CN108543533A - A kind of titanium dioxide of supporting Pt/hydroxyapatite nucleocapsid composite photo-catalyst and its preparation method and application - Google Patents
A kind of titanium dioxide of supporting Pt/hydroxyapatite nucleocapsid composite photo-catalyst and its preparation method and application Download PDFInfo
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- CN108543533A CN108543533A CN201810294750.2A CN201810294750A CN108543533A CN 108543533 A CN108543533 A CN 108543533A CN 201810294750 A CN201810294750 A CN 201810294750A CN 108543533 A CN108543533 A CN 108543533A
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- hydroxyapatite
- nucleocapsid
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 189
- 229910052588 hydroxylapatite Inorganic materials 0.000 title claims abstract description 41
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [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 41
- 239000002131 composite material Substances 0.000 title claims abstract description 27
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 24
- 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 43
- 238000000034 method Methods 0.000 claims description 26
- 230000001699 photocatalysis Effects 0.000 claims description 21
- 239000000920 calcium hydroxide Substances 0.000 claims description 18
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 18
- 239000003054 catalyst Substances 0.000 claims description 18
- 239000013067 intermediate product Substances 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 238000010531 catalytic reduction reaction Methods 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 11
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 9
- 238000001704 evaporation Methods 0.000 claims description 9
- 230000008020 evaporation Effects 0.000 claims description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 238000005253 cladding Methods 0.000 claims description 6
- 238000003786 synthesis reaction Methods 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000002073 nanorod Substances 0.000 claims description 5
- 239000000047 product Substances 0.000 claims description 5
- 239000012047 saturated solution Substances 0.000 claims description 5
- 229910052586 apatite Inorganic materials 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[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 VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 claims description 3
- 238000002256 photodeposition Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 abstract description 3
- 238000000576 coating method Methods 0.000 abstract description 3
- 239000011575 calcium Substances 0.000 description 44
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 26
- 238000000151 deposition Methods 0.000 description 10
- 230000008021 deposition Effects 0.000 description 8
- 239000000843 powder Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 238000006722 reduction reaction Methods 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- 102100039384 Huntingtin-associated protein 1 Human genes 0.000 description 5
- 101710140977 Huntingtin-associated protein 1 Proteins 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000012265 solid product Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 239000003426 co-catalyst Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 231100000572 poisoning Toxicity 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 101150009243 HAP1 gene Proteins 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 125000005587 carbonate group Chemical group 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000011086 glassine Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 235000011167 hydrochloric acid Nutrition 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000000243 photosynthetic effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
- 230000005641 tunneling Effects 0.000 description 1
- 230000000280 vitalizing effect Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J23/42—Platinum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/62—Carbon oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
-
- B01J35/39—
-
- B01J35/396—
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Abstract
The present invention provides a kind of TiO of supporting Pt2The core of/hydroxyapatite nucleocapsid composite photo-catalyst and its preparation method and application, the composite photo-catalyst is TiO2Nanometer rods, shell are hydroxyapatite, and load has Pt, the TiO on the hydroxyapatite shell2The length of nanometer rods is 150 500 nm, and the thickness of a diameter of 50 80 nm, hydroxyapatite shell are 2 10 nm.TiO in composite photo-catalyst of the present invention2The contact of the two-phase interface of phase and hydroxyapatite phase is good, compacts, and hydroxyapatite layer coating is uniform, and thickness controllability is strong.
Description
Technical field
The invention belongs to TiO2A kind of photocatalyst technology field, and in particular to TiO of supporting Pt2/ hydroxyapatite nucleocapsid
Structure composite photochemical catalyst and its preparation method and application.
Background technology
CO2As one of the main greenhouse gas for causing Global climate change, the following environment for human survival and the earth are given birth to
State system, which causes, to be seriously threatened.CO in air2Dramatically increasing for concentration has become a serious global problem how
Effectively reduce the CO in air2Content and rationally utilize CO2Have become the whole world strategic project urgently to be resolved hurrily.Currently, in object
Reason utilizes CO2Field achieves certain achievement, develops such as microorganism separation technique for fixing, ocean and underground deep layer and stores skill
Art etc..But physical process only changes CO2Existence form and position, can not fundamentally reduce CO in environment2Contain
Amount.Using heat chemistry, electrochemistry or photocatalysis technology by CO2The fuel for being converted into high added value is to realize CO2Emission reduction and cycle profit
Important means.However, heat chemistry and electrochemical process needs continue consumption fossil energy and provide energy for reaction, it is used
Fossil energy can discharge more CO again in combustion2.On the contrary, photocatalysis technology is using reproducible solar energy is cleaned
Driving force converts CO2For the fuel of high added value, the CO in air on the one hand can be reduced2Concentration alleviates greenhouse effects, another
Aspect can reduce dependence of the mankind to fossil resource, effectively solve the contradiction between energy shortage and environmental protection.
Photo catalytic reduction CO2Technology is to generate photo-generate electron-hole using solar energy vitalizing semiconductor catalysis material, is
CO2And H2O occurs oxidation-reduction reaction and generates CO, CH4And CH3These hydrocarbon fuels of OH.The process carries out at normal temperatures and pressures,
Raw material is simple and easy to get, provides energy using solar energy, fundamentally realizes the recycling of carbon material, it is considered to be most foreground
CO2Method for transformation.TiO2It is a kind of important metal oxide semiconductor material, catalysis good with chemical stability is lived
Property strong, non-toxic inexpensive the features such as.TiO is reported from Japanese scholars Inoue in 1979 etc.2Photo catalytic reduction CO2With gaseous state H2O gives birth to
At gas chromatography, this discovery allows people to start with conductor photocatalysis reduction CO2, realize that manual simulation is photosynthetic
Possibility (Inoue, T., et al. Nature 1979,277,637.).But due to TiO2Light excitation generates electronics and sky
The surface in cave and body phase recombination rate are higher, cause quantum utilization rate low, seriously restrict TiO2Photo catalytic reduction CO2Efficiency it is big
Width improves.In order to improve the photocatalytic activity and selectivity of product of catalyst, usually in TiO2Area load metal such as Pt, Pd,
Cu, Ag, Ru, Rh and Au etc. are as co-catalyst (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).After numerous studies show load cocatalyst,
The reason of photocatalytic activity improves mainly TiO2Fermi level is higher than the fermi level of metal, is generated under the irradiation of light
Electronics is migrated to the low metal direction of fermi level, and is gathered in metal surface, to make light induced electron and hole detach,
Thus photocatalytic activity is improved.In addition to this, CO2It is also to restrict the master of its transformation efficiency in the adsorption of catalyst and activation
Want one of factor.Due to CO2In TiO2Based on linear adsorption, this results in linear CO for absorption on surface2One-electron reduction is
The CO of bending2·-It needs to overcome higher reaction energy barrier（CO2/CO2·-Oxidation-reduction potential is 1.90 V vs NHE,
pH7.00).Recent studies suggest that (Li, Q., et al., Appl. Surf. Sci., 2014. 319,1;Liu, L.,
et al., Catal. Sci.. Technol., 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., the TiO of support type 2013. 49,2451.), is prepared as carrier using alkaline metal oxide MgO2It is compound
Photochemical catalyst can enhance CO2In the chemical adsorption capacity of catalyst surface.Due to CO2Monodentate carbonic acid is formed in MgO adsorptions
Salt has larger structural bending, is conducive to CO2The progress of one-electron reduction reaction, to improve photo catalytic reduction CO2Effect
Rate.But in the system, part CO2Can exist with the bidentate carbonate form of rock-steady structure on the surfaces MgO, lead to MgO/
TiO2Catalyst carbon acidification poisoning.Therefore, it still needs to further develop novel alkaline material and semiconductor composite, makes it can
Enhance catalyst and CO2Between binding force, and can avoid the problem that catalyst poisoning simultaneously.
Hydroxyapatite（It is denoted as HAP）Group become Ca10(PO4)6OH2, there are two types of positions for calcium ion in structure：Ca1 2+
Positioned at 6 PO of upper layer and lower layer4 3-Between tetrahedron, with PO4 3-9 angles top on O2-It is connected, ligancy 9.Upper layer and lower layer
Ca2 2+With additional OH-Form OH-Ca6Coordination is octahedra, the Ca on angle top2 2+With 4 neighbouring PO4 3-In 6 angles top on
O2-And OH-It is connected, ligancy 7.HAP one kind alkaline compounds, have good chemical stability, adsorptivity and
Exchangeability.In view of the basic site in HAP is to CO2Absorption property and HAP insulating layers electron-transport influence, we make
TiO is modified for the HAP thin layers with tunneling effect2Photochemical catalyst, one side HAP can enhance CO2In catalyst surface
On the other hand absorption property prevents the inverse migration of light induced electron, to improve CO2It is reduced to the hydrocarbon combustion of high added value system
The efficiency of material realizes the cycle of carbon with this.Chinese patent literature CN103551170 A disclose a kind of hydroxyapatite layer package
Photocatalytic nano titanium dioxide powder and its application, it is proposed that it is a kind of using surfactant prepare HAP wrap up TiO again2
The method of the photocatalytic powder of grain, but found in practical operation, the HAP that this method obtains wraps up TiO2The product of particle exists
HAP layers do not wrap up, the various defects such as wrapping layer is uneven, and the raising of photocatalytic activity is acted on extremely limited.
Invention content
The present invention wraps up TiO for hydroxyapatite layer in the prior art2Particle there are the problem of, a kind of supporting Pt is provided
TiO2/ hydroxyapatite nucleocapsid composite photo-catalyst and its preparation method and application, TiO2Phase and hydroxyapatite phase
Two-phase interface contact is good, compacts, and hydroxyapatite layer coating is uniform, and thickness controllability is strong.
The present invention adopts the following technical scheme that：
A kind of TiO of supporting Pt2The core of/hydroxyapatite nucleocapsid composite photo-catalyst, the composite photo-catalyst is TiO2
Nanometer rods, shell are hydroxyapatite, and load has Pt, the TiO on the hydroxyapatite shell2The length of nanometer rods is 150-
The thickness of 500 nm, a diameter of 50-80 nm, hydroxyapatite shell are 2-10 nm.
The TiO of above-mentioned supporting Pt2The preparation method of/hydroxyapatite nucleocapsid composite photo-catalyst, synthesis is obtained
TiO2Nanometer rods carry out Ca (OH) first2Cladding, obtains TiO2/Ca(OH)2The intermediate product of nucleocapsid, then should
TiO2/Ca(OH)2The intermediate product of nucleocapsid directly carries out phosphorating treatment so that Ca (OH)2Shell is converted into hydroxyapatite
Shell, to obtain TiO2The intermediate product of/hydroxyapatite nucleocapsid, finally to the TiO2/ hydroxyapatite nucleocapsid
Intermediate product supporting Pt, you can obtain the TiO of supporting Pt2/ hydroxyapatite nucleocapsid composite photo-catalyst.
Preferably, the Ca (OH)2The specific method of cladding is：The TiO that synthesis is obtained2Nanometer rods are added to Ca (OH)2
In saturated solution, and heating evaporation reaction system under protection of argon gas, with continuing for heating evaporation process, Ca (OH)2By
Gradually deposit to TiO2Nanorod surfaces.
Preferably, the parkerized specific method is：By TiO2/Ca(OH)2The intermediate product of nucleocapsid is added to
(NH4)2HPO4In solution, the pH value of the reaction system is adjusted to 8-12, then carries out hydro-thermal reaction, you can obtain TiO2/ hydroxyl
The intermediate product of apatite nucleocapsid；Wherein, (NH4)2HPO4Dosage be：Ensure (NH4)2HPO4The mole of middle P element
With TiO2/Ca(OH)2The ratio between mole of Ca elements in the intermediate product of nucleocapsid is more than 1:1.67 TiO2/Ca(OH)2
The mole of Ca elements in the intermediate product of nucleocapsid is detected by ICP and is determined.
Preferably, 100-180 DEG C of the temperature of the hydro-thermal reaction, reaction time are 4-12 h.
Preferably, the specific method of the supporting Pt is：Using Photodeposition in TiO2/ hydroxyapatite nucleocapsid
Middle 0.5%-5%.
The TiO of above-mentioned supporting Pt2/ hydroxyapatite nucleocapsid composite photo-catalyst is in photo catalytic reduction CO2In answer
With.
Beneficial effects of the present invention are as follows：
The present invention has following features compared with prior art：
The present invention prepares TiO using in-situ deposition/hydro-thermal two-step method2/ HAP Core-shell structure materials, two-phase interface contact is good,
It compacts, HAP packages are complete, and Jacket thickness is uniform and can be adjusted flexibly according to sedimentation time, after supporting Pt, obtains supporting Pt
TiO2/ hydroxyapatite nucleocapsid composite photo-catalyst is applied to photo catalytic reduction CO2In, illumination 8h, CH4Yield is high
Up to 37 μm of ol/g, compared with TiO2CH4Yield is about 38 times high.So high CH4The reason of yield, is：The present invention is prepared compound
Photochemical catalyst, using TiO2/ HAP nucleocapsids, two are in contact well, and HAP shells are evenly coated and compact, and thus can enhance CO2
In the chemical adsorption capacity of catalyst surface, at the same under the synergistic effect of Pt co-catalysts promote electronics migration, effectively hinder
Only photo-generated carrier is compound, improves quantum yield, to have good photocatalytic activity.In addition, light of the present invention is urged
Agent is not necessarily to high-temperature process in the preparation, smaller on catalyst surface structure and performance influence, while without using organic molten
Agent, it is at low cost, environmentally friendly, but it can be still precisely controlled building-up process, target material surface coating is uniform, thickness controllability
By force, it can be seen that, photochemical catalyst cost of material of the invention is low, prepares simply, in CO2There is potential application in terms of recycling
Value and good application and development foreground.
Description of the drawings
Fig. 1 is TiO2And TiO2/Ca(OH)2And TiO2/ HAP-4 nanometer rods core-shell photocatalyst XRD diagram；
Fig. 2 is TiO2And TiO2The x ray diffration pattern x of/HAP-4 nanometer rods nucleocapsid composite photo-catalysts；
Fig. 3 is TiO2、TiO2/Ca(OH)2And TiO2The scanning electron microscope (SEM) photograph of/HAP composite photo-catalysts；In Fig. 3, (a) TiO2；(b)
HAP/TiO2(N)；(c) Ca(OH)2/TiO2；(d)HAP/TiO2-1；(e)HAP/TiO2- 2 and (f) HAP/TiO2-4；
Fig. 4 is TiO2/ HAP-4 transmission electron microscope pictures；
Fig. 5 is TiO2And TiO2The UV-Vis DRS figures of/HAP composite catalysts；
Fig. 6 is the TiO of supporting Pt2/ HAP-4 transmission electron microscope pictures；
Fig. 7 is the 2 photo catalytic reduction CO of serial composite catalyst, comparative example 1 and comparative example prepared by the embodiment of the present invention 12Institute
Obtain product CO and CH4Yield comparison figure.
Specific implementation mode
In order to keep the technical purpose, technical solution and advantageous effect of the present invention clearer, below in conjunction with the accompanying drawings and specifically
Embodiment is further illustrated technical scheme of the present invention.
Embodiment
（1）TiO2The synthesis of nanometer rods：It measures 15mL isopropyl titanates to be added in beaker, be added dropwise under stirring
6mL concentrated hydrochloric acids（Mass fraction is 36%-38%）, 10min is stirred, is moved into reaction kettle later, 180 DEG C of reactions 36 h, Zhi Houleng
But, solid product is centrifuged to obtain, is washed with deionized to neutrality, 12 h of last 60 DEG C of vacuum drying obtain TiO2Powder.
As shown in Figure 1, being tested through XRD, the TiO2Powder is Rutile Type；
Such as Fig. 3（a）Shown in scanning electron microscopic picture can be seen that gained TiO2Powder is regular nanometer rods pattern, and nanometer
The length of stick is 150-500 nm, a diameter of 50-80 nm.
（2）TiO2/ Ca(OH)2Synthesis（That is Ca (OH)2Cladding）：The present invention carries out Ca (OH) using in situ deposition method2
Cladding, specifically, at 25 DEG C, weighs 0.1 g steps（1）Prepared TiO2Nanometer rods are added in three-necked flask, then are measured
100mL Ca(OH)2Saturated solution is added in the three-necked flask, and 5 min of ultrasound make it be uniformly mixed later, then pass to argon
Gas stirs evaporation, with the progress of heating evaporation, Ca (OH) under conditions of 100 DEG C2Gradually deposition is coated to TiO2Nanometer rods
Surface forms Ca (OH)2Shell；It is that 15 min, 30 min, 45 min, 60 min and 90 min are obtained to choose evaporation time respectively
To series of samples, and it is labeled as TiO successively2/Ca(OH)2- 1, TiO2/Ca(OH)2- 2, TiO2/ Ca(OH)2- 3, TiO2/ Ca
(OH)2- 4, TiO2/Ca(OH)2- 5, evaporation terminates postcooling, centrifuges to obtain solid product later, then 80 DEG C of dry 8-12h
Obtain the TiO of series2/ Ca(OH)2Intermediate product.
As shown in Figure 1, being tested through XRD（With TiO2/Ca(OH)2For -4 samples, remaining sample is equal with this）, TiO2
Nanometer rods are through Ca (OH)2Occurs Ca (OH) after heat deposition2Peak；
Such as Fig. 3（c）Shown in scanning electron microscopic picture can be seen that（With TiO2/Ca(OH)2For -4 samples, remaining sample with
This is equivalent）, TiO2/ Ca(OH)2Powder still keeps regular nanometer rods pattern, and Ca (OH)2In TiO2Nanorod surfaces deposit
Afterwards, significant change does not occur for surface, illustrates Ca (OH)2Clad is completely uniform.
（3）TiO2The synthesis of/HAP（That is phosphorating treatment）：Weigh 0.5 g (NH4)2HPO4It is added in 250mL volumetric flasks,
With (NH4)2HPO4Solution；Measure (the NH of 20mL4)2HPO4Solution simultaneously adjusts pH to 10 with the NaOH of 2mol/L, then step
Suddenly（2）The TiO being prepared2/Ca(OH)2- 1 is all added to (NH4)2HPO4In solution, ultrasound obtains finely dispersed mixing
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 respectively determine respective Ca constituent contents, accordingly, (NH by ICP detections4)2HPO4The mole of middle P element
With TiO2/Ca(OH)2The ratio between mole of Ca elements in the intermediate product of nucleocapsid is more than 1:1.67；Gained is mixed molten
Liquid pours into reaction kettle, is placed in 120 DEG C of 12 h of hydro-thermal reaction in baking oven；Reaction kettle is taken out, cooled to room temperature centrifuges
Neutrality is washed with deionized in solid product, and then 80 DEG C of 12 h of vacuum drying, obtain TiO2/HAP-1。
Using above-mentioned same method and by TiO therein2/Ca(OH)2- 1 replaces with TiO successively2/Ca(OH)2- 2,
TiO2/ Ca(OH)2- 3, TiO2/ Ca(OH)2- 4 and TiO2/Ca(OH)2- 5, corresponding gained sample is labeled as TiO successively2/
HAP-2, TiO2/ HAP-3, TiO2/ HAP-4, TiO2/ HAP-5。
As shown in Figure 1, being tested through XRD（With TiO2For/HAP-4 samples, remaining sample is equal with this）, TiO2/ Ca
(OH)2Intermediate product is after phosphorating treatment, the Ca (OH) on surface2It is converted into HAP shells；
As shown in Fig. 2, with the extension of evaporation time, i.e. TiO2Nanometer rods are at Ca (OH)2Sedimentation time is longer in saturated solution,
The HAP diffraction maximums of generation are stronger（It can be seen that from the HAP diffraction maximums between 30 ° ~ 35 °）, illustrate the covering amount of HAP with heavy
It accumulates time lengthening and increases, certain Ca (OH)2Covering amount increase with deposition time increases；
Such as Fig. 3（d）、3（e）With 3（f）Shown, counter sample is respectively TiO2/HAP-1、TiO2/ HAP-2 and TiO2/ HAP-4 is raw
At HAP be highly dispersed at TiO2Nanorod surfaces make its surface become coarse, and its degree of roughness is with the improve of HAP covering amounts
And increase, this may be related with the Solution reprecipitation growth mechanism of HAP；
As shown in Figure 4（（With TiO2For/HAP-4 samples, remaining sample is equal with this））, composite catalyst is with nucleocapsid knot
Structure, core TiO2Nanometer rods, shell are HAP layers, and HAP shell thicknesses are about 5 nm；
As shown in Figure 5, it can be seen that HAP shells are to TiO2Absorbing properties be nearly free from influence.
（4）Light deposition supporting Pt：Take 0.2 mL platinum acid chloride solutions（With Pt content meters, a concentration of 10 mg/mL）, first is added
Alcohol, the water of 100 mL and 0.2 g steps（3）Gained TiO2/ HAP-1 obtains mixed solution, after illumination deposits 1h, centrifuges
It is 1wt% samples to get deposition that 3 times, which take solid product, 80 DEG C of 12 h of drying,；
By TiO2/ HAP-1 replaces with TiO with this2/ HAP-2, TiO2/ HAP-3, TiO2/ HAP-4, TiO2/ HAP-5 series of samples,
The TiO that Pt depositions are 1wt% is prepared respectively2/ HAP samples are still labeled as TiO in the figure 72/ HAP-1, TiO2/HAP-
2, TiO2/ HAP-3, TiO2/ HAP-4, TiO2/HAP-5.As shown in fig. 6, Pt is dispersed in the surface of HAP in the form of nano particle
On, particle diameter is about 2-5 nm；
Photo catalytic reduction CO2Experiment
Test example
Add 20 mL water in first phototropic reaction device, then the 0.05g prepared by embodiment 1 is loaded to the TiO of 1%wt Pt2/ HAP-
1 sample is coated on glassine paper, is placed on reactor inner support frame, after reaction system evacuates, is kept 20 DEG C of reaction temperature, is passed through
CO with vapor2Pressure in reactor is 0.1 Mpa, gives illumination（Light source is 300 W Xe lamps）, after reacting 8h
Sampling；Pass through online gas chromatographic analysis gas composition and content.
Ibid, by the TiO of the load 1%wt Pt prepared by embodiment 12/ HAP-2, TiO2/ HAP-3, TiO2/ HAP-
4, TiO2/ HAP-5 carries out photo catalytic reduction CO respectively2Performance evaluation.
Comparative example 1
TiO2The synthetic method of/HAP (N)：Weigh 0.5 g (NH4)2HPO4It is added in 250mL volumetric flasks, matches to obtain (NH4)2HPO4Solution；By Ca/P=1.67,20mL (NH are measured respectively4)2HPO4Solution and 5mL Ca (OH)2Saturated solution is mixed,
It is used in combination the NaOH of 2mol/L to adjust pH to 10, mixed solution is obtained, then by 1 step of embodiment（1）0.1 prepared g
TiO2Powder ultrasonic is scattered in above-mentioned mixed solution；Gained mixed solution is poured into reaction kettle, it is anti-to be placed in 120 DEG C of hydro-thermals in baking oven
12 h are answered, reaction kettle is taken out, cooled to room temperature centrifuges to obtain solid product, neutrality is washed with deionized, then
80 DEG C of 12 h of vacuum drying, gained sample are labeled as TiO2/ HAP (N), by Fig. 3（b）Scanning electron microscope (SEM) photograph can be seen that directly
The TiO of hydrothermal synthesis2/ HAP (N), HAP particles are in TiO2Apparent agglomeration occurs for surface, this is because HAP particle surfaces
There are a large amount of unsaturated bonds, have very high surface-active, are in the extremely unstable state of thermodynamics, easily spontaneous to agglomerate into two
Secondary particle.
Then by above-mentioned gained TiO2/ HAP (N) product uses and 1 step of embodiment（4）Identical method is in TiO2/HAP
(N) light deposition loads 1%wt Pt as co-catalyst on sample, is still labeled as TiO in the figure 72/ HAP (N), investigates its light
Catalysis reduction CO2Performance, the same test example of experiment condition.
Comparative example 2
Using the TiO synthesized in embodiment 12Nanometer rods compare, using with 1 step of embodiment（4）Identical method is in its table
Face light deposition loads 1%wt Pt as co-catalyst, investigates its photo catalytic reduction CO2Performance, the same test example of experiment condition.
As shown in fig. 7, comparison is as it can be seen that with simple TiO2Nanometer rods are compared, and the present invention, can after its surface modification HAP
Significantly improve TiO2Photo catalytic reduction CO2Generate CH4Efficiency and selectivity, wherein TiO2/ HAP-4 has highest CH4Production
Amount, the significantly improving of photocatalytic activity are mainly due to HAP shells and enhance CO2Chemical adsorption capacity, while HAP and Pt
Synergistic effect promote the separation of photo-generated carrier, to improve photo catalytic reduction CO2Generate CH4Yield.With TiO2/
HAP (N) is compared, it has been found that the TiO that the present invention is prepared by in-situ deposition-hydrothermal synthesis two-step method2/ HAP exists
CH4Yield and selectivity aspect are superior to the sample of " one kettle way " direct hydrothermal synthesis, this absolutely proves the preparation side of the present invention
Method is coated on TiO with can not only making HAP shell uniform, controllables2Nanorod surfaces, and HAP shells and TiO2The contact of nanometer rods
Interface is well compacted, and efficiently avoids HAP particles in TiO2The agglomeration on surface.
It should be noted last that：Technical scheme of the present invention that the above embodiments are only illustrative and not limiting is any right
The equivalent replacement and do not depart from the modification of spirit and scope of the invention or local replacement that the present invention carries out, should all cover in this hair
Within bright protective scope of the claims.
Claims (7)
1. a kind of TiO of supporting Pt2/ hydroxyapatite nucleocapsid composite photo-catalyst, which is characterized in that the composite photocatalyst
The core of agent is TiO2Nanometer rods, shell are hydroxyapatite, and load has Pt, the TiO on the hydroxyapatite shell2Nanometer rods
Length be 150-500 nm, the thickness of a diameter of 50-80 nm, hydroxyapatite shell are 2-10 nm.
2. the TiO of supporting Pt described in claim 12The preparation method of/hydroxyapatite nucleocapsid composite photo-catalyst, it is special
Sign is, will synthesize obtained TiO2Nanometer rods carry out Ca (OH) first2Cladding, obtains TiO2/Ca(OH)2In nucleocapsid
Between product, then by the TiO2/Ca(OH)2The intermediate product of nucleocapsid directly carries out phosphorating treatment so that Ca (OH)2Shell turns
Hydroxyapatite shell is turned to, to obtain TiO2The intermediate product of/hydroxyapatite nucleocapsid, finally to the TiO2/ hydroxyl
The intermediate product supporting Pt of apatite nucleocapsid, you can obtain the TiO of supporting Pt2/ hydroxyapatite nucleocapsid complex light
Catalyst.
3. the TiO of supporting Pt according to claim 22The preparation side of/hydroxyapatite nucleocapsid composite photo-catalyst
Method, which is characterized in that the Ca (OH)2The specific method of cladding is：The TiO that synthesis is obtained2Nanometer rods are added to Ca (OH)2
In saturated solution, and heating evaporation reaction system under protection of argon gas, with continuing for heating evaporation process, Ca (OH)2By
Gradually deposit to TiO2Nanorod surfaces.
4. the TiO of supporting Pt according to claim 22The preparation side of/hydroxyapatite nucleocapsid composite photo-catalyst
Method, which is characterized in that the parkerized specific method is：By TiO2/Ca(OH)2The intermediate product of nucleocapsid is added to
(NH4)2HPO4In solution, the pH value of the reaction system is adjusted to 8-12, then carries out hydro-thermal reaction, you can obtain TiO2/ hydroxyl
The intermediate product of apatite nucleocapsid.
5. the TiO of supporting Pt according to claim 42The preparation side of/hydroxyapatite nucleocapsid composite photo-catalyst
Method, which is characterized in that 100-180 DEG C of the temperature of the hydro-thermal reaction, reaction time are 4-12 h.
6. the TiO of supporting Pt according to claim 22The preparation side of/hydroxyapatite nucleocapsid composite photo-catalyst
Method, which is characterized in that the specific method of the supporting Pt is：Using Photodeposition in TiO2/ hydroxyapatite nucleocapsid
Supporting Pt on intermediate product.
7. the TiO of supporting Pt described in claim 12/ hydroxyapatite nucleocapsid composite photo-catalyst is in photo catalytic reduction CO2
In application.
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| CN112914173A (en) * | 2021-01-26 | 2021-06-08 | 张斌翔 | Photocatalysis apatite wrapping technology sterilization and disinfection mask |
| CN115870008A (en) * | 2022-12-12 | 2023-03-31 | 西安交通大学 | Multifunctional composite material for preparing hydrocarbon fuel by carbon capture from water taken from air and photocatalysis, and preparation method and application thereof |
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| CN112889841B (en) * | 2021-01-26 | 2022-04-15 | 张斌翔 | Virus killing spray special for photocatalytic apatite coating technology |
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