warty, Sooyeon Hwang, Stavros Caratzoulas, Dionisios G. Vlachos*, Evan P. Jahrman* and Dongxia Liu*,
{"title":"","authors":"Antara Bhowmick, Sanjana Srinivas, Junyan Zhang, Jorge Moncada, Charles J. Titus, Bruce Ravel, Cherno Jaye, Daniel A. Fischer, Genevieve Yarema, Song Luo, Yuying Shu, Kewei Yu, Akash Warty, Sooyeon Hwang, Stavros Caratzoulas, Dionisios G. Vlachos*, Evan P. Jahrman* and Dongxia Liu*, ","doi":"","DOIUrl":"","url":null,"abstract":"","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"15 12","pages":"XXX-XXX XXX-XXX"},"PeriodicalIF":11.3,"publicationDate":"2025-06-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acscatal.5c00494","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144429086","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Varanasi Sai Subhankar, Charan R. Nallapareddy, C. Buddie Mullins and Thomas C. Underwood*,
{"title":"","authors":"Varanasi Sai Subhankar, Charan R. Nallapareddy, C. Buddie Mullins and Thomas C. Underwood*, ","doi":"","DOIUrl":"","url":null,"abstract":"","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"15 12","pages":"XXX-XXX XXX-XXX"},"PeriodicalIF":11.3,"publicationDate":"2025-06-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acscatal.5c01772","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144429633","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
ACS Catalysis Pub Date : 2025-06-20DOI: 10.1021/acscatal.5c01633
Guangming Cai, Ya-Huei Cathy Chin
{"title":"Thermochemical and Kinetic Correlations of Redox and Lewis Sites on Cobalt–Molybdenum Oxides: Illustrated with Alkanol-O2 Catalysis","authors":"Guangming Cai, Ya-Huei Cathy Chin","doi":"10.1021/acscatal.5c01633","DOIUrl":"https://doi.org/10.1021/acscatal.5c01633","url":null,"abstract":"Electronic properties of redox and Lewis acid sites on bifunctional metal oxides are inherently correlated to each other, a phenomenon that has long been recognized but not yet explicitly and quantitatively illustrated. Using alkanol oxidative dehydrogenation (ODH) and inter- and intramolecular dehydration (inter- and intra-DEH) kinetics as the respective thermochemical/electronic proxies for redox and Lewis acid sites, we elucidate the thermochemical and electronic correlations of these two types of sites on Co<sub><i>y</i></sub>MoO<sub><i>x</i></sub> domains with Co-to-Mo atomic ratio (<i>y</i>) varying from 0 to 1. At redox sites (O*), alkanol ODH occurs via a late, kinetically relevant C<sub>α</sub>–H scission transition state [O···<b>H···</b>RH<b>C</b>O···M<sup><i>n</i>+</sup>]<sup>‡</sup>, involving a net H atom (H<sup>•</sup>), arising from an electron (e<sup>–</sup>) and a proton (H<sup>+</sup>) transfer to a redox site, making hydrogen addition energy (HAE) as the kinetic descriptor, encapsulating the negative of electron (–EA<sub>MO</sub>) and proton (–PA<sub>O<sup>–</sup></sub>) affinities of catalysts. At Lewis acid sites, alkanol inter-DEH proceeds via S<sub>N</sub>2-type substitution with the [O<sup>δ−</sup>···<b>H···</b>RH<sub>2</sub>C<b>O···C</b>H<sub>2</sub>R<b>···O</b>H···M<sup>δ+</sup>]<sup>‡</sup> transition state, while intra-DEH, whether uni- or bimolecular, occurs via E2-type elimination through the [O<sup>δ−</sup>···<b>H···</b>R′H<b>C</b>H<sub>2</sub><b>C</b><sup><b>⊕</b></sup><b>···</b><sup><b>⊖</b></sup><b>O</b>H···M<sup>δ+</sup>]<sup>‡</sup> and [RH<sub>2</sub>C(H)O<sup>δ−</sup>···<b>H···</b>R′H<b>C</b>H<sub>2</sub><b>C</b><sup><b>⊕</b></sup><b>···</b><sup><b>⊖</b></sup><b>O</b>H···M<sup>δ+</sup>]<sup>‡</sup> transition states. These DEH pathways involve C–O scission in their respective transition states, where an electron and a <sup>•</sup>OH radical transfer as a <sup>⊖</sup>OH group to the Lewis acid center (<b>M</b><sup><b>δ+</b></sup>–O<sup>δ–</sup>). Consequently, the negative <sup>⊖</sup>OH affinity (–HA<sub>⊖OH</sub>) serves as an incomplete kinetic descriptor, encapsulating the same negative electron affinity and the negative <sup>•</sup>OH affinity (–HA<sub>•OH</sub>) of catalysts. The common electron transfer during the evolution of all these transition states in alkanol ODH and DEH entails the electron affinity of metal oxides to determine their relative activation enthalpies. On Co<sub><i>y</i></sub>MoO<sub><i>x</i></sub>, introducing Co cations as electronic perturbators increases the electron affinity of these oxides, thereby reducing both HAE at redox sites and –HA<sub>⊖OH</sub> at Lewis acid sites, which proportionally decreases the activation enthalpies for C<sub>α</sub>–H scission in methanol, ethanol, <i>n</i>-propanol, and <i>n</i>-butanol ODH; C–O formation in methanol and ethanol inter-DEH; and C<sub>β</sub>–H scission in uni- and bimolecular <i>n</i>-propanol and <i>n</i>-butanol intra-DEH, as th","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"4 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-06-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144335214","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}