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The Electrophilicity of Surface Carbon Species in the Redox Reactions of CuO-CeO₂ Catalysts.

ABSTRACT: Electronic metal-support interactions (EMSI) describe the electron flow between metal sites and a metal oxide support. It is generally used to follow the mechanism of redox reactions. In this study of CuO-CeO₂ redox, an additional flow of electrons from metallic Cu to surface carbon species is observed via a combination of operando X-ray absorption spectroscopy, synchrotron X-ray powder diffraction, near ambient pressure near edge X-ray absorption fine structure spectroscopy, and diffuse reflectance infrared Fourier transform spectroscopy. An electronic metal-support-carbon interaction (EMSCI) is proposed to explain the reaction pathway of CO oxidation. The EMSCI provides a complete picture of the mass and electron flow, which will help predict and improve the catalytic performance in the selective activation of CO₂ , carbonate, or carbonyl species in C1 chemistry.

SUBMITTER: Kang L

PROVIDER: S-EPMC8251948 | biostudies-literature | 2021 Jun

REPOSITORIES: biostudies-literature

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The Electrophilicity of Surface Carbon Species in the Redox Reactions of CuO-CeO<sub>2</sub> Catalysts.

Kang Liqun L Wang Bolun B Güntner Andreas T AT Xu Siyuan S Wan Xuhao X Liu Yiyun Y Marlow Sushila S Ren Yifei Y Gianolio Diego D Tang Chiu C CC Murzin Vadim V Asakura Hiroyuki H He Qian Q Guan Shaoliang S Velasco-Vélez Juan J JJ Pratsinis Sotiris E SE Guo Yuzheng Y Wang Feng Ryan FR

Angewandte Chemie (International ed. in English) 20210408 26

Electronic metal-support interactions (EMSI) describe the electron flow between metal sites and a metal oxide support. It is generally used to follow the mechanism of redox reactions. In this study of CuO-CeO<sub>2</sub> redox, an additional flow of electrons from metallic Cu to surface carbon species is observed via a combination of operando X-ray absorption spectroscopy, synchrotron X-ray powder diffraction, near ambient pressure near edge X-ray absorption fine structure spectroscopy, and diff ...[more]

PMID: 33729669

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Project description:BackgroundTo better assess potential hepatotoxicity of nanomaterials, human liver HepG2 cells were exposed for 3 days to five different CeO2 (either 30 or 100 μg/ml), 3 SiO2 based (30 μg/ml) or 1 CuO (3 μg/ml) nanomaterials with dry primary particle sizes ranging from 15 to 213 nm. Metabolomic assessment of exposed cells was then performed using four mass spectroscopy dependent platforms (LC and GC), finding 344 biochemicals.ResultsFour CeO2, 1 SiO2 and 1 CuO nanomaterials increased hepatocyte concentrations of many lipids, particularly free fatty acids and monoacylglycerols but only CuO elevated lysolipids and sphingolipids. In respect to structure-activity, we now know that five out of six tested CeO2, and both SiO2 and CuO, but zero out of four TiO2 nanomaterials have caused this elevated lipids effect in HepG2 cells. Observed decreases in UDP-glucuronate (by CeO2) and S-adenosylmethionine (by CeO2 and CuO) and increased S-adenosylhomocysteine (by CuO and some CeO2) suggest that a nanomaterial exposure increases transmethylation reactions and depletes hepatic methylation and glucuronidation capacity. Our metabolomics data suggests increased free radical attack on nucleotides. There was a clear pattern of nanomaterial-induced decreased nucleotide concentrations coupled with increased concentrations of nucleic acid degradation products. Purine and pyrimidine alterations included concentration increases for hypoxanthine, xanthine, allantoin, urate, inosine, adenosine 3',5'-diphosphate, cytidine and thymidine while decreases were seen for uridine 5'-diphosphate, UDP-glucuronate, uridine 5'-monophosphate, adenosine 5'-diphosphate, adenosine 5'-monophophate, cytidine 5'-monophosphate and cytidine 3'-monophosphate. Observed depletions of both 6-phosphogluconate, NADPH and NADH (all by CeO2) suggest that the HepG2 cells may be deficient in reducing equivalents and thus in a state of oxidative stress.ConclusionsMetal oxide nanomaterial exposure may compromise the methylation, glucuronidation and reduced glutathione conjugation systems; thus Phase II conjugational capacity of hepatocytes may be decreased. This metabolomics study of the effects of nine different nanomaterials has not only confirmed some observations of the prior 2014 study (lipid elevations caused by one CeO2 nanomaterial) but also found some entirely new effects (both SiO2 and CuO nanomaterials also increased the concentrations of several lipid classes, nanomaterial induced decreases in S-adenosylmethionine, UDP-glucuronate, dipeptides, 6-phosphogluconate, NADPH and NADH).

Dataset Information

The Electrophilicity of Surface Carbon Species in the Redox Reactions of CuO-CeO₂ Catalysts.

Publications

The Electrophilicity of Surface Carbon Species in the Redox Reactions of CuO-CeO<sub>2</sub> Catalysts.

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Dataset Information

The Electrophilicity of Surface Carbon Species in the Redox Reactions of CuO-CeO2 Catalysts.

Publications

The Electrophilicity of Surface Carbon Species in the Redox Reactions of CuO-CeO<sub>2</sub> Catalysts.

Similar Datasets

OmicsDI is part of the ELIXIR infrastructure

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The Electrophilicity of Surface Carbon Species in the Redox Reactions of CuO-CeO₂ Catalysts.