CN116005172A - Method and device for continuously and fully electrolyzing seawater by photo-thermal and electro-catalytic double-functional composite nano carbon film - Google Patents
Method and device for continuously and fully electrolyzing seawater by photo-thermal and electro-catalytic double-functional composite nano carbon film Download PDFInfo
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Abstract
The invention relates to the field of renewable clean energy, in particular to a method and a device for continuously and fully electrolyzing seawater by using a photo-thermal and electro-catalytic double-function composite nano carbon film. The method utilizes a composite nano carbon film with high photo-thermal conversion efficiency and high electrolysis water catalytic activity to absorb sunlight to generate heat to evaporate seawater to generate fresh water, and simultaneously takes the film as a cathode of electrolysis water, designs an electrolytic cell with a communicating vessel to introduce electrolyte solution, and realizes continuous seawater desalination-full electrolysis after illumination and electrifying. The composite film is constructed by loading nano particles/nano wires with electrocatalytic activity on a porous nano carbon material film by adopting a physical deposition/wet chemical synthesis method, spreading water absorbing materials such as bacterial cellulose and the like under the film, placing the water absorbing materials on a heat insulation carrier, and immersing the other end of the bacterial cellulose into seawater to form a water channel for connecting the seawater and the composite film. The composite film can realize continuous desalination and electrolysis of seawater, and clean energy hydrogen can be efficiently obtained under low carbon emission.
Description
Technical Field
The invention relates to the field of renewable clean energy, in particular to a method and a device for continuously and fully electrolyzing seawater by using a photo-thermal and electro-catalytic double-function composite nano carbon film, which are used for desalting the seawater by utilizing interfacial water evaporation and continuously and fully decomposing the water by using the composite nano carbon film as a catalytic electrode to generate high-purity hydrogen and oxygen.
Background
Hydrogen as an important clean energy carrier with unit energy density as high as 285MJ/Mol will play an increasingly important role in the future sustainable energy economy. The global hydrogen energy market demand in 2029 is expected to scale well to 2090 billion dollars. However, with the proposal of carbon peak and carbon neutralization targets, the problems of high energy consumption, environmental pollution and the like caused by preparing the gray hydrogen by thermally cracking the fossil raw materials are increasingly remarkable. In recent years, with the progress of clean energy power generation technologies such as solar energy, wind energy and tidal energy, the production of green hydrogen by electrolysis of water is considered as one of the most promising hydrogen production technologies.
However, the global fresh water amount only accounts for 3.5% of the total water resource, and the shortage of fresh water resource severely restricts the development of hydrogen production by water electrolysis. Thus, the electrolysis of seawater to produce hydrogen is considered one of the ideal ways to achieve green hydrogen economy. Based on this, researchers have proposed two solutions: directly electrolyzing seawater to prepare hydrogen and desalting seawater to prepare hydrogen. The problems that the high-concentration chloride ions in the seawater corrode an electrolytic cell, insoluble substances block electrode catalytic active sites, the anode reaction of the chloride ions competes with the oxygen evolution reaction and the like cannot be solved, so that the industrial application standard cannot be met.
The electrolysis technology after sea water desalination benefits from the development of reverse osmosis, multi-stage flash evaporation, multi-effect distillation and other technologies, and the hydrogen production cost is greatly reduced. Along with the proposal of a double-carbon target and the progress of renewable energy technologies such as offshore wind power generation, the electrolysis after sea water desalination is one of the most ideal schemes. However, some problems still exist in electrolysis after sea water desalination, which need to be solved:
(1) The method for desalting the seawater by reverse osmosis, multi-stage flash evaporation, multi-effect distillation and the like still has certain energy consumption, and increases the cost of hydrogen production by seawater electrolysis;
(2) The desalted seawater is required to be collected and then is led into an electrolytic cell for electrolysis, so that the process flow is increased, and the hydrogen production cost is further increased;
(3) The noble metal-based water electrolysis catalyst is costly and needs to be bonded to the electrode by naphthol or the like, resulting in a decrease in the activity and stability of the catalyst.
Therefore, the development of a method for desalting seawater by using renewable energy sources and continuously carrying out seawater desalination and water electrolysis has important significance, the activity and stability of the full-electrolysis water catalyst are improved while the cost of the full-electrolysis water catalyst is reduced in the process, and the continuous hydrogen production with low carbon emission, low cost and high efficiency is expected to be realized.
Disclosure of Invention
The invention aims to provide a method and a device for continuously and fully electrolyzing seawater by a photo-thermal and electro-catalytic double-functional composite nano carbon film, wherein the composite nano carbon film is constructed by carrying components with electro-catalytic full water-dissolving activity on the nano carbon film and can be directly used as a cathode and an anode of electrolyzed water; wherein, the composite nano carbon film used as the cathode is used as an interface evaporation material to realize seawater desalination, the desalinated seawater generates hydrogen evolution reaction on the cathode film after being electrified, and OH - Then the electrolyte in the communicating vessel diffuses to the anode film and then generates oxygen evolution reaction, thereby realizing the full electrolysis of the seawater; the interfacial water evaporation capacity and the electrocatalytic full water decomposition performance of the composite nano carbon film are regulated and controlled, so that the continuous electrolysis of seawater with low cost and high efficiency is realized.
The technical scheme of the invention is as follows:
a method for continuously and fully electrolyzing seawater by using a photo-thermal and electro-catalytic dual-functional composite nano carbon film utilizes the composite nano carbon film with high photo-thermal conversion efficiency to desalinate the seawater, and the film is used as an electrode to electro-catalytically decompose water at the same time, so that continuous and efficient electrolysis of the seawater is realized; the composite nano carbon film realizes interfacial water evaporation by sunlight energy supply, and the evaporated fresh water realizes electrolyte exchange in the electrolytic cell through the communicating vessel; the composite nano carbon film loaded with electrocatalytic active matters is used as an electrocatalytic hydrogen evolution cathode, the film loaded with catalytic oxygen evolution function is inserted into an electrolytic cell connected with a communicating vessel to be used as an anode, and the seawater is continuously and efficiently electrolyzed after the power is electrified.
According to the method for continuously and fully electrolyzing seawater by using the photo-thermal and electro-catalytic dual-functional composite nano carbon film, the seawater desalination is realized by utilizing the interfacial water evaporation of the composite nano carbon film, the film body is a porous film constructed by carbon nano tubes, graphene or nano carbon fibers, the film has strong light absorption capacity and Gao Guangre conversion efficiency, more than 98% of light can be absorbed in a spectrum of 400-2000 nm, the photo-thermal conversion efficiency is about 71%, and the noble metal, the high-entropy alloy nano particles or the nano wires carried by the composite nano carbon film have plasma primitive effect to improve the photo-thermal conversion efficiency, so that the efficient seawater desalination can be realized by sunlight energy supply.
According to the method for continuously and fully electrolyzing seawater by using the photo-thermal and electro-catalytic dual-functional composite nano carbon film, the photo-thermal conversion efficiency and the water evaporation rate are regulated and controlled by regulating the thickness, the pore structure and the hydrophilic-hydrophobic film structure of the film; or, the plasmon effect is utilized to enhance the photothermal conversion efficiency and improve the water evaporation rate by regulating and controlling the size of the metal nano particles or nano wires carried by the composite nano carbon film.
According to the method for continuously and fully electrolyzing seawater by using the photo-thermal and electro-catalytic dual-functional composite nano carbon film, the composite nano carbon film has the characteristics of high conductivity and high specific surface area, and the sheet resistance of the composite nano carbon film is only 1-2 omega and the specific surface area is 300-400 m through tests 2 /g, nanoparticle or nanowire catalysts carrying different active components by physical deposition or wet chemical synthesis; wherein, the nano carbon material film used as the cathode carries noble metal platinum nano particles or nano wires with high electrocatalytic hydrogen evolution activity; the nano carbon material film used as the anode carries iridium or ruthenium oxide nano particles with high electrocatalytic oxygen evolution activity, and high entropy transition metal nano particles or nano wires.
According to the method for continuously and fully electrolyzing seawater by using the photo-thermal and electro-catalytic dual-functional composite nano carbon film, the composite nano carbon film has a proper specific surface area for carrying the high-density, high-activity and high-stability electro-catalytic hydrogen evolution and electro-catalytic oxygen evolution catalyst, so that high-efficiency and stable electro-catalytic full water decomposition is realized.
In the method for continuously and fully electrolyzing seawater by using the photo-thermal and electro-catalytic dual-functional composite nano carbon film, two communicated electrolytic cells are needed for realizing the thermal evaporation desalination of the seawater and the electrolytic water at the interface of the composite nano carbon film, wherein the electrolytic cell with a larger volume is continuously filled with seawater and is paved with the dual-functional electro-catalytic hydrogen evolution composite nano carbon film for desalinating the seawater and the electrolytic water, and the thickness of the dual-functional electro-catalytic hydrogen evolution composite nano carbon film is 1-50 mu m; the other electrolytic cell is added with sulfuric acid or potassium hydroxide electrolyte and is inserted with an electrocatalytic oxygen-evolving composite nano carbon film as an anode of the electrolyzed water, and the thickness of the film is 1-50 mu m.
According to the method for continuously and fully electrolyzing seawater by the photo-thermal and electro-catalytic double-functional composite nano carbon film, the composite nano carbon film in the thermal evaporation-hydrogen evolution electrolytic cell is paved on the heat insulation substrate to improve the thermal evaporation efficiency, and bacterial cellulose with water absorption capacity is soaked in the seawater between the composite nano carbon film and the heat insulation substrate to serve as a water transport channel.
In order to realize the functions of continuous interfacial thermal evaporation of seawater and electrolysis of water, the method adopts illumination to realize efficient evaporation of seawater, electrifying electrolysis, and the seawater desalination rate is matched with the electrolysis rate, so that the efficient electrolysis of the seawater is realized, and high-purity hydrogen and oxygen are respectively collected in a cathode electrolytic cell and an anode electrolytic cell.
The utility model provides a continuous full electrolysis sea water device of photo-thermal and electrocatalysis dual-functional compound nano carbon film, includes positive pole oxygen film, evaporation fresh water, intercommunication mass transfer pipeline, sea water injection port, photo-thermal/hydrogen evolution compound nano carbon film, water delivery channel, adiabatic supporting die, and specific structure is as follows:
the anode oxygen-separating film and the photo-thermal/hydrogen-separating composite nano carbon film are respectively connected with a power supply through a circuit, the anode oxygen-separating film supports the nano carbon composite film with electrocatalytic oxygen-separating activity, the communicating mass transfer pipeline is an intermediate pipeline for connecting an evaporation fresh water electrolytic cell where the anode oxygen-separating film is positioned and a seawater electrolytic cell where the photo-thermal/hydrogen-separating composite nano carbon film is positioned, the photo-thermal/hydrogen-separating composite nano carbon film is a composite film integrating a photo-thermal interface thermal evaporation function and an electrocatalytic hydrogen-separating function, the photo-thermal/hydrogen-separating composite nano carbon film generates evaporation fresh water through interface thermal evaporation, and the communicating mass transfer pipeline is used for conveying the evaporation fresh water electrolytic cell to the evaporation fresh water;
the seawater electrolytic cell is filled with seawater to be evaporated and purified, and a seawater water inlet is arranged on the side surface of the seawater electrolytic cell and is used for injecting seawater, so that the continuity of interface thermal evaporation and full water decomposition reaction is ensured; the photo-thermal/hydrogen evolution composite nano carbon film, the water conveying channel and the heat insulation supporting die are arranged at the upper part of the seawater electrolytic cell from top to bottom, and the water conveying channel sucks and conveys the lower seawater to the photo-thermal/hydrogen evolution composite nano carbon film to realize interfacial thermal evaporation; the heat-insulating support die supports the photo-thermal/hydrogen evolution composite nano-carbon film, separates the photo-thermal/hydrogen evolution composite nano-carbon film from the sea water liquid level to reduce heat dissipation, and simultaneously facilitates the accumulation of fresh water on the photo-thermal/hydrogen evolution composite nano-carbon film for electrocatalytic.
The design idea of the invention is as follows:
according to the invention, by utilizing the characteristics of excellent photo-thermal conversion performance, higher specific surface area, adjustable hydrophilicity and hydrophobicity, abundant pore structures and the like of the nano carbon material film such as carbon nano tube/graphene and the like, the nano particles with high density, high activity, small size and low dimension are directly carried on the film by physical deposition/wet chemical synthesis and other methods, so that the film has two functions of sea water desalination and electrolyzed water simultaneously; the electrolytic cell is designed to enable the cathode and the anode to be connected through a communicating vessel, the cathode composite nano carbon film is subjected to electrolysis after seawater desalination through interfacial water evaporation after illumination and energization, fresh water is subjected to diffusion transmission through the communicating vessel and an anode containing electrolyte solution, and the anode is subjected to oxygen evolution reaction to realize complete water dissolution; the photo-thermal conversion performance and the electrocatalytic full water-dissolving performance of the composite nano carbon film are regulated, so that the desalted seawater is completely electrolyzed, and the low-cost high-efficiency continuous full electrolysis of the seawater is realized.
The invention has the advantages and beneficial effects that:
(1) The invention utilizes the characteristics of excellent photo-thermal conversion performance, rich pore structure, higher specific surface area and adjustable hydrophilic and hydrophobic property of the low-dimensional nano carbon material film macroscopic body, and has the dual functions of desalting sea water and electrolyzing water by thermal evaporation through carrying the low-dimensional nano particles/wires.
(2) The invention designs an electrolytic cell with two separated electrolytic chambers, so that the cathode chamber evaporates the collected seawater and is connected with the electrolyte solution of the anode chamber through a communicating vessel, and continuous seawater evaporation and water electrolysis are realized after illumination is electrified.
(3) According to the method, the sunlight is used as a light source for sea water desalination, the hydrogen is produced by utilizing the sea water with rich reserves while the carbon emission is reduced, and the large-scale production of hydrogen energy and the recycling of sea water are hopeful to be promoted.
Drawings
FIG. 1 is a schematic diagram of a device for continuously and fully electrolyzing seawater by using a photo-thermal and electro-catalytic dual-functional composite nano carbon film. In the figure, an anode oxygen-separating film 1, a fresh water evaporation film 2, a mass transfer pipeline 3, 4 seawater, a 5 seawater water filling port, a 6 photo-thermal/hydrogen-separating composite nano carbon film, a 7 water conveying channel, an 8 heat insulation supporting die and a 9 power supply are communicated.
Fig. 2. Microstructure of pt nanoparticle/single-walled carbon nanotube composite film.
FIG. 3 hydrogen evolution performance of Pt nanoparticle/single walled carbon nanotube composite films.
FIG. 4 IrO 2 Microstructure of nanoparticle/single-walled carbon nanotube composite films.
IrO FIG. 5 2 Oxygen evolution performance of nanoparticle/single-walled carbon nanotube composite films.
FIG. 6 illustrates the interfacial thermal evaporation performance of a photo-thermal/electro-catalytic hydrogen evolution dual-functional single-walled carbon nanotube.
FIG. 7 is a graph showing the stability test of continuous full electrolysis of seawater by using the photo-thermal and electro-catalytic dual-functional composite nano carbon film.
Detailed Description
In the specific implementation process, the composite nano carbon film with high photo-thermal conversion efficiency and high electrolyzed water catalytic activity is used for absorbing sunlight to generate heat to evaporate seawater to generate fresh water, meanwhile, the film is used as a cathode of electrolyzed water, an electrolytic cell with a communicating vessel is designed to introduce electrolyte solution, and continuous sea water desalination-full electrolysis is realized after illumination and electrifying. The porous nano carbon material (such as graphene, carbon nanotube and nano carbon fiber with porosity up to 99.9% and pore diameter varying from several nanometers to several micrometers) is prepared through physical deposition/wet chemical synthesis, loading nano particles/nano wires with electrocatalytic activity onto the film to form a composite film, spreading water-absorbing material such as bacterial cellulose under the film, placing the film on a heat-insulating carrier, immersing the other end of bacterial cellulose into seawater to form a water channel for connecting seawater with the composite film, irradiating the composite film with sunlight and other light sources, collecting evaporated fresh water, immersing the composite film, and connecting the composite film with an electrolytic cell with electrolyte solution on one side by a communicating vessel to realize continuous full electrolysis of seawater.
As shown in figure 1, the device for continuously and fully electrolyzing seawater by using the photo-thermal and electro-catalytic double-functional composite film mainly comprises an anode oxygen-separating film 1, evaporated fresh water 2, a communicating mass transfer pipeline 3, seawater 4, a seawater water filling port 5, a photo-thermal/hydrogen-separating composite nano carbon film 6, a water conveying channel 7 and a heat insulation supporting die 8, and has the following specific structure:
the anode oxygen-separating film 1 and the photo-thermal/hydrogen-separating composite nano carbon film 6 are respectively connected with a power supply 9 through lines, the anode oxygen-separating film 1 is loaded with nano carbon (such as single-wall carbon nano tubes) composite films with electrocatalytic oxygen-separating activity, and the communicating mass transfer pipeline 3 is a middle pipeline for connecting an evaporation fresh water electrolytic cell where the anode oxygen-separating film 1 is positioned and a seawater electrolytic cell where the photo-thermal/hydrogen-separating composite nano carbon film 6 is positioned, and is mainly used for mass transfer of electrolyte in the electrocatalytic full water-decomposing process; the photo-thermal/hydrogen evolution composite nano carbon film 6 is a composite film integrating a photo-thermal interface thermal evaporation function and an electrocatalytic hydrogen evolution function, the photo-thermal/hydrogen evolution composite nano carbon film 6 generates evaporation fresh water 2 through interface thermal evaporation, and the evaporation fresh water 2 is conveyed into an electrolytic cell of the evaporation fresh water 2 through a communicating mass transfer pipeline 3.
The seawater electrolytic cell is provided with seawater 4 to be evaporated and purified, and the side surface of the seawater electrolytic cell is provided with a seawater filling port 5 for filling seawater, so that the continuity of interface thermal evaporation and full water decomposition reaction is ensured. The photo-thermal/hydrogen evolution composite nano carbon film 6, the water conveying channel 7 and the heat insulation supporting die 8 are arranged at the upper part of the seawater electrolytic cell from top to bottom, the water conveying channel 7 consists of wood pulp fiber, bacterial cellulose and the like, and a material with better water absorption is generally selected and is mainly used for absorbing and transmitting the lower seawater to the photo-thermal/hydrogen evolution composite nano carbon film 6 to realize interfacial thermal evaporation. The heat-insulating support die 8 is made of polytetrafluoroethylene, and is mainly used for supporting the photo-thermal/hydrogen-evolution composite nano carbon film, separating the photo-thermal/hydrogen-evolution composite nano carbon film 6 from the sea water liquid level to reduce heat dissipation, and simultaneously, accumulating fresh water on the photo-thermal/hydrogen-evolution composite nano carbon film for electrocatalysis.
The invention is further described below by way of examples and figures.
Example 1
The embodiment takes a nano particle/single-wall carbon nano tube composite nano carbon film as a film for evaporating electrode and interface water, and comprises the following specific experimental steps:
(1) Preparation of photo-thermal/electro-catalytic hydrogen evolution dual-functional composite nano carbon film and hydrogen evolution performance test;
the floating catalyst chemical vapor deposition method is utilized to directly prepare and collect the high-quality single-wall carbon nanotube film, and the thickness of the film is 5 mu m. And (3) adopting a magnetron sputtering high-purity platinum target, controlling the sputtering power to be 50W, and depositing for 500s to obtain the Pt nano particle/single-walled carbon nanotube composite film after two-sided deposition. As shown in fig. 2, the microstructure of the composite film was obtained, and it was seen that high-density small-sized Pt nanoparticles were supported on bundles of carbon nanotubes. The electrocatalytic hydrogen evolution performance of the composite film was tested in a three-electrode electrochemical workstation (working electrode: rotating disk electrode; counter electrode: graphite electrode; reference electrode: ag/AgCl electrode; electrolyte solution: 0.5mol/L H) 2 SO 4 Solution) was scanned linearly at a scan rate of 0.005V/s, as shown in fig. 3, and the electrocatalytic hydrogen evolution initiation potential of the composite film was 20mv,10ma cm -2 The overpotential was 71mV at the current density.
(2) Preparing an electrocatalytic oxygen evolution composite film and testing oxygen evolution performance;
preparation of single-wall carbon nanotube filmThe preparation method is the same as step 1. 5mg of ammonium hexachloroiridium ((NH) are taken 4 ) 3 IrCl 6 ·1.5H 2 O) was dissolved in 40mL of deionized water, and the suspension was heated to 70℃to completely dissolve ammonium hexachloroiridate, and then sealed in a hydrothermal kettle, and incubated at 100℃for 3h. Taking out the film after the reaction and cleaning the film with deionized water to obtain IrO 2 Nanoparticle/single-walled carbon nanotube composite films. As shown in FIG. 4, the microstructure of the composite film was obtained, and IrO was produced 2 The size of the nano particles is smaller than 2nm, and the nano particles are in a monodisperse state. The electrocatalytic oxygen evolution performance of the composite film was tested in a three-electrode electrochemical workstation (working electrode: rotating disk electrode; counter electrode: platinum wire electrode; reference electrode: ag/AgCl electrode; electrolyte solution: 1mol/L KOH aqueous solution), and linear scanning was performed at a scanning rate of 0.005V/s, as shown in FIG. 5, and the electrocatalytic oxygen evolution initial potential of the composite film was 1.460V, 10 mA.cm by electrochemical test -2 The potential at the current density was 1.664V.
(3) Evaporating seawater under photothermal action;
the photo-thermal/electro-catalytic hydrogen evolution difunctional composite nano carbon film prepared in the step 1 is attached to a polytetrafluoroethylene heat insulation supporting die 8 shown in fig. 1, a layer of wood pulp fiber is paved below the composite nano carbon film as a water transportation channel, a solar simulator is used as a light source, and 1 solar illumination intensity is simulated to irradiate the composite nano carbon film above the device for interfacial water evaporation to desalinate seawater. Illuminating and measuring the sea water quality change, and calculating the sea water desalting rate of 1.2 kg.m after weighing -2 ·h -1 。
(4) Electrocatalytic full water decomposition;
after the photo-thermal desalination of seawater is carried out for 6 hours, a certain amount of pure water is collected at one side of the anode of the device, a certain amount of electrolyte (KOH) is added into the pure water to adjust the pH value of the solution to 14, a certain height of liquid level exists at the center of the photo-thermal/hydrogen evolution composite nano carbon film so that the composite nano carbon film is fully contacted with the electrolyte solution, and then the full decomposition of fresh water can be realized by applying voltage, as shown in figure 6, the full water decomposition performance is tested, and the total water decomposition performance is measured at 10mA cm -2 Can be operated continuously for 24 hours at the current density of (3). To realize continuous interfacial thermal evaporation of seaThe functions of water and electrolyzed water are realized by adopting illumination to realize efficient evaporation of seawater, electrifying electrolysis, and the efficient electrolysis of seawater is realized by matching the seawater desalination rate with the electrolysis rate, and high-purity hydrogen (volume purity is 99.999%) and oxygen (volume purity is 99.99%) are respectively collected in a cathode electrolytic cell and an anode electrolytic cell.
As shown in FIG. 7, the stability test result of the continuous full electrolysis of seawater by the photo-thermal and electro-catalytic dual-function composite nano carbon film can be seen that the composite film is in the range of 10mA.cm -2 Can stably hydrogen out for 24 hours under the current density of (2) and the current density only decays by 10 percent, which shows that the catalyst has good electrocatalytic hydrogen out stability.
Example 2
The embodiment takes the nano particles/graphene film as the electrode and the film for interfacial water evaporation, and comprises the following specific experimental steps:
(1) Preparing a photo-thermal/electro-catalytic hydrogen evolution dual-functional composite nano carbon film;
firstly, preparing a graphene film with the thickness of about 10 mu m by using a chemical vapor deposition method, and treating the graphene film by using plasma to improve the hydrophilicity. Subsequently, pt nanoparticles were deposited on the graphene film as in example 1, step (1).
(2) Preparing an electrocatalytic oxygen evolution composite nano carbon film;
the preparation method and the treatment method of the graphene film are the same as those of the step (1) of the embodiment 2, and then IrO is deposited on the graphene film 2 The nanoparticles were as in example 1 step (2).
(3) Evaporating seawater under photothermal action;
step (3) was performed as in example 1.
(4) Electrocatalytic full water decomposition;
step (4) was performed as in example 1.
In this embodiment, the interface thermal evaporation performance index of the photo-thermal/electro-catalytic hydrogen evolution dual-functional composite nano carbon film is as follows: under the simulation of 1 sunlight, the interfacial sea water evaporation rate is 0.95 kg.m -2 ·h -1 . The stability test performance indexes of the photo-thermal/electro-catalytic double-functional composite nano carbon film continuous full electrolysis seawater are as follows: at 10 mA.cm -2 The full water dissolution can be stabilized for 24 hours under the current density of (2), and the current density is only attenuated by 14%.
Example 3
The embodiment takes the nano particle/nano carbon fiber film as the film for evaporating the electrode and the interfacial water, and the specific experimental steps are as follows:
(1) Preparing a photo-thermal/electro-catalytic hydrogen evolution dual-functional composite nano carbon film;
commercial carbon nanofiber films were purchased with a thickness of 30 μm, and Pt nanoparticles were subsequently deposited on the film as in example 1, step (1).
(2) Preparing an electrocatalytic oxygen evolution composite nano carbon film;
the carbon nanofiber thin film was obtained and treated in the same manner as in step (1) of example 3, followed by deposition of IrO on the carbon fiber thin film 2 The nanoparticles were as in example 1 step (2).
(3) Evaporating seawater under photothermal action;
step (3) was performed as in example 1.
(4) Electrocatalytic full water decomposition;
step (4) was performed as in example 1.
In this embodiment, the interface thermal evaporation performance index of the photo-thermal/electro-catalytic hydrogen evolution dual-functional composite nano carbon film is as follows: under the simulation of 1 sunlight, the interfacial sea water evaporation rate is 0.83 kg.m -2 ·h -1 . The stability test performance indexes of the photo-thermal/electro-catalytic double-functional composite nano carbon film continuous full electrolysis seawater are as follows: at 10 mA.cm -2 The full water dissolution can be stabilized for 24 hours under the current density of (2), and the current density is only attenuated by 17%.
Example 4
The embodiment takes a metal nanowire/single-wall carbon nanotube composite nano carbon film as a film for electrode and interfacial water evaporation, and comprises the following specific experimental steps:
(1) Preparing a photo-thermal/electro-catalytic hydrogen evolution dual-functional composite nano carbon film;
a certain amount of platinum acetylacetonate, iron acetylacetonate, nickel acetylacetonate (10 mg each) and 30mg of didodecyl dimethyl ammonium bromide and 40mg of anhydrous glucose were taken, placed in 10ml of an oleylamine solvent for ultrasonic dispersion to form a solution, and a single-walled carbon nanotube film with a thickness of 50 μm was placed in the solution and heated in an oil bath at 170℃for 30 minutes. And taking out the film after the reaction is finished, and washing the film with absolute ethyl alcohol to remove the surfactant to obtain the superfine PtFeNi nanowire/single-wall carbon nanotube composite nano carbon film, wherein the radial dimension of the superfine PtFeNi nanowire is 1-2 nm.
(2) Preparing an electrocatalytic oxygen evolution composite nano carbon film;
step (1) was performed as in example 4.
(3) Evaporating seawater under photothermal action;
step (3) was performed as in example 1.
(4) Electrocatalytic full water decomposition;
step (4) was performed as in example 1.
In this embodiment, the interface thermal evaporation performance index of the photo-thermal/electro-catalytic hydrogen evolution dual-functional composite nano carbon film is as follows: under the simulation of 1 sunlight, the interfacial sea water evaporation rate is 1.13 kg.m -2 ·h -1 . The stability test performance indexes of the photo-thermal/electro-catalytic double-functional composite nano carbon film continuous full electrolysis seawater are as follows: at 10 mA.cm -2 The full water dissolution can be stabilized for 24 hours under the current density of (2), and the current density is only attenuated by 12 percent.
The implementation result shows that the composite nano carbon film can realize continuous desalination and electrolysis of seawater, can efficiently obtain clean energy hydrogen under low carbon emission, and is expected to promote low-cost large-scale application of hydrogen energy.
While the invention has been described in detail in the foregoing general description and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that modifications and improvements can be made thereto. Accordingly, such modifications or improvements may be made without departing from the spirit of the invention and are intended to be within the scope of the invention as claimed.
Claims (9)
1. A method for continuously and fully electrolyzing seawater by using a photo-thermal and electro-catalytic dual-functional composite nano carbon film is characterized in that the seawater is desalted by using the composite nano carbon film with high photo-thermal conversion efficiency, and the film is used as an electrode to electro-catalytically decompose water at the same time, so that continuous and efficient electrolysis of the seawater is realized; the composite nano carbon film realizes interfacial water evaporation by sunlight energy supply, and the evaporated fresh water realizes electrolyte exchange in the electrolytic cell through the communicating vessel; the composite nano carbon film loaded with electrocatalytic active matters is used as an electrocatalytic hydrogen evolution cathode, the film loaded with catalytic oxygen evolution function is inserted into an electrolytic cell connected with a communicating vessel to be used as an anode, and the seawater is continuously and efficiently electrolyzed after the power is electrified.
2. The method for continuously and fully electrolyzing seawater by using the photo-thermal and electro-catalytic dual-functional composite nano carbon film according to claim 1, wherein the seawater desalination is realized by utilizing the interfacial water evaporation of the composite nano carbon film, the film main body is a porous film constructed by carbon nano tubes, graphene or nano carbon fibers, the porous film has strong light absorption capacity and Gao Guangre conversion efficiency, and noble metals, high-entropy alloy nano particles or nano wires carried by the composite nano carbon film have plasma primitive effect to improve the photo-thermal conversion efficiency, so that the efficient seawater desalination is realized by sunlight energy supply.
3. The method for continuously and fully electrolyzing seawater by using the photo-thermal and electro-catalytic double-functional composite nano-carbon film according to claim 1 or 2, wherein the photo-thermal conversion efficiency and the water evaporation rate are regulated and controlled by regulating the thickness, the pore structure and the hydrophilic-hydrophobic film structure of the film; or, the plasmon effect is utilized to enhance the photothermal conversion efficiency and improve the water evaporation rate by regulating and controlling the size of the metal nano particles or nano wires carried by the composite nano carbon film.
4. The method for continuously and fully electrolyzing seawater by using the photo-thermal and electro-catalytic dual-functional composite nano-carbon film as claimed in claim 1, wherein the composite nano-carbon film has the characteristics of high conductivity and high specific surface area, and the sheet resistance of the composite nano-carbon film is only 1-2 omega, and the specific surface area is 300-400 m 2 /g, nanoparticle or nanowire catalysts carrying different active components by physical deposition or wet chemical synthesis; wherein the nano carbon material film as the cathode is carried with high electrocatalytic hydrogen evolutionActive noble metal platinum nanoparticles or nanowires; the nano carbon material film used as the anode carries iridium or ruthenium oxide nano particles with high electrocatalytic oxygen evolution activity, and high entropy transition metal nano particles or nano wires.
5. The method for continuously and fully electrolyzing seawater by using the photo-thermal and electro-catalytic dual-functional composite nano-carbon film according to claim 1 or 4, wherein the composite nano-carbon film has a proper specific surface area for carrying high-density, high-activity and high-stability electro-catalytic hydrogen evolution and electro-catalytic oxygen evolution catalysts, so that high-efficiency and stable electro-catalytic full water decomposition is realized.
6. The method for continuously and fully electrolyzing seawater by using the photo-thermal and electro-catalytic dual-functional composite nano-carbon film according to claim 1, wherein two communicated electrolytic cells are needed for realizing the thermal evaporation desalination of the seawater and the electrolytic water at the interface of the composite nano-carbon film, wherein one electrolytic cell with a larger volume is continuously filled with seawater and is tiled with the dual-functional electro-catalytic hydrogen evolution composite nano-carbon film with the seawater desalination and the electrolytic water, and the thickness of the dual-functional electro-catalytic hydrogen evolution composite nano-carbon film is 1-50 mu m; the other electrolytic cell is added with sulfuric acid or potassium hydroxide electrolyte and is inserted with an electrocatalytic oxygen-evolving composite nano carbon film as an anode of the electrolyzed water, and the thickness of the film is 1-50 mu m.
7. The method for continuously and fully electrolyzing seawater by using the photo-thermal and electro-catalytic dual-functional composite nano-carbon film according to claim 1 or 6, wherein the composite nano-carbon film in the thermal evaporation-hydrogen evolution electrolytic cell is laid on a heat insulation substrate to improve the thermal evaporation efficiency, and bacterial cellulose with water absorption capacity is immersed in the seawater between the composite nano-carbon film and the heat insulation substrate to serve as a water transportation channel.
8. The method for continuously and fully electrolyzing seawater by using the photo-thermal and electro-catalytic dual-functional composite nano carbon film according to claim 1, wherein in order to realize the function of continuously and thermally evaporating seawater and electrolyzing water at an interface, the high-efficiency evaporation of the seawater is realized by adopting illumination, the power-on electrolysis is realized, the seawater desalting rate is matched with the electrolysis rate, and the high-efficiency electrolysis of the seawater is realized, and high-purity hydrogen and oxygen are respectively collected in a cathode electrolytic cell and an anode electrolytic cell.
9. A device for continuously and fully electrolyzing seawater by using a photo-thermal and electro-catalytic double-functional composite nano carbon film according to one of claims 1 to 8, which is characterized by comprising an anode oxygen-separating film, evaporating fresh water, communicating mass transfer pipelines, seawater, a seawater water injection port, a photo-thermal/hydrogen-separating composite nano carbon film, a water conveying channel and a heat insulation supporting die, wherein the device comprises the following specific structures:
the anode oxygen-separating film and the photo-thermal/hydrogen-separating composite nano carbon film are respectively connected with a power supply through a circuit, the anode oxygen-separating film supports the nano carbon composite film with electrocatalytic oxygen-separating activity, the communicating mass transfer pipeline is an intermediate pipeline for connecting an evaporation fresh water electrolytic cell where the anode oxygen-separating film is positioned and a seawater electrolytic cell where the photo-thermal/hydrogen-separating composite nano carbon film is positioned, the photo-thermal/hydrogen-separating composite nano carbon film is a composite film integrating a photo-thermal interface thermal evaporation function and an electrocatalytic hydrogen-separating function, the photo-thermal/hydrogen-separating composite nano carbon film generates evaporation fresh water through interface thermal evaporation, and the communicating mass transfer pipeline is used for conveying the evaporation fresh water electrolytic cell to the evaporation fresh water;
the seawater electrolytic cell is filled with seawater to be evaporated and purified, and a seawater water inlet is arranged on the side surface of the seawater electrolytic cell and is used for injecting seawater, so that the continuity of interface thermal evaporation and full water decomposition reaction is ensured; the photo-thermal/hydrogen evolution composite nano carbon film, the water conveying channel and the heat insulation supporting die are arranged at the upper part of the seawater electrolytic cell from top to bottom, and the water conveying channel sucks and conveys the lower seawater to the photo-thermal/hydrogen evolution composite nano carbon film to realize interfacial thermal evaporation; the heat-insulating support die supports the photo-thermal/hydrogen evolution composite nano-carbon film, separates the photo-thermal/hydrogen evolution composite nano-carbon film from the sea water liquid level to reduce heat dissipation, and simultaneously facilitates the accumulation of fresh water on the photo-thermal/hydrogen evolution composite nano-carbon film for electrocatalytic.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116764627A (en) * | 2023-06-30 | 2023-09-19 | 福州大学 | Ag/TiO 2 Carbon fiber membrane based on @ lignin, preparation method and application thereof |
| CN116764627B (en) * | 2023-06-30 | 2024-04-23 | 福州大学 | Ag/TiO2Carbon fiber membrane based on @ lignin, preparation method and application thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116764627A (en) * | 2023-06-30 | 2023-09-19 | 福州大学 | Ag/TiO 2 Carbon fiber membrane based on @ lignin, preparation method and application thereof |
| CN116764627B (en) * | 2023-06-30 | 2024-04-23 | 福州大学 | Ag/TiO2Carbon fiber membrane based on @ lignin, preparation method and application thereof |
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