CN114272926B - Difunctional catalytic type yin-yang ball micromotor and preparation method and application thereof - Google Patents
Difunctional catalytic type yin-yang ball micromotor and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a difunctional catalytic type yin-yang microsphere micro motor and a preparation method and application thereof. Dripping PMMA ethyl acetate solution on a glass slide to form a PMMA film, rapidly and uniformly scattering MgAl-LDHs micrometer flower spheres on the PMMA film, standing, drying, and dipping the glass slide into a solution prepared from Co (NO 3 ) 2 •6H 2 In a precursor solution consisting of O and 2-methylimidazole, after reacting for 20-30 hours, washing a glass slide for 3-5 times, dissolving a PMMA film in ethyl acetate to release MgAl-LDHs/ZIF-67, filtering and drying, and calcining in a muffle furnace to obtain MgAl-CLDHs/Co 3 O 4 C, a cathode-anode microsphere micro motor, is uniformly dispersed in laccase solution, stirred, adsorbed, filtered, washed and dried at room temperature to obtain laccase functionalized La-MgAl-CLDHs/Co 3 O 4 -C yin-yang sphere micro-motor. The laccase functionalization is carried out on the yin-yang ball micro motor by utilizing the electrostatic adsorption effect, so that the laccase has the dual functions of detection and degradation, and the rapid detection and high-efficiency degradation of trace catechol in water are realized.
Description
Technical Field
The invention belongs to the field of environment detection and restoration, and in particular relates to a bifunctional catalytic La-MgAl-CLDHs/Co 3 O 4 -C yin-yang ball micro-motor, its preparation method and application.
Background
In the process of urban industrialization, the discharge of industrial waste causes serious environmental pollution. Wherein phenolic pollutants discharged by petrochemical industry, dyes and pharmaceutical enterprises have carcinogenic and mutagenic toxicity, which poses a threat to human health. Methods for monitoring phenolic contaminants in water include chromatography and electroanalysis. These methods require cumbersome instrumentation and complex pretreatment procedures, are not suitable for rapid on-site analysis, and do not allow for degradation of the detected phenolic contaminants, so it is very necessary to develop and design a simple, reliable, rapid method for detecting and degrading phenolic contaminants.
The hierarchical multi-layer structured micro-nano material assembled by the low-dimensional nano material has high specific surface area and porosity, provides a channel for the diffusion of target pollutants, can realize the rapid response and high-sensitivity detection of the target pollutants, and is a good choice for designing a trace pollutant colorimetric detection sensor. In addition, the high exposed active sites also increase their catalytic activity while achieving efficient and rapid degradation of the target contaminant. Aluminum magnesium layered double hydroxides (Mg-Al LDHs) are a class of mixed metal hydroxides having a layered crystal structure of hydrotalcite consisting of divalent and trivalent metal ions, wherein part of the divalent metal ions are replaced by trivalent metal ions, the lamellae carry a permanent positive charge, and anions are present in the layer-to-layer channels in order to maintain electroneutrality, so as to balance the permanent positive charge carried by the lamellae. The unique structure of the catalyst has a plurality of excellent performances, and is widely applied to various fields of catalysis, adsorption separation, obstruction and absorption, biology, medicine, photo-electromagnetism and the like.
At present, many colorimetric sensing devices and degradation devices are static, and in order to improve detection sensitivity and degradation efficiency, additional stirring and other operations are needed, so that cost and difficulty are increased. The micro-nano motor is a device capable of being driven independently, and the motion process of the micro-nano motor can effectively induce the mixing of the solution and accelerate the mass transfer in the solution, so that the effective contact between the catalyst and the pollutant is increased, the quick response and the high-sensitivity detection are realized, and the degradation of the pollutant is accelerated.
In conclusion, research and development of the method capable of being driven autonomously has important significance for realizing rapid detection and degradation of the phenolic compounds.
Disclosure of Invention
Aiming at the problems that the prior art has complex procedures for phenolic pollutants, is not suitable for on-site rapid analysis, can not degrade the detected phenolic pollutants, has low sensitivity and can not be driven independently, the invention discloses a bifunctional catalytic La-MgAl-CLDHs/Co 3 O 4 -C yin-yang ball micro-motor, preparation method and application thereof, co 3 O 4 Catalytic H 2 O 2 Decomposition to produce O 2 The micro-motor has the advantages that the micro-motor is driven to move, the micro-motor has peroxidase-like activity, colorimetric detection of organic pollutants can be achieved, the laccase can effectively reduce catechol pollutants in water, the unique 3D open structure of the micro-motor provides a larger specific surface area, more active sites are exposed, catechol molecules are adsorbed to the surface of the micro-motor in the self-driving process, the catechol molecules directly reach the active sites, and rapid detection and high-efficiency degradation are achieved under the catalysis of active species.
The invention is realized by the following technical scheme:
difunctional catalytic La-MgAl-CLDHs/Co 3 O 4 -C yin-yang sphere micro-motor, prepared by the following method:
(1) Preparation of MgAl-LDHs/ZIF-67: dissolving PMMA in ethyl acetate, heating to dissolve PMMA, dripping the dissolved PMMA ethyl acetate solution on a glass slide to form a PMMA film, rapidly and uniformly scattering MgAl-LDHs micrometer flower spheres on the PMMA film, standing and drying to volatilize ethyl acetate, and impregnating the glass slide fixed with the MgAl-LDHs micrometer flower spheres into a glass slide prepared from Co (NO 3 ) 2 •6H 2 In a precursor solution consisting of O and 2-methylimidazole, standing for reaction for 20-30 h, washing a glass slide for 3-5 times after the reaction is finished, and then re-preparing the PMMA filmDissolving in ethyl acetate, releasing MgAl-LDHs/ZIF-67, filtering and drying;
（2）La-MgAl-CLDHs/Co 3 O 4 -C preparation of yin-yang sphere micro-motor: calcining MgAl-LDHs/ZIF-67 in a muffle furnace to obtain MgAl-CLDHs/Co 3 O 4 -C yin-yang sphere micro-motor, mgAl-CLDHs/Co 3 O 4 Uniformly dispersing the-C yin-yang sphere micro-motor in laccase solution, stirring, adsorbing, filtering, washing and drying to obtain laccase functionalized La-MgAl-CLDHs/Co 3 O 4 -C yin-yang sphere micro-motor.
Further, the MgAl-LDHs micro-flower spheres are prepared by the following method: mgSO 4 •7H 2 O and Al (NO) 3 ) 3 •9H 2 O is mixed and dissolved, urea is slowly added to form a mixed solution, hydrothermal reaction is carried out, and reactants are centrifuged, washed and dried to obtain MgAl-LDHs micron flower spheres.
Further, mgSO 4 •7H 2 O、Al(NO 3 ) 3 •9H 2 The molar ratio of O to urea is 3:1:9, the hydrothermal reaction temperature is 120 ℃, and the reaction time is 12h.
Further, mgAl-LDHs micrometer flower ball, co (NO) 3 ) 2 •6H 2 The mass ratio of O to 2-methylimidazole is 1: 388: 328, the precursor solution had a concentration of 7.16g/mL.
Further, 20mL of ethyl acetate was added per 1g of PMMA for dissolution.
Further, in the step (2), the muffle furnace calcining temperature is 600 ℃ and the calcining time is 1 h.
Further, the laccase solution concentration in step (2) is 1 mg/mL, and the solvent is a NaAc-HAc buffer solution with pH of 5.0 and 0.2M.
In the invention, the difunctional catalytic La-MgAl-CLDHs/Co 3 O 4 -C method for preparing a negative and positive sphere micromotor, comprising the following steps:
(1) The MgAl-LDHs/ZIF-67 is prepared by dissolving PMMA in ethyl acetate, heating to dissolve PMMA to form uniform solution, dripping the dissolved PMMA ethyl acetate solution on a glass slide to form PMMA film, and rapidly dissolving PMMA in waterUniformly scattering MgAl-LDHs micrometer flower spheres on PMMA film, standing and drying to volatilize ethyl acetate, and soaking slide glass fixed with MgAl-LDHs micrometer flower spheres in a solution prepared by Co (NO) 3 ) 2 •6H 2 In a precursor solution consisting of O and 2-methylimidazole, standing for reaction for 20-30 h, washing a glass slide for 3-5 times after the reaction is finished, dissolving a PMMA film in ethyl acetate again, releasing MgAl-LDHs/ZIF-67, filtering and drying;
（2）La-MgAl-CLDHs/Co 3 O 4 -C preparation of yin-yang sphere micro-motor: calcining MgAl-LDHs/ZIF-67 in a muffle furnace to obtain MgAl-CLDHs/Co 3 O 4 -C yin-yang sphere micro-motor, mgAl-CLDHs/Co 3 O 4 Uniformly dispersing the-C yin-yang sphere micro-motor in laccase solution, stirring, adsorbing, filtering, washing and drying to obtain laccase functionalized La-MgAl-CLDHs/Co 3 O 4 -C yin-yang sphere micro-motor.
The invention relates to a difunctional catalytic La-MgAl-CLDHs/Co 3 O 4 -C use of a yin-yang sphere micromotor in catechol detection.
The invention relates to a difunctional catalytic La-MgAl-CLDHs/Co 3 O 4 -C use of a yin-yang sphere micromotor in the catalytic degradation of catechol.
According to the invention, mgAl-LDHs micrometer flower spheres are prepared by a hydrothermal method, the micrometer flower spheres are fixed on a glass slide coated with a PMMA film and are immersed into a ZIF-67 precursor solution, and ZIF-67 nanocrystals are grown in situ on one side of the exposed MgAl-LDHs micrometer flower spheres, so that MgAl-LDHs/ZIF-67 is obtained. Calcining at high temperature to obtain MgAl-CLDHs/Co 3 O 4 C yin-yang sphere micro-motor, then performing laccase La functionalization to obtain catalytic La-MgAl-CLDHs/Co 3 O 4 -C yin-yang sphere micro-motor. In the micromotor, co 3 O 4 Catalytic H 2 O 2 Decomposition to produce O 2 The motor is driven to move, and the organic pollutant colorimetric detection device has peroxidase-like activity, so that colorimetric detection of the organic pollutant can be realized. Laccase is a polyphenol oxidase, and can effectively reduce catechol pollutants in water. The unique 3D open structure of the micro-motor provides a larger specific surface area, exposes more active sites, and is characterized in thatIn the self-driving process, catechol molecules are adsorbed on the surface of a micro-motor and directly reach an active site, and rapid detection and high-efficiency degradation are realized under the catalysis of active species. MgAl-CLDHs/Co 3 O 4 And the negative and positive ball micro motor has the double functions of detection and degradation, and realizes the rapid detection and efficient degradation of trace catechol in water.
Advantageous effects
The invention designs and constructs MgAl-LDHs micrometer flower spheres assembled by 2D nano-sheets as a carrier, ZIF-67 nano-crystals are grown on one side of the MgAl-LDHs micrometer flower spheres in situ, then MgAl-CLDHs/Co3O4-C catalytic yin-yang sphere micro-motors which are more stable and have nano-enzyme activity are formed by high-temperature calcination, and laccase functionalization is carried out on the yin-yang sphere micro-motors by utilizing electrostatic adsorption, so that the MgAl-LDHs micrometer flower spheres have double functions of detection and degradation, and rapid detection and high-efficiency degradation of trace catechol in water are realized.
Drawings
FIG. 1 shows a catalytic La-MgAl-CLDHs/Co prepared according to the present invention 3 O 4 -C XRD pattern of the yin-yang sphere micro-motor;
FIG. 2 shows a catalytic La-MgAl-CLDHs/Co prepared according to the present invention 3 O 4 -SEM and TEM images of a yin-yang sphere micromotor. (a) and (b) are SEM pictures of MgAl-LDHs micrometer flower spheres with different magnifications, and (c) and (d) are SEM pictures of MgAl-CLDHs/ZIF-67 with different magnifications, and (e) and (f) are catalytic La-MgAl-CLDHs/Co with different magnifications 3 O 4 -C SEM image of a yin-yang sphere micromotor. (g) Is a TEM image of MgAl-LDHs, and (h) and (i) are catalytic La-MgAl-CLDHs/Co with different magnification factors 3 O 4 -C TEM images of a yin-yang sphere micromotor;
FIG. 3 shows a catalytic La-MgAl-CLDHs/Co prepared according to the present invention 3 O 4 C yin-yang sphere micro motor at 5% H 2 O 2 The motion screenshot and the corresponding motion trail graph in the (a) and the micro-motor at different concentrations H 2 O 2 And H 2 O 2 Concentration graph. In the figure, (a-e) is a time-delay moving image with a time interval of 1s, (f) is a moving track of a micro motor of 0-4s, (g) is the micro motor in different concentrationsDegree H 2 O 2 A histogram of motion velocity in (a);
FIG. 4 is a catalytic La-MgAl-CLDHs/Co 3 O 4 -C uv-vis absorption spectrum of catechol detected colorimetrically by a micromotor. FIG. (a) is a catalytic La-MgAl-CLDHs/Co 3 O 4 -C ultraviolet-visible absorption spectrum of a yin-yang sphere micro-motor chromogenic system in the presence of catechol with different concentrations, wherein (b) is a calibration curve of catechol detection linear relation, and (C) is a catechol colorimetric detection mechanism diagram;
FIG. 5 is a graph showing the degradation rate of catechol with time under various conditions. FIG. (a) is a catalytic La-MgAl-CLDHs/Co under different pH conditions 3 O 4 -C, graph of degradation rate of catechol by yin-yang ball micro motor versus time, graph (b) is graph of degradation rate of catechol by different catalysts versus time, graph (C) is graph of influence of micro motor motion state on catechol degradation rate.
Detailed Description
The following description will clearly and completely describe the technical solutions in the embodiments of the present invention, and the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
(1) And (3) preparing MgAl-LDHs micron flower spheres:
1.476 g of MgSO was taken 4 •7H 2 O and 0.75 g Al (NO) 3 ) 3 •9H 2 O, dissolving the mixture in 160 mL distilled water, magnetically stirring the mixture to completely dissolve the mixture to form a uniform solution, slowly adding 1.082, 1.082 g urea, magnetically stirring the mixture for 10 min to form a mixed solution, transferring the mixed solution into a stainless steel high-pressure reaction kettle, placing the stainless steel high-pressure reaction kettle in a forced air drying oven to react at 120 ℃ for 12h, naturally cooling the reaction kettle to room temperature after the reaction is finished, centrifuging, washing and drying a sample to obtain white MgAl-LDHs micrometer flower spheres;
(2) Preparation of MgAl-LDHs/ZIF-67:
repeatedly cleaning six glass slides with deionized water for 3-5 times, and drying for later use; 0.5 g of PMMA is weighed and dissolved in 10 mL ethyl acetate, the temperature is slowly heated to 60 ℃, the PMMA is magnetically stirred until being dissolved to form uniform solution, 500 mu L of PMMA ethyl acetate solution is dripped on a clean glass slide by a liquid-transferring gun and is uniformly smeared to form a PMMA film with the thickness of 8 mu m, 100 mg of MgAl-LDHs micrometer flower balls are rapidly scattered on six glass slides coated with the PMMA film, the glass slide is stood and dried, the ethyl acetate is volatilized, and the glass slide fixed with the MgAl-LDHs micrometer flower balls is immersed into a precursor solution (0.388 g of Co (NO) 3 ) 2 •6H 2 Mixing O and 0.328 g of 2-methylimidazole uniformly, adding into 100 mL methanol solution, magnetically stirring for 10 min to form uniform solution), standing at room temperature for 24 h, washing a glass slide with methanol for several times after the reaction is finished, dissolving a PMMA film in ethyl acetate again, magnetically stirring for 30 min, releasing MgAl-LDHs/ZIF-67, filtering, and drying;
(3) La-MgAl-CLDHs/Co 3 O 4 -C preparation of yin-yang sphere micro-motor: 100 mg of MgAl-LDHs/ZIF-67 is placed in a corundum crucible, and calcined in a muffle furnace at 600 ℃ for 1 h to obtain MgAl-CLDHs/Co 3 O 4 -C cathode-anode microsphere micro-motor, uniformly dispersing in 30 mL 1 mg/mL laccase solution, magnetically stirring for 3h, filtering, washing, and drying at room temperature to obtain laccase functionalized catalytic La-MgAl-CLDHs/Co 3 O 4 -C yin-yang sphere micro-motor.
FIG. 1 is a catalytic La-MgAl-CLDHs/Co prepared 3 O 4 -C XRD pattern of the yin-yang sphere micro-motor. As can be seen from XRD patterns, the MgAl-LDHs and ZIF-67 have sharp diffraction peaks and good crystallinity, the diffraction peaks of the MgAl-LHDs and ZIF-67 after calcination disappear, the MgAl-LDHs gradually lose interlayer water molecules and anions, and the MgAl-LDHs is oxidized into corresponding metal oxides through a dissolution-recrystallization mechanism. And the catalytic La-MgAl-CLDHs/Co 3 O 4 After the C-type yin-yang microsphere micro-motor is immersed into the aqueous solution again, the diffraction peak of MgAl-LDHs appears again, which shows that MgAl-LDHs is rehydrated, and water molecules are absorbed again into the interlayer of the LDHs. At 2θ=11.55°,23.38 °,34.84 °,39.42 °,46.86 °,60.66 °,62.13 ° diffraction peaks,the (003), (006), (012), (015), (018), (110) and (113) crystal planes (JCPDS 00-014-0191) corresponding to MgAl-LDHs, respectively. The characteristic diffraction peaks at 7.53 °,10.08 °,12.91 °,16.53 °,18.10 °,23.19 ° correspond to the (011), (002), (112), (013), (222) and (114) crystal planes of ZIF-67, respectively, and the diffraction peaks at 44.72 ° and 60.95 ° correspond to the (200) and (220) crystal planes of MgO (pdf#65-0476), respectively. In addition, diffraction peaks at 19.00 °,31.21 °,36.89 °,38.65 °,55.67 °,59.39 °, and 65.26 ° correspond to Co, respectively 3 O 4 (111), (220), (311), (222), (422), (511), (440) crystal planes (PDF#42-1467), confirming successful conversion of ZIF-67 to Co upon calcination 3 O 4 。
Fig. 2 is an SEM image and a TEM image of the prepared micro motor. From the figures (a, b), it can be seen that the MgAl-LDHs micrometer flower ball is assembled by 2D nano-sheets, is in the shape of flower ball and has the size of about 15 mu m. The graph (c, d) shows that a layer of nano-scale ZIF-67 grows in situ on one side of the MgAl-LDHs micrometer flower ball, the asymmetric structure is constructed to provide good driving force for the micro motor movement, and the enlarged graph shows that the ZIF-67 is a regular rhombic dodecahedron. FIG. (e, f) is catalytic La-MgAl-CLDHs/Co 3 O 4 The microscopic morphology of the-C yin-yang sphere micromotor can be seen from the figure that ZIF-67 is derived into nano-scale Co after high-temperature calcination 3 O 4 The particles are distributed on the surfaces of MgAl-CLDHs micron flower spheres in coral shapes. MgAl-LDHs micrometer flower ball and La-MgAl-CLDHs/Co observed by TEM image (g-i) 3 O 4 The microscopic morphology of the-C male and female ball micro-motor is consistent with SEM images.
Example 2
For the catalytic La-MgAl-CLDHs/Co prepared in example 1 3 O 4 C yin-yang sphere micro motor at 5% H 2 O 2 The exercise situation in (a) was studied, see in particular figure 3. FIG. 3 is a catalytic La-MgAl-CLDHs/Co 3 O 4 C yin-yang sphere micro motor at 5% H 2 O 2 The motion screenshot and the corresponding motion trail graph in the process, and the yin-yang ball micro motor is used for controlling the concentration H 2 O 2 Is a histogram of the velocity of motion. In the figure, (a-e) is a time-lapse moving image with a time interval of 1s, and (f) is a micromotor of 0-4sThe motion track (g) is the micro motor at different concentrations H 2 O 2 Is a histogram of the velocity of motion. From the time-delay image, the movement direction of the micro-motor is opposite to the shedding direction of the generated bubbles, which indicates that the micro-motor decomposes H 2 O 2 Is Co grown on one side thereof 3 O 4 The falling of the oxygen bubbles provides reverse driving force for the motion of the micro motor, and the autonomous motion of the micro motor is realized. The micro motor is at H 2 O 2 This is probably due to the asymmetric distribution of the catalyst causing the oxygen bubbles to fall off at one side of the micro-motor, creating an axially asymmetric force, which results in a change of the direction of motion of the micro-motor. From the speed of motion and H 2 O 2 As can be seen in the concentration dependence bar graph, with H 2 O 2 The concentration increases and the movement speed of the micro motor increases.
Example 3
Colorimetric detection of catechol
Preparing catechol solutions (1-100. Mu.M) with different concentrations, adding 300. Mu.L of catechol solution into NaAc-HAc buffer solution (0.2M, pH 4.0) containing 2 ml, 400. Mu.L of TMB (1 mM), 200. Mu.L of H 2 O 2 (0.1. 0.1M) and 400. Mu.L of La-MgAl-CLDHs/Co 3 O 4 In the chromogenic solution of the negative and positive microsphere micro motor suspension (1.2 mg/mL), the mixture is incubated for 2 min at room temperature, and La-MgAl-CLDHs/Co is removed by centrifugation 3 O 4 And C, after the microsphere and the yin-yang microsphere are used for colorimetric detection of catechol.
FIG. 4 is a catalytic La-MgAl-CLDHs/Co 3 O 4 -C ultraviolet visible absorption spectrum of catechol by yin-yang sphere micro motor colorimetric detection. FIG. (a) is La-MgAl-CLDHs/Co 3 O 4 -C ultraviolet-visible absorption spectrum of a yin-yang sphere micro-motor chromogenic system in the presence of catechol with different concentrations, wherein (b) is a calibration curve of catechol detection linear relation, and (C) is a catechol colorimetric detection mechanism diagram. As is clear from the graph (a), the absorbance at 652. 652 nm gradually decreased with the increase in catechol concentration in the range of 0 to 100. Mu.M. Thus, the color of the solution changed from blue to colorless (fig. b inset). In additionThe absorbance at 652 nm is well linearly related to catechol concentration, and the linear regression equation is abs= 0.55269-0.00526[ s ]] (R 2 = 0.9917). The LOD of catechol was 0.24 μm (S/n=3).
Example 4
Catalytic degradation of catechol
A stock solution of catechol was prepared at a concentration of 1 g/L at 50 mL. 300 mu L catechol stock solution is respectively taken in 50 mL centrifuge tubes, no. 1, no. 2, no. 3, no. 4 and No. 5 are sequentially added into each centrifuge tube with NaAc-HAc buffer solution (0.2M) with different pH values of 8.7 mL, and 1 mL H is added 2 O 2 (30 wt%) and 10 mg La-MgAl-CLDHs/Co 3 O 4 And C, uniformly mixing and starting timing by using a yin-yang ball micro motor. And 5 min,15 min,30 min,60 min,90 min,120 min,150 min after the degradation reaction starts is sampled and centrifuged, 300 mu L of supernatant is added into a colorimetric system for color development, the mixture is kept stand for 2 min and centrifuged, and the supernatant is taken to measure absorbance.
300. Mu.L of catechol stock solution was placed in 50 mL centrifuge tubes, numbered 1#, 2#, 3#, and 8.7 mL of NaAc-HAc buffer (0.2M) having a pH of 6.0, 1 mL of H, were sequentially added to each centrifuge tube 2 O 2 (30 wt%) into a 1# centrifuge tube 10 mg La-MgAl-CLDHs/Co was added 3 O 4 -C yin-yang ball micro motor, 4.5 mg free laccase is added into a No. 2 centrifuge tube, and 10 mg MgAl-CLDHs/Co is added into a No. 3 centrifuge tube 3 O 4 And C, uniformly mixing and starting timing by using a yin-yang ball micro motor. And 5 min,15 min,30 min,60 min,90 min,120 min,150 min after the degradation reaction starts is sampled and centrifuged, 300 mu L of supernatant is added into a colorimetric system for color development, the mixture is kept stand for 2 min and centrifuged, and the supernatant is taken to measure absorbance.
300 mu L catechol stock solution is respectively taken in 50 mL centrifuge tubes, no. 1 and No. 2, 8.7 mL pH 6.0 NaAc-HAc buffer (0.2M) and 10 mg La-MgAl-CLDHs/Co are sequentially added into each centrifuge tube 3 O 4 C yin-yang ball micro motor, 1 mL H is added into a 1# centrifuge tube 2 O 2 (30%) in a 2# centrifuge tube, add 1 mL distilled water, mix well and start timing. 5 min,15 min,30 min after the start of the degradation reaction respectively,60 Sampling for min,90 min,120 min,150 min, centrifuging, adding 300 μl of supernatant into a colorimetric system for color development, standing for 2 min, centrifuging, and collecting supernatant to measure absorbance.
FIG. 5 is a graph showing the degradation rate of catechol with time under various conditions. FIG. (a) is a catalytic La-MgAl-CLDHs/Co under different pH conditions 3 O 4 -C, graph of degradation rate of catechol by yin-yang ball micro motor versus time, graph (b) is graph of degradation rate of catechol by different catalysts versus time, graph (C) is graph of influence of micro motor motion state on catechol degradation rate. As can be seen from FIG. (a), la-MgAl-CLDHs/Co 3 O 4 The catalyst activity of the-C yin-yang microsphere micro-motor is highest at pH 6.0, and the degradation rate of catechol is 95%. La-MgAl-CLDHs/Co at pH above or below 6.0 3 O 4 The catalytic activity of the-C yin-yang sphere micromotor is obviously reduced, and the degradation rate is respectively reduced to 71.27 percent and 27.49 percent at pH value of 4.0 and 8.0. As can be seen from FIG. (b), the ratio of La-MgAl-CLDHs/Co 3 O 4 In the reaction system of the-C yin-yang microsphere micro motor, the degradation rate of catechol is the highest and is about 95.9%, and the free laccase and MgAl-CLDHs/Co 3 O 4 The degradation rate of the yin-yang ball micro motor to catechol is lower, and the stability and the catalytic activity are further improved, so that the stability and the catalytic activity of the laccase are obviously better than those of the laccase using free laccase because the laccase is immobilized to improve the adaptability to the pH value and the temperature. In addition, la-MgAl-CLDHs/Co 3 O 4 Autonomous motion and O of a negative and positive sphere micro-motor 2 The rupture of the bubbles can enhance the disturbance of the solution and the active diffusion of pollutants, thereby improving the collision probability of the catalyst and catechol molecules and accelerating the degradation process. As can be seen from the graph (c), at H 2 O 2 In the presence of catechol, the degradation rate of catechol within 150 min was 96.2%, while in the absence of H 2 O 2 The degradation rate under mechanical stirring was 52.44%, therefore La-MgAl-CLDHs/Co 3 O 4 -C/H 2 O 2 The system has higher degradation rate, on one hand, the autonomous motion process of the micro motor accelerates the contact of pollutants and active species, and on the other hand, H 2 O 2 The presence of (C) contributes to laccase catalysis and Co 3 O 4 Induced byThe synergistic effect of Fenton-like reaction greatly promotes the degradation of catechol. And the additional mechanical stirring can realize effective mixing of the target substances, but does not trigger Fenton-like reaction, and only single laccase is used for catalytic degradation, so that the catechol removal efficiency is reduced. FIG. d is La-MgAl-CLDHs/Co 3 O 4 -C, a reaction mechanism diagram of the catalytic degradation of catechol by a yin-yang ball micro motor.
Claims (10)
1. The preparation method of the difunctional catalytic type yin-yang sphere micro motor is characterized by comprising the following steps of:
(1) Preparation of MgAl-LDHs/ZIF-67: dissolving PMMA in ethyl acetate, heating to dissolve PMMA, dripping the dissolved PMMA ethyl acetate solution on a glass slide to form a PMMA film, rapidly and uniformly scattering MgAl-LDHs micrometer flower spheres on the PMMA film, standing and drying to volatilize ethyl acetate, and impregnating the glass slide fixed with the MgAl-LDHs micrometer flower spheres into a glass slide prepared from Co (NO 3 ) 2 •6H 2 Standing for reaction for 20-30 h in a precursor solution consisting of O and 2-methylimidazole, washing a glass slide for 3-5 times after the reaction is finished, dissolving the washed PMMA film in ethyl acetate again, releasing MgAl-LDHs/ZIF-67, and filtering and drying;
(2) Laccase functionalized MgAl-CLDHs/Co 3 O 4 -C preparation of yin-yang sphere micro-motor: calcining MgAl-LDHs/ZIF-67 in a muffle furnace to obtain MgAl-CLDHs/Co 3 O 4 -C yin-yang sphere micro-motor, mgAl-CLDHs/Co 3 O 4 Uniformly dispersing the-C yin-yang sphere micro-motor in laccase solution, stirring, adsorbing, filtering, washing and drying to obtain laccase functionalized MgAl-CLDHs/Co 3 O 4 -C yin-yang sphere micro-motor.
2. The difunctional catalytic yin-yang microsphere micro motor of claim 1, wherein the MgAl-LDHs micrometer flower spheres are prepared by the following method: mgSO 4 •7H 2 O and Al (NO) 3 ) 3 •9H 2 O is mixed and dissolved, urea is slowly added to form a mixed solution, and hydrothermal reaction is carried outAnd centrifuging, washing and drying reactants to obtain MgAl-LDHs micron flower spheres.
3. The dual function catalytic yin-yang microsphere micro-motor according to claim 2, wherein MgSO 4 •7H 2 O、Al(NO 3 ) 3 •9H 2 The molar ratio of O to urea is 3:1:9, the hydrothermal reaction temperature is 120 ℃, and the reaction time is 12h.
4. The bifunctional catalytic microsphere/negative-type micromotor of claim 1, wherein MgAl-LDHs are microsphere/negative-type micromotor of the type consisting of MgAl-LDHs, co (NO 3 ) 2 •6H 2 The mass ratio of O to 2-methylimidazole is 1: 388: 328, the precursor solution had a concentration of 7.16g/mL.
5. The bi-functional catalytic yin-yang microsphere micro motor according to claim 1, wherein 20mL of ethyl acetate is added per 1g of pmma for dissolution.
6. The bi-functional catalytic yin-yang microsphere micro-motor according to claim 1, wherein the muffle furnace calcination temperature in step (2) is 600 ℃ and the calcination time is 1 h.
7. The bifunctional catalytic pellet motor of claim 1, wherein the laccase solution in step (2) has a concentration of 1 mg/mL and the solvent is a pH 5.0, 0.2M NaAc-HAc buffer solution.
8. A method for preparing the difunctional catalytic type yin-yang sphere micromotor according to any one of claims 1 to 7, which is characterized by comprising the following steps:
(1) The preparation method of MgAl-LDHs/ZIF-67 comprises dissolving PMMA in ethyl acetate, heating to dissolve PMMA to form uniform solution, dripping the dissolved PMMA ethyl acetate solution on a glass slide to form PMMA film, rapidly spreading MgAl-LDHs micrometer flower balls on the PMMA film uniformly, standing and drying to volatilize ethyl acetate, and soaking the glass slide fixed with MgAl-LDHs micrometer flower balls in the solution prepared by the methodCo(NO 3 ) 2 •6H 2 Standing for reaction for 20-30 h in a precursor solution consisting of O and 2-methylimidazole, washing a glass slide for 3-5 times after the reaction is finished, dissolving the washed PMMA film in ethyl acetate again, releasing MgAl-LDHs/ZIF-67, and filtering and drying;
(2) Laccase functionalized MgAl-CLDHs/Co 3 O 4 -C preparation of yin-yang sphere micro-motor: calcining MgAl-LDHs/ZIF-67 in a muffle furnace to obtain MgAl-CLDHs/Co 3 O 4 -C yin-yang sphere micro-motor, mgAl-CLDHs/Co 3 O 4 Uniformly dispersing the-C yin-yang sphere micro-motor in laccase solution, stirring, adsorbing, filtering, washing and drying to obtain laccase functionalized MgAl-CLDHs/Co 3 O 4 -C yin-yang sphere micro-motor.
9. Use of the bifunctional catalytic type yin-yang sphere micromotor of any one of claims 1-7 in catechol detection.
10. Use of the bifunctional catalytic type yin-yang sphere micromotor of any one of claims 1-7 in catechol catalytic degradation.
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