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CN111905748B - Hollow columnar ZnFe 2 O 4 /CaTiO 3 Composite material and preparation and application thereof - Google Patents

Hollow columnar ZnFe 2 O 4 /CaTiO 3 Composite material and preparation and application thereof Download PDF

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CN111905748B
CN111905748B CN202010843218.9A CN202010843218A CN111905748B CN 111905748 B CN111905748 B CN 111905748B CN 202010843218 A CN202010843218 A CN 202010843218A CN 111905748 B CN111905748 B CN 111905748B
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CN111905748A (en
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孙青�
占文卿
张俭
盛嘉伟
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Zhejiang University of Technology ZJUT
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Abstract

The invention provides a magnetic recyclable hollow columnar ZnFe 2 O 4 /CaTiO 3 A composite material and a preparation method and application thereof. The invention adopts leaf vein as a structural carrier to prepare the hollow columnar composite material, and CaCO which is cheap and easy to obtain 3 The calcium source replaces soluble calcium salt, the acid mixed in the titanium source dissolves the calcium source to obtain calcium ions, and the weak acid H 2 C 2 O 4 Substitute H 2 SO 4 Or HNO 3 Isostrongly acidic regulator, weakly basic CO (NH) 2 ) 2 Replaces strong alkalinity regulators such as NaOH or KOH and the like, effectively avoids strong acid and strong alkali pollution in the preparation process, and provides the hollow columnar ZnFe which saves energy, is green and environment-friendly, does not need strong acid and strong alkali and is prepared by high-temperature calcination, has adsorption effect, recoverable magnetism and hollow columnar ZnFe 2 O 4 /CaTiO 3 The composite material prepared by the method is in a hollow cylindrical shape, is uniformly distributed, has excellent magnetic property, effectively improves the recycling of the composite material, has a certain adsorption effect and good photocatalytic performance, and has a good application prospect.

Description

Hollow columnar ZnFe 2 O 4 /CaTiO 3 Composite material and preparation and application thereof
(I) technical field
The invention relates to a hollow columnar ZnFe 2 O 4 /CaTiO 3 A composite material and a preparation method and application thereof.
(II) background of the invention
With the continuous development of society, environmental problems come with the development of society, and water resources and pollution problems thereof are becoming more severe, bringing unprecedented challenges to the production and life of human beings. The traditional water treatment method has the advantages of high price, high energy consumption, difficult recovery and low efficiency, and the finding of a green, efficient and easily-recovered photocatalyst has important significance under the background.
Perovskite is excellent in dielectric property, catalytic property and biological propertyHas the capacity and the optical performance, and is widely applied to electroceramic materials and CO photocatalytic reduction 2 Corrosion resistance, building coating, low-temperature co-fired ceramic, living cell imaging, organic pollutant degradation and the like. CaTiO 3 The perovskite type oxide which has been found at the earliest is receiving wide attention from researchers at home and abroad. Such as Pei J, etc. with Ti (C) 4 H 9 O) 4 、Ca(NO 3 ) 2 And KOH and the like are taken as raw materials to prepare CaTiO 3 /Ca (OH) 2 Composite photocatalysts (Pei J, Meng J, Wu S, et al. effects of Ca/Ti ratio on hydroxyl control and photocatalytic activity of CaTiO) 3 /Ca (OH) 2 composite photocatalyst[J]Materials Letters,2020: 128229). SHU QIANG et al as CaCO 3 And TiO 2 Calcining the raw material at 1400 ℃ for 2-12 h to prepare CaTiO 3 (SHUQIANG,JIAO,KRISHNANKUTTY-NAIR,et al. Preparation and electrical properties of xCaRuO 3 /(1-x)CaTiO 3 perovskite composites[J].Materials Research Bulletin, 2009:1738-1742.)。
ZnFe 2 O 4 As a magnetic ferrite, the magnetic ferrite has the advantages of stable structure, low cost and the like, can be used as a photocatalytic material carrier, and can increase the cyclic utilization rate of the photocatalytic material when compounded with the photocatalytic material. For ZnFe 2 O 4 The researchers have conducted many studies on the preparation of (1) FeSO (e.g. Chimonanthus nitens) 4 And ZnSO 4 The raw material is used, NaOH is used for adjusting the pH value twice, and ZnFe is prepared 2 O 4 Material (Zhumeiying, Liuhui, Weiyu, preparation of nano-level zinc ferrite from ferric hydroxide and product property research [ J ]]Inorganic salt industry, 2007,039(008): 19-21.).
The veins of the leaves can transport water, inorganic salt, organic nutrients and the like for the plants, and the veins are connected with each other and staggered to form a vascular system. Leaves are used as a biological membrane plate, Fe ions, Zn ions and the like enter veins, and products can grow along the veins by regulating and controlling reaction conditions, so that ZnFe with special shapes is prepared 2 O 4 /CaTiO 3 A composite material. If can convert CaTiO into 3 And ZnFe 2 O 4 Effectively combine together to obtainThe hollow cylindrical composite material can be prepared, and the magnetic recoverability of the composite photocatalytic material can be improved, so that the magnetic recoverable hollow cylindrical ZnFe is developed 2 O 4 /CaTiO 3 The preparation method of the composite material has important significance.
Disclosure of the invention
The invention aims to provide a hollow columnar ZnFe with magnetic property and recoverability 2 O 4 /CaTiO 3 A composite material and a preparation method and application thereof.
The technical scheme adopted by the invention is as follows:
preparation of hollow columnar ZnFe by taking leaf veins of leaves as structural carrier 2 O 4 /CaTiO 3 A method of compounding a material, the method comprising:
(1) cleaning fresh leaves, cutting off edges, cutting the rest parts into pieces, and storing in dark for later use;
(2) weighing CaCO 3 、TiOSO 4 、ZnSO 4 ·7H 2 O、FeSO 4 ·7H 2 O、H 2 C 2 O 4 、 CO(NH 2 ) 2 Respectively placing in deionized water, stirring to obtain calcium source suspension, titanium source solution, zinc source solution, iron source solution, and H 2 C 2 O 4 Solution and CO (NH) 2 ) 2 A solution;
(3) mixing the zinc source solution and the iron source solution prepared in the step (2) according to ZnSO 4 ·7H 2 O： FeSO 4 ·7H 2 The molar ratio of O is 1: 1.8-2.2, uniformly mixing to obtain a first mixed solution;
(4) weighing the leaf fragments obtained in the step (1), and adding the leaf fragments into the mixed solution I to obtain a leaf blending solution;
(5) placing the leaf blending solution obtained in the step (4) in a constant-temperature magnetic stirrer for continuous stirring at 75-90 ℃, and dropwise adding H 2 C 2 O 4 The solution is obtained to ZnFe attached to the leaves 2 O 4 Precursor of ZnSO 4 ·7H 2 O and H 2 C 2 O 4 The mass ratio of (1): 1 to 1.4;
(6) taking out the leaves reacted in the step (5), and washing the leaves by using deionized water and absolute ethyl alcohol in sequence for later use;
(7) placing the zinc source solution in a constant-temperature magnetic stirrer, continuously stirring at 20-30 ℃, slowly adding the calcium source suspension, and uniformly stirring to obtain a mixed solution II;
(8) adding CO (NH) 2 ) 2 Dropwise adding the solution into the mixed solution II, and adjusting the pH value of the solution to 6.5-7.5 to obtain a mixed solution III;
(9) ZnFe adhered to the obtained product in the step (6) 2 O 4 Placing the leaves of the precursor in the third mixed solution, standing for 8-12 h, and transferring to a reaction kettle for hydrothermal reaction;
(10) filtering, washing and drying the hydrothermal reaction product in the step (9), transferring the hydrothermal reaction product to a muffle furnace for calcining, and washing, drying and grinding the calcined product to obtain the reddish brown ZnFe 2 O 4 /CaTiO 3 Solid powders, i.e. said hollow cylindrical ZnFe 2 O 4 /CaTiO 3 A composite material.
The invention adopts leaf vein as a structural carrier to prepare the hollow columnar composite material, and CaCO which is cheap and easy to obtain 3 The calcium source replaces soluble calcium salt, the acid mixed in the titanium source dissolves the calcium source to obtain calcium ions, and the weak acid H 2 C 2 O 4 Substitute H 2 SO 4 Or HNO 3 Isostrong acid regulator, weak base CO (NH) 2 ) 2 Replaces strong alkalinity regulators such as NaOH or KOH and the like, effectively avoids strong acid and strong alkali pollution in the preparation process, and provides the hollow columnar ZnFe which saves energy, is green and environment-friendly, does not need strong acid and strong alkali and is prepared by high-temperature calcination, has adsorption effect, recoverable magnetism and hollow columnar ZnFe 2 O 4 /CaTiO 3 A method of compounding a material.
Further, in the step (1), after the edges of the leaves are cut off, the leaves are cut into pieces of about 3mm by 3mm, and the pieces are stored in a dark place for later use.
The preparation method of the calcium source suspension in the step (2) is as follows: mixing CaCO 3 Placing the mixture in deionized water, and ultrasonically stirring the mixture for 15 to 30min at room temperature to obtain CaCO 3 A suspension; CaCO 3 The proportion of the water to the water is 1 g:10-30 mL, and the ultrasonic power is 60-180W.
The preparation method of the titanium source solution in the step (2) comprises the following steps: TiOSO is added 4 Mixing with deionized water, carrying out ultrasonic stirring for 15-30 min, and then continuously stirring at 20-40 ℃ to obtain TiOSO 4 A solution; wherein, TiOSO 4 The proportion of the water is 1 g: 10-30 mL, and the ultrasonic power is 60-180W.
Preferably, in step (2): ZnSO in solution of zinc source 4 ·7H 2 The proportion of O and water is 1 g: 20-40 mL; FeSO in iron source solution 4 ·7H 2 The proportion of O to water is 1 g: 20-40 mL; h 2 C 2 O 4 H in solution 2 C 2 O 4 The proportion of the water is 0.5 g: 20-40 mL; CO (NH) 2 ) 2 CO (NH) in solution 2 ) 2 The proportion of the water is 1 g: 10-15 mL.
Specifically, ZnSO in the leaf blending solution in the step (4) 4 ·7H 2 The mass ratio of O to leaves is 1: 6 to 14.
Preferably, CaCO in the mixed solution II in the step (7) 3 And TiOSO 4 The mass ratio of (A) to (B) is 1: 1-2, and the stirring time is 20-40 min.
Preferably, the hydrothermal reaction in the step (9) is carried out at 130-170 ℃, and the reaction time is 8-14 h.
Preferably, the calcination in the step (10) is carried out at 400-600 ℃ for 2-3 h. The drying is drying by an air blast drying oven, the drying temperature is 70-100 ℃, and the drying time is 2-4 hours.
The invention also relates to the hollow columnar ZnFe prepared by the method 2 O 4 /CaTiO 3 Composite material, and the hollow columnar ZnFe 2 O 4 /CaTiO 3 The application of the composite material in preparing a photocatalyst can be used for treating water pollution by photocatalysis.
The invention has the following beneficial effects:
(1) the method adopts the leaf vein of the tree as a structural carrier, and the product is generated along the inner wall of the vein by the ion transportation into the vein, thereby preparing the ZnFe 2 O 4 /CaTiO 3 A composite material;
(2) the method utilizes acid mixed in a titanium source reagent to prepare calcium source CaCO 3 Is dissolved and converted into calcium ions, H 2 C 2 O 4 Is pH regulator, and avoids the use of H 2 SO 4 、HNO 3 An isostrong acid substance;
(3) the method adopts alkalescent CO (NH) 2 ) 2 Is a pH regulator, and avoids strong alkali pollution caused by NaOH, KOH and the like as the pH regulator;
(4) the method has the advantages of energy conservation and environmental protection in the reaction process;
(5) ZnFe of the invention 2 O 4 /CaTiO 3 The composite material is in a hollow column shape and is uniformly distributed;
(6) ZnFe of the invention 2 O 4 /CaTiO 3 The composite material has excellent magnetic property, and the recycling of the composite material is effectively improved;
(7) ZnFe of the invention 2 O 4 /CaTiO 3 The composite material has certain adsorption effect and good photocatalytic performance.
(IV) description of the drawings
FIG. 1 is a hollow columnar ZnFe prepared in example 1 2 O 4 /CaTiO 3 XRD pictures of the materials.
FIG. 2 is a hollow cylindrical ZnFe film obtained in example 1 2 O 4 /CaTiO 3 SEM pictures of the material.
FIG. 3 is ZnFe of hollow column shape obtained in example 1 2 O 4 /CaTiO 3 Magnetic effect pattern of the material.
FIG. 4 shows ZnFe of hollow cylinder type obtained in example 1 2 O 4 /CaTiO 3 The photocatalytic effect of the material is shown.
FIG. 5 shows ZnFe obtained without adding leaves 2 O 4 /CaTiO 3 The photocatalytic effect of the material is shown.
(V) detailed description of the preferred embodiments
The invention will be further described with reference to specific examples, but the scope of the invention is not limited thereto:
example 1:
(1) cleaning fresh leaves with deionized water, cutting off the edges of the leaves with scissors, cutting the leaves into fragments of about 3mm by 3mm, and storing in a dark place for later use;
(2) 0.3525g of CaCO was weighed 3 Placing in 10mL deionized water, ultrasonic stirring at 180W for 20min to obtain calcium source suspension, weighing 0.5287g TiOSO 4 Placing the mixture in 10mL deionized water, carrying out ultrasonic stirring at 180W for 20min, then continuing stirring at 40 ℃ to obtain a titanium source solution, weighing 0.1438g of ZnSO 4 ·7H 2 Dissolving O in 5mL deionized water to obtain a zinc source solution, weighing 0.2781g FeSO 4 ·7H 2 Dissolving O in 8mL deionized water to obtain iron source solution, weighing 0.1796g H 2 C 2 O 4 Placing the mixture into 10mL deionized water to be stirred and dissolved to obtain H 2 C 2 O 4 Solution, 1.000g of CO (NH) was weighed 2 ) 2 Placing the mixture into 10mL deionized water to be uniformly stirred to obtain CO (NH) 2 ) 2 A solution;
(3) uniformly mixing and stirring the zinc source solution and the iron source solution prepared in the step (2) to obtain a mixed solution I;
(4) weighing 1.250g of the standby leaves in the step (1), placing the standby leaves in the mixed solution in the step (3), uniformly stirring, and standing for 12 hours to obtain a leaf blending solution;
(5) placing the blending solution obtained in the step (4) in a constant-temperature magnetic stirrer, continuously stirring at medium speed at 75 ℃, and dropwise adding 10mL of H prepared in the step (2) 2 C 2 O 4 Obtaining ZnFe attached to the leaves by the solution 2 O 4 A precursor;
(6) taking out the leaves reacted in the step (5), and washing the leaves by using deionized water and absolute ethyl alcohol sequentially for later use;
(7) placing the titanium source solution prepared in the step (2) in a constant-temperature magnetic stirrer, slowly adding 10mL of the calcium source suspension prepared in the step (2) under continuous medium-speed stirring at 25 ℃, and stirring for 20min to obtain a mixed solution II;
(8) the CO (NH) prepared in the step (2) 2 ) 2 The solution is dripped into the mixed solution continuously stirred at medium speed in the step (7), and the pH value of the solution is adjusted to 6.8 to obtainTo mixed solution III;
(9) ZnFe attached to the obtained product in the step (6) 2 O 4 Placing leaves of the precursor in the mixed solution III obtained in the step (8), standing for 10h, and transferring to a reaction kettle for hydrothermal reaction at 160 ℃ for 12 h;
(10) filtering and washing the hydrothermal reaction product in the step (9), drying the hydrothermal reaction product in a blast drying oven at 70 ℃ for 4 hours, transferring the hydrothermal reaction product to a muffle furnace, calcining the hydrothermal reaction product for 2 hours at 600 ℃, washing a sample for the second time, drying the sample at 70 ℃ for 4 hours, and grinding the sample to obtain reddish brown ZnFe 2 O 4 /CaTiO 3 The XRD spectrum of the solid powder is shown in figure 1, and the SEM picture is shown in figure 2.
XRD spectrogram shows that the prepared material is ZnFe 2 O 4 /CaTiO 3 Composite material, SEM picture shows that ZnFe is prepared 2 O 4 /CaTiO 3 The shape of the composite material is uniform hollow column shape.
Example 2:
(1) cleaning fresh leaves with deionized water, cutting off the edges of the leaves with scissors, cutting the leaves into fragments of about 3mm by 3mm, and storing in a dark place for later use;
(2) 0.5000g of CaCO was weighed 3 Placing in 15mL deionized water, ultrasonic stirring at 180W for 30min to obtain calcium source suspension, and weighing 0.7000g of TiOSO 4 Placing the mixture in 15mL deionized water, carrying out ultrasonic stirring at 180W for 30min, then continuing stirring at 40 ℃ to obtain a titanium source solution, weighing 0.1650g of ZnSO 4 ·7H 2 Dissolving O in 5mL deionized water to obtain a zinc source solution, weighing 0.3350g FeSO 4 ·7H 2 Dissolving O in 10mL deionized water to obtain iron source solution, weighing 0.2178g H 2 C 2 O 4 Placing the mixture into 10mL deionized water to be stirred and dissolved to obtain H 2 C 2 O 4 Solution, 1.000g of CO (NH) was weighed 2 ) 2 Placing the mixture into 15mL deionized water to be uniformly stirred to obtain CO (NH) 2 ) 2 A solution;
(3) uniformly mixing and stirring the zinc source solution and the iron source solution prepared in the step (2) to obtain a mixed solution I;
(4) weighing 1.6000g of the standby leaves in the step (1), placing the standby leaves in the mixed solution in the step (3), uniformly stirring and standing for 10 hours to obtain a leaf blending solution;
(5) placing the blending solution obtained in the step (4) in a constant-temperature magnetic stirrer, continuously stirring at medium speed at 80 ℃, and dropwise adding 10mL of H prepared in the step (2) 2 C 2 O 4 The solution is obtained to ZnFe attached to the leaves 2 O 4 A precursor;
(6) taking the leaves reacted in the step (5) out, and washing the leaves by using deionized water and absolute ethyl alcohol for later use;
(7) placing the titanium source solution prepared in the step (2) in a constant-temperature magnetic stirrer, slowly adding 10mL of the calcium source suspension prepared in the step (2) under continuous medium-speed stirring at 30 ℃, and stirring for 30min to obtain a mixed solution II;
(8) the CO (NH) prepared in the step (2) 2 ) 2 Dropwise adding the solution into the mixed solution continuously stirred at medium speed in the step (7), and adjusting the pH value of the solution to 6.9 to obtain a third mixed solution;
(9) ZnFe attached to the obtained material in the step (6) 2 O 4 Placing leaves of the precursor in the mixed solution III obtained in the step (8), standing for 12h, and transferring to a reaction kettle for hydrothermal reaction at 150 ℃ for 14 h;
(11) filtering and washing the hydrothermal reaction product in the step (9), drying the hydrothermal reaction product in a blast drying oven at 80 ℃ for 3h, transferring the hydrothermal reaction product to a muffle furnace at 550 ℃ for calcining for 2.5h, washing the calcined sample for the second time, drying the calcined sample at 80 ℃ for 3h, and grinding the calcined sample to obtain the reddish brown ZnFe 2 O 4 /CaTiO 3 And (3) solid powder.
Example 3:
(1) cleaning fresh leaves with deionized water, cutting the edges of the leaves with scissors, cutting the leaves into pieces of about 3mm by 3mm, and storing in a dark place for later use;
(2) 0.8000g of CaCO are weighed 3 Placing the mixture in 15mL deionized water, carrying out ultrasonic stirring at 180W for 25min to obtain a calcium source suspension, and weighing 1.3280g of TiOSO 4 Placing the mixture in 15mL deionized water, carrying out ultrasonic stirring at 180W for 30min, then continuing stirring at 40 ℃ to obtain a titanium source solution, weighing 0.2180g of ZnSO 4 ·7H 2 Dissolving O in 8mL of deionized water to obtain a zinc source solution, and weighing 0.4500g of FeSO 4 ·7H 2 O dissolved in 15mL to removeObtaining iron source solution in the seed water, weighing 0.2870g H 2 C 2 O 4 Placing the mixture into 12mL of deionized water, stirring and dissolving to obtain H 2 C 2 O 4 Solution, 1.000gCO (NH) was weighed 2 ) 2 Placing the mixture into 10mL deionized water to be uniformly stirred to obtain CO (NH) 2 ) 2 A solution;
(3) uniformly mixing and stirring the zinc source solution and the iron source solution prepared in the step (2) to obtain a mixed solution I;
(4) weighing 2.000g of the standby leaves in the step (1), placing the standby leaves in the mixed solution in the step (3), uniformly stirring, and standing for 8 hours to obtain a leaf blending solution;
(5) placing the blending solution obtained in the step (4) in a constant-temperature magnetic stirrer, continuously stirring at medium speed at 80 ℃, and dropwise adding 12mL of H prepared in the step (2) 2 C 2 O 4 Obtaining ZnFe attached to the leaves by the solution 2 O 4 A precursor;
(6) taking the leaves reacted in the step (5) out, and washing the leaves by using deionized water and absolute ethyl alcohol for later use;
(7) placing the titanium source solution prepared in the step (2) in a constant-temperature magnetic stirrer, slowly adding 15mL of the calcium source suspension prepared in the step (2) under continuous medium-speed stirring at 20 ℃, and stirring for 20min to obtain a mixed solution II;
(8) the CO (NH) prepared in the step (2) 2 ) 2 Dropwise adding the solution into the mixed solution continuously stirred at medium speed in the step (7), and adjusting the pH of the solution to 7.3 to obtain a third mixed solution;
(9) ZnFe attached to the obtained product in the step (6) 2 O 4 Placing leaves of the precursor in the mixed solution III obtained in the step (8), standing for 9 hours, and transferring to a reaction kettle for hydrothermal reaction at 170 ℃ for 9 hours;
(11) filtering and washing the hydrothermal reaction product in the step (9), drying the hydrothermal reaction product in an air drying oven at 90 ℃ for 2.5h, transferring the hydrothermal reaction product to a muffle furnace for calcining at 500 ℃ for 3h, washing the calcined sample for the second time, drying the calcined sample at 90 ℃ for 2.5h, and grinding the calcined sample to obtain the reddish brown ZnFe 2 O 4 /CaTiO 3 And (3) solid powder.
Performance test experiments:
of catalystsAnd (3) testing magnetic separation performance: 0.045g of ZnFe prepared in example 1 are weighed out 2 O 4 /CaTiO 3 Placing the composite material in a transparent glass bottle filled with deionized water, ultrasonically stirring uniformly to obtain a suspension, and after the magnet is close to one side of the glass bottle for 15s, obviously separating the sample from the solution, wherein ZnFe is formed 2 O 4 /CaTiO 3 The composite material is adsorbed on one side of the magnet, the magnetic separation effect is shown in figure 3, the figure 3(a) shows that the magnet is not added, and the figure 3(b) shows that the magnet is added for 15s, so that the composite material has excellent magnetic property and is convenient to recycle.
Dark adsorption performance test of the catalyst: 25mL of methylene blue solution (MB) with an initial concentration of 10mg/L was added to a quartz reaction tube, and 0.025mg of ZnFe prepared in examples 1 to 3 was weighed 2 O 4 /CaTiO 3 Adding the composite material into the 25mL MB solution, carrying out ultrasonic treatment for 5min, placing the mixture in a magnetic stirrer in the dark, continuously stirring the mixture for 1h, centrifuging the mixture by a centrifuge after reaction, taking supernatant, detecting the absorbance of the solution by an ultraviolet spectrophotometer, calculating the concentration of the MB in the solution according to a standard curve, and calculating the dark adsorption efficiency. ZnFe prepared without leaf addition (other parameters as in example 1) was tested under the same experimental conditions 2 O 4 /CaTiO 3 The dark adsorption effect of the composite material is shown in table 1.
Table 1: dark adsorption detection analysis result of sample
Sample name Dark adsorption efficiency (%)
Example 1 38.2
Example 2 35.4
Example 3 36.6
Not adding leaf sample 24.8
As shown by the results of MB dark adsorption efficiency (%) detection and analysis of the samples of examples 1 to 3 in Table 1, the MB dark adsorption efficiency (%) of the samples of examples 1 to 3 is more than 35%, which indicates that the samples of examples 1 to 3 have certain adsorption performance, the MB dark adsorption efficiency (%) of the samples without leaves is less than 25%, and the adsorption performance is lower than that of the ZnFe samples prepared in the examples 2 O 4 /CaTiO 3 A composite material.
Testing the photocatalytic performance: hollow columnar ZnFe 2 O 4 /CaTiO 3 The photocatalytic performance test of the composite material is carried out in a photochemical reactor, firstly, 25mL of MB solution with the initial concentration of 10mg/L is added into a quartz reaction tube, and 0.025g of the hollow column ZnFe prepared in the embodiment is weighed 2 O 4 /CaTiO 3 Adding the composite material into the 25mL MB solution, after dark adsorption for 1h, starting a 350w xenon lamp to illuminate for 2.5h, testing the residual MB concentration of the solution after photocatalysis for 2.5h by an ultraviolet-visible spectrophotometer, and calculating the degradation rate (%) after illumination for 2.5h according to a standard curve. Under the same experimental conditions, the hollow columnar ZnFe is compared 2 O 4 /CaTiO 3 Composite and ZnFe without added leaves 2 O 4 /CaTiO 3 Photocatalytic effect of composite material, hollow columnar ZnFe 2 O 4 /CaTiO 3 The graph of the photocatalytic effect of the composite material is shown in fig. 4, the left side is the MB solution before photocatalysis, and the right side is the MB solution after photocatalysis of the sample in the embodiment 1. ZnFe without added leaves 2 O 4 /CaTiO 3 The photocatalytic effect of the composite material is shown in figure 5, the left side is MB solution before photocatalysis, the right side is MB solution after sample photocatalysis, and the experimental result is shown in table 2.
Table 2: MB detection and analysis result of sample photocatalytic degradation
Sample name MB degradation Rate (%)
Example 1 99.8
Example 2 97.2
Example 3 97.6
Not adding leaf sample 88.6
As shown by MB degradation rate (%) detection analysis results of the samples of examples 1 to 3 in Table 2, the MB degradation rate of the samples of examples 1 to 3 is more than 97%, which shows that the samples of examples 1 to 3 have excellent photocatalytic performance, and the MB degradation rate of the samples without leaves is less than 90%, which is lower than that of ZnFe prepared in the examples 2 O 4 /CaTiO 3 A composite material.
Testing the circulating photocatalytic performance: in addition, to examine the reusability of the photocatalyst prepared, the ZnFe prepared in example 1 was selected 2 O 4 /CaTiO 3 The composite material was subjected to a cyclic photocatalytic experiment. The degradation rate of the photocatalytic degradation MB was shown in Table 3, after repeated use 3 times under the same conditions as those of the photocatalytic test.
Table 3: detection and analysis result of circulating photocatalytic performance of sample
Sample name MB degradation Rate (%)
Example 1 99.8
Repeating for 1 time 95.9
Repeating for 2 times 93.7
Repeating for 3 times 91.4
From Table 3, it can be seen that ZnFe was prepared in the examples 2 O 4 /CaTiO 3 After the composite material is repeatedly used for 3 times, the degradation rate of the composite material to MB still exceeds 90 percent, which shows that ZnFe 2 O 4 /CaTiO 3 The composite material has stable photocatalytic performance.

Claims (7)

1. Preparation of hollow columnar ZnFe by taking leaf veins of leaves as structural carrier 2 O 4 /CaTiO 3 A method of compounding a material, the method comprising:
(1) cleaning fresh leaves, cutting off edges, cutting the rest parts into pieces, and storing in dark for later use;
(2) weighing CaCO 3 、TiOSO 4 、ZnSO 4 ·7H 2 O、 FeSO 4 ·7H 2 O、H 2 C 2 O 4 、CO(NH 2 ) 2 Respectively placing the mixture into deionized water, uniformly stirring to obtain calcium source suspension,Titanium source solution, zinc source solution, iron source solution and H 2 C 2 O 4 Solution and CO (NH) 2 ) 2 A solution;
(3) mixing the zinc source solution and the iron source solution prepared in the step (2) according to ZnSO 4 ·7H 2 O：FeSO 4 ·7H 2 The molar ratio of O is 1: 1.8-2.2, uniformly mixing to obtain a first mixed solution;
(4) weighing the leaf fragments obtained in the step (1), and adding the leaf fragments into the mixed solution I to obtain a leaf blending solution;
(5) placing the leaf blending solution obtained in the step (4) in a constant-temperature magnetic stirrer for continuous stirring at 75-90 ℃, and dropwise adding H 2 C 2 O 4 The solution is obtained to ZnFe attached to the leaves 2 O 4 Precursor of ZnSO therein 4 ·7H 2 O and H 2 C 2 O 4 The mass ratio of (1): 1 to 1.4;
(6) taking out the leaves reacted in the step (5), and washing the leaves by using deionized water and absolute ethyl alcohol in sequence for later use;
(7) placing the zinc source solution in a constant-temperature magnetic stirrer, continuously stirring at 20-30 ℃, slowly adding the calcium source suspension, and uniformly stirring to obtain a mixed solution II; CaCO in mixed solution II 3 And TiOSO 4 The mass ratio of (A) to (B) is 1: 1-2;
(8) adding CO (NH) 2 ) 2 Dropwise adding the solution into the mixed solution II, and adjusting the pH value of the solution to 6.5-7.5 to obtain a mixed solution III;
(9) ZnFe adhered to the obtained product in the step (6) 2 O 4 Placing the leaves of the precursor in the third mixed solution, standing for 8-12 h, and transferring to a reaction kettle for hydrothermal reaction; the hydrothermal reaction is carried out at 130-170 ℃, and the reaction time is 8-14 h;
(10) filtering, washing and drying the hydrothermal reaction product obtained in the step (9), transferring the hydrothermal reaction product to a muffle furnace for calcination, washing, drying and grinding the calcined product to obtain reddish brown ZnFe 2 O 4 /CaTiO 3 Solid powders, i.e. said hollow cylindrical ZnFe 2 O 4 /CaTiO 3 A composite material; the calcination is carried out at 400-600 DEG CThe process is carried out for 2-3 h.
2. The method according to claim 1, wherein the suspension of the calcium source in the step (2) is prepared by the following method: mixing CaCO 3 Placing the mixture in deionized water, and ultrasonically stirring the mixture for 15 to 30min at room temperature to obtain CaCO 3 A suspension; CaCO 3 The proportion of the water to the water is 1 g: 10-30 mL, and the ultrasonic power is 60-180W.
3. The method according to claim 1, wherein the titanium source solution in the step (2) is prepared by the following method: TiOSO is added 4 Mixing with deionized water, carrying out ultrasonic stirring for 15-30 min, and then continuously stirring at 20-40 ℃ to obtain TiOSO 4 A solution; wherein, TiOSO 4 The proportion of the water is 1 g: 10-30 mL, and the ultrasonic power is 60-180W.
4. The method of claim 1, wherein in step (2): ZnSO in solution of zinc source 4 ·7H 2 The proportion of O and water is 1 g: 20-40 mL; FeSO in iron source solution 4 ·7H 2 The proportion of O and water is 1 g: 20-40 mL; h 2 C 2 O 4 H in solution 2 C 2 O 4 The proportion of the water to the water is 0.5 g: 20-40 mL; CO (NH) 2 ) 2 CO (NH) in solution 2 ) 2 The proportion of the water is 1 g: 10-15 mL.
5. The method of claim 1, wherein ZnSO is present in the leaf blend solution in step (4) 4 ·7H 2 The mass ratio of O to leaves is 1: 6 to 14.
6. ZnFe of hollow cylindrical shape obtained by the method according to any one of claims 1 to 5 2 O 4 /CaTiO 3 A composite material.
7. The hollow columnar ZnFe of claim 6 2 O 4 /CaTiO 3 The application of the composite material in preparing a photocatalyst.
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