A method for preparing high-valent MOF crystal film for dehydration and purification of organic matter
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- DALIAN INSTITUTE OF CHEMICAL PHYSICS CHINESE ACADEMY OF SCIENCES
- Filing Date
- 2024-12-10
- Publication Date
- 2026-06-12
AI Technical Summary
Existing technologies make it difficult to apply high-stability, high-valence MOF membranes on a large scale, especially to prepare high-quality, high-valence MOF crystal membranes on ceramic support surfaces, which limits their application in the dehydration and purification of organic matter.
A porous γ-Al2O3 support was used as an inorganic aluminum source to prepare a γ-AlOOH precursor film via a solvothermal reaction. Then, it was reacted with carboxylic acid ligands and hydrated nitrates in an in-situ hydrothermal reaction to form a high-valence MOF crystal film.
It achieves efficient and stable organic dehydration performance, and the preparation process is simple and environmentally friendly. It is suitable for the separation of organic matter/water systems, especially the dehydration and purification of alcohols and ketones.
Smart Images
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Abstract
Description
Technical Field
[0001] This invention relates to a method for preparing a high-valent MOF crystal membrane for dehydration and purification of organic matter, belonging to the field of membrane separation materials. Background Technology
[0002] Pervaporation (PV) is currently a hot research topic in the field of organic matter separation. PV offers advantages such as ease of operation, low energy consumption, and no secondary pollution. Furthermore, it overcomes the limitations of traditional distillation methods in separating near-boiling and azeotropic organic mixtures, demonstrating significant advantages in energy conservation, emission reduction, cost savings, and improved separation stability.
[0003] Membrane materials are the core components, and their structure and performance determine the separation efficiency of the entire pervaporation process. Compared with traditional separation materials, metal-organic frameworks (MOFs) have many advantages, such as large specific surface area, diverse topologies, and tunable pore structures, and are expected to play a role in liquid separation (V. Cristina, EJ Mater Chem. A. 2020). The vast majority of MOF materials are composed of divalent metal ions, such as Zn. 2+ Cu 2+ For nodes. Numerous studies have confirmed that high-valent MOF materials, such as MOF materials with trivalent aluminum ions as metal nodes, exhibit superior hydrothermal stability compared to common divalent metal MOFs, meeting the stringent requirements of pervaporation separation. However, due to constraints in coordination chemistry, the nucleation of high-valent MOF crystal materials is difficult, and the preparation of high-quality crystalline films on ceramic carrier surfaces is rarely reported, greatly limiting the large-scale application of high-stability MOF films. Summary of the Invention
[0004] The purpose of this invention is to provide a method for preparing high-valence MOF crystal membranes with stable structure and excellent dehydration performance of organic matter (including alcohols and ketones).
[0005] A method for preparing a high-valence MOF crystal membrane for dehydration of organic matter involves a solvothermal reaction of a porous γ-Al₂O₃ support as an inorganic aluminum source with an aqueous acetic acid solution to obtain a γ-AlOOH precursor membrane (layer); then, the support modified with the γ-AlOOH precursor layer is placed in an aqueous solution containing a carboxylic acid ligand and hydrated nitrate, and subjected to an in-situ hydrothermal reaction to obtain the final membrane. The method specifically includes the following steps:
[0006] (1) Preparation of γ-AlOOH precursor layer (film)
[0007] A porous γ-Al₂O₃ support was placed in an aqueous acetic acid solution and subjected to a solvothermal reaction under sealed conditions to pre-seed a nanosheet-like γ-AlOOH precursor layer on the support surface, resulting in a γ-AlOOH precursor film, i.e., a precursor-modified support. The reaction temperature was 130–220 °C, and the reaction time was 2–48 h.
[0008] After the reaction was completed, the membrane was cooled to room temperature and then washed and dried. Specifically, after the reaction was completed, the membrane was allowed to cool naturally to room temperature. The membrane was then placed in a beaker filled with water and sonicated at 50-400 W for 5-30 seconds. After that, it was washed with deionized water or anhydrous ethanol for 5-120 minutes. The washed product was then dried overnight in an oven at 50-80°C.
[0009] Preferably, the porous Al2O3 support is placed horizontally in the mother liquor (reaction solution) and reacted at 180-200°C for 4-12 hours.
[0010] Preferably, the pH of the acetic acid aqueous solution is 2 to 4.
[0011] Preferably, the ultrasonic treatment time of the γ-AlOOH precursor membrane is 10-30 seconds.
[0012] Preferably, the porous γ-Al2O3 support has a diameter of 18 mm and a pore size of 5 nm.
[0013] (2) Preparation of high-valence MOF crystal films
[0014] Hydrated nitrate, chloride or aluminum sulfate, carboxylic acid ligands, and sodium hydroxide are dissolved in water or a mixture of water and DMF. The mixture is stirred to ensure thorough mixing. The molar ratio of the three reactants (hydrated nitrate, chloride or aluminum sulfate: carboxylic acid ligand: sodium hydroxide: water) is adjusted to 1:0.25–4:0–4:400–2000, preferably 1:0.25–4:1–4:400–2000. The mixture is stirred at room temperature (generally 25°C) for 10 minutes to ensure thorough mixing. The γ-AlOOH precursor membrane is placed in the mother liquor (reaction solution) and reacted at 100–200°C for 6–72 hours. Through secondary growth, a porous MOF (MIL) crystal membrane is obtained.
[0015] The hydrated nitrate is one or two of aluminum nitrate nonahydrate, chromium nitrate nonahydrate, and ferric nitrate nonahydrate; the hydrated chloride is one or two of aluminum chloride hexahydrate and ferric chloride hexahydrate; the hydrated aluminum sulfate is aluminum sulfate octadecahydrate; the carboxylic acid ligand is one or more of terephthalic acid, isophthalic acid, trimesic acid, 2-aminoterephthalic acid, 3,5-pyrazoledicarboxylic acid, and 2,5-furandicarboxylic acid.
[0016] After the reaction is complete, the membrane is washed and dried. Specifically, the membrane is placed in a beaker containing deionized water and sonicated at 50-400W for 5-30 seconds. After washing with N,N-dimethylformamide or anhydrous ethanol for 5-120 minutes, it is placed in an oven to dry at 50-100℃ overnight.
[0017] Preferably, the ratio of the three reactants (hydrated nitrate, chloride or aluminum sulfate: carboxylic acid ligand: sodium hydroxide: water) is 1:0.5-2:1-2:600-1500.
[0018] Preferably, the volume ratio of water to DMF in the mixed solvent of water and DMF is 1 to 8:1, and more preferably 4:1.
[0019] Preferably, the γ-AlOOH precursor membrane is placed vertically in the mother liquor (reaction solution) for reaction.
[0020] Preferably, the optimal temperature for the secondary growth step is 120–180°C, and the optimal time is 12–36 hours.
[0021] Preferably, the membrane immersion and washing step includes immersion and washing in N,N-dimethylformamide or anhydrous ethanol at room temperature for 30 to 60 minutes.
[0022] Another object of the present invention is to provide a high-valence MOF crystal film prepared by the above method.
[0023] Another object of the present invention is to provide the application of the above-mentioned high-valence MOF crystal membrane in the dehydration of organic matter (i.e., separation of organic matter / water system), wherein the organic matter includes at least one of methanol, ethanol, n-propanol, isopropanol, n-butanol, and acetone.
[0024] Compared with the prior art, the advantages of the present invention are:
[0025] (1) The preparation process is rapid and simple, and it is a green chemical synthesis method;
[0026] (2) The experimental strategy is ingenious. By using the γ-AlOOH modified support method, a layer of γ-AlOOH precursor was pre-seeded on the surface of the porous γ-Al2O3 support as an inorganic Al source to prepare the γ-AlOOH precursor layer. Subsequently, high-valence MOF crystal membrane with excellent performance and good stability was prepared by in-situ hydrothermal growth using γ-AlOOH as the precursor template. It has excellent separation performance for organic matter / water system separation and is an ideal material for organic matter dehydration and purification. Attached Figure Description
[0027] This invention appendix Figure 7 Size:
[0028] Figure 1 These are X-ray diffraction patterns of γ-AlOOH precursor films at different reaction temperatures in Examples 1-4.
[0029] Figure 2 These are scanning electron microscope (SEM) images of the γ-AlOOH precursor films obtained at different reaction temperatures in Examples 1-4.
[0030] Figure 3 These are scanning electron microscope images of MOF-303 films obtained at different reaction times in Examples 5-8.
[0031] Figure 4 This describes the separation performance of the MOF-303 crystal membrane in Example 8 for different concentrations of n-butanol / water systems.
[0032] Figure 5 This refers to the separation performance of the MOF-303 crystal membrane in Example 8 for other alcohol / water systems.
[0033] Figure 6 This refers to the separation performance of the MIL crystal membrane in Examples 9-11 for the n-butanol / water system.
[0034] Figure 7 The results show the separation stability test results of the MOF-303 crystal membrane for the n-butanol / water system in Example 8. Detailed Implementation
[0035] The present invention will be further illustrated below with reference to specific embodiments. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the invention. Furthermore, it should be understood that after reading the teachings of this invention, those skilled in the art can make various alterations or modifications to the invention, and these equivalent forms also fall within the scope defined by the appended claims.
[0036] Example 1. Preparation of γ-AlOOH-1 precursor membrane
[0037] Measure 20 ml of acetic acid aqueous solution (pH=3) and transfer it to a 25 ml polytetrafluoroethylene-lined reactor. Place a circular porous γ-Al2O3 support with a diameter of 18 mm and a pore size of 5 nm horizontally in the above aqueous solution. Then, seal the reactor in a stainless steel autoclave and place it in an oven to heat to 135 °C, maintaining the temperature for 4 hours for reaction.
[0038] After the reaction was completed, the mixture was allowed to cool naturally to room temperature. The inner liner of the reactor was opened and the supernatant was poured off. The γ-AlOOH precursor membrane was first placed in water and ultrasonically treated at 300W for 20s. Then it was immersed and washed with deionized water for 60min. After that, it was placed in a 60℃ oven to dry overnight to obtain the γ-AlOOH-1 precursor membrane.
[0039] Example 2. Preparation of γ-AlOOH-2 precursor membrane
[0040] Measure 20 ml of acetic acid aqueous solution (pH=3) and transfer it to a 25 ml polytetrafluoroethylene-lined reactor. Place a circular porous γ-Al2O3 support with a diameter of 18 mm and a pore size of 5 nm horizontally in the above aqueous solution. Then, seal the reactor in a stainless steel autoclave and place it in an oven to heat to 150 °C, maintaining the temperature for 4 hours for reaction.
[0041] After the reaction was completed, the mixture was allowed to cool naturally to room temperature. The inner liner of the reactor was opened and the supernatant was poured off. The γ-AlOOH precursor membrane was first placed in water and ultrasonically treated at 300W for 20s. Then it was immersed and washed with deionized water for 60min. After that, it was placed in a 60℃ oven to dry overnight to obtain the γ-AlOOH-2 precursor membrane.
[0042] Example 3. Preparation of γ-AlOOH-3 precursor membrane
[0043] Measure 20 ml of acetic acid aqueous solution (pH=3) and transfer it to a 25 ml polytetrafluoroethylene-lined reactor. Place a circular porous γ-Al2O3 support with a diameter of 18 mm and a pore size of 5 nm horizontally in the above aqueous solution. Then, seal the reactor in a stainless steel autoclave and place it in an oven to heat to 180 °C, maintaining the temperature for 4 hours.
[0044] After the reaction was completed, the mixture was allowed to cool naturally to room temperature. The inner liner of the reactor was opened and the supernatant was poured off. The γ-AlOOH precursor membrane was first placed in water and ultrasonically treated at 300W for 20s. Then it was immersed and washed with deionized water for 60min and dried in a 60℃ oven overnight to obtain the γ-AlOOH-3 precursor membrane.
[0045] Example 4. Preparation of γ-AlOOH-4 precursor membrane
[0046] Measure 20 ml of acetic acid aqueous solution (pH=3) and transfer it to a 25 ml polytetrafluoroethylene-lined reactor. Place a circular porous γ-Al2O3 support with a diameter of 18 mm and a pore size of 5 nm horizontally in the above aqueous solution. Then, seal the reactor in a stainless steel autoclave and place it in an oven to heat to 220 °C, maintaining the temperature for 4 hours for reaction.
[0047] After the reaction was completed, the mixture was allowed to cool naturally to room temperature. The inner liner of the reactor was opened and the supernatant was poured off. The γ-AlOOH precursor membrane was first placed in water and ultrasonically treated at 300W for 20s. Then it was immersed and washed with deionized water for 60min. After that, it was placed in a 60℃ oven to dry overnight to obtain the γ-AlOOH-4 precursor membrane.
[0048] Example 5. Preparation of MOF-303-1 crystal film
[0049] The γ-AlOOH precursor membrane (i.e., the γ-AlOOH-3 precursor membrane) was prepared using the method described in Example 3.
[0050] Weigh 0.241 g of aluminum chloride hexahydrate, 0.156 g of 3,5-pyrazole dicarboxylic acid, and 0.08 g of sodium hydroxide and dissolve them in 25 ml of water. After stirring and reacting at room temperature for 10 min, transfer the solution to a 100 ml polytetrafluoroethylene-lined reactor. Place the γ-AlOOH precursor membrane vertically in the above mother liquor, then seal the reactor in a stainless steel autoclave and heat it to 100 °C in an oven, maintaining the temperature for 6 h.
[0051] After the reaction was completed, the membrane was transferred to a beaker containing deionized water, ultrasonically treated for 15 seconds using a 200W ultrasonic cleaner, washed with DMF for 30 minutes, and then dried overnight in a 60℃ oven to obtain MOF-303-1 crystal membrane.
[0052] Example 6. Preparation of MOF-303-2 crystal film
[0053] The γ-AlOOH precursor membrane (i.e., γ-AlOOH-3 precursor membrane) was prepared using the method of Example 3. 0.241 g of aluminum chloride hexahydrate, 0.156 g of 3,5-pyrazole dicarboxylic acid, and 0.08 g of sodium hydroxide were weighed and dissolved in 25 ml of water. After stirring at room temperature for 10 min, the solution was transferred to a 100 ml polytetrafluoroethylene-lined reactor. The γ-AlOOH precursor membrane was placed vertically in the above mother liquor. The reactor was then sealed in a stainless steel autoclave and placed in an oven heated to 100°C, maintaining a constant temperature for 12 h.
[0054] After the reaction was completed, the membrane was transferred to a beaker containing deionized water, ultrasonically treated for 15 seconds using a 200W ultrasonic cleaner, washed with DMF for 30 minutes, and then dried overnight in a 60℃ oven to obtain MOF-303-2 crystal membrane.
[0055] Example 7. Preparation of MOF-303-3 crystal film
[0056] The γ-AlOOH precursor membrane (i.e., γ-AlOOH-3 precursor membrane) was prepared using the method of Example 3. 0.241 g of aluminum chloride hexahydrate, 0.156 g of 3,5-pyrazole dicarboxylic acid, and 0.08 g of sodium hydroxide were weighed and dissolved in 25 ml of water. After stirring at room temperature for 10 min, the solution was transferred to a 100 ml polytetrafluoroethylene-lined reactor. The γ-AlOOH precursor membrane was placed vertically in the above mother liquor. Subsequently, the reactor was sealed in a stainless steel autoclave and placed in an oven heated to 100°C, maintaining a constant temperature for 24 h.
[0057] After the reaction was completed, the membrane was transferred to a beaker containing deionized water, ultrasonically treated for 15 seconds using a 200W ultrasonic cleaner, washed with DMF for 30 minutes, and then dried overnight in a 60℃ oven to obtain MOF-303-3 crystal membrane.
[0058] Example 8. Preparation of MOF-303-4 crystal film
[0059] The γ-AlOOH precursor membrane (i.e., the γ-AlOOH-3 precursor membrane) was prepared using the method described in Example 3. 0.241 g of aluminum chloride hexahydrate, 0.156 g of 3,5-pyrazole dicarboxylic acid, and 0.08 g of sodium hydroxide were weighed and dissolved in 25 ml of water. After stirring at room temperature for 10 min, the solution was transferred to a 100 ml polytetrafluoroethylene-lined reactor. The γ-AlOOH precursor membrane was placed vertically in the mother liquor. The reactor was then sealed in a stainless steel autoclave and placed in an oven heated to 100°C, maintaining this temperature for 36 h.
[0060] After the reaction was completed, the membrane was transferred to a beaker containing deionized water, ultrasonically treated for 15 seconds using a 200W ultrasonic cleaner, washed with DMF for 30 minutes, and then dried overnight in a 60℃ oven to obtain MOF-303-4 crystal membrane.
[0061] Example 9. Preparation of MIL-53 crystal film
[0062] The γ-AlOOH precursor membrane (i.e., γ-AlOOH-3 precursor membrane) was prepared using the method described in Example 3. 0.750 g of aluminum nitrate nonahydrate and 0.166 g of terephthalic acid were weighed and dissolved in 25 ml of water. After stirring at room temperature for 10 min, the solution was transferred to a 100 ml polytetrafluoroethylene-lined reactor. The γ-AlOOH precursor membrane was placed vertically in the mother liquor. The reactor was then sealed in a stainless steel autoclave and placed in an oven heated to 150 °C, maintaining this temperature for 24 h.
[0063] After the reaction was completed, the membrane was transferred to a beaker containing deionized water, ultrasonically treated for 15 seconds using a 200W ultrasonic cleaner, washed with DMF for 30 minutes, and then dried overnight in a 60℃ oven to obtain the MIL-53 crystal membrane.
[0064] Example 10. Preparation of MIL-101 crystal film
[0065] The γ-AlOOH precursor membrane (i.e., γ-AlOOH-3 precursor membrane) was prepared using the method described in Example 3. 0.400 g of chromium nitrate nonahydrate and 0.166 g of terephthalic acid were weighed and dissolved in 25 ml of water. After stirring at room temperature for 10 min, the solution was transferred to a 100 ml polytetrafluoroethylene-lined reactor. The γ-AlOOH precursor membrane was placed vertically in the mother liquor. The reactor was then sealed in a stainless steel autoclave and placed in an oven heated to 150 °C, maintaining this temperature for 24 h.
[0066] After the reaction was completed, the membrane was transferred to a beaker containing deionized water, ultrasonically treated for 15 seconds using a 200W ultrasonic cleaner, washed with DMF for 30 minutes, and then dried overnight in a 60℃ oven to obtain the MIL-101 crystal membrane.
[0067] Example 11. Preparation of CAU-10-H crystal film
[0068] The γ-AlOOH precursor membrane (i.e., the γ-AlOOH-3 precursor membrane) was prepared using the method described in Example 3. 0.666 g of aluminum sulfate octadecylhydrate and 0.166 g of isophthalic acid were weighed and dissolved in 20 ml of water and 5 ml of DMF. After stirring at room temperature for 10 min, the solution was transferred to a 100 ml polytetrafluoroethylene-lined reactor. The γ-AlOOH precursor membrane was placed vertically in the mother liquor. The reactor was then sealed in a stainless steel autoclave and placed in an oven heated to 135 °C, maintaining this temperature for 24 h.
[0069] After the reaction was completed, the membrane was transferred to a beaker containing deionized water, ultrasonically treated for 15 seconds using a 200W ultrasonic cleaner, washed with DMF for 30 minutes, and then dried overnight in a 60℃ oven to obtain the CAU-10-H crystal membrane.
[0070] The structure of the high-valent MOF crystal membrane was characterized using X-ray diffraction (XRD) and scanning electron microscopy (SEM), and its separation performance for the butanol / water system was tested using a pervaporation apparatus. The morphology, structure, and butanol / water separation performance of the high-valent MOF crystal membrane prepared in this invention are as follows:
[0071] Figure 1X-ray diffraction patterns of γ-AlOOH precursor films at different reaction temperatures in Examples 1-4 are given. The characteristic peak of the γ-AlOOH layer can be observed at 14.4°, and the intensity of the characteristic peak is stronger at higher reaction temperatures, indicating that the γ-Al2O3 surface is transformed into the γ-AlOOH precursor layer.
[0072] Figure 2 The images are scanning electron microscope (SEM) images of γ-AlOOH precursor films obtained at different reaction temperatures in Examples 1-4, showing that after reaction at 135-220℃, nanosheet-like γ-AlOOH precursor layers are formed on the surface of the support.
[0073] Figure 3 The images are scanning electron microscope (SEM) images of MOF-303 films obtained at different reaction times in Examples 5-8, showing that as the reaction time increases to 36 h, the MOF-303 films obtained on the support surface become uniform and dense.
[0074] Figure 4 The separation performance of the MOF-303 crystal membrane in Example 8 for a 75.5wt% to 99.5wt% n-butanol / water system demonstrates that the MOF-303 membrane can achieve efficient enrichment of butanol / water solutions with different compositions.
[0075] Figure 5 The separation performance of the MOF-303 crystal membrane in Example 8 for a 90 wt.% organic matter (ethanol, n-propanol, isopropanol, n-butanol) / water system demonstrates that the MOF-303 crystal membrane can achieve efficient separation of various alcohol / water systems.
[0076] Figure 6 The diagrams show the separation selectivity and permeability of the high-valent MOF crystal membranes in Examples 9-11 with 1 wt.% n-butanol aqueous solution, indicating that the prepared high-valent MOF membranes all have excellent butanol / water enrichment performance.
[0077] Figure 7 The results show the separation stability test of the MOF-303 crystal membrane in Example 8 for a 90 wt.% n-butanol / water system. During a 160-h pervaporation test, the total permeate flow and separation factor of the crystal membrane remained stable, indicating that the crystal membrane possesses excellent stability.
Claims
1. A method for preparing a high-valence MOF crystalline film, characterized in that, Includes the following steps: (1) Preparation of γ-AlOOH precursor membrane A porous γ-Al2O3 support was placed in an aqueous acetic acid solution and subjected to a solvothermal reaction under closed conditions to obtain a nanosheet-like γ-AlOOH precursor film. The reaction temperature is 130–220°C, and the reaction time is 2–48 h. (2) Preparation of high-valence MOF crystal films Hydrated nitrates, chlorides or aluminum sulfate, carboxylic acid ligands and sodium hydroxide are dissolved in water or a mixed solvent of water and DMF, and the reaction solution is stirred to ensure thorough mixing; the γ-AlOOH precursor membrane is placed in the reaction solution and reacted at 100-200℃ for 6-72h to obtain a porous MOF crystal membrane. The molar ratio of hydrated nitrates, chlorides or aluminum sulfate, carboxylic acid ligands to water is 1:0.25~4:0~4:400~2000; The hydrated nitrate is one or two of aluminum nitrate nonahydrate, chromium nitrate nonahydrate, and ferric nitrate nonahydrate; the hydrated chloride is one or two of aluminum chloride hexahydrate and ferric chloride hexahydrate; the hydrated aluminum sulfate is aluminum sulfate octadecahydrate; and the carboxylic acid ligand is one or more of terephthalic acid, isophthalic acid, trimesic acid, 2-aminoterephthalic acid, 3,5-pyrazoledicarboxylic acid, and 2,5-furandicarboxylic acid.
2. The method for preparing MOF crystal films according to claim 1, characterized in that, In step (1), the pH of the acetic acid aqueous solution is 2 to 4.
3. The method for preparing MOF crystal films according to claim 1, characterized in that, In step (1), after the reaction is complete, the γ-AlOOH precursor membrane is washed and dried.
4. The method for preparing MOF crystal films according to claim 3, characterized in that, The washing process involves first placing the γ-AlOOH precursor membrane in water, then ultrasonically treating it at 50-400W for 5-30 seconds, followed by immersion in deionized water or anhydrous ethanol for 5-120 minutes. The drying temperature is 50-80℃, and the membrane is dried overnight.
5. The method for preparing MOF crystal films according to claim 1, characterized in that, In step (2), the volume ratio of water to DMF in the mixed solvent of water and DMF is 1 to 8:1; The γ-AlOOH precursor membrane was placed vertically in the reaction solution.
6. The method for preparing MOF crystal films according to claim 1, characterized in that, In step (2), after the reaction is complete, the crystal film is washed and dried.
7. The method for preparing MOF crystal films according to claim 5, characterized in that, The washing process involves first placing the crystal membrane in water and then ultrasonically treating it at 50-400W for 5-30 seconds, followed by immersion and washing with N,N-dimethylformamide or anhydrous ethanol for 5-120 minutes. The drying temperature is 50-100℃, and the membrane is dried overnight.
8. The MOF crystal film prepared by the method according to any one of claims 1-7.
9. The application of the MOF crystal membrane according to claim 8 in the separation of organic matter / water systems.
10. The application according to claim 9, characterized in that, The organic compound is methanol, ethanol, n-propanol, isopropanol, n-butanol, or acetone.