CN114957805B - Two-dimensional cellulose nano fluid channel membrane and preparation method and application thereof - Google Patents
Two-dimensional cellulose nano fluid channel membrane and preparation method and application thereof Download PDFInfo
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- 229920002678 cellulose Polymers 0.000 title claims abstract description 81
- 239000001913 cellulose Substances 0.000 title claims abstract description 75
- 239000012528 membrane Substances 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000012530 fluid Substances 0.000 title claims abstract description 11
- 239000002131 composite material Substances 0.000 claims abstract description 54
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 239000002121 nanofiber Substances 0.000 claims abstract description 22
- 239000002086 nanomaterial Substances 0.000 claims abstract description 20
- 239000002090 nanochannel Substances 0.000 claims abstract description 9
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002135 nanosheet Substances 0.000 claims abstract description 8
- 239000002064 nanoplatelet Substances 0.000 claims abstract description 5
- 230000003647 oxidation Effects 0.000 claims abstract description 4
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 4
- 239000000725 suspension Substances 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 239000008367 deionised water Substances 0.000 claims description 21
- 229910021641 deionized water Inorganic materials 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 10
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 8
- 239000013049 sediment Substances 0.000 claims description 7
- 238000000265 homogenisation Methods 0.000 claims description 6
- 239000012982 microporous membrane Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000000967 suction filtration Methods 0.000 claims description 6
- 239000003153 chemical reaction reagent Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- 238000010008 shearing Methods 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 3
- 238000009830 intercalation Methods 0.000 claims description 3
- 230000002687 intercalation Effects 0.000 claims description 3
- 229910001416 lithium ion Inorganic materials 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 239000012467 final product Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000003204 osmotic effect Effects 0.000 abstract description 15
- 230000005540 biological transmission Effects 0.000 abstract description 8
- 238000005286 illumination Methods 0.000 abstract description 7
- 230000037427 ion transport Effects 0.000 abstract description 4
- 230000004907 flux Effects 0.000 abstract description 3
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 24
- 150000002500 ions Chemical class 0.000 description 18
- 239000003792 electrolyte Substances 0.000 description 17
- 239000001103 potassium chloride Substances 0.000 description 12
- 235000011164 potassium chloride Nutrition 0.000 description 12
- 239000004205 dimethyl polysiloxane Substances 0.000 description 8
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 8
- 239000000806 elastomer Substances 0.000 description 8
- 229920001971 elastomer Polymers 0.000 description 8
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 description 8
- 238000004987 plasma desorption mass spectroscopy Methods 0.000 description 8
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 8
- 229920001131 Pulp (paper) Polymers 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229910021607 Silver chloride Inorganic materials 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 4
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 3
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- -1 polyethylene terephthalate Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- KZEVSDGEBAJOTK-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[5-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CC=1OC(=NN=1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O KZEVSDGEBAJOTK-UHFFFAOYSA-N 0.000 description 2
- IHCCLXNEEPMSIO-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 IHCCLXNEEPMSIO-UHFFFAOYSA-N 0.000 description 2
- 102000004310 Ion Channels Human genes 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000010907 mechanical stirring Methods 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 239000013535 sea water Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- JQMFQLVAJGZSQS-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-N-(2-oxo-3H-1,3-benzoxazol-6-yl)acetamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)NC1=CC2=C(NC(O2)=O)C=C1 JQMFQLVAJGZSQS-UHFFFAOYSA-N 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000003278 mimic effect Effects 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01L—CHEMICAL OR PHYSICAL LABORATORY APPARATUS FOR GENERAL USE
- B01L3/00—Containers or dishes for laboratory use, e.g. laboratory glassware; Droppers
- B01L3/50—Containers for the purpose of retaining a material to be analysed, e.g. test tubes
- B01L3/502—Containers for the purpose of retaining a material to be analysed, e.g. test tubes with fluid transport, e.g. in multi-compartment structures
- B01L3/5027—Containers for the purpose of retaining a material to be analysed, e.g. test tubes with fluid transport, e.g. in multi-compartment structures by integrated microfluidic structures, i.e. dimensions of channels and chambers are such that surface tension forces are important, e.g. lab-on-a-chip
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01L—CHEMICAL OR PHYSICAL LABORATORY APPARATUS FOR GENERAL USE
- B01L2200/00—Solutions for specific problems relating to chemical or physical laboratory apparatus
- B01L2200/02—Adapting objects or devices to another
- B01L2200/026—Fluid interfacing between devices or objects, e.g. connectors, inlet details
- B01L2200/027—Fluid interfacing between devices or objects, e.g. connectors, inlet details for microfluidic devices
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01L—CHEMICAL OR PHYSICAL LABORATORY APPARATUS FOR GENERAL USE
- B01L2300/00—Additional constructional details
- B01L2300/12—Specific details about materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2301/04—Oxycellulose; Hydrocellulose
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3009—Sulfides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/28—Nitrogen-containing compounds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
Abstract
The invention discloses a two-dimensional cellulose nano fluid channel membrane, a preparation method and application thereof, wherein a two-dimensional nano material and cellulose nano fiber are combined to form a two-dimensional nano material/cellulose composite membrane, and the two-dimensional nano material/cellulose composite membrane is internally provided with rich layered nano channels, shows ultra-fast ion transmission and can realize high-efficiency osmotic energy conversion. The cellulose nanofiber in the two-dimensional cellulose nanofluid channel membrane is obtained by TEMPO oxidation, and the two-dimensional nanomaterial comprises g-C 3 N 4 Nanoplatelets and WS 2 A nano-sheet. The nanofluidic channel membrane has high charge density and lamellar nanochannels, has high ion flux, exhibits ultra-fast ion transport, exhibits high osmotic energy conversion performance in energy conversion applications, and can further enhance osmotic energy conversion performance by increasing temperature or providing illumination.
Description
Technical Field
The invention belongs to the field of nanofluidic devices, and particularly relates to a two-dimensional cellulose nanofluidic channel membrane, and a preparation method and application thereof.
Background
The rapid development of human society has led to a rapid increase in energy consumption, and thus the development of green new energy has received increasing attention. Osmotic energy is a renewable energy source derived from the salinity gradient between seawater and river water, also known as salinity gradient energy, and the heuristic that the powered eel can convert osmotic energy stored in the concentration gradient into electrical energy (voltage up to 600V) through ion channels, so far, many studies have been developed to mimic the function of ion channels in living beings with various types of nanofluidic channel membranes to exploit this potentially enormous energy source. One-dimensional nanofluidic channels, including silica channels, anodic Aluminum Oxide (AAO) channels, and track etched polyethylene terephthalate (PET) nanopores, have been commonly used in the past for conversion of osmotic energy, but high resistance and low pore density have limited their application, and to address this problem, more and more scientists have focused on two-dimensional nanofluidic channel membranes. Two-dimensional nanofluidic channel membranes continuous nanofluidic channels formed by stacking two-dimensional nanofluidic sheets, various two-dimensional materials such as boron nitride, graphene derivatives, transition metal tungsten carbide/nitride, transition metal dichalcogenide and the like are assembled into nanofluidic channel membranes in recent years, and research shows that the nanochannels of two-dimensional nanofluidic exhibit ultra-fast ion transmission, and the surface charges of the nanochannels can control selective ion transmission, however, the preparation is complex, the cost is high, the performance is low, the long-term stability is poor and other challenges limit the application of the nanofluidic channel membranes on an industrial scale. Therefore, efficient ion transport of nanofluids with controllable material build structures with superior stability, mechanical flexibility, high efficiency, sustainability, and low economic cost is sought.
Disclosure of Invention
The invention aims to: aiming at the defects of the prior art, the invention provides a two-dimensional cellulose nano fluid channel membrane and a preparation method thereof, which have high charge density and lamellar nano channels, have high ion flux, show ultra-fast ion transmission and have higher osmotic energy conversion performance in energy conversion application.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a two-dimensional cellulose nano fluid channel membrane is formed by combining a two-dimensional nano material and cellulose nano fibers, and the two-dimensional nano material/cellulose composite membrane is internally provided with rich lamellar nano channels, so that ultra-fast ion transmission is realized, and high-efficiency osmotic energy conversion can be realized.
Preferably, the two-dimensional nanomaterial is g-C 3 N 4 Nanoplatelets or WS 2 A nano-sheet.
Further, the invention also provides a preparation method of the two-dimensional cellulose nanofluidic channel membrane, which comprises the following steps:
(1) Preparation of g-C 3 N 4 Nanoplatelets or WS 2 Two-dimensional nanomaterial of nanoplatelets;
(2) Preparing a cellulose nanofiber solution;
(3) And preparing the two-dimensional nano material/cellulose composite membrane by adopting a vacuum suction filtration method.
In step (1), the g-C 3 N 4 The nano-sheet is prepared by the following method:
urea is used as a raw material, the raw material is heated to 823K at a heating rate of 3K/min, the constant temperature is used for pyrolysis reaction for 4 hours, and the product is naturally cooled to room temperature, so that yellowish carbon nitride powder is obtained.
In step (1), the WS 2 The nano-sheet is prepared by a lithium ion intercalation stripping method.
In the step (2), the cellulose nanofiber is obtained by a TEMPO oxidation method, and the specific method comprises the following steps:
dispersing the dried pulp in deionized water to form a uniform pulp suspension; TEMPO reagent and NaBr were completely dispersed in deionized water, followed by addition to the pulp suspension, ph=10 adjustment, and stirring reaction at room temperature for 2 hours; after the reaction is finished, washing the pulp after the reaction to be neutral by adopting deionized water; finally, obtaining the transparent gel-like cellulose nanofiber solution through high-pressure homogenization mechanical shearing.
In the step (3), the two-dimensional nano material/cellulose composite film is prepared by adopting a vacuum suction filtration method, and the method comprises the following steps:
s1: mixing the two-dimensional nano material obtained in the step (1) and the cellulose nanofiber solution obtained in the step (2) in deionized water to obtain a mixed solution;
s2: mechanically stirring and ultrasonically treating the mixed solution to obtain a suspension;
s3: homogenizing the suspension at high pressure to obtain a uniform suspension;
s4: vacuum filtering the suspension with a vacuum filter equipped with cellulose ester microporous membrane, drying the obtained sediment, and stripping from the substrate.
Preferably, in the step S1, the mass fraction of the two-dimensional nano material in the obtained solution is 65-90%; preferably g-C 3 N 4 67wt%, WS 2 90wt%.
Preferably, in step S4, the cellulose ester microporous membrane has a pore size in the range of 0.2 to 0.3. Mu.m.
Furthermore, the invention also claims the application of the two-dimensional cellulose nanofluidic channel membrane in preparing nanofluidic devices.
The two-dimensional cellulose nanofluidic channel membrane is used for preparing a nanofluidic device, and the osmotic energy conversion efficiency is improved by increasing the working temperature or applying light.
The beneficial effects are that:
(1) The raw materials involved in the invention are wide in sources, green and environment-friendly, the preparation method is simple, convenient and universal, the prepared composite membrane material has high ion flux and ultra-fast ion transmission, and the membrane material can be applied to energy conversion to realize efficient conversion from osmotic energy to electric energy under different salinity gradients; under the synergistic effect of salinity gradient and temperature or light stimulus, the transmembrane ion current generates a summation effect to generate high output power density.
(2) The nano fluid channel membrane prepared by the invention has g-C under the condition of simulating sea water/river water at room temperature 3 N 4 The actual power density of the cellulose composite film can reach 0.15 and 0.15W m -2 By increasing the operating temperature to 333K, the actual power density can be increased to 0.22W m -2 。WS 2 The actual power density of the cellulose composite film can reach 1.8W m -2 By applying light to one side, the actual power density can be increased to 2.7W m -2 。
Drawings
The foregoing and/or other advantages of the invention will become more apparent from the following detailed description of the invention when taken in conjunction with the accompanying drawings and detailed description.
FIG. 1 is a graph of g-C prepared in example 1 3 N 4 Cellulose compositePhoto and electron microscope image of the film;
FIG. 2 is a WS prepared in example 2 2 Photo and electron microscope image of cellulose composite film;
FIG. 3 is a graph of g-C as described in example 3 3 N 4 Ion conductivity diagrams of cellulose composite films in potassium chloride electrolytes with different concentrations;
FIG. 4 is a graph of g-C as described in example 3 3 N 4 Temperature dependence graph of ionic conductivity of cellulose composite membrane;
FIG. 5 is a graph of g-C as described in example 4 3 N 4 Output power density diagram of cellulose composite film in different concentration gradient potassium chloride electrolyte;
FIG. 6 is a graph of g-C as described in example 4 3 N 4 Temperature dependence graph of output power density of cellulose composite membrane;
FIG. 7 is a WS as described in example 5 2 Ion conductivity diagrams of cellulose composite films in potassium chloride electrolytes with different concentrations;
FIG. 8 is a WS as described in example 5 2 I-t graph of the cellulose composite film before and after application of light;
FIG. 9 is a WS as described in example 6 2 Short-circuit current Isc of the cellulose composite film in potassium chloride electrolyte with different concentration gradients;
FIG. 10 is a WS as described in example 6 2 Output power density plot of the cellulose composite film before and after illumination.
Detailed Description
The invention will be better understood from the following examples.
Example 1
g-C 3 N 4 The preparation of the cellulose composite membrane comprises the following specific implementation steps:
(1) Preparation of g-C 3 N 4 Nanosheets: placing 10g urea into a crucible, heating in a muffle furnace, slowly heating to 823K at a heating rate of 3K/min, reacting at the temperature for 4h to ensure sufficient pyrolysis, then closing the furnace to naturally cool the product to room temperature, and obtaining a light yellow carbon nitride powder sediment for further separationAnd (5) separating.
(2) Preparation of cellulose nanofibers: firstly, weighing 3g of paper pulp dried in an oven, and dispersing the paper pulp in 300mL of deionized water through mechanical stirring to form a uniform paper pulp suspension; next, 0.045g TEMPO reagent and 0.3g NaBr were thoroughly dispersed in deionized water and then added to the above suspension; the pH of the suspension was adjusted to 10 by adding 0.5M NaOH aqueous solution to the suspension using a pH meter, the suspension was stirred at room temperature for 2 hours, the reacted pulp was then washed with deionized water until neutral, and finally a transparent gel-like fiber solution was obtained by mechanical shearing at high pressure homogenization. Before use, the prepared cellulose nanofiber is stored at the temperature of 4 ℃.
(3) Preparation of g-C 3 N 4 Cellulose composite membrane: weighing quantitative g-C 3 N 4 Powder and gel cellulose nanofibers maintained at a total mass of 0.5g, 33wt% cellulose nanofibers, 67wt% g-C 3 N 4 Placing the powder into a beaker, and adding deionized water into the mixture until the volume is 100mL; then, mechanically stirring the mixture for 30min and ultrasonically treating the mixture for 60min, and adding deionized water to obtain 300mL of suspension; subsequently subjecting the suspension to a high-pressure homogenization treatment for 10 cycles at a pressure of 550MPa to obtain a uniform suspension; finally g-C 3 N 4 Vacuum filtering cellulose nanofiber suspension with a suction filtration device equipped with cellulose ester microporous membrane, washing the sediment with 20mL deionized water for 3 times to remove foreign ions, drying the sediment in air for 4 days, and stripping the composite membrane from the substrate to obtain g-C 3 N 4 The photo and electron microscope of the cellulose composite film is shown in FIG. 1.
Example 2
WS 2 The preparation of the cellulose composite membrane comprises the following specific implementation steps:
(1) Preparation of WS by conventional lithium ion intercalation stripping method 2 A nano-sheet.
(2) Preparation of cellulose nanofibers: firstly, weighing 3g of paper pulp dried in an oven, and dispersing the paper pulp in 300mL of deionized water through mechanical stirring to form a uniform paper pulp suspension; next, 0.045g TEMPO reagent and 0.3g NaBr were thoroughly dispersed in deionized water and then added to the above suspension; the pH of the suspension was adjusted to 10 by adding 0.5M NaOH aqueous solution to the suspension using a pH meter, the suspension was stirred at room temperature for 2 hours, the reacted pulp was then washed with deionized water until neutral, and finally a transparent gel-like fiber solution was obtained by mechanical shearing at high pressure homogenization. Before use, the prepared cellulose nanofiber is stored at the temperature of 4 ℃.
(3) Preparation of WS 2 Cellulose composite membrane: weigh 90wt% WS 2 And 10wt% gel-like cellulose nanofibers, maintaining a total mass of 0.5g, placing in a beaker according to a desired mass ratio, adding deionized water to the mixture to a volume of 100mL; then, mechanically stirring the mixture for 30min and ultrasonically treating the mixture for 60min, and adding deionized water to obtain 300mL of suspension; subsequently subjecting the suspension to a high-pressure homogenization treatment for 10 cycles at a pressure of 550MPa to obtain a uniform suspension; finally WS is processed 2 Vacuum filtering cellulose nanofiber suspension with a suction filtration device equipped with cellulose ester microporous membrane, washing the sediment with 20mL deionized water for 3 times to remove foreign ions, drying the sediment in air for 4 days, and stripping the composite membrane from the substrate to obtain WS 2 The photo and electron microscope of the cellulose composite film is shown in FIG. 2.
Example 3
For g-C prepared in example 1 3 N 4 The cellulose composite film is subjected to ion transmission performance test, and specifically comprises the following steps:
(1) Cutting the composite membrane into rectangular blocks, and then coating in a two-chamber electrochemical cell; to avoid leakage, a top sealing layer composed of a transparent PDMS elastomer was attached to the composite membrane, and then two electrolyte reservoirs were engraved in the PDMS elastomer to expose both ends of the composite membrane.
(2) The ionic conductivity of the composite membrane was measured using a CHI660B electrochemical workstation at a specific concentration of potassium chloride electrolyte, with a scan voltage ranging from-1V to +1v.
(3) The transmembrane potential was measured with a standard Ag/AgCl electrode and the result is shown in fig. 3, where CNF is cellulose nanofiber.
(4) The temperature dependence of the ion transport properties of the composite membrane was tested by increasing the operating temperature from room temperature (283K) and the ion conductivity of the composite membrane increased linearly with temperature over the temperature range 283-333K studied, as shown in FIG. 4.
Example 4
For g-C prepared in example 1 3 N 4 The osmotic energy conversion performance of the cellulose composite membrane is tested, and the method specifically comprises the following steps:
(1) Cutting the composite membrane into rectangular blocks, and then coating in a two-chamber electrochemical cell; to avoid leakage, a top sealing layer composed of a transparent PDMS elastomer was attached to the composite membrane, and then two electrolyte reservoirs were engraved in the PDMS elastomer to expose both ends of the composite membrane.
(2) Determining I-V curves under different concentration gradients in potassium chloride electrolyte with concentration gradients by using CHI660B electrochemical workstation to obtain short-circuit current I SC And open circuit voltage V OC The concentration of the low-concentration side fixed potassium chloride electrolyte is 10 -4 M, changing the concentration of the high-concentration side potassium chloride electrolyte, and scanning the voltage from-1V to +1V.
(3) The transmembrane potential was measured with a standard Ag/AgCl electrode.
(4) The circuit is communicated through an external load resistor box, the external resistor is adjusted to be from 1000 omega to 10MΩ, an electrochemical workstation is used for recording the change value of ion current along with the increase of the load resistor, and the change value of ion current is calculated by the formula P=I 2 The R/S obtains an output power density value so as to reflect the osmotic energy conversion performance of the composite membrane nano channel. The results are shown in FIG. 5.
(5) The temperature dependence of the osmotic energy conversion performance of the composite membrane was tested by increasing the operating temperature from room temperature (283K) and the output power density of the composite membrane was positively correlated with temperature over the temperature range 283-333K studied, as shown in FIG. 6.
Example 5
WS prepared in example 2 2 Cellulose compositeThe membrane is subjected to ion transmission performance test, and specifically comprises the following steps:
(1) Cutting the composite membrane into rectangular blocks, and then coating in a two-chamber electrochemical cell; to avoid leakage, a top sealing layer composed of a transparent PDMS elastomer was attached to the composite membrane, and then two electrolyte reservoirs were engraved in the PDMS elastomer to expose both ends of the composite membrane.
(2) The ionic conductivity of the composite membrane was measured using a CHI660B electrochemical workstation at a specific concentration of potassium chloride electrolyte, with a scan voltage ranging from-1V to +1v.
(3) The transmembrane potential was measured with a standard Ag/AgCl electrode as shown in fig. 7.
(4) Using xenon lamp to stimulate the illumination of simulated sunlight on one side of the film, keeping dark environment on the other side, applying alternating current illumination to record current value, and researching the illumination to WS 2 Effect of ion transport properties of cellulose Complex film As shown in FIG. 8, light is applied through WS 2 The cellulose composite film rapidly produced photocurrent exceeding 125nA, turned off the light, and the current gradually decreased to disappear.
Example 6
WS prepared in example 2 2 The osmotic energy conversion performance of the cellulose composite membrane is tested, and the method specifically comprises the following steps:
(1) Cutting the composite membrane into rectangular blocks, and then coating the rectangular blocks in a self-made two-chamber electrochemical cell; to avoid leakage, a top sealing layer composed of a transparent PDMS elastomer was attached to the composite membrane, and then two electrolyte reservoirs were engraved in the PDMS elastomer to expose both ends of the composite membrane.
(2) Measuring I-V curves at different concentration gradients in potassium chloride electrolyte with concentration gradients using CHI660B electrochemical workstation, recording short-circuit current I SC The concentration of the low-concentration side fixed potassium chloride electrolyte is 10 -4 M, changing the concentration of the high concentration side potassium chloride electrolyte, the scanning voltage is from-1V to +1V, as shown in FIG. 9, the short-circuit current I is increased from 10 times to 1000 times as the concentration gradient of the electrolyte SC Gradually increasing from 0.6. Mu.A to 1.5. Mu.A.
(3) The circuit was connected via an external load resistor box and the transmembrane potential was measured with a standard Ag/AgCl electrode.
(4) By adjusting the external resistance from 1000 omega to 10MΩ, the electrochemical workstation is used to record the change value of the ion current with the increase of the load resistance under different conditions, and the change value of the ion current is represented by the formula P=I 2 The R/S obtains an output power density value so as to reflect the osmotic energy conversion performance of the composite membrane nano channel.
(5) Using xenon lamp to give simulated sunlight illumination stimulus to one side of the film, keeping dark environment on the other side, recording actual power density values before and after illumination, and testing WS 2 Light control Properties of the permeation energy conversion Property of cellulose Complex film As shown in FIG. 10, WS under dark conditions 2 The output power density of the cellulose composite film is 1.8W/m 2 After one side is illuminated with light, WS 2 The output power density of the cellulose composite membrane can be improved to 2.7W/m 2 。
The invention provides a two-dimensional cellulose nano-fluid channel membrane, a preparation method and an application thought and a method thereof, and particularly the method and the way for realizing the technical scheme are a plurality of preferred embodiments of the invention, and it should be pointed out that a plurality of improvements and modifications can be made by those skilled in the art without departing from the principle of the invention, and the improvements and modifications are also considered as the protection scope of the invention. The components not explicitly described in this embodiment can be implemented by using the prior art.
Claims (5)
1. A two-dimensional cellulose nano fluid channel membrane is characterized in that a two-dimensional nano material/cellulose composite membrane is formed by combining a two-dimensional nano material and cellulose nano fibers, and the inside of the two-dimensional cellulose nano fluid channel membrane is provided with rich lamellar nano channels;
the two-dimensional nanomaterial is WS 2 Nanosheets
The two-dimensional cellulose nano-fluid channel membrane is prepared through the following steps:
(1) Preparation of WS 2 Two-dimensional nanomaterial of nanoplatelets;
(2) Preparing a cellulose nanofiber solution by adopting a TEMPO oxidation method;
(3) Preparing a two-dimensional nano material/cellulose composite membrane by adopting a vacuum suction filtration method;
the two-dimensional nano material/cellulose composite membrane is prepared by adopting a vacuum suction filtration method, and comprises the following steps:
s1: mixing the two-dimensional nano material obtained in the step (1) and the cellulose nanofiber solution obtained in the step (2) in deionized water to obtain a mixed solution;
s2: mechanically stirring and ultrasonically treating the mixed solution to obtain a suspension;
s3: homogenizing the suspension at high pressure to obtain a uniform suspension;
s4: vacuum filtering the suspension with a vacuum filter equipped with cellulose ester microporous membrane, drying the obtained sediment, and stripping from the substrate to obtain the final product;
in the step S1, the mass fraction of the two-dimensional nano material in the obtained solution is 65-90%.
2. The two-dimensional cellulose nanofluidic channel membrane of claim 1, wherein in step (1), the WS 2 The nano-sheet is prepared by a lithium ion intercalation stripping method.
3. The two-dimensional cellulose nano-fluid passage membrane according to claim 1, wherein in the step (2), the cellulose nano-fibers are obtained by a TEMPO oxidation method, and the specific method is as follows:
dispersing the dried pulp in deionized water to form a uniform pulp suspension; completely dispersing TEMPO reagent and NaBr in deionized water, then adding the deionized water into pulp suspension, adjusting the pH to be 9-11, and stirring and reacting at room temperature for 2-4 h; after the reaction is finished, washing the pulp after the reaction to be neutral by adopting deionized water; finally, obtaining the transparent gel-like cellulose nanofiber solution through high-pressure homogenization mechanical shearing.
4. The two-dimensional cellulose nanofluidic channel membrane of claim 1, wherein in step S4, the cellulose ester microporous membrane has a pore size ranging from 0.2 to 0.3 μm.
5. Use of the two-dimensional cellulose nanofluidic channel film of claim 1 in the manufacture of a nanofluidic device.
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