The High-Temperature Acidity Paradox of Oxidized Carbon: An in situ DRIFTS Study

doi:10.1002/cctc.202101586

IMR OpenIR

	The High-Temperature Acidity Paradox of Oxidized Carbon: An in situ DRIFTS Study
	Herold, Felix 1,2; Oefner, Niklas 1; Zakgeym, Dina 3; Drochner, Alfons 1; Qi, Wei 4; Etzold, Bastian J. M.1
通讯作者	Etzold, Bastian J. M.(bastian.etzold@tu-darmstadt.de)
	2022-01-10
发表期刊	CHEMCATCHEM
ISSN	1867-3880
页码	13
摘要	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.
关键词	acid base catalysis carbon materials carbon surface chemistry heterogeneous catalysis in situ spectroscopy
资助者	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
收录类别	SCI
语种	英语
资助项目	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研究方向	Chemistry
WOS类目	Chemistry, Physical
WOS记录号	WOS:000741472500001
出版者	WILEY-V C H VERLAG GMBH
引用统计	被引频次：4[WOS] [WOS记录] [WOS相关记录]
文献类型	期刊论文
条目标识符	http://ir.imr.ac.cn/handle/321006/173738
专题	中国科学院金属研究所
通讯作者	Etzold, Bastian J. M.
作者单位	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
推荐引用方式 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.