Investigation of the Formation, Characterization, and Oxidative Catalytic Valorization of Humins
Abstract
:1. Introduction
2. Materials and Methods
2.1. General Procedure for Humin Formation Experiments
2.2. General Procedure for Catalytic Oxidation of Humins
2.3. Analytical Methods
- The nuclear magnetic resonance (NMR) spectra were measured using a Bruker AVANCEII 600 MHz spectrometer. Samples were prepared by mixing 0.4 mL of the filtered reaction solutions with 0.2 mL of D2O. Spectra of the reaction solutions can be found in the Supporting Information.
- Elemental analyses were carried out using the Model EA-3000 analyzer of Fa. EuroVector (Milano, Italy).
- SEM micrographs were recorded using a LEO Gemini 15505 from Zeiss (Oberkochen, Germany).
- MALDI-TOF measurements were taken with a Bruker ultrafleXtreme (Billerica, MA, USA) in positive reflector mode. A 2 mg/mL dispersion of the humic acid in water and a 20 mg/mL dihydroxybenzoic acid/TA30 (ACN/H2O 30/70 + 0.1%TFA) solution were prepared for the measurements. A total of 0.7 μL of both solutions were then mixed and left to crystallize.
3. Results and Discussion
3.1. Influence of Sugar, Acid, and Solvent on Humin Formation, Composition, and Structure
3.2. Oxidative Conversion of Humins Using Polyoxometalate Catalysts
4. Conclusions
Supplementary Materials
Author Contributions
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Conflicts of Interest
References
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Humin | H2O | EtOH/H2O | DMSO/H2O | ||||
---|---|---|---|---|---|---|---|
Designation | H2SO4 | p-TSA | AA | H2SO4 | p-TSA | AA | H2SO4 |
Fructose | F1 | F2 | F3 | F4 | F5 | F6 | F7 |
Glucose | G1 | G2 | G3 | G4 | G5 | G6 | G7 |
Xylose | X1 | X2 | X3 | X4 | X5 | X6 | X7 |
Sucrose | S1 | S2 | S3 | S4 | S5 | S6 | S7 |
H2O | EtOH/H2O | DMSO/H2O | |||||
---|---|---|---|---|---|---|---|
X (%) | H2SO4 a | p-TSA a | AA a | H2SO4 b | p-TSA b | AA b | H2SO4 b |
Fructose | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
Glucose | 90 | 74 | 69 | 100 | 100 | 100 | 100 |
Xylose | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
Sucrose | 90.5 | 94 | 84 | 100 | 100 | 100 | 100 |
Wavenumber [cm−1] | Assignment |
750 + 795 965 | C-H Out of plane vibration substituted furan ring C-H vibration furan ring |
1020 | C=C stretch vibration |
1090 | C-O-C ether vibration |
1160 + 1200 | C-O-C deformation vibration furan ring |
1295 | C-H rocking vibration |
1360 | C-C framework vibration (furan) C6 sugars |
1395 | C-C framework vibration (furan) C5 sugars |
1420 | C=S stretch |
1460 | C-H aliphatic chain vibration |
1510 | C=C vibration aromatic double bonds of poly substituted furans |
1600 | C=C stretch vibration conjugated with carbonyl |
1670 | C=O carbyonyl, aldehyde vibrations |
1700 | C=O stretch of acids, aldehydes and ketons |
1775 | C-S Thioester |
(a) Product Yields | F1 | G1 | X1 | S1 |
---|---|---|---|---|
CO2 | 39% | 46% | 36% | 47% |
Acetic acid | 6% | 7% | 5% | 7% |
Formic acid | 4% | 4% | 4% | 5% |
Succinic acid | 1% | 1% | 1% | 1% |
Combined Yield | 49% | 59% | 45% | 61% |
(a) Product Yields | F1 | F2 | F3 | F4 | F5 | F6 | F7 |
---|---|---|---|---|---|---|---|
CO2 | 39% | 35% | 44% | 38% | 31% | 46% | 16% |
Acetic acid | 6% | 6% | 5% | 9% | 7% | 9% | 3% |
Formic acid | 4% | 4% | 3% | 7% | 5% | 7% | 6% |
Succinic acid | 1% | 1% | 1% | 1% | 1% | 1% | 1% |
Combined Yield | 52% | 61% | 65% | 74% | 53% | 82% | 73% |
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Wassenberg, A.; Esser, T.; Poller, M.J.; Albert, J. Investigation of the Formation, Characterization, and Oxidative Catalytic Valorization of Humins. Materials 2023, 16, 2864. https://doi.org/10.3390/ma16072864
Wassenberg A, Esser T, Poller MJ, Albert J. Investigation of the Formation, Characterization, and Oxidative Catalytic Valorization of Humins. Materials. 2023; 16(7):2864. https://doi.org/10.3390/ma16072864
Chicago/Turabian StyleWassenberg, André, Tobias Esser, Maximilian J. Poller, and Jakob Albert. 2023. "Investigation of the Formation, Characterization, and Oxidative Catalytic Valorization of Humins" Materials 16, no. 7: 2864. https://doi.org/10.3390/ma16072864