Cargando…

Uranium-Doped Zinc, Copper, and Nickel Oxides for Enhanced Catalytic Conversion of Furfural to Furfuryl Alcohol: A Relativistic DFT Study

Transition metal oxides (TMOs) and actinide ones (AnOs) have been widely applied in catalytic reactions due to their excellent physicochemical properties. However, the reaction pathway and mechanism, especially involving TM–An heterometallic centers, remain underexplored. In this respect, relativist...

Descripción completa

Detalles Bibliográficos
Autores principales: Li, Shuang, Hou, Yu-Chang, Guo, Yuan-Ru, Pan, Qing-Jiang
Formato: Online Artículo Texto
Lenguaje:English
Publicado: MDPI 2022
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9502827/
https://www.ncbi.nlm.nih.gov/pubmed/36144824
http://dx.doi.org/10.3390/molecules27186094
_version_ 1784795801604587520
author Li, Shuang
Hou, Yu-Chang
Guo, Yuan-Ru
Pan, Qing-Jiang
author_facet Li, Shuang
Hou, Yu-Chang
Guo, Yuan-Ru
Pan, Qing-Jiang
author_sort Li, Shuang
collection PubMed
description Transition metal oxides (TMOs) and actinide ones (AnOs) have been widely applied in catalytic reactions due to their excellent physicochemical properties. However, the reaction pathway and mechanism, especially involving TM–An heterometallic centers, remain underexplored. In this respect, relativistic density functional theory (DFT) was used to examine uranium-doped zinc, copper, and nickel oxides for their catalytic activity toward the conversion of furfural to furfuryl alcohol. A comparison was made with their undoped TMOs. It was found that the three TMOs were capable of catalyzing the reaction, where the free energies of adsorption, hydrogenation, and desorption fell between −33.93 and 45.00 kJ/mol. The uranium doping extremely strengthened the adsorption of CuO-U and NiO-U toward furfural, making hydrogenation or desorption much harder. Intriguingly, ZnO-U showed the best catalytic performance among all six catalyst candidates, as its three reaction energies were very small (−10.54–8.12 kJ/mol). The reaction process and mechanism were further addressed in terms of the geometrical, bonding, charge, and electronic properties.
format Online
Article
Text
id pubmed-9502827
institution National Center for Biotechnology Information
language English
publishDate 2022
publisher MDPI
record_format MEDLINE/PubMed
spelling pubmed-95028272022-09-24 Uranium-Doped Zinc, Copper, and Nickel Oxides for Enhanced Catalytic Conversion of Furfural to Furfuryl Alcohol: A Relativistic DFT Study Li, Shuang Hou, Yu-Chang Guo, Yuan-Ru Pan, Qing-Jiang Molecules Article Transition metal oxides (TMOs) and actinide ones (AnOs) have been widely applied in catalytic reactions due to their excellent physicochemical properties. However, the reaction pathway and mechanism, especially involving TM–An heterometallic centers, remain underexplored. In this respect, relativistic density functional theory (DFT) was used to examine uranium-doped zinc, copper, and nickel oxides for their catalytic activity toward the conversion of furfural to furfuryl alcohol. A comparison was made with their undoped TMOs. It was found that the three TMOs were capable of catalyzing the reaction, where the free energies of adsorption, hydrogenation, and desorption fell between −33.93 and 45.00 kJ/mol. The uranium doping extremely strengthened the adsorption of CuO-U and NiO-U toward furfural, making hydrogenation or desorption much harder. Intriguingly, ZnO-U showed the best catalytic performance among all six catalyst candidates, as its three reaction energies were very small (−10.54–8.12 kJ/mol). The reaction process and mechanism were further addressed in terms of the geometrical, bonding, charge, and electronic properties. MDPI 2022-09-18 /pmc/articles/PMC9502827/ /pubmed/36144824 http://dx.doi.org/10.3390/molecules27186094 Text en © 2022 by the authors. https://creativecommons.org/licenses/by/4.0/Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (https://creativecommons.org/licenses/by/4.0/).
spellingShingle Article
Li, Shuang
Hou, Yu-Chang
Guo, Yuan-Ru
Pan, Qing-Jiang
Uranium-Doped Zinc, Copper, and Nickel Oxides for Enhanced Catalytic Conversion of Furfural to Furfuryl Alcohol: A Relativistic DFT Study
title Uranium-Doped Zinc, Copper, and Nickel Oxides for Enhanced Catalytic Conversion of Furfural to Furfuryl Alcohol: A Relativistic DFT Study
title_full Uranium-Doped Zinc, Copper, and Nickel Oxides for Enhanced Catalytic Conversion of Furfural to Furfuryl Alcohol: A Relativistic DFT Study
title_fullStr Uranium-Doped Zinc, Copper, and Nickel Oxides for Enhanced Catalytic Conversion of Furfural to Furfuryl Alcohol: A Relativistic DFT Study
title_full_unstemmed Uranium-Doped Zinc, Copper, and Nickel Oxides for Enhanced Catalytic Conversion of Furfural to Furfuryl Alcohol: A Relativistic DFT Study
title_short Uranium-Doped Zinc, Copper, and Nickel Oxides for Enhanced Catalytic Conversion of Furfural to Furfuryl Alcohol: A Relativistic DFT Study
title_sort uranium-doped zinc, copper, and nickel oxides for enhanced catalytic conversion of furfural to furfuryl alcohol: a relativistic dft study
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9502827/
https://www.ncbi.nlm.nih.gov/pubmed/36144824
http://dx.doi.org/10.3390/molecules27186094
work_keys_str_mv AT lishuang uraniumdopedzinccopperandnickeloxidesforenhancedcatalyticconversionoffurfuraltofurfurylalcoholarelativisticdftstudy
AT houyuchang uraniumdopedzinccopperandnickeloxidesforenhancedcatalyticconversionoffurfuraltofurfurylalcoholarelativisticdftstudy
AT guoyuanru uraniumdopedzinccopperandnickeloxidesforenhancedcatalyticconversionoffurfuraltofurfurylalcoholarelativisticdftstudy
AT panqingjiang uraniumdopedzinccopperandnickeloxidesforenhancedcatalyticconversionoffurfuraltofurfurylalcoholarelativisticdftstudy