RESUMO
Ethylene glycol (EG) is obtained by a novel, two-step approach combining a biotechnological and a heterogeneously catalyzed step. First, microalgae are cultivated to photobiocatalytically yield glycolic acid (GA) by means of photosynthesis from CO2 and water. GA is continuously excreted into the surrounding medium. In the second step, the GA-containing algal medium is used as feedstock for catalytic reduction with H2 to EG over a Ru/C catalyst. The present study focuses on the conversion of an authentic algae-derived GA solution. After identification of the key characteristics of the algal medium (compared to pure aqueous GA), the influence of pH, numerous salt additives, pH buffers and other relevant organic molecules on the catalytic GA reduction was investigated. Nitrogen- and sulfur-containing organic molecules can strongly inhibit the reaction. Moreover, pH adjustment by acidification is required, for which H2 SO4 is found most suitable. In combination with a modification of the biotechnological process to mitigate the use of inhibitory compounds, and after acidifying the algal medium, over Ru/C a EG yield of up to 21 % even at non-optimized reaction conditions was achieved.
Assuntos
Microalgas , Catálise , Etilenoglicol/química , Glicolatos , Concentração de Íons de Hidrogênio , Hidrogenação , ÁguaRESUMO
[This corrects the article DOI: 10.1039/D1RA06500A.].
RESUMO
Solar energy-driven processes for biomass valorization are priority for the growing industrialized society. To address this challenge, efficient visible light-active photocatalyst for the selective oxidation of biomass-derived platform chemical is highly desirable. Herein, selective oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-diformylfuran (DFF) was achieved by visible light-driven photocatalysis over titania. Pristine titania is photocatalytically inactive under visible light, so an unconventional approach was employed for the visible light (λ=515â nm) sensitization of titania via a formation of a visible light-absorbing complex of HMF (substrate) on the titania surface. Surface-complexation of HMF on titania mediated ligand-to-metal charge transfer (LMCT) under visible light, which efficiently catalyzed the oxidation of HMF to DFF. A high DFF selectivity of 87 % was achieved with 59 % HMF conversion after 4â h of illumination. The apparent quantum yield obtained for DFF production was calculated to be 6.3 %. It was proposed that the dissociative interaction of hydroxyl groups of HMF and the titania surface is responsible for the surface-complex formation. When the hydroxyl groups of titania were modified via surface-fluorination or calcination the oxidation of HMF was inhibited under visible light, signifying that hydroxyl groups are decisive for photocatalytic activity.
RESUMO
Developing functional materials from biomass is a significant research subject due to its unique structure, abundant availability, biodegradability and low cost. A series of chitosan-lignin (CL) composites were prepared through a hydrothermal method by varying the weight ratio of chitosan and lignin. Subsequently, these CL composites were combined with titania (T) to form a nanocomposite (T/CL) using sol-gel and hydrothermal based methods. T/CL nanocomposites exhibited improved photocatalytic performance in comparison with sol-gel and hydrothermally prepared pristine titania (SGH-TiO2), towards the selective oxidation of benzyl alcohol (BnOH) to benzaldehyde (Bnald) under UV (375 nm) and visible light (515 nm). More specifically, the 75T/CL(25 : 75) nanocomposite (a representative photocatalyst from the 75T/CL nanocomposite series) showed very high selectivity (94%) towards Bnald at 55% BnOH conversion under UV light. Whereas, SGH-TiO2 titania exhibited much lower (68%) selectivity for Bnald at similar BnOH conversion. Moreover, the 75T/CL(25 : 75) nanocomposite also showed excellent Bnald selectivity (100%) at moderate BnOH conversion (19%) under visible light. Whereas, SGH-TiO2 did not show any activity for BnOH oxidation under visible light. XPS studies suggest that the visible light activity of the 75T/CL(25 : 75) nanocomposite is possibly related to the doping of nitrogen into titania from chitosan. However, according to UV-visible-DRS results, no direct evidence pertaining to the decrease in band-gap energy of titania was found upon coupling with the CL composite and the visible light activity was attributed to N-doping of titania. Overall, it was found that T/CL nanocomposites enhanced the photocatalytic performance of titania via improved light harvesting and higher selectivity through mediation of active radical species.
RESUMO
La3+ cation exchange is shown to improve the hydrothermal stability and catalytic activity of bifunctional zeolite Pt/Y catalysts in the aqueous-phase hydrogenation of levulinic acid (LA) with formic acid (FA) as hydrogen source. La3+ cation exchange of zeolite Y (n Si/n Al = 16) was conducted both in aqueous solution and in the solid state. The hydrothermal stability of La3+-containing zeolite Y probed by exposure to the reaction mixture (0.2 mol L-1 LA, 0.6 mol L-1 FA) at 473 K under autogenous pressure for 24 h improves with increasing La content. The material exhibiting the highest La content (0.5 mmol g-1) is the most stable with a preservation of 25% of the initial specific micropore volume after the hydrothermal treatment, whereas unmodified zeolite Y completely loses its microporosity. A new procedure using DRIFTS is a useful supplementary tool for quantifying the framework degradation of Y-type zeolites after hydrothermal treatment. Bifunctional Pt/Y catalysts after La3+ cation exchange are more active than the parent Y-zeolite for the hydrogenation of LA to γ-valerolactone (GVL), with significant enhancements in LA conversion, i.e., 94% vs. 42%, and GVL yield, i.e., 72% vs. 34%., after 24 h.
