Nachhaltige Umwandlung von Biomasse-Plattformmolekülen zu wertvollen C1-Synthesebausteinen durch selektive heterogenkatalytische Oxidation

• Antragstellerin: Professorin Dr. Angelika Brückner
• Fachliche Zuordnung: Festkörper- und Oberflächenchemie, Materialsynthese ; Organische Molekülchemie - Synthese, Charakterisierung ; Physikalische Chemie von Festkörpern und Oberflächen, Materialcharakterisierung
• Förderung: Förderung von 2020 bis 2024
• Projektkennung: Deutsche Forschungsgemeinschaft (DFG) - Projektnummer 431189789

• Erstellungsjahr: 2025

Zusammenfassung der Projektergebnisse

We have developed a series of non-noble metal heterogeneous catalysts with isolated CuII active sites such as Cu/5A and Cuphen/C3N4, with bimetal centers such as CuZr/5A, MnO2/Goethite as well as CuAlOx containing Cu2O-Cu interface sites, by ion-exchange, ballmilling, co-precipitation and polycondensation methods. These catalysts have been successfully applied in the selective oxidative valorization of biomass platform molecules derived from glycerol, such as glycerolaldehyde (GLCA), 1,3-dihydroxyacetone (DHA), glycolic acid (GA) and glycolaldehyde (GLA). The following significant progress going beyond the state of the art has been realized: 1) Selective oxidation of DHA to GA and FA at room temperature with very high yields (93 and 83 %, respectively); 2) Use of these platform molecules as carbonyl sources in the selective oxidative N-formylation of amines to formamides with good to excellent yields using H2O2 but also O2 as oxidant; 3) The challenging reductive N-formylation of amines with CO2 and H2 to valuable formamides over a heterogeneous CuAlOx non-noble metal catalyst. Comprehensive characterizations using a multitude of methods such as ICP-AES, XRD, XPS, BET, HAADF-STEM, EELS, NH3-TPD, EPR and XAFS revealed the formation of active sites such as isolated CuII species in Cu/5A and CuZr/5A, single CuN4 sites in Cuphen/C3N4, synergetic interaction between Fe and Mn in MnO2/Goethite and Cu2O-Cu interface sites in CuAlOx, respectively. Reaction mechanism studies by in situ EPR, operando ATR-FTIR experiments and DFT calculations showed that the generation of carbonylcontaining C1 intermediates (FA, C1 radical species) via selective oxidative cleavage of C-C bonds in the biomass-based molecules is vital for formamide formation in the oxidative N- formylation of amines. It has been shown that this reaction is governed by the selective formation of different reactive oxygen species such as ●OH, ●OOH and O2-●. In summary, this project can make a theoretical basis for the understanding of the selective activation and transformation of biomass derivative molecules to synthesize nitrogen-containing fine chemicals, and provide new ideas for valorization of other bio-based platform molecules.

Projektbezogene Publikationen (Auswahl)

• Construction of active single CuII sites for valorization of biomass-based platform molecules, Poster, 54. Jahrestreffen Deutscher Katalytiker 2021, March 16-19, Weimar, Germany
  X. Dai, J. Rabeah, F. Shi & A. Brückner
  
• Dihydroxyacetone valorization with high atom efficiency via controlling radical oxidation pathways over natural mineral-inspired catalyst. Nature Communications, 12(1).
  Wang, Jinling; Dai, Xingchao; Wang, Hualin; Liu, Honglai; Rabeah, Jabor; Brückner, Angelika; Shi, Feng; Gong, Ming & Yang, Xuejing
  
• Extending the potential of CuOx catalysts for valorization of biomass-based platform molecules by downsizing clusters to active single sites, Poster, Cluster Meeting 2021, May 9-14, Prague, Czech Republic
  X. Dai, J. Rabeah, F. Shi & A. Brückner
  
• Supported CuII Single‐Ion Catalyst for Total Carbon Utilization of C2 and C3 Biomass‐Based Platform Molecules in the N‐Formylation of Amines. Chemistry – A European Journal, 27(68), 16889-16895.
  Dai, Xingchao; Wang, Xinzhi; Rabeah, Jabor; Kreyenschulte, Carsten; Brückner, Angelika & Shi, Feng
  
• Effect of a second metal component on Cu/5A activity in the N-formylation of amines with biomass-based feedstocks, Oral presentation, ISGC 2022, May 16-20, La Rochelle, France
  X. Dai, X. Wang, J. Rabeah, F. Shi & A. Brückner
  
• Supported CuII single ion catalyst for total-carbon utilization of C2-C3 biomass-based platform molecules in N- formylation of amines, Poster, 55. Jahrestreffen Deutscher Katalytiker 2022, June 27-29, Weimar, Germany
  X. Dai, X. Wang, J. Rabeah, C. Kreyenschulte, F. Shi & A. Brückner
  
• Cu-Catalysed sustainable synthesis of formamide with glycerol derivatives as a carbonyl source via a radical-relay mechanism. Green Chemistry, 25(4), 1464-1472.
  Dai, Xingchao; Wang, Xinzhi; Kreyenschulte, Carsten; Yuan, Hangkong; Brückner, Angelika; Shi, Feng & Rabeah, Jabor
  
• Glycerol derivatives as bio-based C1 building blocks for N-formylation of amines to formamides with O2 as the oxidant, Oral presentation, EUROPACAT 2023, August 27-September 1, Prague, Czech Republic
  X. Dai, J. Rabeah, F. Shi & A. Brückner
  
• Tailoring Active Cu2O/Copper Interface Sites for N‐Formylation of Aliphatic Primary Amines with CO2/H2. Angewandte Chemie International Edition, 62(21).
  Dai, Xingchao; Li, Teng; Wang, Bin; Kreyenschulte, Carsten; Bartling, Stephan; Liu, Shujuan; He, Dongcheng; Yuan, Hangkong; Brückner, Angelika; Shi, Feng; Rabeah, Jabor & Cui, Xinjiang
  
• Aerobic Oxidative Synthesis of Formamides from Amines and Bioderived Formyl Surrogates. Angewandte Chemie International Edition, 63(26).
  Dai, Xingchao; Han, Yunyan; Jiao, Haijun; Shi, Feng; Rabeah, Jabor & Brückner, Angelika
  
• Selective aerobic oxidative cleavage and amidation of C-C bond, Poster, 18th ICC 2024, July 14-19, Lyon, France
  X. Dai, Y. Han, H. Jiao, A. Brückner, F. Shi & J. Rabeah
  
• Mild oxidative N-formylation of amines with biobased glycolaldehyde over C3N4 supported Cu catalyst under green solvent. Chemical Engineering Journal, 508, 160963.
  Dai, Xingchao; Han, Yunyan; Jiao, Haijun; Brückner, Angelika; Shi, Feng & Rabeah, Jabor