Direct Synthesis of Acetone by Aerobic Propane Oxidation Promoted by Photoactive Iron(III) Chloride under Mild Conditions

Author(s):Show less -

Rogolino, Andrea ; Filho, Jose B. G. ; Fritsch, Lorena ; Ardisson, Jose D. ; da Silva, Marcos A. R. ; Atta Diab, Gabriel Ali ; Silva, Ingrid Fernandes ; Ferreira Moraes, Carlos Andree ; Forim, Moacir Rossi ; Bauer, Matthias ; Kuehne, Thomas D. ; Antonietti, Markus ; Teixeira, Ivo F.

• Document type: Journal article
• Source: ACS CATALYSIS; v. 13, n. 13, p. 8-pg., 2023-06-15.

Abstract

C-H activation of hydrocarbons is extremely challenging,especially in short-chain hydrocarbons like propane. In industry,propane is first converted to propylene mostly by steam cracking,which is only oxidized to acetone in the cumene process, yieldingacetone and phenol. In this work, we show that the simple FeCl3 salt in acetonitrile photocatalyzes the oxidation of propaneto acetone at room temperature under aerobic conditions and visible-lightirradiation. We achieved 100% conversion of propane with 67% selectivityin acetone after 4 h of irradiation and TON up to 600. Mechanisticstudies, including electrospray ionization mass spectrometry, Mo''ssbauer,and electroparamagnetic resonance spectroscopy, concluded that thereaction is driven by chlorine radicals generated by Fe-Clbond photolysis. These results not only hold promise for the developmentof solar-based oxidation of hydrocarbons but more importantly alsodisclose deeper insights into the largely overlooked photochemistryof FeCl3. (AU)

• FAPESP's process: 21/14006-7 - PHI/PTI-single-atoms controlled synthesis and energy applications
• Grantee: Gabriel Ali Atta Diab
• Support Opportunities: Scholarships in Brazil - Doctorate (Direct)
• FAPESP's process: 21/13271-9 - Single atoms coordinated on graphitic carbon nitrides to photocatalytic conversion of methane
• Grantee: Marcos Augusto Ribeiro da Silva
• Support Opportunities: Scholarships in Brazil - Doctorate
• FAPESP's process: 20/14741-6 - Graphitic carbon nitrides as platforms for single-atom photocatalysis: moving towards design principles for improved performance
• Grantee: Ivo Freitas Teixeira
• Support Opportunities: Research Grants - Young Investigators Grants
• FAPESP's process: 21/11162-8 - Multi-user equipment approved in grant 2020/14741-6: GC-MS/FID/TCD (2 injetores+Loop+Sistema valvulado)
• Grantee: Ivo Freitas Teixeira
• Support Opportunities: Multi-user Equipment Program