CN109453799A - The nanometer titanic oxide material of nitrogen-doped carbon material cladding and its application - Google Patents

The nanometer titanic oxide material of nitrogen-doped carbon material cladding and its application Download PDF

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CN109453799A
CN109453799A CN201811098479.1A CN201811098479A CN109453799A CN 109453799 A CN109453799 A CN 109453799A CN 201811098479 A CN201811098479 A CN 201811098479A CN 109453799 A CN109453799 A CN 109453799A
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nitrogen
doped carbon
carbon material
nano
tio
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CN109453799B (en
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张宝华
王醇平
刘迪
谢磊
计广和
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Shanghai Trail New Material Polytron Technologies Inc
University of Shanghai for Science and Technology
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Shanghai Trail New Material Polytron Technologies Inc
University of Shanghai for Science and Technology
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24Nitrogen compounds
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation 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
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/74General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86Catalytic processes
    • B01D53/8668Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/30Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/39Photocatalytic properties
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/32Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/36Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/46Oxides or hydroxides of elements of Groups 4 or 14 of the Periodic Table; Titanates; Zirconates; Stannates; Plumbates
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/73Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof
    • D06M11/74Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof with carbon or graphite; with carbides; with graphitic acids or their salts
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2255/00Catalysts
    • B01D2255/80Type of catalytic reaction
    • B01D2255/802Photocatalytic

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Environmental & Geological Engineering (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Textile Engineering (AREA)
  • Biomedical Technology (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Catalysts (AREA)

Abstract

The present invention relates to a kind of nanometer titanic oxide material of nitrogen-doped carbon material cladding and its applications.The nanometer titanic oxide material is: being coated with nitrogen-doped carbon material, the mass ratio of the nanometer titanium dioxide carbon and nitrogen-doped carbon material are as follows: 1:1~1:3 in nanometer titanium dioxide carbon surface;The partial size of the nano-titanium dioxide is 20~80nm, and the nitrogen-doped carbon material is: being made of chemical structures such as pyrroles, pyridine, graphite, amorphous carbon.Nitrogen-doped carbon material of the invention itself oxygen reduction catalytic activity with higher, by nitrogen-doped carbon material to nano-TiO2It is modified to carry out in-stiu coating, nano-TiO can not only be improved2Dispersibility and photocatalysis stability, and its adsorptivity is improved, to improve its catalytic performance and efficiency.On this basis, by the carbon-coated nano-TiO of N doping2It is dispersed in water, textile is impregnated, obtain air automatically cleaning textile, there is technical advantage and novelty.

Description

The nanometer titanic oxide material of nitrogen-doped carbon material cladding and its application
Technical field
The present invention relates to a kind of nanometer titanic oxide material of nitrogen-doped carbon material cladding and its applications.
Background technique
Pollutant in air is mainly volatile organic compounds, including vehicle exhaust, industrial discharge pernicious gas, The irritative gas etc. generated when aldehydes pernicious gas that indoor furniture releases, smoking.By nano-TiO2Arrange indoor spinning On fabric, such as carpet, curtain and cushion, or arrange onto automobile interior trim material, using photocatalysis characteristic degradation room Harmful substance in interior air environment, for the environment of living of improvement people, improving people's health level has ten for this Divide important meaning.Therefore, the research of air cleaning textile and application have significant economic value and social value.
Nano-TiO2With excellent photocatalysis characteristic, but nano-TiO2There is bad dispersibility in application process in powder And catalytic performance the problem of declining, nano-TiO at present2Method of modifying have its dispersion improved by method chemically or physically Property, and and Nano-meter SiO_22The methods of doping vario-property, for nano-TiO2Dispersibility and application performance be significantly improved, but work Skill is complicated, and practical application difficulty is larger.
Summary of the invention
One of the objects of the present invention is to provide a kind of nanometer titanic oxide materials of nitrogen-doped carbon material cladding.
The second object of the present invention is to provide the preparation method of the nanometer titanic oxide material of nitrogen-doped carbon material cladding.
The third object of the present invention is that the nanometer titanic oxide material for providing nitrogen-doped carbon material cladding is urged as light Application of the agent in degradation organic compound.
In order to achieve the above objectives, the present invention adopts the following technical scheme:
A kind of nanometer titanic oxide material of nitrogen-doped carbon material cladding, it is characterised in that the nanometer titanic oxide material It is: is coated with nitrogen-doped carbon material, the matter of the nanometer titanium dioxide carbon and nitrogen-doped carbon material in nanometer titanium dioxide carbon surface Measure ratio are as follows: 1:1~1:3;The partial size of the nano-titanium dioxide is 20~80nm, and the nitrogen-doped carbon material is: by pyrrole It coughs up, the chemical structures composition such as pyridine, graphite, amorphous carbon.
A method of preparing the nanometer titanic oxide material of above-mentioned nitrogen-doped carbon material cladding, it is characterised in that the party The specific steps of method are as follows:
A. the organic compound simultaneously containing nitrogen and oxygen element is dissolved in deionized water or the HCL solution of 1mol/L In, form the aqueous solution of 3~10wt%;Then in aqueous solution according to nano-TiO2With simultaneously containing nitrogen and oxygen element Nano-TiO is added in the ratio of organic compound mass ratio 1:1~1:32, stir and be allowed to uniformly mixed;Then by gained mixture Dry 8~10h in 120~150 DEG C of baking oven, by moisture removal;
B. it is small to be heat-treated 8~12 under an inert atmosphere under the conditions of 700~1000 DEG C for mixture step a obtained When, obtain black powder, i.e. the modified Nano TiO of nitrogen-doped carbon material cladding2
Contain the organic compound of nitrogen and oxygen element while above-mentioned are as follows: chitosan, gelatin, phenolic aldehyde amine, three hydroxyl first Base aminopropane or trimethylol melamine.
A kind of nanometer titanic oxide material of above-mentioned nitrogen-doped carbon material cladding is as light-catalysed application.
A kind of nanometer titanic oxide material of above-mentioned nitrogen-doped carbon material cladding is as photocatalysis in organic compound of degrading The application of object.
A kind of air automatically cleaning textile, the nanometer titanic oxide material conduct coated using above-mentioned nitrogen-doped carbon material Photocatalysis, it is characterised in that the air automatically cleaning textile is the nanometer titanium dioxide titanium for coating the nitrogen-doped carbon material Material is dispersed in water, and is impregnated to textile surface, and air automatically cleaning textile is obtained.
The specific steps of the preparation method of above-mentioned air automatically cleaning textile are as follows: the N doping carbon materials for obtaining step b The nanometer titanic oxide material of material cladding is fully ground partial size < 1 μm, is dispersed in containing the water-soluble of the aqueous hyper-dispersant of 2wt% In liquid, the aqueous hyper-dispersant is according to patent " aqueous hyper-dispersant of nonionic polyurethane class and preparation method thereof (201510979174.1) " method preparation, obtains modified Nano TiO2Content is the dispersion liquid of 10wt%;Textile is impregnated 5~10min in the dispersion liquid, it is dry under room temperature, obtain air automatically cleaning textile.
The present invention is by nitrogen-doped carbon material to nano-TiO2The method of in-stiu coating realizes nano-TiO2Stable dispersion With the raising of catalytic performance.Nitrogen-doped carbon material oxygen reduction catalytic activity with higher itself, passes through nitrogen-doped carbon material pair Nano-TiO2It is modified to carry out in-stiu coating, nano-TiO can not only be improved2Dispersibility and photocatalysis stability, and improve it Adsorptivity, to improve its catalytic performance and efficiency.On this basis, by the carbon-coated nano-TiO of N doping2It is dispersed in water In, textile is impregnated, air automatically cleaning textile is obtained, there is technical advantage and novelty.
Specific embodiment
The contents of the present invention are exemplified below, but not limited to the examples range.
Embodiment one: air automatically cleaning textile 1#Preparation
(a) trihydroxy methyl aminopropane 30g is weighed, is dissolved in 330mL deionized water, stirring and dissolving.Then nanometer is added TiO210g is dispersed with stirring uniformly.Then the dispersion liquid is transferred in baking oven, dry 10h, removes water under the conditions of 120 DEG C Point.
(b) mixture for eliminating moisture for obtaining step a is put into quartz boat, is placed in tube furnace, in N2Under protection, It is heat-treated 12h under the conditions of 700 DEG C, obtains the modified Nano TiO of nitrogen-doped carbon material cladding2
(c) the modified Nano TiO for obtaining step b2On the basis of being fully ground, it is dispersed in and makes water by oneself containing 2wt% In the water of property hyper-dispersant, modified Nano TiO is obtained2Content is the dispersion liquid of 10wt%.By this modified Nano TiO2Dispersion liquid It is impregnated into the surface of textile, drying under room temperature obtains air automatically cleaning textile 1#
Embodiment two: air automatically cleaning textile 2#Preparation
(a) trimethylol melamine 20g is weighed, is dissolved in 330mL deionized water, stirring and dissolving.Then nanometer is added TiO210g is dispersed with stirring uniformly.Then the dispersion liquid is transferred in baking oven, dry 10h, removes water under the conditions of 130 DEG C Point.
(b) mixture for eliminating moisture for obtaining step a is put into quartz boat, is placed in tube furnace, in N2Under protection, It is heat-treated 11h under the conditions of 800 DEG C, obtains the modified Nano TiO of nitrogen-doped carbon material cladding2
(c) the modified Nano TiO for obtaining step b2On the basis of being fully ground, it is dispersed in and makes water by oneself containing 2wt% In the water of property hyper-dispersant, modified Nano TiO is obtained2Content is the dispersion liquid of 10wt%.By this modified Nano TiO2Dispersion liquid It is impregnated into the surface of textile, drying under room temperature obtains air automatically cleaning textile 2#
Embodiment three: air automatically cleaning textile 3#Preparation
(a) chitosan 10g is weighed, is dissolved in the HCL solution of 330mL 1mol/L, stirring and dissolving.Then nanometer is added TiO210g is dispersed with stirring uniformly.Then the dispersion liquid is transferred in baking oven, dry 10h, removes water under the conditions of 140 DEG C Point.
(b) mixture for eliminating moisture for obtaining step a is put into quartz boat, is placed in tube furnace, in N2Under protection, It is heat-treated 10h under the conditions of 900 DEG C, obtains the modified Nano TiO of nitrogen-doped carbon material cladding2
(c) the modified Nano TiO for obtaining step b2On the basis of being fully ground, it is dispersed in and makes water by oneself containing 2wt% In the water of property hyper-dispersant, modified Nano TiO is obtained2Content is the dispersion liquid of 10wt%.By this modified Nano TiO2Dispersion liquid It is impregnated into the surface of textile, drying under room temperature obtains air automatically cleaning textile 3#
Example IV: air automatically cleaning textile 4#Preparation
(a) phenolic aldehyde amine 10g is weighed, is dissolved in the HCL solution of 330mL 1mol/L, stirring and dissolving.Then nanometer is added TiO210g is dispersed with stirring uniformly.Then the dispersion liquid is transferred in baking oven, dry 10h, removes water under the conditions of 150 DEG C Point.
(b) mixture for eliminating moisture for obtaining step a is put into quartz boat, is placed in tube furnace, in N2Under protection, It is heat-treated 8h under the conditions of 1000 DEG C, obtains the modified Nano TiO of nitrogen-doped carbon material cladding2
(c) the modified Nano TiO for obtaining step b2On the basis of being fully ground, it is dispersed in and makes water by oneself containing 2wt% In the water of property hyper-dispersant, modified Nano TiO is obtained2Content is the dispersion liquid of 10wt%.By this modified Nano TiO2Dispersion liquid It is impregnated into the surface of textile, drying under room temperature obtains air automatically cleaning textile 4#
Embodiment five: air automatically cleaning textile 5#Preparation
(a) gelatin 10g is weighed, is dissolved in 330mL deionized water, stirring and dissolving.Then nano-TiO is added210g, stirring It is uniformly dispersed.Then the dispersion liquid is transferred in baking oven, dry 10h, removes moisture under the conditions of 150 DEG C.
(b) mixture for eliminating moisture for obtaining step a is put into quartz boat, is placed in tube furnace, in N2Under protection, It is heat-treated 9h under the conditions of 800 DEG C, obtains the modified Nano TiO of nitrogen-doped carbon material cladding2
(c) the modified Nano TiO for obtaining step b2On the basis of being fully ground, it is dispersed in and makes water by oneself containing 2wt% In the water of property hyper-dispersant, modified Nano TiO is obtained2Content is the dispersion liquid of 10wt%.By this modified Nano TiO2Dispersion liquid It is impregnated into the surface of textile, drying under room temperature obtains air automatically cleaning textile 5#
Embodiment six: the detection of air automatically cleaning properties of textile
Air automatically cleaning textile in above-described embodiment is taken to be tested for the property, test result is shown in Table 1.
Test method is as follows: selecting the identical organic glass drier of two specifications as reaction unit, organic glass is not It can be reacted with formaldehyde gas, and translucency is good.Compound concentration is the formalin 100mL of 10ppm, is placed in surface plate, is placed In drier bottom, for simulating formaldehyde environment, ceramic air permeable plate is put in centre.Put in culture dish 100mL distilled water be used as to Liquid is surveyed, fabric is held in culture dish upper layer with rubber band, is placed on permeable-gas ceramics plate, covers grournd glass lid.Entirely filling Place the ultraviolet lamp of 48W (wavelength 365nm) in top set portion.Ultraviolet lamp is opened, after 3h, light is divided using acetylacetone,2,4-pentanedione Degree method measures content of formaldehyde in prepare liquid.Fabric photocatalysis Degradation Formaldehyde performance is characterized by Degradation Formaldehyde rate.Degradation Formaldehyde rate It is calculated with following formula:
In formula: M-Degradation Formaldehyde rate;C0The absorbance of prepare liquid after-placement original cloth;It is to be measured after C-placement finish fabric The absorbance of liquid.
The Degradation Formaldehyde rate of 1 air automatically cleaning textile of table
Sample number into spectrum Degradation Formaldehyde rate
1# 50%
2# 55%
3# 70%
4# 60%
5# 65%
As it can be seen from table 1 air automatically cleaning textile PARA FORMALDEHYDE PRILLS(91,95) has obvious degradation effect under ultraviolet light.

Claims (7)

1. a kind of nanometer titanic oxide material of nitrogen-doped carbon material cladding, it is characterised in that the nanometer titanic oxide material is: Nitrogen-doped carbon material, the mass ratio of the nano-titanium dioxide and nitrogen-doped carbon material are coated on nano-titanium dioxide surface Are as follows: 1:1~1:3;The partial size of the nano-titanium dioxide is 20~80nm.
2. a kind of method for the nanometer titanic oxide material for preparing nitrogen-doped carbon material cladding according to claim 1, It is characterized in that the specific steps of this method are as follows:
A. the organic compound simultaneously containing nitrogen and oxygen element is dissolved in the HCL solution of deionized water or 1mol/L, Form the aqueous solution of 3~10wt%;Then in aqueous solution according to itrogenous organic substance and nano-TiO2The ratio of mass ratio 1:1~3:1 Nano-TiO is added in example2, stir and be allowed to uniformly mixed;Then by gained mixture dry 8 in 120~150 DEG C of baking oven~ 10h, by moisture removal;
B. mixture step a obtained is heat-treated 8~12 hours under the conditions of 700~1000 DEG C, obtains under an inert atmosphere To black powder, i.e. the modified Nano TiO of nitrogen-doped carbon material cladding2
3. according to the method described in claim 2, it is characterized in that containing organising for nitrogen and oxygen element while described Close object are as follows: chitosan, gelatin, phenolic aldehyde amine, trihydroxy methyl aminopropane or trimethylol melamine.
4. a kind of nanometer titanic oxide material of nitrogen-doped carbon material cladding according to claim 1 is answered as light-catalysed With.
5. a kind of nanometer titanic oxide material of nitrogen-doped carbon material cladding according to claim 1 is being dropped as photocatalysis Solve the application of organic compound.
6. a kind of air automatically cleaning textile, the nano-silica coated using nitrogen-doped carbon material according to claim 1 Change titanium material as photocatalysis, it is characterised in that the air automatically cleaning textile is received what the nitrogen-doped carbon material coated Rice titanic oxide material is dispersed in water, and is impregnated to textile surface, is obtained air automatically cleaning textile.
7. air automatically cleaning textile according to claim 6, it is characterised in thatThe airThe preparation of automatically cleaning textile The specific steps of method are as follows: the nanometer titanic oxide material for the nitrogen-doped carbon material cladding that step b is obtained is fully ground grain Diameter < 1 μm;It is dispersed in the aqueous solution containing the aqueous hyper-dispersant of 2wt%, obtains modified Nano TiO2Content is the dispersion of 10wt% Liquid;Textile is immersed in 5~10min in the dispersion liquid, drying under room temperature obtains air automatically cleaning textile.
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CN111530467A (en) * 2019-10-23 2020-08-14 宁夏大学 Carbon modified copper-based catalyst and preparation method and application thereof
CN111871446A (en) * 2020-08-14 2020-11-03 大连工业大学 Preparation method of biomass-based carbon @ tantalum nitride composite photocatalytic material and application of composite photocatalytic material in photocatalytic degradation of methylene blue
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CN112999404A (en) * 2021-04-30 2021-06-22 河北宁纺集团有限责任公司 Stretchable nanofiber membrane and preparation method and application thereof
WO2023241152A1 (en) * 2022-06-16 2023-12-21 天津大学 Preparation method for hollow nitrogen-doped carbon-coated titanium dioxide photocatalyst

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CN111530467A (en) * 2019-10-23 2020-08-14 宁夏大学 Carbon modified copper-based catalyst and preparation method and application thereof
CN111313025A (en) * 2020-02-25 2020-06-19 厦门理工学院 Nitrogen-doped carbon-coated flaky titanium oxide material and preparation method and application thereof
CN111871446A (en) * 2020-08-14 2020-11-03 大连工业大学 Preparation method of biomass-based carbon @ tantalum nitride composite photocatalytic material and application of composite photocatalytic material in photocatalytic degradation of methylene blue
CN112206833A (en) * 2020-10-19 2021-01-12 陕西科技大学 Hollow titanium dioxide @ MIL-101 composite nano microsphere and preparation method and application thereof
CN112999404A (en) * 2021-04-30 2021-06-22 河北宁纺集团有限责任公司 Stretchable nanofiber membrane and preparation method and application thereof
CN112999404B (en) * 2021-04-30 2022-01-11 河北宁纺集团有限责任公司 Stretchable nanofiber membrane and preparation method and application thereof
WO2022161505A1 (en) * 2021-04-30 2022-08-04 河北宁纺集团有限责任公司 Stretchable nanofiber membrane, preparation method therefor and application thereof
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JP7288148B2 (en) 2021-04-30 2023-06-06 河北寧紡集団有限責任公司 Stretchable nanofiber film and its manufacturing method and application
WO2023241152A1 (en) * 2022-06-16 2023-12-21 天津大学 Preparation method for hollow nitrogen-doped carbon-coated titanium dioxide photocatalyst

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