CN113651978A - PEDOT (PEDOT/PSS) hydrogel as well as preparation method and application thereof - Google Patents
PEDOT (PEDOT/PSS) hydrogel as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of photo-thermal conversion, and particularly relates to PEDOT (Poly ethylene terephthalate) PSS (Poly ethylene terephthalate) hydrogel as well as a preparation method and an application thereof, wherein the preparation method comprises the following steps of mixing methanol with PEDOT PSS solution; adding concentrated sulfuric acid, and partially removing the PSS in the PEDOT PSS to obtain a mixed solution; and heating the mixed solution to obtain the PEDOT/PSS hydrogel. The method uses the PEDOT and PSS solution as the main raw material to prepare the hydrogel, has simple and convenient preparation process and easy operation, and reduces the evaporation enthalpy of the water molecules through the activation effect on the water molecules, so that the water evaporation rate breaks through the theoretical limit. Due to the combined action of PEDOT and PSS, the interface photothermal conversion water evaporation device still has excellent durability, stability and salt rejection while realizing efficient photothermal conversion water evaporation. In the interface photo-thermal conversion water evaporation device, an all-dimensional wrapped heat insulation structure is designed, so that the heat loss can be greatly reduced, and the energy utilization efficiency is improved.
Description
Technical Field
The invention belongs to the technical field of photothermal conversion, and particularly relates to PEDOT (poly (3, 4-ethylenedioxythiophene) (polystyrene sulfonate)) hydrogel and a preparation method and application thereof.
Background
Fresh water resources play an important role in the development of human society and the promotion of ecological civilization construction. In order to realize sustainable development, a high-efficiency seawater desalination method needs to be explored to obtain enough fresh water resources. Large scale industrial desalination of sea water has become a strategic solution in many coastal countries to alleviate the shortage of fresh water resources and to cope with climate change. Seawater occupies about 70% of the earth's surface, and obtaining fresh water from seawater is a viable method. Solar energy is a renewable energy source, and reaches the earth's surface at energies of 173000 TW. The interface photo-thermal conversion water evaporation can efficiently convert solar energy into heat energy, and a water body is heated in a gas-liquid interface in a centralized manner to realize seawater desalination. Compare in water evaporation under the natural condition, use the light and heat conversion material can greatly accelerate evaporation rate, light and heat conversion material absorbs moisture and produces vapour, retrieves the water vapour after the condensation and can obtain the fresh water of preliminary treatment. High-temperature water vapor is generated in the photo-thermal conversion process, protein of thalli is denatured at instantaneous high temperature, the structure is destroyed, and the thalli become unstable and are further killed, and most of microorganisms, bacteria, viruses and the like can be killed by the method. In the interface photothermal conversion water evaporation system, free solar energy is used for supplying energy, the photothermal conversion material has better durability, only water needs to be consumed and replaced, and the system has no harsh requirement on water quality, so that the cost of the system is greatly reduced.
The commonly used photothermal conversion materials include plasma-based materials, semiconductor materials, carbon-based materials, and the like.
Among them, due to its unique optical characteristics, plasma metal generates huge heat under solar irradiation due to the surface plasmon resonance effect. When the oscillation frequency of delocalized electrons in the plasma metal matches the wave frequency of the incident light, a collective excitation of electrons and subsequent generation of thermal electrons is triggered, and the excited thermal electrons oscillate coherently with the incident electromagnetic field, generating heat by the joule mechanism. Hot carriers rapidly redistribute energy through electron-electron scattering processes, heating the plasma elements themselves.
When the excited electrons eventually return to a low energy level, energy is released by radiative relaxation in the form of photons or non-radiative relaxation in the form of phonons, transferred to impurities or surface dangling bonds of the material. When energy is released by phonons, local heating of the crystal lattice may be induced, thereby establishing a temperature distribution according to light absorption and bulk/surface recombination characteristics. In a narrow bandgap semiconductor, since most of the photons of the incident sunlight have energies above the bandgap, electron-hole pairs with energies above the bandgap are generated. These electron-hole pairs will relax to the band edges, converting additional energy into heat through a thermalization process.
The carbon-based material absorbs light energy and converts it into heat by lattice vibration. E.g. a single carbon bond has a larger energy gap between σ and σ, corresponding to incident light below 350nm in the solar spectrum. The conversion from σ to σ @cannotbe achieved under solar radiation. Since the bonding electrons are weak, pi bonds are generally weaker than sigma bonds, and electrons can be excited from pi to pi-x orbitals with lower energy input. Moreover, conjugated pi bonds can also cause a red shift in the absorption spectrum. As the number of pi bonds increases, the energy gap between the highest occupied molecular orbital and the lowest occupied molecular orbital decreases. This allows a large number of loose electrons to be easily excited from pi-orbital to pi-orbital with only a small input of energy. When the photon energy of the incident light matches the energy of an electron transition that may occur within the molecule, the excited electrons will be lifted from the ground state to a higher energy orbit, and heat will be released when the excited electrons relax back to the ground state.
Among the above photothermal conversion materials, the plasma-based photothermal conversion material has high-efficiency and localized heat energy conversion capability, but only absorbs narrow-band light around the resonance peak, and the absorption of the material to light and the corresponding temperature rise performance are greatly influenced by the structural form and the composition, and has high cost and poor expansibility.
The spectral absorption range of semiconductor materials depends on the band gap energy, which is very large and therefore absorbs little energy in the infrared region. However, the infrared region accounts for about 50% of the solar energy, and the energy absorption range can be increased by adjusting the energy band gap through doping.
The carbon-based material has generally low water evaporation rate and single preparation method, and is difficult to realize high-efficiency and rapid water evaporation.
Use 1kW m-2The illumination intensity of the composite material is difficult to combine quick water evaporation, efficient energy utilization, low cost, excellent salt resistance, excellent stability and durability by utilizing the three materials under normal temperature and normal pressure.
Disclosure of Invention
The invention aims to solve the problems and provides a PEDOT/PSS hydrogel as well as a preparation method and application thereof.
According to the technical scheme of the invention, the preparation method of the PEDOT/PSS hydrogel comprises the following steps,
s1: dissolving a PEDOT PSS solution in a solvent;
s2: adding concentrated sulfuric acid, and partially removing the PSS in the PEDOT (polyethylene glycol terephthalate)/PSS (styrene sulfonate) to obtain a mixed solution, wherein the mass ratio of solute in the concentrated sulfuric acid to the PEDOT/PSS is 6-14: 1;
s3: and heating the mixed solution to obtain the PEDOT/PSS hydrogel.
Further, the solvent is selected from one or more of methanol, ethylene glycol and isopropanol.
Further, in the step S1, the volume ratio of the PEDOT to the PSS solution to the solvent is 1: 1-2.
Further, in the step S2, the concentrated sulfuric acid is added dropwise.
Further, in the step S3, the heating temperature is 40-70 ℃ and the time is 2.5-4 h.
In a second aspect, the invention provides a PEDOT PSS hydrogel prepared by the above preparation method.
According to a third aspect of the invention, there is provided the use of the above-described PEDOT: PSS hydrogel in photothermal conversion.
The interface photo-thermal conversion water evaporation device comprises a heat insulation device, a water delivery device and a photo-thermal conversion device, wherein the heat insulation device comprises a heat insulation block, a heat insulation ring and a heat insulation plate;
the water delivery device wraps the top surface and the side surfaces of the heat insulation blocks and extends downwards, and the heat insulation ring is sleeved outside the side edge of the water delivery device;
the photothermal conversion device is placed on top of the water delivery device, the photothermal conversion device using the PEDOT: PSS hydrogel of claim 5;
the heat insulation plate covers the top of the water delivery device, and a through hole is formed in the position, corresponding to the photothermal conversion device, of the heat insulation plate.
Specifically, the heat insulation block can be in various shapes such as square, round and the like, and is used for realizing bottom heat insulation; the middle part of the heat insulation ring is provided with a through hole in the shape of a heat insulation block for realizing side heat insulation; the heat insulation plate is used for realizing heat insulation and shading of the top; the whole device realizes the heat insulation combination of the top, the side and the bottom and the omnibearing heat management.
Furthermore, the heat insulation block and the heat insulation ring are made of polystyrene foam materials, and the heat insulation plate is a glass fiber resin plate.
Further, the water delivery device is a wood pulp fiber felt.
The PEDOT PSS hydrogel can reduce the required evaporation enthalpy by changing the specific gravity of three states of water molecules (bound water, free water, meso-state water). PSS hydrogel can capture nearby water molecules through strong interactions to form bound water, while free water separates from the polymer chains due to the hydration effect. Free water can evaporate as a single molecule, or in small clusters consisting of tens of molecules, compared to free water and bound water, which requires relatively less energy to be consumed. Therefore, the interface photothermal conversion water evaporation system containing the PEDOT/PSS hydrogel can achieve a higher evaporation rate under the condition of inputting the same energy.
Compared with the prior art, the technical scheme of the invention has the following advantages:
the method uses the PEDOT and PSS solution as the main raw material to prepare the hydrogel, has simple and convenient preparation process and easy operation, and reduces the evaporation enthalpy of the water molecules through the activation effect on the water molecules, so that the water evaporation rate breaks through the theoretical limit. Due to the combined action of PEDOT and PSS, the interface photothermal conversion water evaporation device still has excellent durability, stability and salt rejection while efficiently photothermal conversion water evaporation is carried out in advance; in the interface photo-thermal conversion water evaporation device, an all-dimensional wrapped heat insulation structure is designed, so that the heat loss can be greatly reduced, and the energy utilization efficiency is improved.
Drawings
FIG. 1 is a scanning electron micrograph of a PEDOT PSS hydrogel of the present invention.
Fig. 2 is a short time (a) and long time (b) duty cycle test chart.
FIG. 3 is a flow chart of the preparation of the PEDOT PSS hydrogel of the present invention.
Fig. 4 is a schematic structural view of the interface photothermal conversion water evaporation device.
FIG. 5 model diagram of the outdoor interface photothermal conversion water evaporation before condensation (a) and during condensation (b)
Description of reference numerals: 1-heat insulation ring, 2-heat insulation block, 3-water conveying device, 4-photo-thermal conversion device, 5-heat insulation plate and 6-seawater.
Detailed Description
The present invention is further described below in conjunction with the following figures and specific examples so that those skilled in the art may better understand the present invention and practice it, but the examples are not intended to limit the present invention.
EXAMPLE 1 preparation of PEDOT PSS hydrogel
As shown in fig. 3, methanol and PEDOT: PSS solutions were mixed in a volume ratio of 1: 1 mixing, and dropping concentrated sulfuric acid into the mixed solution to partially remove the PSS. The PEDOT: PSS hydrogel was formed after heating the mixed solution in a 60 ℃ silicone oil bath for 3 hours, the hydrogel having a thickness of about 3mm and a diameter of about 2.8 cm. The PEDOT PSS hydrogel was repeatedly washed with deionized water to remove excess methanol and sulfuric acid until the pH reached 7. The scanning electron micrograph of the obtained PEDOT PSS hydrogel is shown in figure 1.
The using amount of the methanol is increased, so that the volume ratio of the methanol to the PEDOT/PSS solution is 2:1, the hydrogel can still be synthesized, and the final performance has no obvious difference.
Hydrogels can also be synthesized by replacing methanol with ethylene glycol or isopropanol.
Using concentrated sulfuric acid and PEDOT, wherein PSS solution is used as raw material; or concentrated sulfuric acid, deionized water and PEDOT and PSS solution are used as raw materials, and the hydrogel cannot be synthesized.
The optimal raw material ratio is researched by taking the mass ratio of solute in concentrated sulfuric acid to PEDOT to PSS (the solid content ratio of the concentrated sulfuric acid to the PEDOT to PSS solution) as 6:1, 8:1, 10:1, 12:1 and 14:1 as variables, and the corresponding water evaporation rates are respectively 1.99 kg.m-2·h-1、2.44kg·m-2·h-1、2.76kg·m-2·h-1、2.39kg·m-2·h-1And 2.11 kg. m-2·h-1The water evaporation efficiencies were 78.3%, 85.7%, 93.2%, 86.5%, and 81.6%, respectively. The optimal raw material ratio is that the solid content ratio of the sulfuric acid to the PEDOT to PSS solution is 10: 1.
The temperature of the silicon oil bath is adjusted to be 40 ℃, 50 ℃, 70 ℃ or 80 ℃, the time is fixed for 3 hours, and the solid content ratio of the sulfuric acid to the PEDOT to PSS solution is 10: 1. Under the condition of low temperature, the reaction is incomplete, so that the gel is not uniformly formed; under the condition of over-high temperature, the reaction is over violent, the raw material solution can be evaporated to be dry, and the surface of the gel is slightly cracked; the final water evaporation rate was 2.39kg · m, respectively-2·h-1、2.52kg·m-2·h-1、2.5kg·m-2·h-1And 1.66kg m-2·h-1。
Example 2 use of PEDOT PSS hydrogel
As shown in fig. 4, the interface photothermal conversion water evaporation device was placed on the surface of seawater 6, and 4 layers of hydrophilic wood pulp fiber felt were used as the water transport device 3. Polystyrene foam having a thickness of 2.5cm, an outer side length of 10cm and an inner side length of 3cm was used as the heat insulating ring 1 (side heat insulating structure)A square polystyrene foam having a thickness of 2.5cm and a side length of 2.8cm was used as the heat insulating block 2 (bottom heat insulating structure), and a glass fiber resin sheet having an opening of 2cm in diameter was used as the heat insulating panel 5 (top heat insulating and light shielding structure). The PEDOT PSS hydrogel as the photothermal conversion device 4 is placed on the opening of the heat insulation plate 5 on the water delivery device 3. The light source intensity is adjusted to 1 kW.m-2For subsequent measurements. The mass change was recorded every 30 seconds using a balance and the resulting data was processed to calculate the water evaporation rate.
As shown in FIG. 5, in order to simulate the practical application scenario, an outdoor interface photothermal conversion water evaporation model was assembled, which uses polystyrene foam with a diameter of 15cm and a thickness of 2.5cm and with 4 holes drilled inside and with a diameter of 3cm as a side insulation structure, 4 cylindrical polystyrene foams with a thickness of 2.5cm and a diameter of 2.8cm as a bottom insulation structure, and 4 sets of PEDOT: PSS hydrogels were evaporated simultaneously, each set using 4 layers of hydrophilic wood pulp fiber felt as a water transport structure.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications of the invention may be made without departing from the spirit or scope of the invention.
Claims (10)
1. A preparation method of PEDOT PSS hydrogel is characterized by comprising the following steps,
s1: dissolving a PEDOT PSS solution in a solvent;
s2: adding concentrated sulfuric acid, and partially removing the PSS in the PEDOT (polyethylene glycol terephthalate)/PSS (styrene sulfonate) to obtain a mixed solution, wherein the mass ratio of solute in the concentrated sulfuric acid to the PEDOT/PSS is 6-14: 1;
s3: and heating the mixed solution to obtain the PEDOT/PSS hydrogel.
2. The method of claim 1, wherein the solvent is selected from one or more of methanol, ethylene glycol, and isopropanol.
3. The method for preparing the PEDOT to PSS hydrogel according to claim 1 or 2, wherein the volume ratio of the PEDOT to PSS solution to the solvent in the step S1 is 1: 1-2.
4. The method of claim 1, wherein the step S2 comprises adding concentrated sulfuric acid dropwise.
5. The method of claim 1, wherein the step S3 comprises heating at 40-70 deg.C for 2.5-4 h.
6. PSS hydrogel prepared by the preparation method according to any one of claims 1 to 5.
7. PSS hydrogel according to claim 6 for use in photothermal conversion.
8. The use according to claim 7, for an interfacial photothermal conversion water evaporation device comprising a thermal insulation means, a water delivery means and a photothermal conversion means, said thermal insulation means comprising a thermal insulation block, a thermal insulation ring and a thermal insulation plate;
the water delivery device wraps the top surface and the side surfaces of the heat insulation blocks and extends downwards, and the heat insulation ring is sleeved outside the side edge of the water delivery device;
the photothermal conversion device is placed on top of the water delivery device, the photothermal conversion device using the PEDOT: PSS hydrogel of claim 5;
the heat insulation plate covers the top of the water delivery device, and a through hole is formed in the position, corresponding to the photothermal conversion device, of the heat insulation plate.
9. The use of claim 8, wherein the insulation blocks and rings are formed of polystyrene foam and the insulation panels are formed of fiberglass resin sheets.
10. The use of claim 8, wherein the water transport device is a wood pulp fiber mat.
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| WO2020000062A1 (en) * | 2018-06-29 | 2020-01-02 | The University Of Sydney | Hydrogel-based ph sensors for wet environments |
| CN112708148A (en) * | 2020-12-24 | 2021-04-27 | 江西科技师范大学 | Preparation method of conductive polymer hydrogel applied to solar water purification |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2020000062A1 (en) * | 2018-06-29 | 2020-01-02 | The University Of Sydney | Hydrogel-based ph sensors for wet environments |
| CN112708148A (en) * | 2020-12-24 | 2021-04-27 | 江西科技师范大学 | Preparation method of conductive polymer hydrogel applied to solar water purification |
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| YAO, B.ET. AL.: "Ultrahigh-Conductivity Polymer Hydrogels with Arbitrary Structures", 《ADV. MATER.》 * |
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