CN112546976B - Preparation method of carbon nitride based cathode-anode type visible light driven colloid motor - Google Patents

Preparation method of carbon nitride based cathode-anode type visible light driven colloid motor Download PDF

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CN112546976B
CN112546976B CN202011268273.6A CN202011268273A CN112546976B CN 112546976 B CN112546976 B CN 112546976B CN 202011268273 A CN202011268273 A CN 202011268273A CN 112546976 B CN112546976 B CN 112546976B
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carbon nitride
motor
microspheres
colloid
visible light
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CN112546976A (en
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吴英杰
王贺
刘松
张琪涵
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Harbin Institute of Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • 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
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Abstract

The invention discloses a preparation method of a carbon nitride based cathode-anode type visible light driven colloidal motor, and relates to a preparation method of a visible light driven colloidal motor. The invention aims to solve the problem that the existing photocatalytic-driven colloid motor mainly depends on ultraviolet light excitation. The method comprises the following steps: firstly, preparing a template microsphere modified by polyelectrolyte; secondly, preparing the microspheres coated with the carbon nitride shell layers; and thirdly, vacuum sputtering. The preparation method is used for preparing the carbon nitride based yin-yang type visible light driven colloid motor.

Description

Preparation method of carbon nitride based cathode-anode type visible light driven colloid motor
Technical Field
The invention relates to a preparation method of a visible light driven colloid motor.
Background
The colloid motor is colloid particles which can convert chemical energy or energy such as light, electricity, magnetism and the like in the surrounding environment into mechanical motion per se, and is also called as active colloid and a micro-nano motor. Among the driving methods of the colloid motor, the optical driving is a method that depends on external photons as an energy source to generate optical response, and the colloid motor is driven to move by asymmetric force. In a specific reaction process, photons are irradiated to the surface of the semiconductor material on the colloid motor. If the photon carries energy greater than the semiconductor material bandgap, the absorbed photon is conducted to the conduction band and a hole is generated in the conduction band. The carriers excited by photocatalysis can be diffused to the surface of the particles so as to participate in the redox reaction in the surrounding environment. Compared with other driving modes, the photocatalytic driving has the advantages that the moving speed and the starting/stopping behavior of the colloid motor can be controlled by controlling the light with specific wavelength, and the photocatalytic driving has the advantages of cleanness and low pollution as a mode of controlling an external physical field.
Heretofore, photocatalytic-driven colloidal motors have relied primarily on ultraviolet-excited semiconductor materials such as titanium dioxide and zinc oxide. However, the uv light only accounts for a part of the light energy and is harmful to human body, which undoubtedly limits the further application of the gel motor. The visible radiation accounts for 45-50% of the total radiation of the nature, and has wider application prospect.
Disclosure of Invention
The invention provides a preparation method of a carbon nitride based cathode-anode type visible light driven colloidal motor, aiming at solving the problem that the existing photocatalytic driven colloidal motor mainly depends on ultraviolet light excitation.
A preparation method of a carbon nitride based cathode-anode type visible light driven colloid motor is carried out according to the following steps:
firstly, preparing a template microsphere modified by polyelectrolyte:
dipping a polyetherimide modified template microsphere in a polyelectrolyte aqueous solution with 1-3 mg/mL positive charges, oscillating for 4-6 min, then washing for 3-5 times by using a NaCl aqueous solution with 0.5-1 mol/L concentration, dipping in a polyelectrolyte aqueous solution with 1-3 mg/mL negative charges, oscillating for 4-6 min, and finally washing for 3-5 times by using a NaCl aqueous solution with 0.5-1 mol/L concentration;
secondly, repeating the first step for 8 to 12 times to obtain the polyelectrolyte-modified template microspheres;
secondly, preparing the microspheres coated with the carbon nitride shell layer:
dispersing template microspheres modified by polyelectrolyte in molten cyanamide;
the mass ratio of the molten cyanamide to the polyelectrolyte-modified template microspheres is 1 (0.5-1);
secondly, dipping for 5-10 min at the temperature of 65-70 ℃, and then oscillating for 20-40 s on an oscillator at room temperature;
thirdly, repeating the second step for 15 to 25 times to obtain template microspheres for adsorbing the molten cyanamide;
placing the template microspheres adsorbing and melting the cyanamide into a quartz boat, placing the quartz boat in a tube furnace, heating to 500-550 ℃ at a heating rate of 2.5-5 ℃/min under the protection of argon, calcining for 4-5 h at the calcining temperature of 500-550 ℃, and finally washing, centrifuging and drying to obtain the microspheres coated with the carbon nitride shell layer;
thirdly, vacuum sputtering:
dispersing the microspheres coated with the carbon nitride shell layer in deionized water to obtain a microsphere dispersion coated with the carbon nitride shell layer, dropwise adding the microsphere dispersion coated with the carbon nitride shell layer on a hydrophilic substrate, standing for 10-18 h to naturally spread into single-layer particles, and carrying out electrostatic precipitation at a current of 20 mA-30 mUnder the condition of A, semi-modifying a metal shell on the surface of the microsphere coated with the carbon nitride shell layer by a vacuum sputtering method for 2-5 min, washing off particles on a hydrophilic substrate by deionized water, and centrifuging for 2-3 min under the condition that the rotating speed is 3000-4500 r/min to obtain Pt/g-C 3 N 4 A Janus colloid motor;
the concentration of the microsphere dispersion liquid coated with the carbon nitride shell layer is 0.5 mg/mL-1 mg/mL.
The beneficial effects of the invention are:
the carbon nitride based yin-yang type visible light driven colloidal motor prepared by the invention comprises a carbon nitride photocatalytic material shell, a silicon dioxide inner core and an outermost layer hemispherical metal layer, and has a yin-yang type asymmetric structure, namely a Janus (asymmetric) structure is formed.
The invention makes full use of g-C 3 N 4 The photoelectric current response characteristic under visible light enables the Janus colloid motor to have an obvious acceleration effect under the excitation of visible light, avoids the use of the traditional colloid motor to ultraviolet light, and can generate about 4 multiplied by 10 under the irradiation of a 500W xenon lamp under the open circuit voltage of 0.4V -7 A photo-generated current. Under the condition that the illumination intensity is 100W, the motion speed of the colloid motor irradiated by green light is gradually increased to 74.0 μm/s, and the motion speed of the colloid motor irradiated by blue light is gradually increased to 84.5 μm/s.
The invention respectively researches the concentration of hydrogen peroxide, the illumination intensity and the wavelength of light on Pt/g-C 3 N 4 And (3) counting the influence of the motion behavior of the Janus colloid motor, and further counting the motion rule: research shows that the motion speed of the colloid motor under blue light is higher than that under green light under the same power and hydrogen peroxide concentration; under the same illumination intensity, the movement speed of the colloid motor under the conditions of no light, green light and blue light is increased along with the increase of the concentration of the hydrogen peroxide; under the same hydrogen peroxide concentration, the movement speed of the colloid motor under green light and blue light is increased along with the increase of the illumination intensity; therefore, the relationship between the motion speed of the colloid motor prepared by the invention and the hydrogen peroxide concentration, the illumination intensity and the wavelength of light is further realizedThe motion of the colloid motor is effectively controlled, an idea is provided for designing a novel photocatalysis driving colloid motor, and a theoretical basis is provided for improving the motion efficiency of the colloid motor.
The invention relates to a preparation method of a carbon nitride based yin-yang visible light driven colloidal motor.
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FIG. 1 is a schematic flow chart of a method for manufacturing a carbon nitride based yin-yang type visible light driven colloidal motor according to the present invention;
FIG. 2 shows Pt/g-C prepared in example one 3 N 4 Macroscopic scanning electron micrographs of Janus colloidal motor;
FIG. 3 shows Pt/g-C prepared in example one 3 N 4 High power scanning electron microscope image of Janus colloid motor;
FIG. 4 is a diagram of Pt/g-C prepared in example one 3 N 4 The Janus colloid motor energy dispersion X-ray spectrogram, wherein a is an N element, b is a C element, and C is a Pt element;
FIG. 5 shows Pt/g-C prepared in the first example under irradiation with an open circuit voltage of 0.4V and a xenon lamp power of 500W 3 N 4 A photocurrent test pattern of the Janus colloid motor;
FIG. 6 shows Pt/g-C prepared in example one under the condition of 100W of light intensity 3 N 4 A relational graph of the movement speed of the Janus colloid motor and the concentration of the hydrogen peroxide solution is shown, wherein 1 is no light, 2 is green light, and 3 is basket light;
FIG. 7 shows Pt/g-C prepared in example one, with 15% hydrogen peroxide solution by weight 3 N 4 A relation graph of the movement speed of the Janus colloid motor and the illumination intensity, wherein 1 is green light, and 2 is basketry light;
FIG. 8 is a graph of Pt/g-C prepared in example one under the conditions of a blue light intensity of 100W and a hydrogen peroxide solution mass percent of 10% 3 N 4 Motion pictures of the Janus colloid motor;
FIG. 9 shows Pt/g-C prepared in example one 3 N 4 Janus colloid motor photocatalysis driving principle diagram.
Detailed Description
The technical solution of the present invention is not limited to the specific embodiments listed below, and includes any combination of the specific embodiments.
The first specific implementation way is as follows: specifically, referring to fig. 1, the method for preparing a carbon nitride based yin-yang type visible light driven colloidal motor according to the present embodiment is performed according to the following steps:
firstly, preparing a polyelectrolyte modified template microsphere:
dipping a polyetherimide modified template microsphere in a polyelectrolyte aqueous solution with 1-3 mg/mL positive charges, oscillating for 4-6 min, then washing for 3-5 times by using a NaCl aqueous solution with 0.5-1 mol/L concentration, dipping in a polyelectrolyte aqueous solution with 1-3 mg/mL negative charges, oscillating for 4-6 min, and finally washing for 3-5 times by using a NaCl aqueous solution with 0.5-1 mol/L concentration;
secondly, repeating the first step for 8 to 12 times to obtain the polyelectrolyte-modified template microspheres;
secondly, preparing the microspheres coated with the carbon nitride shell layer:
dispersing template microspheres modified by polyelectrolyte in molten cyanamide;
the mass ratio of the molten cyanamide to the polyelectrolyte-modified template microspheres is 1 (0.5-1);
secondly, dipping for 5-10 min at the temperature of 65-70 ℃, and then oscillating for 20-40 s on an oscillator at room temperature;
thirdly, repeating the second step for 15 to 25 times to obtain template microspheres for adsorbing the molten cyanamide;
placing the template microspheres adsorbing and melting the cyanamide into a quartz boat, placing the quartz boat in a tube furnace, heating to 500-550 ℃ at a heating rate of 2.5-5 ℃/min under the protection of argon, calcining for 4-5 h at the calcining temperature of 500-550 ℃, and finally washing, centrifuging and drying to obtain the microspheres coated with the carbon nitride shell layer;
thirdly, vacuum sputtering:
will coatDispersing microspheres with a carbon nitride shell layer in deionized water to obtain microsphere dispersion liquid coated with the carbon nitride shell layer, dropwise adding the microsphere dispersion liquid coated with the carbon nitride shell layer on a hydrophilic substrate, standing for 10-18 h to spread into single-layer particles naturally, semi-modifying a metal shell on the surface of the microspheres coated with the carbon nitride shell layer by a vacuum sputtering method under the condition of 20-30 mA current, wherein the sputtering time is 2-5 min, washing the particles on the hydrophilic substrate by deionized water, and centrifuging for 2-3 min under the condition of 3000-4500 r/min rotation speed to obtain Pt/g-C 3 N 4 A Janus colloid motor;
the concentration of the microsphere dispersion liquid coated with the carbon nitride shell layer is 0.5 mg/mL-1 mg/mL.
In the third step of the embodiment, the semi-modification of the metal shell on the surface of the microsphere coated with the carbon nitride shell layer by a vacuum sputtering method specifically comprises the following steps: because the sputtering is from top to bottom, the metal is sputtered on the microsphere, and the metal is not sputtered on the lower surface, so the half-decoration is realized.
The carbon nitride (g-C3N4) of the present embodiment, which is a visible light range light-absorbing material composed of elements abundant on earth, has a unique two-dimensional structure, excellent chemical stability, and adjustable electronic structure, and thus is widely used in photocatalytic reactions. The novel photocatalysis driving colloid motor based on the carbon nitride can continuously and efficiently control the movement of the motor by controlling the wavelength, the intensity and the direction of light. In addition, the carbon nitride matrix material has strong oxidizing capability to organic matters under the excitation of visible light, and the colloidal motor is expected to be applied to photocatalytic degradation of pollutants such as phenol, methyl orange and the like.
The principle is as follows: the embodiment provides a preparation method of a carbon nitride based positive and negative colloid motor driven by visible light catalysis. Silicon dioxide microspheres, cyanamide, polyelectrolyte with positive charges and polyelectrolyte with negative charges are used, a uniform carbon nitride shell is formed on the surfaces of the silicon dioxide microspheres by a method of combining polymer layer-by-layer self-assembly, high-temperature calcination and metal vacuum sputtering, and then a positive and negative visible light driven colloidal motor is formed after platinum sputtering treatment. The surface structure of the silica template microsphere is enriched through the layer-by-layer self-assembly of the polymer under the electrostatic attraction effect of polyelectrolyte, the cyanamide precursor is conveniently and uniformly adsorbed, the cyanamide is converted into a carbon nitride shell after high-temperature calcination, and then a negative and positive asymmetric structure is formed by the method of vacuum sputtering. The silicon dioxide inner core provides reliable support for the colloid motor, so that the colloid motor has higher structural stability, the carbon nitride shell can respond to visible light to generate photoproduction electrons and photoproduction holes, the platinum metal layer part has the function of enriching the photoproduction electrons, and the photoproduction holes are reserved on one side of the carbon nitride to react with hydrogen peroxide. The carbon nitride material has different response capabilities to light with different wavelengths, and the efficiency of the semiconductor material for generating photo-generated electrons and holes can be influenced by controlling the wavelength of irradiated light and the intensity of the light, so that the decomposition speed of hydrogen peroxide is influenced, and further the speed is controlled. Or the movement speed of the micro-nano motor is directly influenced by changing the concentration of the hydrogen peroxide. Therefore, the motion control can be realized by adjusting the concentration of the hydrogen peroxide, the illumination power, the wavelength of the light and other factors. According to the embodiment, the influences of the hydrogen peroxide concentration, the illumination power and the light wavelength on the speed of the colloid motor are researched, the motion states of the colloid motor under different conditions are respectively analyzed, and the motion rule of the colloid motor is researched.
The beneficial effects of the embodiment are as follows:
the carbon nitride based cathode-anode type visible light driven colloidal motor prepared by the embodiment comprises a carbon nitride photocatalytic material shell, a silicon dioxide inner core and an outermost layer hemispherical metal layer, and has a cathode-anode type asymmetric structure, namely a Janus (asymmetric) structure is formed.
The present embodiment makes full use of g-C 3 N 4 The photoelectric current response characteristic under visible light enables the Janus colloid motor to have an obvious acceleration effect under the excitation of visible light, avoids the use of the traditional colloid motor to ultraviolet light, and can generate about 4 multiplied by 10 under the irradiation of a 500W xenon lamp under the open circuit voltage of 0.4V -7 A photo-generated current. Under the condition that the illumination intensity is 100W, the movement speed of the colloid motor irradiated by green light is gradually increased to 74.0 mu m/s, and the movement speed of the colloid motor irradiated by blue light is gradually increasedThe increase was gradually increased to 84.5 μm/s.
In this embodiment, the concentration of hydrogen peroxide, the intensity of light irradiation, and the wavelength of light were investigated for Pt/g-C 3 N 4 The influence of the motion behavior of the Janus colloid motor is further counted to obtain the motion rule: research shows that the motion speed of the colloid motor under blue light is higher than that under green light under the same power and hydrogen peroxide concentration; under the same illumination intensity, the movement speed of the colloid motor under the conditions of no light, green light and blue light is increased along with the increase of the concentration of the hydrogen peroxide; under the same hydrogen peroxide concentration, the movement speed of the colloid motor under green light and blue light is increased along with the increase of the illumination intensity; therefore, the relationship between the movement speed of the colloid motor prepared by the embodiment and the concentration of hydrogen peroxide, the illumination intensity and the wavelength of light can be realized, the effective control on the movement of the colloid motor can be realized, the thought can be provided for designing a novel photocatalysis driving colloid motor, and the theoretical basis can be provided for improving the movement efficiency of the colloid motor.
The second embodiment is as follows: the first difference between the present embodiment and the specific embodiment is: the polyetherimide modified template microsphere in the step one is prepared according to the following steps: the template microsphere is dipped in polyetherimide aqueous solution with the concentration of 1 mg/mL-3 mg/mL, and is shaken for 4 min-6 min under the condition that the power is 30W-40W. The rest is the same as the first embodiment.
The third concrete implementation mode: this embodiment is different from the first or second embodiment in that: the template microsphere is a silicon dioxide microsphere, a polystyrene sphere, a carbon microsphere or a metal-organic framework microsphere. The other is the same as in the first or second embodiment.
The fourth concrete implementation mode: the difference between this embodiment and one of the first to third embodiments is: the diameter of the template microsphere is 100 nm-30 μm. The others are the same as the first to third embodiments.
The fifth concrete implementation mode: the difference between this embodiment and one of the first to fourth embodiments is: the polyelectrolyte with positive charges in the step one is polyacrylamide hydrochloride or polydiallyldimethylammonium chloride; the polyelectrolyte with negative charges in the step one is sodium polystyrene sulfonate or sodium alginate. The rest is the same as the first to fourth embodiments.
The sixth specific implementation mode: the difference between this embodiment and one of the first to fifth embodiments is: in the first step, the polyetherimide modified template microsphere is soaked in a polyelectrolyte aqueous solution with 1-3 mg/mL of positive charge, is vibrated for 4-6 min under the condition that the power is 30-40W, is washed for 3-5 times by a NaCl aqueous solution with 0.5-1 mol/L of negative charge, is soaked in a polyelectrolyte aqueous solution with 1-3 mg/mL of negative charge, and is vibrated for 4-6 min under the condition that the power is 30-40W. The rest is the same as the first to fifth embodiments.
The seventh embodiment: the difference between this embodiment and one of the first to sixth embodiments is: the metal shell in the third step is a platinum layer. The others are the same as the first to sixth embodiments.
The specific implementation mode is eight: the present embodiment differs from one of the first to seventh embodiments in that: the thickness of the metal shell in the third step is 10 nm-50 nm. The others are the same as in the first to seventh embodiments.
The specific implementation method nine: the present embodiment differs from the first to eighth embodiments in that: and putting the template microspheres for adsorbing and melting the cyanamide into a quartz boat, placing the quartz boat in a tube furnace, heating to 520-550 ℃ at the heating rate of 2.5-5 ℃/min under the protection of argon, calcining for 4-5 h at the calcining temperature of 520-550 ℃, and finally washing, centrifuging and drying to obtain the microspheres coated with the carbon nitride shell. The others are the same as in the first to eighth embodiments.
The specific implementation mode is ten: the difference between this embodiment and one of the first to ninth embodiments is that: in the third step, under the condition of current 25 mA-30 mA, the metal shell is semi-modified on the surface of the microsphere coated with the carbon nitride shell layer by a vacuum sputtering method, and the sputtering time is 3 min-5 min. The others are the same as in the first to ninth embodiments.
The following examples were employed to demonstrate the beneficial effects of the present invention:
the first embodiment is as follows:
a preparation method of a carbon nitride based cathode-anode type visible light driven colloidal motor is carried out according to the following steps:
firstly, preparing a polyelectrolyte modified template microsphere:
dipping a polyetherimide modified template microsphere into a positively charged polyelectrolyte aqueous solution with the concentration of 2mg/mL, oscillating for 5min under the condition of power of 30W, then washing for 3 times by using a NaCl aqueous solution with the concentration of 0.5-1 mol/L, dipping into a negatively charged polyelectrolyte aqueous solution with the concentration of 2mg/mL, oscillating for 5min under the condition of power of 30W, and finally washing for 3 times by using a NaCl aqueous solution with the concentration of 0.5 mol/L;
secondly, repeating the first step for 10 times to obtain the polyelectrolyte-modified template microspheres;
secondly, preparing the microspheres coated with the carbon nitride shell layer:
dispersing 0.05g of polyelectrolyte-modified template microspheres in 0.10g of molten cyanamide;
soaking for 8min at 70 ℃, and then oscillating for 30s on an oscillator at room temperature;
thirdly, repeating the second step and the second step for 20 times to obtain template microspheres for adsorbing the molten cyanamide;
placing the template microspheres adsorbing and melting the cyanamide into a quartz boat, placing the quartz boat in a tube furnace, heating the quartz boat to 550 ℃ at a heating rate of 2.5 ℃/min under the protection of argon, calcining the quartz boat for 4 hours at the calcining temperature of 550 ℃, washing the quartz boat with deionized water, centrifuging the quartz boat, and drying the quartz boat in vacuum at the temperature of 60 ℃ to obtain microspheres coated with a carbon nitride shell layer;
thirdly, vacuum sputtering:
dispersing 20mg of microspheres coated with a carbon nitride shell layer into 40mL of deionized water to obtain a microsphere dispersion coated with the carbon nitride shell layer, dropwise adding the microsphere dispersion coated with the carbon nitride shell layer onto a hydrophilic glass sheet, standing for 10h, naturally spreading into single-layer particles, and under the condition of current of 30mA, coating the microspheres coated with the carbon nitride shell layerSemi-modifying metal shell on the surface of the microsphere by a vacuum sputtering method, wherein the sputtering time is 3min, washing off particles on a glass sheet by deionized water, and centrifuging for 3min under the condition that the rotating speed is 4000r/min to obtain Pt/g-C 3 N 4 A Janus colloid motor;
the polyetherimide modified template microsphere in the step one is prepared according to the following steps: dipping the silicon dioxide microspheres in a polyetherimide aqueous solution with the concentration of 2mg/mL, and oscillating for 5min under the condition that the power is 30W;
the diameter of the template microsphere in the first step is 5 microns;
the polyelectrolyte with positive charges in the step one is polyacrylamide hydrochloride; the polyelectrolyte with negative charges in the step one is sodium polystyrene sulfonate;
the metal shell in the third step is a platinum layer;
the thickness of the metal shell described in step three is 20 nm.
FIG. 2 shows Pt/g-C prepared in example one 3 N 4 Macroscopic scanning electron micrographs of Janus colloidal motor; as can be seen from the figure, the particle size of the calcined micro-nano particles is uniform, and the monodisperse property is obvious.
FIG. 3 is a diagram of Pt/g-C prepared in example one 3 N 4 High power scanning electron microscope image of Janus colloid motor; as can be seen from the figure, the surface of the silica with the polyelectrolyte assembled thereon has a certain roughness after adsorbing the cyanamide precursor and calcining at high temperature.
FIG. 4 is a diagram of Pt/g-C prepared in example one 3 N 4 The Janus colloid motor energy dispersion X-ray spectrogram, wherein a is an N element, b is a C element, and C is a Pt element; as can be seen from the figure, C, N and Pt elements are distributed on the colloid particles, C and N elements are distributed uniformly and are distributed all over the microspheres, and the C and N elements are introduced into the microspheres after the microspheres are soaked in cyanamide and calcined at high temperature. The Pt element exhibits a roughly hemispherical shape, and the platinum metal layer of the outermost hemispherical shape was verified.
The Pt/g-C prepared in example one was irradiated under an open circuit voltage of 0.4V and a xenon lamp power of 500W 3 N 4 JanusAnd performing photocurrent test on the colloid motor, wherein the colloid motor is illuminated every 20s and the colloid motor shields the light source every 20s as a period in the test process.
FIG. 5 shows Pt/g-C prepared in example one under irradiation with an open circuit voltage of 0.4V and a xenon lamp power of 500W 3 N 4 A photocurrent test pattern of the Janus colloid motor; as can be seen, the colloid motor can generate about 4X 10 under the irradiation of a 500W xenon lamp under the open circuit voltage of 0.4V -7 A, the generation of the photo-generated current has a direct relation with the condition of illumination. Therefore, the colloidal motor can generate photo-generated electrons under the excitation of visible light.
10mg of Pt/g-C prepared in the first example were taken 3 N 4 The Janus colloid motor was dispersed in 20mL deionized water and dropped into the H-bearing 2 O 2 On glass slides of the solution (H) 2 O 2 The mass percentage of the solution is 0%, 10%, 15% and 20%), and the illumination intensity and the wavelength of light are directly adjusted by adjusting a built-in mercury lamp of a microscope. The motion state of the colloid motor is observed and recorded through an upright optical microscope. Due to g-C 3 N 4 The light with different wavelengths has different absorption capacities, so that the movement can be effectively controlled by adjusting the hydrogen peroxide concentration, the illumination intensity and the wavelength of the light. The moving speed of the colloid motor and the later moving track can be processed and analyzed by Image J software.
FIG. 6 shows Pt/g-C prepared in example one under the condition of 100W of light intensity 3 N 4 A relational graph of the movement speed of the Janus colloid motor and the concentration of the hydrogen peroxide solution is shown, wherein 1 is no light, 2 is green light, and 3 is basket light; as can be seen from the figure, the movement speeds of all three increase with the increase of the hydrogen peroxide concentration, and the increase is obvious. With the increase of the hydrogen peroxide concentration, the movement speed of the colloid motor without light irradiation is gradually increased to 61.3 mu m/s, the movement speed of the colloid motor with green light irradiation is gradually increased to 74.0 mu m/s, and the movement speed of the colloid motor with blue light irradiation is gradually increased to 84.5 mu m/s. This shows that the moving speed of the colloid motor exhibits a positive correlation with the concentration of the fuel.
FIG. 7 shows the reaction of an alcohol in the presence of oxygenPt/g-C prepared in example one under the condition that the hydrogen hydride solution mass percentage is 15 percent 3 N 4 A relation graph of the movement speed of the Janus colloid motor and the illumination intensity, wherein 1 is green light, and 2 is basketry light; it can be seen from the figure that the moving speed of the colloid motor with relatively slow moving speed under the irradiation of green light is in positive correlation with the increase of the illumination intensity, but the increase is relatively small, and the maximum power green light is increased by about 23.15% compared with the speed of the non-applied light source. The motion speed of the colloid motor under blue light is in positive correlation with the increase of the illumination intensity, but the increase range of the speed is obvious, and the motion speed of the colloid motor is improved by about 70.54 percent by full-power irradiation of the blue light relative to that without an additional light source
From the above, the moving speed of the colloid motor under blue light irradiation is significantly higher than that of green light, no matter under different hydrogen peroxide concentrations or under different intensities of light. And the hydrogen peroxide concentration, the light intensity and the light wavelength were investigated for Pt/g-C 3 N 4 And (3) counting the influence of the motion behavior of the Janus colloid motor, and further counting the motion rule: research shows that the motion speed of the colloid motor under blue light is higher than that under green light under the same power and hydrogen peroxide concentration; under the same illumination intensity, the movement speed of the colloid motor under the conditions of no light, green light and blue light is increased along with the increase of the concentration of the hydrogen peroxide; the motion speed of the colloid motor under green light and blue light increases along with the increase of the illumination intensity under the same hydrogen peroxide concentration.
FIG. 8 is a graph of Pt/g-C prepared in example one under the conditions of a blue light intensity of 100W and a hydrogen peroxide solution weight percentage of 10% 3 N 4 Photographs of the motion of the Janus colloid motor; as can be seen from the figure, the motion of the colloid motor is realized by photocatalytic drive, and the colloid motor in the figure is uniformly distributed and is in different motion states, and the motion direction is in a disordered state.
FIG. 9 is a Pt/g-C sample prepared in example one 3 N 4 Schematic diagram of Janus colloid motor photocatalytic drive. The movement of the colloid motor is realized by generating bubbles through photocatalytic control of the decomposition of hydrogen peroxide, g-C 3 N 4 In the visibleAnd the photo-generated electrons can be conducted to the metal side, photo-generated holes are reserved on the carbon nitride side, and the electrons and the holes can promote the decomposition of hydrogen peroxide, so that the movement speed is effectively controlled.

Claims (10)

1. A preparation method of a carbon nitride based cathode-anode type visible light driven colloid motor is characterized by comprising the following steps:
firstly, preparing a polyelectrolyte modified template microsphere:
dipping a polyetherimide modified template microsphere in a polyelectrolyte aqueous solution with 1-3 mg/mL positive charges, oscillating for 4-6 min, then washing for 3-5 times by using a NaCl aqueous solution with 0.5-1 mol/L concentration, dipping in a polyelectrolyte aqueous solution with 1-3 mg/mL negative charges, oscillating for 4-6 min, and finally washing for 3-5 times by using a NaCl aqueous solution with 0.5-1 mol/L concentration;
secondly, repeating the first step for 8 to 12 times to obtain the polyelectrolyte-modified template microspheres;
secondly, preparing the microspheres coated with the carbon nitride shell layer:
dispersing template microspheres modified by polyelectrolyte in molten cyanamide;
the mass ratio of the molten cyanamide to the polyelectrolyte-modified template microspheres is 1 (0.5-1);
secondly, dipping for 5-10 min at the temperature of 65-70 ℃, and then oscillating for 20-40 s on an oscillator at room temperature;
thirdly, repeating the second step for 15 to 25 times to obtain template microspheres for adsorbing the molten cyanamide;
placing the template microspheres adsorbing and melting the cyanamide into a quartz boat, placing the quartz boat in a tube furnace, heating to 500-550 ℃ at a heating rate of 2.5-5 ℃/min under the protection of argon, calcining for 4-5 h at the calcining temperature of 500-550 ℃, and finally washing, centrifuging and drying to obtain the microspheres coated with the carbon nitride shell layer;
thirdly, vacuum sputtering:
dispersing the microspheres coated with the carbon nitride shell layer in deionized water to obtain microsphere dispersion coated with the carbon nitride shell layer, dropwise adding the microsphere dispersion coated with the carbon nitride shell layer on a hydrophilic substrate, standing for 10-18 h to naturally spread into single-layer particles, semi-modifying metal shells on the surfaces of the microspheres coated with the carbon nitride shell layer by a vacuum sputtering method under the condition of 20-30 mA current, wherein the sputtering time is 2-5 min, washing the particles on the hydrophilic substrate by using deionized water, centrifuging for 2-3 min under the condition of 3000-4500 r/min rotation speed, and obtaining Pt/g-C 3 N 4 A Janus colloid motor;
the concentration of the microsphere dispersion liquid coated with the carbon nitride shell layer is 0.5 mg/mL-1 mg/mL.
2. The method for preparing a carbon nitride-based yin-yang visible light driven colloidal motor according to claim 1, wherein the polyetherimide-modified template microsphere prepared in the step one is prepared by the following steps: the template microsphere is dipped in polyetherimide aqueous solution with the concentration of 1 mg/mL-3 mg/mL, and is shaken for 4 min-6 min under the condition that the power is 30W-40W.
3. The method for preparing a carbon nitride-based yin-yang visible light driven colloidal motor as claimed in claim 2, wherein the template microspheres are silica microspheres, polystyrene spheres, carbon microspheres or metal-organic framework microspheres.
4. The method for preparing a carbon nitride based yin-yang visible light driven colloidal motor as claimed in claim 3, wherein the diameter of the template microsphere is 100 nm-30 μm.
5. The method according to claim 1, wherein the positively charged polyelectrolyte in the first step is poly (allylamine hydrochloride) or poly (diallyldimethylammonium chloride); the polyelectrolyte with negative charges in the step one is sodium polystyrene sulfonate or sodium alginate.
6. The preparation method of the carbon nitride based positive-negative visible light driven colloidal motor according to claim 1, wherein in the first step, the polyetherimide modified template microspheres are immersed in a positively charged polyelectrolyte aqueous solution with a concentration of 1 mg/mL-3 mg/mL, shaken for 4 min-6 min under a power of 30W-40W, then washed for 3 times-5 times with a NaCl aqueous solution with a concentration of 0.5 mol/L-1 mol/L, immersed in a negatively charged polyelectrolyte aqueous solution with a concentration of 1 mg/mL-3 mg/mL, and shaken for 4 min-6 min under a power of 30W-40W.
7. The method according to claim 1, wherein the metal shell is a platinum layer.
8. The method for preparing a carbon nitride based yin-yang type visible light driven colloidal motor according to claim 1, wherein the thickness of the metal shell in step three is 10nm to 50 nm.
9. The method for preparing a carbon nitride based yin-yang visible light driven colloidal motor according to claim 1, wherein in the second step, the template microspheres for adsorbing and melting cyanamide are placed in a quartz boat and placed in a tube furnace, the temperature is raised to 520-550 ℃ at a temperature raising rate of 2.5-5 ℃/min under the protection of argon, then the microspheres are calcined for 4-5 h at a calcination temperature of 520-550 ℃, and finally the microspheres coated with the carbon nitride shell layer are obtained by washing, centrifuging and drying.
10. The preparation method of the carbon nitride based yin-yang type visible light driven colloidal motor as claimed in claim 1, wherein in the third step, under the condition of 25 mA-30 mA of current, the metal shell is semi-modified on the surface of the microsphere coated with the carbon nitride shell layer by a vacuum sputtering method, and the sputtering time is 3 min-5 min.
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