CN108543533B - Pt-loaded titanium dioxide/hydroxyapatite core-shell structure composite photocatalyst and preparation method and application thereof - Google Patents
Pt-loaded titanium dioxide/hydroxyapatite core-shell structure composite photocatalyst and preparation method and application thereof Download PDFInfo
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 159
- 229910052588 hydroxylapatite Inorganic materials 0.000 title claims abstract description 42
- 239000011258 core-shell material Substances 0.000 title claims abstract description 38
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical group [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 title claims abstract description 34
- 239000002131 composite material Substances 0.000 title claims abstract description 28
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000004408 titanium dioxide Substances 0.000 title description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000002073 nanorod Substances 0.000 claims abstract description 31
- 239000000920 calcium hydroxide Substances 0.000 claims description 18
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- 239000011575 calcium Substances 0.000 description 43
- 230000001699 photocatalysis Effects 0.000 description 22
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
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- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 4
- 229910001868 water Inorganic materials 0.000 description 4
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- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
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- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
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- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
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Abstract
The invention provides Pt-loaded TiO2Hydroxyapatite core-shell structure composite photocatalyst, preparation method and application thereof, wherein the core of the composite photocatalyst is TiO2The nano-rod, the shell is hydroxyapatite, and the shell layer of the hydroxyapatite is loaded with Pt, the TiO is2The length of the nano rod is 150-500 nm, the diameter is 50-80 nm, and the thickness of the hydroxyapatite shell layer is 2-10 nm. TiO in the composite photocatalyst of the invention2The two-phase interface of the phase and the hydroxyapatite phase is well contacted and compact, and the hydroxyapatite layer has uniform covering layer and strong thickness controllability.
Description
Technical Field
The invention belongs to TiO2The technical field of photocatalyst, in particular to Pt-loaded TiO2Hydroxyapatite core-shell structure composite photocatalyst and a preparation method and application thereof.
Background
CO2Being one of the major greenhouse gases causing global climate change, it poses a serious threat to the future human living environment and the global ecosystem. CO in air2The obvious increase of the concentration becomes a serious global problem, and how to effectively reduce CO in the air2In combination with a reasonable utilization of CO2Has become a strategic subject to be solved in the world. At present, CO is physically utilized2The field obtains certain achievements, and develops microorganism separation and fixation technology, ocean and underground deep storage technology and the like. But the physical process only changes CO2The existence form and the position of the catalyst can not radically reduce the CO in the environment2The content of (a). By thermochemical, electrochemical or photocatalytic techniques2The conversion into high value-added fuel is to realize CO2And (4) important means of emission reduction and recycling. However, the thermochemical and electrochemical processes require the continued consumption of fossil energy, which in turn emits more CO during the combustion process, to provide energy for the reaction2. In contrast, photocatalytic technology utilizes clean and renewable solar energy as the driving force to convert CO2Is a high value-added fuel, on the one hand, the fuel can beTo reduce atmospheric CO2Concentration, alleviating greenhouse effect, reducing the dependence of human on fossil resources, and effectively solving the contradiction between energy shortage and environmental protection.
Photocatalytic reduction of CO2The technology is to use solar energy to excite semiconductor photocatalytic material to generate photoproduction electron-hole, namely CO2And H2O is subjected to oxidation-reduction reaction to generate CO and CH4And CH3OH these hydrocarbon fuels. The process is carried out at normal temperature and normal pressure, the raw materials are simple and easy to obtain, the solar energy is adopted to provide energy, the recycling of the carbon material is fundamentally realized, and the CO is considered to be the most promising CO2And (3) a transformation method. TiO 22Is an important metal oxide semiconductor material and has the characteristics of good chemical stability, strong catalytic activity, low price, no toxicity and the like. TiO was reported since 1979 by Inoue et al, Japanese scholars2Photocatalytic reduction of CO2And gaseous H2The discovery that O forms a variety of organic species led to the initiation of photocatalytic reduction of CO by semiconductors2The possibility of artificially simulating photosynthesis is achieved (Inoue, T., et al Nature 1979, 277, 637.). But due to TiO2The surface and bulk phase recombination rate of electrons and holes generated by light excitation is higher, so that the quantum utilization rate is low, and TiO is seriously restricted2Photocatalytic reduction of CO2The efficiency is greatly improved. In order to increase the photocatalytic activity and the product selectivity of the catalyst, it is customary to use TiO2Metals such as Pt, Pd, Cu, Ag, Ru, Rh and Au are supported on the surface as promoters (Ishitani O., et al, J Photochem. Photobiol. A, 1993, 72: 269; Tseng I. H., et al, J Catal, 2004, 221: 432; Varghese O.K. et al, Nano Lett, 2009, 9, 731). A great deal of research shows that the reason for the improvement of the photocatalytic activity of the supported cocatalyst is mainly TiO2The fermi level is higher than that of the metal, and electrons generated under light irradiation migrate toward the metal having a lower fermi level and are collected on the metal surface, thereby separating the photo-generated electrons from the holes, thereby improving the photocatalytic activity. In addition to this, CO2Adsorption and activation on the surface of the catalyst are also one of the main factors limiting the conversion efficiency. Due to CO2At TiO2Adsorption on the surface is dominated by linear adsorption, which results in linear CO2Single electron reduction to curved CO2·-Need to overcome the higher reaction energy barrier (CO)2/CO2·-Redox potential-1.90V vs NHE, pH 7.00). Recent studies have shown (Li, Q., et al.,. appl. surf. Sci., 2014.319, 1; Liu, L., et al., Cat. Sci.. Techniol., 2014, 4,1539; Manzanares, M., et al., appl. Catal. B: environ., 2014.150-151, 57; Xie, S., et al., ACS Catalysis, 2014.4, 3644; Liu, L., chem. Commun., 2013.49, 3664; Xie, S., et al., chem. Commun., 2013.49, 2451.) that a supported TiO is prepared using a basic metal oxide MgO as a carrier2The composite photocatalyst can enhance CO2Chemisorption capacity on the catalyst surface. Due to CO2The monodentate carbonate adsorbed on the surface of MgO has larger structural curvature, which is beneficial to CO2The single electron reduction reaction is carried out, thereby improving the photocatalytic reduction of CO2Efficiency. However, in this system, part of the CO2Will exist in the form of bi-dentate carbonate with stable structure on the surface of MgO, resulting in MgO/TiO2The catalyst is poisoned by carbonation. Therefore, there is still a need to develop new alkaline materials and semiconductor composites that can enhance both catalyst and CO2The binding force between the catalyst and the catalyst can also avoid the problem of catalyst poisoning.
The hydroxyapatite (noted as HAP) has a composition of Ca10(PO4)6OH2The calcium ion has two positions in the structure: ca1 2+6 POs on the upper and lower layers4 3-Between tetrahedra, and PO4 3-At 9 vertices of the cylinder2-And connected, the coordination number is 9. Ca of upper and lower layers2 2+With additional OH-Formation of OH-Ca6Coordination of octahedral, zenithal Ca2 2+With 4 adjacent POs4 3-O on 6 vertices of2-And OH-The coordination number of the bound molecules is 7. HAP alkalescent compounds have good chemical stability, adsorbability and exchangeability. Taking into account the basic site pairs in the HAPCO2The adsorption performance and the influence of the electron transmission of the HAP insulating layer, we prepare HAP thin layer modified TiO with tunneling effect2On the one hand, HAP can enhance CO2The adsorption performance on the surface of the catalyst, on the other hand, the reverse migration of photo-generated electrons is prevented, thereby improving CO2The efficiency of the hydrocarbon fuel reduced to a high value-added system, thereby realizing the carbon cycle. Chinese patent document CN 103551170A discloses a hydroxyapatite layer coated photocatalytic nano titanium dioxide powder and application thereof, and provides a method for preparing HAP and then coating TiO by using a surfactant2Method for photocatalytic powder of particles, but in practice it was found that HAP-coated TiO obtained by this method2The product of the particles has various defects of non-coating of HAP layer, non-uniform coating layer and the like, and has very limited effect of improving the photocatalytic activity.
Disclosure of Invention
The invention aims at the problem that the hydroxyapatite layer wraps the TiO in the prior art2Problems with the particles, providing a Pt-loaded TiO2Hydroxyapatite core-shell structure composite photocatalyst, preparation method and application thereof, and TiO2The two-phase interface of the phase and the hydroxyapatite phase is well contacted and compact, and the hydroxyapatite layer has uniform covering layer and strong thickness controllability.
The invention adopts the following technical scheme:
pt-loaded TiO2Hydroxyapatite core-shell structure composite photocatalyst, the core of the composite photocatalyst is TiO2The nano-rod, the shell is hydroxyapatite, and the shell layer of the hydroxyapatite is loaded with Pt, the TiO is2The length of the nano rod is 150-500 nm, the diameter is 50-80 nm, and the thickness of the hydroxyapatite shell layer is 2-10 nm.
The above Pt-loaded TiO2Preparation method of hydroxyapatite core-shell structure composite photocatalyst, and synthesized TiO2Nanorods were first subjected to Ca (OH)2Coating to obtain TiO2/Ca(OH)2An intermediate product of core-shell structure, and then adding the TiO2/Ca(OH)2Directly carrying out phosphorization on intermediate products with core-shell structuresTo make Ca (OH)2The shell is converted into a hydroxyapatite shell, thereby obtaining TiO2Intermediate product of hydroxyapatite core-shell structure, and final treatment of the TiO2Pt is loaded on an intermediate product with a hydroxyapatite core-shell structure to obtain Pt-loaded TiO2Hydroxyapatite core-shell structure composite photocatalyst.
Preferably, the Ca (OH)2The coating method comprises the following specific steps: the synthesized TiO is2Nanorod addition to Ca (OH)2Saturated solution, heating and evaporating the reaction system under the protection of argon, and Ca (OH) continuously heating and evaporating2Gradually depositing on TiO2And (4) the surface of the nano rod.
Preferably, the specific method of the phosphating treatment is as follows: adding TiO into the mixture2/Ca(OH)2Adding the intermediate product of core-shell structure into (NH)4)2HPO4In the solution, adjusting the pH value of the reaction system to 8-12, and then carrying out hydrothermal reaction to obtain TiO2Intermediate products of hydroxyapatite core-shell structure; wherein (NH)4)2HPO4The dosage of the composition is as follows: guarantee (NH)4)2HPO4Molar amount of the middle P element and TiO2/Ca(OH)2The molar weight ratio of Ca element in the intermediate product with the core-shell structure is more than 1:1.67, and TiO2/Ca(OH)2The molar amount of Ca element in the intermediate product of the core-shell structure was determined by ICP detection.
Preferably, the temperature of the hydrothermal reaction is 100-180 ℃, and the reaction time is 4-12 h.
Preferably, the specific method for loading Pt is as follows: by photo-deposition on TiO20.5-5% of the core-shell structure of hydroxyapatite.
The above Pt-loaded TiO2Hydroxyapatite core-shell structure composite photocatalyst for photocatalytic reduction of CO2The use of (1).
The invention has the following beneficial effects:
compared with the prior art, the invention has the following characteristics:
the invention adopts an in-situ deposition/hydrothermal two-step method to prepare TiO2The HAP core-shell structure material has good and compact two-phase interface contact, complete HAP package, uniform package thickness and flexible adjustment according to deposition time, and Pt-loaded TiO is obtained after Pt is loaded2Hydroxyapatite core-shell structure composite photocatalyst applied to photocatalytic reduction of CO2In 8h, its CH4The yield is as high as 37 mu mol/g compared with TiO2CH (A) of4The yield is about 38 times. CH of such high4The reason for the yield is: the composite photocatalyst prepared by the invention adopts TiO2The HAP core-shell structure has good two-phase contact and the HAP shell layer is uniformly and compactly coated, thereby being capable of enhancing CO2The catalyst has good photocatalytic activity by promoting the migration of electrons under the synergistic action of Pt promoter, effectively preventing the recombination of photon-generated carriers and improving the quantum yield. In addition, the photocatalyst disclosed by the invention does not need a high-temperature treatment process during preparation, has small influence on the surface structure and performance of the catalyst, does not use an organic solvent, is low in cost and environment-friendly, can still accurately control a synthesis process, and has uniform surface covering layer of a target material and strong thickness controllability, so that the photocatalyst disclosed by the invention is low in raw material cost and simple to prepare, and can be used for preparing CO2Has potential application value and good application and development prospect in the aspect of resource utilization.
Drawings
FIG. 1 is TiO2And TiO2/Ca(OH)2And TiO2XRD pattern of photocatalyst with HAP-4 nanorod core-shell structure;
FIG. 2 is TiO2And TiO2A ray diffraction pattern of the HAP-4 nanorod core-shell structure composite photocatalyst;
FIG. 3 is TiO2、TiO2/Ca(OH)2And TiO2A scanning electron microscope image of the HAP composite photocatalyst; in FIG. 3, (a) TiO2；(b) HAP/TiO2(N)；(c) Ca(OH)2/TiO2；(d)HAP/TiO2-1；(e)HAP/TiO 22 and (f) HAP/TiO2-4；
FIG. 4 is TiO2A transmission electron micrograph of/HAP-4;
FIG. 5 is TiO2And TiO2UV-Vis DRS diagram of/HAP composite catalyst;
FIG. 6 is a Pt-supported TiO2A transmission electron micrograph of/HAP-4;
FIG. 7 shows a series of composite catalysts prepared in example 1 of the present invention, comparative examples 1 and 2, and photocatalytic reduction of CO2The resulting products CO and CH4Yield comparison of (2).
Detailed Description
In order to make the technical purpose, technical solutions and advantages of the present invention clearer, the technical solutions of the present invention are further described below with reference to the accompanying drawings and specific embodiments.
Examples
（1）TiO2And (3) synthesis of nanorods: weighing 15mL of titanium isopropoxide, adding the titanium isopropoxide into a beaker, dropwise adding 6mL of concentrated hydrochloric acid (the mass fraction is 36% -38%) under the stirring state, stirring for 10min, transferring the mixture into a reaction kettle, reacting for 36 h at 180 ℃, cooling, performing centrifugal separation to obtain a solid product, washing the solid product to be neutral by using deionized water, and finally performing vacuum drying for 12h at 60 ℃ to obtain TiO2And (3) powder.
As shown in FIG. 1, the TiO was measured by XRD2The powder is in rutile phase;
as can be seen from the SEM image shown in FIG. 3 (a), the obtained TiO was2The powder is in regular nanorod morphology, the length of the nanorod is 150-500 nm, and the diameter of the nanorod is 50-80 nm.
（2）TiO2/ Ca(OH)2(i.e., Ca (OH))2Coating): the invention adopts an in-situ deposition method to carry out Ca (OH)2Coating, specifically, 0.1g of TiO prepared in step (1) is weighed at 25 ℃2The nanorods are added into a three-neck flask, and 100mL Ca (OH) is measured2Adding saturated solution into the three-neck flask, performing ultrasonic treatment for 5 min to mix well, introducing argon, stirring and evaporating at 100 deg.C, and heating to evaporate Ca (OH)2Coating onto TiO by gradual deposition2Nanorod surface, formation of Ca (OH)2A shell layer; the evaporation time is 15 min, 30 min and 45 mi respectivelyn, 60 min and 90 min to obtain series of samples, and sequentially marking as TiO2/Ca(OH)2-1，TiO2/Ca(OH)2-2，TiO2/ Ca(OH)2-3，TiO2/ Ca(OH)2-4，TiO2/Ca(OH)2-5, cooling after evaporation, then centrifugally separating to obtain a solid product, and then drying at 80 ℃ for 8-12h to obtain a series of TiO2/ Ca(OH)2And (3) intermediate products.
As shown in fig. 1, XRD testing (as TiO)2/Ca(OH)2 Sample 4 as an example, the rest being equivalent) TiO2Nanorod scale Ca (OH)2Appearance of Ca (OH) after thermal deposition2A peak of (a);
the SEM image shown in FIG. 3 (c) can be seen (in terms of TiO)2/Ca(OH)2 Sample 4 as an example, the rest being equivalent) TiO2/ Ca(OH)2The powder still keeps regular nanorod morphology, and Ca (OH)2In TiO2After the surface of the nano rod is deposited, the surface of the nano rod is not obviously changed, which shows that Ca (OH)2The coating layer is complete and uniform.
（3）TiO2Synthesis of/HAP (i.e., phosphating): 0.5 g (NH) was weighed4)2HPO4Adding the solution into a 250mL volumetric flask to prepare (NH)4)2HPO4A solution; measuring 20mL (NH)4)2HPO4Adjusting the pH of the solution to 10 by using 2mol/L NaOH, and then adding the TiO prepared in the step (2)2/Ca(OH)2-1 is added in its entirety to (NH)4)2HPO4In the solution, ultrasonic treatment is carried out to obtain a uniformly dispersed mixed solution, wherein TiO2/Ca(OH)2-1，TiO2/Ca(OH)2-2，TiO2/ Ca(OH)2-3，TiO2/ Ca(OH)2-4，TiO2/Ca(OH)2-5 determining the respective Ca element content, respectively, (NH) by ICP detection4)2HPO4Molar amount of the middle P element and TiO2/Ca(OH)2The molar weight ratio of Ca element in the intermediate product with the core-shell structure is more than 1: 1.67; the resulting mixed solution was poured into a reactionThe kettle is placed in an oven for hydrothermal reaction for 12 hours at 120 ℃; taking out the reaction kettle, naturally cooling to room temperature, centrifugally separating to obtain a solid product, washing the solid product to be neutral by using deionized water, and then carrying out vacuum drying at 80 ℃ for 12 hours to obtain TiO2/HAP-1。
By the same method and using TiO therein2/Ca(OH)2-1 is replaced in turn by TiO2/Ca(OH)2-2，TiO2/ Ca(OH)2-3，TiO2/ Ca(OH)2-4 and TiO2/Ca(OH)2-5, labeling the samples obtained in turn as TiO2/HAP-2，TiO2/ HAP-3，TiO2/ HAP-4，TiO2/ HAP-5。
As shown in fig. 1, XRD testing (as TiO)2Example of/HAP-4 sample, the remaining samples being equivalent thereto), TiO2/ Ca(OH)2After the intermediate product is phosphorized, Ca (OH) on the surface2Converting into HAP shell;
as shown in FIG. 2, with the evaporation time longer, i.e., TiO2Nanorods on Ca (OH)2The longer the deposition time in the saturated solution, the stronger the HAP diffraction peak generated (as can be seen from the HAP diffraction peak between 30 DEG and 35 ℃), indicating that the coating amount of HAP increases with the longer the deposition time, of course Ca (OH)2The amount of coating increases with longer deposition time;
as shown in FIGS. 3 (d), 3 (e) and 3 (f), the corresponding samples are TiO, respectively2/HAP-1、TiO2HAP-2 and TiO2HAP-4, the HAP formed being highly dispersed in TiO2The surface of the nanorod becomes rough, and the roughness thereof increases with the increase of the coating amount of HAP, which may be related to the dissolution-reprecipitation growth mechanism of HAP;
as shown in FIG. 4 ((in TiO)2example/HAP-4 sample, the rest being equivalent thereto)), the composite catalyst has a core-shell structure in which the core is TiO2The nano-rod, the shell is HAP layer, the thickness of HAP shell layer is about 5 nm;
as shown in FIG. 5, it can be seen that the HAP shell layer is on TiO2The light absorption property of (2) has little influence.
（4）Carrying out photo-deposition on Pt: 0.2 mL of a chloroplatinic acid solution (10 mg/mL in terms of Pt content) was taken, and methanol, 100mL of water and 0.2 g of TiO obtained in step (3) were added2HAP-1 to obtain a mixed solution, performing illumination deposition for 1h, performing centrifugal separation for 3 times to obtain a solid product, and drying at 80 ℃ for 12h to obtain a sample with the deposition amount of 1 wt%;
adding TiO into the mixture2HAP-1 substituted by TiO2/HAP-2，TiO2/HAP-3，TiO2/HAP-4，TiO2HAP-5 series samples, respectively prepared to obtain TiO with Pt deposition of 1wt%2the/HAP sample, still labeled TiO in FIG. 72/HAP-1，TiO2/HAP-2，TiO2/HAP-3，TiO2/HAP-4，TiO2HAP-5. As shown in fig. 6, Pt is dispersed on the surface of HAP in the form of nanoparticles, the particle diameter of which is about 2-5 nm;
photocatalytic reduction of CO2Test of
Test examples
20mL of water were added to the photobioreactor, and then 0.05g of the 1% wt Pt-loaded TiO prepared in example 1 was added2Coating the HAP-1 sample on glass paper, placing on a support frame in a reactor, evacuating the reaction system, maintaining the reaction temperature at 20 deg.C, and introducing CO with water vapor2When the pressure in the reactor is 0.1 Mpa, giving illumination (the light source is a 300W Xe lamp), and sampling after reacting for 8 h; the gas composition and content were analyzed by on-line gas chromatography.
As above, the 1% wt Pt-loaded TiO prepared in example 1 was used2/ HAP-2，TiO2/ HAP-3，TiO2/ HAP-4，TiO2HAP-5 respectively carrying out photocatalytic reduction on CO2And (6) evaluating the performance.
Comparative example 1
TiO2The synthesis method of/HAP (N): 0.5 g (NH) was weighed4)2HPO4Adding the solution into a 250mL volumetric flask to prepare (NH)4)2HPO4A solution; 20mL (NH) was measured for Ca/P =1.674)2HPO4Solution and 5mL Ca (OH)2Mixing the saturated solutions, adjusting the pH to 10 with 2mol/L NaOH to obtain a mixed solution, and mixing the mixed solutionExample 1 step (1) 0.1g of TiO2Ultrasonically dispersing the powder in the mixed solution; pouring the obtained mixed solution into a reaction kettle, placing the reaction kettle in an oven for hydrothermal reaction at 120 ℃ for 12h, taking out the reaction kettle, naturally cooling to room temperature, centrifugally separating to obtain a solid product, washing the solid product to be neutral by using deionized water, then drying the solid product in vacuum at 80 ℃ for 12h, and marking the obtained sample as TiO2HAP (N), as can be seen from the scanning electron micrograph of FIG. 3 (b), TiO synthesized directly by hydrothermal synthesis2HAP (N) in TiO particles2Obvious agglomeration occurs on the surface, which is because a large number of unsaturated bonds exist on the surface of HAP particles, the HAP particles have high surface activity and are in a thermodynamically extremely unstable state, and the HAP particles are extremely easy to spontaneously agglomerate to form secondary particles.
Then the obtained TiO is mixed2the/HAP (N) product was reacted on TiO in the same manner as in the step (4) in example 12the/HAP (N) sample was photoproduced with 1% wt Pt as promoter, again labelled TiO 72HAP (N) for the photocatalytic reduction of CO2The performance and experimental conditions are the same as those of the experimental example.
Comparative example 2
Using the TiO synthesized in example 12For comparison, the nanorods were photo-deposited on the surface thereof with 1% wt Pt supported thereon as a promoter in the same manner as in step (4) of example 1, and examined for photocatalytic reduction of CO2The performance and experimental conditions are the same as those of the experimental example.
As shown in FIG. 7, it can be seen by comparison with pure TiO2Compared with the nano-rod, the invention can obviously improve TiO after modifying HAP on the surface2Photocatalytic reduction of CO2Generating CH4Efficiency and selectivity of wherein TiO2HAP-4 has the highest CH4The remarkable improvement of the photocatalytic activity of the yield is mainly attributed to the fact that the HAP shell layer strengthens CO2The chemical adsorption capacity of the catalyst, and the synergistic effect of HAP and Pt promotes the separation of photon-generated carriers, thereby improving the photocatalytic reduction of CO2Generating CH4The yield of (2). With TiO2HAP (N) by contrast, we have found that the TiO prepared by the two-step method of in-situ deposition-hydrothermal synthesis according to the present invention2HAP in CH4Yield ofAnd the selectivity is superior to that of a sample directly hydrothermally synthesized by a one-pot method, which fully shows that the preparation method of the invention can ensure that the HAP shell layer is uniformly and controllably coated on TiO2Nanorod surface, HAP shell and TiO2The contact interface of the nano rod is good and compact, and HAP particles are effectively prevented from being on TiO2Agglomeration of the surface.
Finally, it should be noted that: the above embodiments are merely illustrative and not restrictive of the technical solutions of the present invention, and any equivalent substitutions and modifications or partial substitutions made without departing from the spirit and scope of the present invention should be included in the scope of the claims of the present invention.
Claims (5)
1. Pt-loaded TiO2The preparation method of the hydroxyapatite core-shell structure composite photocatalyst is characterized in that the synthesized TiO is2Nanorods were first subjected to Ca (OH)2Coating to obtain TiO2/Ca(OH)2An intermediate product of core-shell structure, and then adding the TiO2/Ca(OH)2The intermediate product of the core-shell structure is directly phosphated to make Ca (OH)2The shell is converted into a hydroxyapatite shell, thereby obtaining TiO2Intermediate product of hydroxyapatite core-shell structure, and final treatment of the TiO2Pt is loaded on an intermediate product with a hydroxyapatite core-shell structure to obtain Pt-loaded TiO2Hydroxyapatite core-shell structure composite photocatalyst, the core of the composite photocatalyst is TiO2The nano-rod, the shell is hydroxyapatite, and the shell layer of the hydroxyapatite is loaded with Pt, the TiO is2The length of the nano rod is 150-500 nm, the diameter is 50-80 nm, and the thickness of the hydroxyapatite shell layer is 2-10 nm.
2. The Pt-loaded TiO of claim 12The preparation method of the hydroxyapatite core-shell structure composite photocatalyst is characterized in that Ca (OH)2The coating method comprises the following specific steps: the synthesized TiO is2Nanorod addition to Ca (OH)2Saturated solution, heating and evaporating the reaction system under the protection of argon, and then evaporatingWith continuation of the evaporation process by heating, Ca (OH)2Gradually depositing on TiO2And (4) the surface of the nano rod.
3. The Pt-loaded TiO of claim 12The preparation method of the hydroxyapatite core-shell structure composite photocatalyst is characterized by comprising the following specific steps: adding TiO into the mixture2/Ca(OH)2Adding the intermediate product of core-shell structure into (NH)4)2HPO4In the solution, adjusting the pH value of the reaction system to 8-12, and then carrying out hydrothermal reaction to obtain TiO2Intermediate product of core-shell structure of hydroxyapatite.
4. The Pt-loaded TiO of claim 32The preparation method of the hydroxyapatite core-shell structure composite photocatalyst is characterized in that the temperature of the hydrothermal reaction is 100-180 ℃, and the reaction time is 4-12 h.
5. The Pt-loaded TiO of claim 12The preparation method of the composite photocatalyst with the hydroxyapatite core-shell structure is characterized in that the specific method for loading Pt comprises the following steps: by photo-deposition on TiO2Pt is loaded on the intermediate product of the hydroxyapatite core-shell structure.
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