| The High-Temperature Acidity Paradox of Oxidized Carbon: An in situ DRIFTS Study | |
| Herold, Felix1,2; Oefner, Niklas1; Zakgeym, Dina3; Drochner, Alfons1; Qi, Wei4; Etzold, Bastian J. M.1 | |
| Corresponding Author | Etzold, Bastian J. M.(bastian.etzold@tu-darmstadt.de) |
| 2022-01-10 | |
| Source Publication | CHEMCATCHEM
 |
| ISSN | 1867-3880 |
| Pages | 13 |
| Abstract | Until now, oxygen functionalized carbon materials were not considered to exhibit significant acidity at high temperatures, since carboxylic acids, the most prominent acidic functionality, are prone to decarboxylation at temperatures exceeding 250 degrees C. Paradoxically, we could show that oxidized carbon materials can act as highly active high-temperature solid acid catalysts in the dehydration of methanol at 300 degrees C, showing an attractive selectivity to dimethyl ether (DME) of up to 92 % at a conversion of 47 %. Building on a tailor-made carbon model material, we developed a strategy to utilize in situ DRIFT spectroscopy for the analysis of carbon surface species under process conditions, which until now proofed to be highly challenging due to the high intrinsic absorbance of carbon. By correlating the catalytic behavior with a comprehensive in situ DRIFTS study and extensive post mortem analysis we could attribute the high-temperature acidity of oxidized carbons to the interaction of thermally stable carboxylic anhydrides and lactones with nucleophilic constituents of the reaction atmosphere e. g. methanol and H2O. Dynamic equilibria of surface oxides depending on reaction atmosphere and temperature were observed, and a methyl ester, formed by methanolysis of anhydrides and lactones, was identified as key intermediate for DME generation on oxidized carbon catalysts. |
| Keyword | acid base catalysis carbon materials carbon surface chemistry heterogeneous catalysis in situ spectroscopy |
| Funding Organization | Deutsche Bundesstiftung Umwelt (DBU) ; Career Bridging Grant from Technical University of Darmstadt ; Deutsche Forschungsgemeinschaft (DFG, German Research Foundation) ; NSFC of China ; Natural Science Foundation of Liaoning Province of China ; Projekt DEAL |
| DOI | 10.1002/cctc.202101586 |
| Indexed By | SCI |
| Language | 英语 |
| Funding Project | Deutsche Bundesstiftung Umwelt (DBU) ; Career Bridging Grant from Technical University of Darmstadt ; Deutsche Forschungsgemeinschaft (DFG, German Research Foundation)[ET-101/13-1] ; NSFC of China[22072163] ; NSFC of China[21761132010] ; Natural Science Foundation of Liaoning Province of China[2020-YQ-02] ; Projekt DEAL |
| WOS Research Area | Chemistry |
| WOS Subject | Chemistry, Physical |
| WOS ID | WOS:000741472500001 |
| Publisher | WILEY-V C H VERLAG GMBH |
| Citation statistics | |
| Document Type | 期刊论文 |
| Identifier | http://ir.imr.ac.cn/handle/321006/173738 |
| Collection | 中国科学院金属研究所 |
| Corresponding Author | Etzold, Bastian J. M. |
| Affiliation | 1.Tech Univ Darmstadt, Ernst Berl Inst Tech & Makromolekulare Chem, Dept Chem, Alarich Weiss Str 8, D-64287 Darmstadt, Germany 2.Norwegian Univ Sci & Technol, Dept Chem Engn, Sem Saelandsvei 4, N-7491 Trondheim, Norway 3.Forschungszentrum Julich, Helmholtz Inst Erlangen Nurnberg Renewable Energy, Egerlandstr 3, D-91058 Erlangen, Germany 4.Chinese Acad Sci, Inst Met Res, Shenyang Natl Lab Mat Sci, Wenhua Rd 72, Shenyang 110016, Peoples R China |
| Recommended Citation GB/T 7714 | Herold, Felix,Oefner, Niklas,Zakgeym, Dina,et al. The High-Temperature Acidity Paradox of Oxidized Carbon: An in situ DRIFTS Study[J]. CHEMCATCHEM,2022:13. |
| APA | Herold, Felix,Oefner, Niklas,Zakgeym, Dina,Drochner, Alfons,Qi, Wei,&Etzold, Bastian J. M..(2022).The High-Temperature Acidity Paradox of Oxidized Carbon: An in situ DRIFTS Study.CHEMCATCHEM,13. |
| MLA | Herold, Felix,et al."The High-Temperature Acidity Paradox of Oxidized Carbon: An in situ DRIFTS Study".CHEMCATCHEM (2022):13. |
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