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CN111013565B - Ytterbium and erbium doped titanium dioxide/attapulgite nano composite material and preparation method and application thereof - Google Patents

Ytterbium and erbium doped titanium dioxide/attapulgite nano composite material and preparation method and application thereof Download PDF

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CN111013565B
CN111013565B CN201911360918.6A CN201911360918A CN111013565B CN 111013565 B CN111013565 B CN 111013565B CN 201911360918 A CN201911360918 A CN 201911360918A CN 111013565 B CN111013565 B CN 111013565B
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titanium dioxide
attapulgite
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ytterbium
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CN111013565A (en
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李霞章
张海光
戴达
左士祥
刘文杰
姚超
严向玉
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Changzhou University
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Abstract

The invention discloses a preparation method and application of ytterbium erbium-doped titanium dioxide/attapulgite nano composite material, which is prepared by mixing Yb (NO)3)3·5H2O、Er(NO3)3·6H2And O is added into the titanium dioxide suspension liquid and fully stirred, attapulgite is added, the mixture is transferred into a polytetrafluoroethylene high-pressure autoclave for constant-temperature reaction, after the reaction is finished, white precursor is obtained by washing and drying, and finally, the white precursor is calcined and ground in a muffle furnace to obtain the ytterbium and erbium-doped titanium dioxide/attapulgite nano composite material which is applied to photocatalytic synthesis of ammonia. The invention can make the titanium dioxide/attapulgite material generate up-conversion by doping ytterbium and erbium elements, thereby improving the utilization rate of the material to sunlight. The preparation method is simple, the industrial titanium dioxide is used as a titanium source, the cost is low, complex and expensive equipment is not needed, the synthesis condition is mild, and the method is favorable for large-scale popularization.

Description

Ytterbium and erbium doped titanium dioxide/attapulgite nano composite material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of novel material preparation and photocatalytic nitrogen fixation, and particularly relates to preparation and application of a titanium dioxide/attapulgite composite material doped with ytterbium (Yb) and erbium (Er).
Technical Field
Ammonia is one of the important basic chemical products, the yield of the ammonia is in front of the chemical products, but the synthesis of the ammonia consumes a large amount of energy. Although many yield-increasing and energy-saving technologies are developed for the traditional ammonia synthesis device, a large amount of fossil fuels are still required to be consumed in the reaction process due to the limitation of the traditional ammonia synthesis method, and certain pollution is caused to the atmospheric environment. Therefore, finding a process or catalyst that can react under low temperature conditions is of great importance for the synthesis of ammonia.
In recent years, the solar energy is used for realizing light nitrogen fixation and ammonia synthesis. TiO 22Is a common photocatalyst and is widely used due to high catalytic activity, stable chemical performance, low toxicity and low consumption. There are reports of TiO2The base photocatalytic material has a certain nitrogen fixation effect, but can only respond to ultraviolet light due to a wider band gap, and the sunlight utilization rate is less than 10%, so how to expand TiO2Becomes the key to improving the photocatalytic efficiency.
Rare earth elements are widely concerned due to unique upconversion luminescence effect, the upconversion luminescence can convert low-energy light into high-energy light, and the invention dopes rare earth elements such as ytterbium, erbium and the like into TiO2The up-conversion luminescence process can be effectively realized, and the photoresponse range can be expanded to a near-infrared region, so that the photocatalysis efficiency is improved. In addition, TiO particle2The nanometer attapulgite clay mineral has obvious agglomeration, and the natural one-dimensional nanometer clay mineral Attapulgite (ATP) has the advantages of low cost, porosity, good stability and the like, and can be used for treating nanometer TiO2The particles are well immobilized, so that the particle agglomeration phenomenon is reduced. The ytterbium erbium doped titanium dioxide/attapulgite nano composite material has quite wide application prospect.
Disclosure of Invention
The invention aims to provide preparation and application of a light nitrogen fixation catalyst material which is easy to obtain raw materials, low in cost and high in solar energy utilization rate. The preparation method is simple, does not need complex and expensive equipment, has mild synthesis conditions, and is beneficial to large-scale popularization.
The ytterbium erbium doped titanium provided by the inventionThe powdery mildew/attapulgite up-conversion composite photocatalytic material has the following general formula: TiYb0.2ErXO2The composition is characterized by comprising/ATP, wherein Yb/Ti is 0.2, Er/Ti is x, the range of x is 0.01-0.04, and TiYb0.2ErXO220% of ATP mass and the sample without erbium ytterbium doping is expressed as TiO2/ATP。
The invention limits Yb/Ti to 0.2, namely Yb in TiO2The doping amount of Yb is 20 mol%, which is a preferable result, Yb is used as a sensitizer, the intensity of luminescence converted therefrom is highest when the doping amount of Yb is 20%, and the intensity of luminescence is lowered when the doping amount is lower or higher, and then Er is used as an activator, and since it has a plurality of excited states, concentration quenching and the like are liable to occur to affect the intensity of luminescence converted therefrom, the doping amount of Er is not so high, and preferably, the ratio thereof is limited to 0.01 to 0.04.
The invention also provides a microwave hydrothermal synthesis method, which comprises the following specific steps:
(1) preparation of the precursor: adopts industrial titanium white (TiO)2) Dissolving the titanium source suspension in a deionized water solvent to prepare a titanium source suspension with the concentration of 1 mol/L; mixing Yb (NO)3)3·5H2Dissolving O in deionized water to prepare Yb source solution with the concentration of 0.2 mol/L; er (NO)3)3·6H2O is dissolved in deionized water to prepare Er source solution with the concentration of 0.01-0.04 mol/L. Dropping Yb source solution and Er source solution into the titanium source solution while stirring, and stirring for 30 minutes. Adding attapulgite powder (ATP) into the mixed solution while stirring, continuously stirring for 30 minutes at 80 ℃ to obtain a white turbid solution, and dropwise adding ammonia water into the turbid solution while stirring to adjust the pH value to 6-12. Transferring the mixture into a microwave hydrothermal reaction kettle, reacting for 60-240 minutes at a constant temperature of 120-200 ℃, washing and centrifuging the precipitate for several times by using water and ethanol respectively, and drying for 24 hours at 80 ℃ to obtain a white precursor;
wherein, TiO2With Yb (NO)3)3·5H2The molar ratio of O is 1: 0.2, TiO2And Er (NO)3)3·6H2The molar ratio of O is 1: 0.01-0.04, calculating the TiYb generated by the reaction0.2ErXO2Accounting for 20 percent of the mass of ATP.
(2) And (3) calcining: carrying out heat treatment on the precursor in the step (1) for 4 hours at 400 ℃ in a muffle furnace, and grinding to obtain TiYb0.2ErXO2ATP powder.
Conventional synthesis of Yb3+，Er3+Doped pair TiO2Modification to produce TiO2Lattice defect and lattice distortion, and improving TiO by inhibiting photo-generated electron recombination and the like2The present invention has not only the above-mentioned effects but also Yb3+，Er3+In TiO2The up-conversion effect is achieved, so that low-energy light (such as near infrared light) can be directly utilized for carrying out photocatalytic reaction, the photoresponse range is widened, and the nitrogen fixation effect is remarkable. In addition, the invention takes titanium dioxide and attapulgite as raw materials, and has the advantages of low price, easy obtainment and the like. Attapulgite as carrier, TiO2The attapulgite clay is uniformly loaded on the attapulgite clay, so that the dispersity and the stability of the composite material in water can be effectively improved, and TiO is avoided2Agglomeration occurs. Further improving the nitrogen fixation effect of the material.
Compared with the prior art, the invention has the beneficial effects that:
(1) in the invention Yb3+，Er3+Titanium dioxide and Yb are introduced into two kinds of rare earth ions3+As a sensitizer, the crystal can absorb the energy of near infrared light and transfer the energy to Er3+The activator emits ultraviolet light. The up-conversion effect of the rare earth ions is utilized to increase the utilization rate of the titanium dioxide to sunlight, and the photocatalytic nitrogen fixation efficiency of the composite material is obviously improved.
(2) The preparation process is simple and easy to implement, the industrial titanium dioxide and the natural attapulgite clay mineral are used as raw materials, the cost is low, the environment is protected, the prepared catalyst has high structural stability and good dispersibility, and the large-scale popularization is facilitated.
Drawings
FIG. 1 is a TiYb prepared in example 10.2Er0.01O2ATP, TiYb prepared in comparative example 20.2Er0.02O2ATP # and TiO2ATP sampleXRD pattern of (a);
FIG. 2 is a TiYb prepared in example 10.2Er0.01O2TEM image of 100nm scale range of ATP sample;
FIG. 3 is a TiYb prepared in example 10.2Er0.01O2ATP sample, TiYb prepared in example 20.2Er0.02O2ATP sample, TiYb prepared in example 30.2Er0.03O2ATP sample, TiYb prepared in example 40.2Er0.04O2ATP and TiO prepared in comparative example2ATP and industrial titanium dioxide (TiO is used as the main component)2) The photocatalytic nitrogen fixation effect diagram.
FIG. 4 is a TiYb prepared in example 20.2Er0.02O2ATP sample (designated Er), TiYb prepared in comparative example 20.2Er0.02O2Sample ATP # (designated Er #), comparative example 3 TiFe0.02O2ATP (noted Fe), TiCu prepared in comparative example 40.02O2ATP (denoted Cu), TiZn prepared in comparative example 50.02O2ATP (noted as Zn) and TiSr prepared in comparative example 60.02O2The photocatalytic nitrogen fixation effect of ATP (denoted as Sr) is shown.
Detailed Description
The best formula and process are preferred as examples, and the summary of the invention is further elaborated.
Example 1
(1) Weighing 0.8g of titanium dioxide (purchased from Shanghai Ling Shu-Ri chemical Co., Ltd.) and dissolving in 10mL of deionized water, and stirring for 30 minutes to obtain a titanium source suspension; take 0.9gYb (NO)3)3·5H2O, another 0.05gEr (NO)3)3·6H2And O is respectively dissolved in 10mL of deionized water, the Yb source solution and the Er source solution are dropwise added into the titanium source suspension while stirring, the stirring is continued for 30 minutes at the temperature of 80 ℃, 4g of attapulgite is added into the obtained solution, the stirring is continued for 30 minutes at the temperature of 80 ℃, and the pH value is adjusted to 6.
(2) And (2) transferring the mixed solution obtained in the step (1) into a microwave hydrothermal reaction kettle, carrying out microwave hydrothermal reaction for 60 minutes at 120 ℃, centrifuging and washing the obtained precipitate, drying for 24 hours at 80 ℃, and grinding to obtain a white precursor.
(3) Placing the sample prepared in the step (2) in a muffle furnace, calcining for 4 hours at 400 ℃, and finally grinding to obtain TiYb with Er doping amount of 0.010.2Er0.01O2ATP powder.
For the TiYb prepared in this example0.2Er0.01O2The ATP composite material is subjected to an X-ray powder diffraction experiment, and the morphology and the structure of the ATP composite material are observed under a transmission electron microscope.
The XRD pattern is shown in figure 1, the composite material has diffraction characteristic peaks which are respectively unique to titanium dioxide and attapulgite in XRD, and in addition, because Yb3+，Er3+The doping amount of the titanium dioxide is small, and a diffraction peak corresponding to the oxide does not exist in an XRD pattern, so that the titanium dioxide enters into the crystal of the titanium dioxide well. Meanwhile, the TEM photograph figure 2 proves that the titanium dioxide nano particles are successfully loaded on the surface of the attapulgite. Furthermore, TiYb produced by the impregnation method0.2Er0.02O2The XRD pattern of/ATP # can show that the intensity of the corresponding diffraction peak is weaker, which indicates that the crystallization process in the hydrothermal reaction is lacked, and the crystallinity of the catalyst is poorer.
The TEM photograph is shown in FIG. 2, and it can be seen from the graph that the surface of the attapulgite is uniformly loaded with titanium dioxide nano-particles, the particle size is uniform, and the particle size is less than 10nm, which is consistent with the XRD result.
The invention also provides application of the composite material in photocatalysis nitrogen fixation.
The application method comprises the following steps: respectively weighing the prepared rare earth doped titanium dioxide loaded attapulgite material (TiYb)0.2ErxO2ATP composite material and titanium dioxide loaded attapulgite material (TiO)2ATP) was dispersed in a proportion of 0.04g each. In 100mL of deionized water, and then adding into a photocatalytic reaction device, N2Introducing into a reaction device at a flow rate of 60mL/min, and introducing N2Irradiating with 300W xenon lamp as simulated light source after 30min, collecting 10mL sample every 30min, adding Nashin's reagent, and chargingAfter the reaction, the supernatant was extracted, and the absorbance was measured by an ultraviolet spectrometer at a wavelength of 420 nm.
NH of the composite measured by the above method4 +The resulting curve is shown in fig. 3. As can be seen from the figure, the TiYb prepared in example 10.2Er0.01O2ATP sample NH after 120min4 +The concentration reaches 0.035g/L-1When the doping amount of Er is 0.02, the nitrogen fixation rate effect of the composite material is best. Furthermore, pure TiO2Because the agglomeration is easy to occur in water, the nitrogen fixation efficiency is gradually reduced after the reaction is carried out for a period of time, and the TiO adopting the attapulgite as the carrier2The ATP has better dispersibility, and can keep higher nitrogen fixation rate in a certain time.
FIG. 4 shows a composite material, NH, prepared by different preparation methods and with various doping elements4 +The generated curve is obviously seen from the figure, the nitrogen fixing effect of the composite material prepared by the hydrothermal method is far higher than that of the composite material prepared by the immersion method, and the hydrothermal method has obvious advantages in the aspect of preparation of the composite material. In addition, the composite material is doped by adopting metal elements, and a photocatalytic nitrogen fixation effect experiment is carried out, and surprisingly, compared with other metal ions, Yb is3+、Er3+The double-doped composite material obtains quite high nitrogen fixation effect, and the up-conversion effect plays a great role in improving the nitrogen fixation performance of the photocatalytic material.
Example 2
(1) Weighing 0.8g of titanium dioxide, dissolving in 10mL of deionized water, and stirring for 30 minutes to obtain a titanium source suspension; take 0.9gYb (NO)3)3·5H2O, separately weighed 0.1gEr (NO)3)3·6H2And dissolving O in 10mL of deionized water respectively, dropwise adding Yb source and Er source solutions into the titanium source suspension while stirring, continuously stirring for 30 minutes at 80 ℃, adding 4g of attapulgite into the obtained solution, continuously stirring for 30 minutes at 80 ℃, and adjusting the pH value to 8.
(2) And (2) transferring the solution obtained in the step (1) into a microwave hydrothermal reaction kettle, carrying out microwave hydrothermal reaction for 90 minutes at 150 ℃, centrifuging and washing the obtained precipitate, drying for 24 hours at 80 ℃, and grinding to obtain a white precursor.
(3) Placing the sample prepared in the step (2) in a muffle furnace, calcining for 4 hours at 400 ℃, and finally grinding to obtain TiYb with the doping amount of 0.020.2Er0.02O2ATP powder.
Subsequent testing As in example 1, NH of the composite was measured4 +The resulting curve is shown in fig. 3. NH after 120min4 +The concentration reaches 0.044g/L-1。
Example 3
(1) Weighing 0.8g of titanium dioxide, dissolving in 10mL of deionized water, and stirring for 30 minutes to obtain a titanium source suspension; take 0.9gYb (NO)3)3·5H2O, separately weighed 0.15gEr (NO)3)3·6H2Dissolving O in 10mL of deionized water respectively, dropwise adding Yb source and Er source solutions into the titanium source suspension while stirring, continuously stirring for 30 minutes at 80 ℃, adding 4g of attapulgite into the obtained solution, continuously stirring for 30 minutes at 80 ℃, and adjusting the pH value to 10.
(2) And (2) transferring the solution obtained in the step (1) into a microwave hydrothermal reaction kettle, carrying out microwave hydrothermal reaction for 160 minutes at 180 ℃, centrifuging and washing the obtained precipitate, drying for 24 hours at 80 ℃, and grinding to obtain a white precursor.
(3) Placing the sample prepared in the step (2) in a muffle furnace, calcining for 4 hours at 400 ℃, and finally grinding to obtain TiYb with Er doping amount of 0.030.2Er0.03O2ATP powder.
Subsequent testing As in example 1, NH of the composite was measured4 +The resulting curve is shown in fig. 3. NH after 120min4 +The concentration reaches 0.038g/L-1。
Example 4
(1) Weighing 0.8g of titanium dioxide, dissolving in 10mL of deionized water, and stirring for 30 minutes to obtain a titanium source suspension; take 0.9gYb (NO)3)3·5H2O, separately weighed 0.20gEr (NO)3)3·6H2O is respectively dissolved in 10mL deionized water and is dripped into the titanium source suspension liquid while stirringAdding Yb source and Er source solution, stirring at 80 deg.C for 30min, adding 4g attapulgite into the obtained solution, stirring at 80 deg.C for 30min, and adjusting pH to 12.
(2) And (2) transferring the solution obtained in the step (1) into a microwave hydrothermal reaction kettle, carrying out microwave hydrothermal reaction for 240 minutes at 200 ℃, centrifuging and washing the obtained precipitate, drying for 24 hours at 80 ℃, and grinding to obtain a white precursor.
(3) Placing the sample prepared in the step (2) in a muffle furnace, calcining for 4 hours at 400 ℃, and finally grinding to obtain TiYb with Er doping amount of 0.040.2Er0.04O2ATP powder.
Subsequent testing As in example 1, NH of the composite was measured4 +The resulting curve is shown in fig. 3. NH after 120min4 +The concentration reaches 0.034g/L-1。
Comparative example 1
(1) Weighing 0.8g of titanium dioxide, dissolving in 10mL of deionized water, and stirring for 30 minutes to obtain a titanium source suspension; stirring was continued for 30 minutes at 80 ℃ and 4g of attapulgite was added to the obtained titanium source suspension, and stirring was continued for 30 minutes at 80 ℃ and the pH was adjusted to 8.
(2) And (2) transferring the solution obtained in the step (1) into a microwave hydrothermal reaction kettle, carrying out microwave hydrothermal reaction for 90 minutes at 150 ℃, centrifuging and washing the obtained precipitate, drying for 24 hours at 80 ℃, and grinding to obtain a white precursor.
(3) Placing the sample prepared in the step (2) in a muffle furnace, calcining for 4 hours at 400 ℃, and finally grinding to obtain TiO2ATP powder.
Subsequent testing As in example 1, NH of the composite was measured4 +The resulting curve is shown in fig. 3. NH after 120min4 +The concentration is only 0.007g/L-1Far below Yb3+，Er3+And (4) doping the composite material.
Comparative example 2
(1) Weighing 0.8g of titanium dioxide, dissolving in 10mL of deionized water, and stirring for 30 minutes to obtain a titanium source suspension; to the solution obtained 4g of attapulgite was added, stirring was continued at 80 ℃ for 30 minutes and the pH was adjusted to 8.
(2) Transferring the solution obtained in the step (1) into a magnetic stirrer, carrying out immersion reaction for 12 hours at the temperature of 80 ℃, centrifuging and washing the obtained precipitate, drying for 24 hours at the temperature of 80 ℃, and grinding to obtain a white precursor.
(3) Putting the white precursor obtained in the step (2) into a beaker, preparing precursor suspension by taking 10mL of deionized water, and taking 0.9gYb (NO) at the moment3)3·5H2O and 0.1gEr (NO)3)3·6H2And dissolving O in 10mL of deionized water respectively, dropwise adding the Yb source and Er source solution into the precursor suspension while stirring, continuously stirring for 180 minutes at 80 ℃, centrifuging and washing the obtained precipitate after the reaction is finished, drying for 24 hours at 80 ℃, and grinding to obtain the white precursor.
(4) Placing the white precursor prepared in the step (3) into a muffle furnace, calcining for 4 hours at 400 ℃, and finally grinding to obtain TiYb with Er doping amount of 0.020.2Er0.02O2ATP powder, denoted TiYb0.2Er0.02O2/ATP#。
Subsequent testing As in example 1, NH of the composite was measured4 +The resulting curve is shown in fig. 3. NH after 120min4 +The concentration reaches 0.012g/L-1。
Comparative example 3
(1) Weighing 0.8g of titanium dioxide, dissolving in 10mL of deionized water, and stirring for 30 minutes to obtain a titanium source suspension; taking 0.081gFe (NO)3)3·9H2Dissolving O in 10mL of deionized water, dropwise adding the Fe source solution into the titanium source suspension while stirring, continuously stirring for 30 minutes at 80 ℃, adding 4g of attapulgite into the obtained solution, continuously stirring for 30 minutes at 80 ℃, and adjusting the pH value to 8.
(2) And (2) transferring the solution obtained in the step (1) into a microwave hydrothermal reaction kettle, carrying out microwave hydrothermal reaction for 90 minutes at 150 ℃, centrifuging and washing the obtained precipitate, drying for 24 hours at 80 ℃, and grinding to obtain a sample.
(3) Placing the sample prepared in the step (2) in a muffle furnace, calcining for 4 hours at 400 ℃, and finally grinding to obtain Fe doped0.02 amount of impurity of TiFe0.02O2ATP powder.
Subsequent testing As in example 1, NH of the composite was measured4 +The resulting curve is shown in fig. 3. NH after 120min4 +The concentration reaches 0.009g/L-1。
Comparative example 4
(1) Weighing 0.8g of titanium dioxide, dissolving in 10mL of deionized water, and stirring for 30 minutes to obtain a titanium source suspension; taking 0.048gCu (NO)3)2·3H2Dissolving O in 10mL of deionized water, dropwise adding the Cu source solution into the titanium source suspension while stirring, continuously stirring for 30 minutes at 80 ℃, adding 4g of attapulgite into the obtained solution, continuously stirring for 30 minutes at 80 ℃, and adjusting the pH value to 8.
(2) And (2) transferring the solution obtained in the step (1) into a microwave hydrothermal reaction kettle, carrying out microwave hydrothermal reaction for 90 minutes at 150 ℃, centrifuging and washing the obtained precipitate, drying for 24 hours at 80 ℃, and grinding to obtain a sample.
(3) Placing the sample prepared in the step (2) in a muffle furnace, calcining for 4 hours at 400 ℃, and finally grinding to obtain TiCu with the Cu doping amount of 0.020.02O2ATP powder.
Subsequent testing As in example 1, NH of the composite was measured4 +The resulting curve is shown in fig. 3. NH after 120min4 +The concentration reaches 0.008g/L-1。
Comparative example 5
(1) Weighing 0.8g of titanium dioxide, dissolving in 10mL of deionized water, and stirring for 30 minutes to obtain a titanium source suspension; take 0.06gZn (NO)3)2·6H2Dissolving O in 10mL of deionized water, dropwise adding a Zn source solution into the titanium source suspension while stirring, continuously stirring for 30 minutes at 80 ℃, adding 4g of attapulgite into the obtained solution, continuously stirring for 30 minutes at 80 ℃, and adjusting the pH value to 8.
(2) And (2) transferring the solution obtained in the step (1) into a microwave hydrothermal reaction kettle, carrying out microwave hydrothermal reaction for 90 minutes at 150 ℃, centrifuging and washing the obtained precipitate, drying for 24 hours at 80 ℃, and grinding to obtain a sample.
(3) Placing the sample prepared in the step (2) in a muffle furnace, calcining for 4 hours at 400 ℃, and finally grinding to obtain TiZn with the Zn doping amount of 0.020.02O2ATP powder.
Subsequent testing As in example 1, NH of the composite was measured4 +The resulting curve is shown in fig. 3. NH after 120min4 +The concentration reaches 0.0045g/L-1。
Comparative example 6
(1) Weighing 0.8g of titanium dioxide, dissolving in 10mL of deionized water, and stirring for 30 minutes to obtain a titanium source suspension; take 0.04gSr (NO)3)2Dissolving in 10mL deionized water, dropwise adding the Sr source solution into the titanium source suspension while stirring, continuously stirring for 30 minutes at 80 ℃, adding 4g of attapulgite into the obtained solution, continuously stirring for 30 minutes at 80 ℃, and adjusting the pH value to 8.
(2) And (2) transferring the solution obtained in the step (1) into a microwave hydrothermal reaction kettle, carrying out microwave hydrothermal reaction for 90 minutes at 150 ℃, centrifuging and washing the obtained precipitate, drying for 24 hours at 80 ℃, and grinding to obtain a sample.
(3) Placing the sample prepared in the step (2) in a muffle furnace, calcining for 4 hours at 400 ℃, and finally grinding to obtain TiSr with the Sr doping amount of 0.020.02O2ATP powder.
Subsequent testing As in example 1, NH of the composite was measured4 +The resulting curve is shown in fig. 3. NH after 120min4 +The concentration reaches 0.003g/L-1。
In summary, the present invention employs Yb3+，Er3+The double-doped system is based on the consideration that the two ions have their own effect in the up-conversion reaction, Yb3+Acting as a sensitizer in the up-conversion, Er3+The catalyst plays a role of an activator, can convert near infrared light into ultraviolet light under the synergistic action of the activator and the ultraviolet light, expands the photoresponse range, cannot utilize the near infrared light in sunlight if the function of certain ions is lacked, and has an obvious reduction in the effect of photocatalytic nitrogen fixation. And Yb in comparison with other metal ions3+、Er3+Double-doped composite material obtainsThe high nitrogen fixation effect plays a great role in improving the nitrogen fixation performance of the photocatalytic material by the up-conversion effect.
The raw materials and equipment used in the invention are common raw materials and equipment in the field if not specified; the methods used in the present invention are conventional in the art unless otherwise specified. The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and all modifications of the above embodiments made according to the technical spirit of the present invention are included in the scope of the present invention.

Claims (3)

1. An application of ytterbium erbium doped titanium dioxide/attapulgite nano composite material in photocatalysis nitrogen fixation is characterized in that: the composite material has a general formula: TiYb0.2ErXO2The ATP is provided with Yb/Ti =0.2, Er/Ti = x, x ranges from 0.01 to 0.04, and TiYb0.2ErXO2Accounting for 20 percent of the mass of ATP,
the preparation method of the ytterbium erbium-doped titanium dioxide/attapulgite nano composite material comprises the following steps:
(1) titanium white (TiO) is adopted2) Adding the titanium source suspension into deionized water to prepare titanium source suspension; mixing Yb (NO)3)3·5H2Dissolving O in deionized water to prepare Yb source solution; er (NO)3)3·6H2Dissolving O in deionized water to prepare Er source solution;
(2) dripping a Yb source solution and an Er source solution into the titanium source solution, stirring to obtain a mixed solution, adding attapulgite powder into the mixed solution, and stirring to obtain a turbid solution;
(3) dropwise adding ammonia water into the turbid liquid to adjust the pH value to be 6-12, then transferring the turbid liquid into a microwave hydrothermal reaction kettle for reaction, collecting precipitates after the reaction, cleaning and drying to obtain a precursor;
(4) heat-treating the precursor in a muffle furnace, and grinding to obtain TiYb0.2ErXO2ATP powder.
2. The application of the ytterbium erbium doped titanium dioxide/attapulgite nanocomposite material in photocatalysis nitrogen fixation as claimed in claim 1, wherein the application comprises: the microwave hydrothermal reaction in the step (3) is a constant temperature reaction at 120-200 ℃ for 60-240 minutes.
3. The application of the ytterbium erbium doped titanium dioxide/attapulgite nanocomposite material in photocatalysis nitrogen fixation as claimed in claim 1, wherein the application comprises: the heat treatment of the step (4) means heat treatment at 400 ℃ for 4 hours.
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