CN104138764B - A kind of efficient visible light excites carbon and the preparation method of fluorin-doped titanium dioxide optical catalyst - Google Patents
A kind of efficient visible light excites carbon and the preparation method of fluorin-doped titanium dioxide optical catalyst Download PDFInfo
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Abstract
The invention belongs to Photocatalitic Technique of Semiconductor field, be specifically related to a kind of efficient visible light and excite carbon and the preparation method of fluorin-doped titanium dioxide optical catalyst.Use dielectric barrier discharge plasma generator, for discharge gas, the titanium deoxide catalyst of pretreatment is doped process with carbon tetrafluoride, carbon and fluorine element are mixed titanium dioxide lattice with activated form.The present invention has one-step synthesis, easy and simple to handle, the shortest, and energy consumption is low, and doping is controlled, catalyst activity advantages of higher.Owing to codope effect reduces the energy gap of photocatalyst, make catalyst that the absorbability of visible ray to be strengthened, there is under the irradiation of visible ray the catalytic degradation ability to organic pollution.This catalyst, for the Photocatalytic Degradation Process of common contaminant 2,4,6 trichlorophenol, 2,4,6,-T (TCP), uses identical evaluating apparatus, compared with other co-doping titanium dioxide photocatalysts prepared by traditional method, shows higher catalysis activity.
Description
Technical field
The invention belongs to Photocatalitic Technique of Semiconductor field, be specifically related to a kind of efficient visible light and excite carbon and fluorin-doped
The preparation method of titanium dioxide optical catalyst.
Background technology
1972, Fujishima and Honda was found that the TiO of illumination2Monocrystalline energy decomposition water, thus cause people couple
The interest of photosensitized oxidation reduction reaction, advances the research of the photoredox reaction of Organic substance and inorganic matter.1976
Semi-conducting material is used for being catalyzed photodissociation pollutant by Canada scientist Carey etc., opens conductor photocatalysis and is applied to environment
The prelude of Protective strategy.At the beginning of the eighties, photochemical applied research emphasis starts to turn to field of environment protection, wherein pollutant
Photochemical degradating is particularly subject to pay attention to.In time subsequently, photocatalysis in terms of the process of organic and inorganic pollution by extensively
Research.Numerous studies show, most photocatalysts at room temperature can realize the degree of depth mineralising to pollutant, consersion unit
Ask the lowest.Current received photocatalysis principle is thought: when quasiconductor is more than or equal to the light of its band gap by energy
During irradiation, the electronics being in valence band is stimulated and transits to conduction band, produces photo-generate electron-hole pair.It is in the photoproduction of excited state
Hole and electronics have two kinds of possible paths, and one is to participate in light-catalyzed reaction, i.e. hole to capture surface adsorbed material or molten
The electronics of agent so that the most light absorbing material is oxidized originally.Electronics, then by surface electronic receptor capture, makes electron acceptor send out
Raw reduction reaction.It is compound that another kind is that photohole and electronics occur, and the energy of generation distributes as heat or light.
TiO2Application as catalysis material mainly runs into two outstanding problems.One is TiO2Band-gap energy is relatively big, can only be by
Ultraviolet excitation, and directly can not be excited by visible ray.Two is that the electron-hole pair recombination rate produced is high, makes quantum efficiency big
Big reduction.So how it is effectively improved TiO by modification2Utilization to visible ray, and reduce electron-hole pair recombination rate,
Improve its quantum efficiency, make catalyst show superior catalytic performance under visible light, be current TiO2Photocatalysis technology
Research emphasis.
Carbon doping is to study more a kind of adulterant at present, and theoretical research shows, after doping, C2p track can be with O2p rail
Road generation hybridism, the energy level of the hybrid orbital of generation is higher than original valence-band level, therefore reduces the band of titanium dioxide
Gap energy.And oxygen vacancies and Ti can be formed at titanium dioxide surface due to electric charge alimentation after Fluorin doped3+, improve photoproduction electricity
The capture effect in son-hole, it is also possible to improve the acidity of catalyst, makes catalyst surface adsorb more organic pollution and divides
Son, therefore has a significant impact photocatalytic activity.
Summary of the invention
Present invention aim at providing a kind of efficient visible light to excite carbon and fluorin-doped titanium dioxide optical catalyst
Preparation method.
The technical solution used in the present invention is for achieving the above object:
A kind of efficient visible light excites carbon and the preparation method of fluorin-doped titanium dioxide optical catalyst, and its feature exists
In: use dielectric barrier discharge plasma generator, with carbon tetrafluoride for the discharge gas Titanium Dioxide to pretreatment
Agent is doped process, and with activated form, carbon and fluorine element are mixed titanium dioxide lattice.
During the electric discharge of described doping treatment, discharge frequency is 8～12kHz, and pressure regulator input voltage is 60～80V, carbon tetrafluoride
Flow velocity is 60～80ml/min, and discharge time is 5～30min.
The pretreatment of described titanium dioxide is by titanium deoxide catalyst roasting 1～4h at 350～450 DEG C, to remove
The material of surface adsorption.
Described carbon and fluorin-doped titanium dioxide optical catalyst are applied in TCP degradation reaction.
In described degradation reaction, TCP concentration is 60 × 10-6g·ml-1, catalyst amount is 1g every liter TCP solution, light source
For 110W high-pressure mercury lamp, filtering off the ultraviolet light of below wavelength 400nm with optical filter, reaction condition is 30 DEG C, normal atmosphere, instead
It is 4h between Ying Shi；The mensuration of TCP concentration uses high performance liquid chromatograph (Jasco LC2000), and detached dowel is ODS-C18Anti-phase color
Spectrum post (250mm × 4.6mm, 5 μm), flow velocity is 1mL/min, and ultraviolet detection wavelength is 210nm, and flowing is methanol/water=90 mutually:
10, column temperature is room temperature, and sampling volume is 20 μ L.
Advantage for present invention: the present invention uses one-step synthesis, easy and simple to handle, the shortest, and energy consumption is low, and doping can
Control, gained catalyst activity is high.Owing to codope effect reduces the energy gap of photocatalyst, make catalyst to visible ray
Absorbability strengthens, and has the catalytic degradation ability to organic pollution under the irradiation of visible ray.Gained catalyst is used for
Common contaminant 2,4, the Photocatalytic Degradation Process of 6-trichlorophenol, 2,4,6,-T (TCP), use identical evaluating apparatus, with traditional method system
Other standby co-doping titanium dioxide photocatalysts are compared, and show higher catalysis activity.
Accompanying drawing explanation
The structure chart of the dielectric barrier discharge reactor that Fig. 1 provides for the embodiment of the present invention, wherein 1 is high-field electrode；2 are
Earthing pole；3 is ground；4 is quartz ampoule；5 is heat insulation layer；6 is catalyst precarsor bed；7 is gas access；8 is gas outlet.
The photocatalyst that Fig. 2 provides for the embodiment of the present invention and the raw material P25 comparison diagram to light absorption ability, wherein a
For raw material P25, b be embodiment 1 preparation carbon and fluorin-doped photocatalyst.
The photocatalyst that Fig. 3 provides for the embodiment of the present invention is through Ar+The x-ray photoelectron of the fluorine element after the sputtering of surface
Energy spectrogram, wherein a is the photocatalyst of embodiment 4 preparation, and b is the photocatalyst of embodiment 1 preparation, and c is embodiment 3 preparation
Photocatalyst, d is the photocatalyst of embodiment 2 preparation.
The photocatalyst that Fig. 4 provides for the embodiment of the present invention and the x-ray photoelectron energy spectrogram of titanium elements in raw material P25,
Wherein a is raw material P25, and b is the carbon of embodiment 1 preparation and fluorin-doped photocatalyst.
The x-ray photoelectron energy spectrogram of carbon in the photocatalyst that Fig. 5 provides for the embodiment of the present invention, wherein a is real
Executing the photocatalyst of example 1 preparation, b is the photocatalyst of embodiment 6 preparation, and c is the photocatalyst of embodiment 5 preparation.
The photocatalyst Ar that Fig. 6 provides for the embodiment of the present invention 1+The x-ray photoelectron of the carbon before and after the sputtering of surface
Energy spectrogram, the spectrogram before wherein a is sputtering, b is the spectrogram after sputtering.
The fluorescence emission spectrogram of the photocatalyst that Fig. 7 provides for the embodiment of the present invention, wherein a is raw material P25, and b is real
Executing the photocatalyst of example 2 preparation, c is the photocatalyst of embodiment 3 preparation, and d is the photocatalyst of embodiment 4 preparation, and e is for implementing
The photocatalyst of example 1 preparation.
Photocatalyst prepared by the photocatalyst that Fig. 8 provides for the embodiment of the present invention and comparative example 3,4 is to organic pollution
The comparison diagram of the absorbability of TCP, wherein a is the photocatalyst of embodiment 1 preparation, and b is the photocatalyst of comparative example 3 preparation, c
Photocatalyst for comparative example 4 preparation.
The photocatalyst that Fig. 9 embodiment of the present invention provides and raw material P25 are to organic pollution TCP photocatalytic degradation effect pair
Than figure, wherein a is raw material P25, and b is the photocatalyst of embodiment 1 preparation, and c is the photocatalyst of embodiment 2 preparation, and d is for implementing
The photocatalyst of example 3 preparation, e is the photocatalyst of embodiment 4 preparation, and f is the photocatalyst of embodiment 5 preparation, and g is embodiment
The photocatalyst of 6 preparations.
Photocatalyst prepared by the photocatalyst that Figure 10 provides for the embodiment of the present invention and comparative example 1～4 is to organic contamination
Thing TCP photocatalytic degradation effect comparison diagram, wherein a is the photocatalyst of embodiment 1 preparation, and b is the photocatalysis of comparative example 1 preparation
Agent, c is the photocatalyst of comparative example 2 preparation, and d is the photocatalyst of comparative example 3 preparation, and e is the photocatalysis of comparative example 4 preparation
Agent.
Detailed description of the invention
Embodiment 1:
A) raw material finished product titanium dioxide P25 being carried out pretreatment, roasting 1h under 400 ° of C, to remove the thing of surface adsorption
Matter.
B) with carbon tetrafluoride as discharge gas, dielectric barrier discharge plasma generator is used carbon and fluorine element to be activated
Rear incorporation titanium dioxide lattice.Reactor is made up of a quartz ampoule and two electrodes.Use the stainless steel wire of a diameter of 2.5mm
For high-field electrode, and being installed on quartz ampoule shaft core position, one end is connected with alternating current power supply.To wind around outside quartz ampoule
Aluminium foil be earthing pole, and make itself and the earth be connected.Plasma producing apparatus structure chart as shown in Figure 1 or uses existing city
Sell plasma producing apparatus.The raw material finished product titanium dioxide P25 of the above-mentioned pretreatment of 1g is put in quartz ampoule, discharge frequency
Being adjusted to 10kHz, pressure regulator input voltage is 80V, and carbon tetrafluoride flow velocity is 80ml/min, and discharge time is 20min.Reaction terminates
After input voltage is slowly returned to zero after close generator.Take out after catalyst cools down, obtain carbon and fluorin-doped titanium dioxide
Catalyst.
The photocatalyst that Fig. 2 provides for the embodiment of the present invention and the raw material P25 comparison diagram to light absorption ability, wherein a
For raw material P25, b be embodiment 1 preparation carbon and fluorin-doped photocatalyst.Can be seen that raw material P25 hardly picks up visible
Light, and the absorption of visible ray is obviously enhanced by the carbon of embodiment 1 preparation and fluorin-doped photocatalyst.By absorption curve slope
The tangent line of general goal and the intersection point of axis of abscissas can be absorbed the wavelength value on border, the most respectively 404nm and
436nm.By formula Eg=1240/ λ, can calculate the band-gap energy of two samples, respectively 3.07eV and 2.84eV.Therefore carbon and fluorine
Codope effect makes titanium dioxide band-gap energy reduce, and the absorption to visible ray is obviously enhanced.
Embodiment 2～4:
Changing the discharge time of step B in embodiment 1, other steps and condition are constant, obtain the carbon in table 1 and fluorine element
Content data: table 1
| Embodiment | Discharge time (min) | Fluorine element doping (at.%) | Carbon doping (at.%) |
| 2 | 5 | 0.6 | 0.4 |
| 3 | 10 | 1.1 | 0.7 |
| 1 | 20 | 1.9 | 1.1 |
| 4 | 30 | 2.7 | 1.3 |
Embodiment 5,6:
Changing the input voltage of step B in embodiment 1, other steps and condition are constant, obtain the carbon in table 2 and fluorine element
Content data: table 2
| Embodiment | Input voltage (V) | Fluorine element doping (at.%) | Carbon doping (at.%) |
| 5 | 60 | 0 | 0.3 |
| 6 | 70 | 0.7 | 0.5 |
| 1 | 80 | 1.9 | 1.1 |
The effect of each embodiment photocatalyst above-mentioned sees Fig. 3-7；
As seen from Figure 3, when catalyst is through Ar+After surface sputtering removes the material of surface adsorption, F element still exists
Go out at 689.7eV in conjunction with energy peak.According to the literature, this combines the Ti-that can should belong to be formed after F element replaces Lattice Oxygen to root
F key [Applied Catalysis B:Environmental96 (2010) 458-465].XPSPEAK41 software according to specialty
The peak area in spectrogram can be calculated, thus can calculate the doping of F element, list table 1 in.
It is visible light catalyst with P25 in the x-ray photoelectron energy spectrogram of titanium elements in raw material P25 at 458.4eV by Fig. 4
With two basic change energy peak occurs at 464.1eV, Ti should be belonged to4+2p3/2And Ti4+2p1/2.The photocatalyst of embodiment 1 preparation removes
Above-mentioned two combines can be beyond peak, and the combination energy root at 457.7eV and 463.3eV two should belong to Ti according to the literature3+
2p3/2And Ti3+2p1/2[Applied Surface Science252(2006)7532-7538].The catalyst of embodiment 1 preparation
Middle Ti3+Generation be owing to causing [the Applied Catalysis caused by the imbalance of electric charge after F-ionic replacement Lattice Oxygen
B:Environmental132-133(2013)460-468].Thus further demonstrate that F element is mixed with the crystalline substance of titanium dioxide
Lattice.
In spectrogram, three samples all occur relatively strong combination energy peak at 284.6eV as seen from Figure 5, should belong to C-C key.This
Being positioned at outward the combination energy peak that two at 288.6eV and 291.6eV are more weak, root according to the literature, is respectively belonging to C element and mixes
The Ti-O-C key formed after lattice and discharge gas CF4In C-F key [Environmental Science
Tcehnology45(2011)6970-6977;Chemistry:an Asian Journal5(2010)1171-1177].Thus
Can confirm that C element is also mixed with titanium dioxide lattice.Additionally, a, b, c tri-sample be positioned at the combination energy peak intensity at 288.6eV
It is gradually reduced, illustrates that the content of doping C element is gradually reduced.XPSPEAK41 software according to specialty can calculate in spectrogram
Peak area, thus can calculate the doping of C element, list table 2 in.Additionally, in table 1 each sample C element doping and
In table 2, the F element doping amount of each sample is also that the XPSPEAK41 computed in software according to specialty draws.Can from above-mentioned two tables
Going out, the doping of C and F increases along with the increase of discharge time.And mix such as 60V, C and F element under relatively low discharge voltage
Miscellaneous amount is significantly lower than the doping of electrion, such as 80V.
Only being left in spectrogram as seen from Figure 6 to be positioned at the combination energy peak at 288.6eV, this combination energy peak belongs to C element and mixes
The Ti-O-C key formed after entering lattice, further demonstrate that C element is mixed with the lattice of titanium dioxide.
It is owing to electron-hole pair is combined produced by the energy discharged due to the peak in fluorescence spectrum as seen from Figure 7,
Therefore peak intensity the least explanation electron hole pair recombination rate is the lowest, and quantum efficiency is the highest.It can be seen that raw material P25 in spectrogram
Peak intensity is maximum, and after adulterating, the peak intensity of sample has reduction in various degree, illustrates that chanza reduces to some extent
The recombination rate of electron hole pair.Additionally, the peak intensity of doped samples first reduces along with the increase of discharge time, when doped
Between when being 20min peak intensity minimum, then continue to increase discharge time, then peak intensity increases.This illustrates that discharge time is 20min
Time doping be optimum doping amount, the F element of doping can form oxygen vacancies and Ti at catalyst surface3+, improve photoproduction electricity
The capture effect in son-hole, improves separation of charge efficiency.But long between upon discharging, when doping is excessive, the F unit of doping
Element becomes the complex centre of electron hole pair on the contrary, and therefore recombination rate increases on the contrary.
Comparative example 1
Use Sol-gel method synthetic nitrogen and fluorin-doped titanium dioxide catalyst [Applied Catalysis B:
Environmental132-133(2013)460-468]。
3.4ml butyl titanate is added drop-wise to 50ml NH under vigorous stirring4In F solution so as to get suspension in mole
Compare Ti/F=1:2.After the suspension room temperature ageing 24h that will obtain, 100 DEG C of dry 48h.The xerogel obtained is at 500 DEG C of roasting 2h
(5 DEG C/min of heating rate), obtains carbon and fluorin-doped titanium dioxide catalyst.
Comparative example 2
Use water heat transfer sulfur and fluorin-doped titanium dioxide catalyst [Applied Catalysis B:
Environmental96(2010)458-465]。
0.015mol NH4F and 0.015mol thiourea joins in 30ml ethanol, strong agitation 30min.0.01mol metatitanic acid
After four butyl esters add above-mentioned mixed liquor, continue stirring 30min.Under vigorous stirring, 1.5ml acetic acid and 1ml deionized water are added
Enter in above-mentioned mixed liquor.The product obtained is loaded autoclave, at 120 DEG C, keeps 20h.After natural cooling, product is taken out,
After deionized water and alcohol flushing 3 times, after 80 DEG C of dry 10h, load Muffle furnace, 450 DEG C of roasting 3h(heating rates 5 DEG C/
Min), sulfur and fluorin-doped titanium dioxide catalyst are obtained.
Comparative example 3
Use Hydrolyze method synthesis sulfur and carbon co-doped titanium deoxide catalyst [Journal of Colloid and
Interface Science311(2007)514-522]。
Under vigorous stirring, 0.031mol isopropyl titanate and 0.124mol thiourea are dispersed in 200ml ethanol, obtain molten
Liquid A.1ml ammonia is added in 0.125mol deionized water and obtains solution B.Under vigorous stirring, solution B is slowly dropped to molten
In liquid A, continue stirring 20min and be allowed to complete hydrolysis.At 60 DEG C after solvent evaporated, 80 DEG C of dry 10h of baking oven put into by solid.Will
Product is 5 DEG C/min of roasting 2h(heating rate at 500 DEG C), obtain sulfur and carbon co-doped titanium deoxide catalyst.
Comparative example 4
Use ionic-implantation synthetic nitrogen and carbon co-doped titanium deoxide catalyst [Journal of Solid State
Chemistry192(2012)305-311]。
Under vigorous stirring, 1g commercial titanium dioxide P25 is joined in 80ml ethylenediamine obtain suspension.By obtain
Suspension proceeds to there-necked flask, 120 DEG C of backflow 24h.This suspension is kept at 80 DEG C 72h, is evaporated remaining ethylenediamine.Will
The solid obtained is 5 DEG C/min of roasting 5h(heating rate at 500 DEG C), obtain nitrogen and carbon co-doped titanium deoxide catalyst.
Gained catalyst and each comparative example catalyst application in TCP degradation reaction be prepared by above-described embodiment:
It is 60 × 10 by 100ml concentration-6g·ml-1Dyestuff TCP add quartz reactor (commercial products), catalyst use
Amount is 0.1g, and light source is 110W high-pressure mercury lamp, filters off the ultraviolet light of below wavelength 400nm with optical filter, under conditions of stirring
Being passed through air in dye solution, reaction condition is 30 DEG C, normal atmosphere, and the response time is 4h.Take out at interval of 30min
Supernatant is proceeded to high performance liquid chromatograph (Jasco LC2000) analysis after removing catalyst and turns by 5ml dye solution centrifugation
Rate, detached dowel is ODS-C18Reversed phase chromatographic column (250mm × 4.6mm, 5 μm), flow velocity is 1mL/min, and ultraviolet detection wavelength is
210nm, flowing is methanol/water=90:10 mutually, and column temperature is room temperature, and sampling volume is that 20 μ L(see Fig. 8,9 and 10).
The catalyst of embodiment 1 preparation is significantly greater than comparative example 3,4 preparations to the absorbability of TCP as seen from Figure 8
Catalyst.This is owing in the catalyst of embodiment 1 preparation, the doping of F element can improve the acidity of catalyst, makes catalysis
The more organic pollutant molecule of agent surface adsorption [Applied Catalysis B:Environmental132-133 (2013)
460-468]。
Raw material P25 is the lowest to the light degradation activity of TCP as seen from Figure 9, and C and F of embodiment 1～6 preparation is co-doped with
Miscellaneous titanium dioxide optical catalyst has raising in various degree to the light degradation activity of TCP.Further, it can be seen that identical
Under discharge voltage in the photocatalyst of preparation, catalysis activity first increases, along with the increase of discharge time presents, the trend reduced afterwards,
Wherein the photocatalyst activity with embodiment 1 preparation is optimal.Although the photocatalyst of embodiment 4 preparation is longer still for discharge time
Activity has declined, and this is owing to the F doping of excess exacerbates the compound of electron hole pair, reduces quantum efficiency.For
The photocatalyst of preparation under different discharge voltages, it can be seen that catalysis activity is gradually increased with the increase of discharge voltage, this be by
Under high voltage, C and F element is easier to mix the lattice of titanium dioxide.
Figure 10 is it can be seen that other dual element codopes of preparing than comparative example 1～4 of photocatalyst of embodiment 1 preparation
Titanium deoxide catalyst shows preferably TCP Photocatalytic activity.This is the hydridization owing to producing after the doping of one side C
The energy level of track is higher than original valence-band level, reduces the band-gap energy of titanium dioxide, makes the titanium dioxide absorption to visible ray
It is obviously enhanced, on the other hand can form oxygen vacancies and Ti at titanium dioxide surface due to charge unbalance after Fluorin doped3+, it is right to improve
The capture effect of photo-generate electron-hole, reduces the recombination rate of electron-hole pair, it is also possible to improves the acidity of catalyst, makes to urge
The more organic pollutant molecule of agent surface adsorption, therefore C and F codope shows good synergism so that light is urged
Change activity to significantly improve.
Claims (3)
1. an efficient visible light excites carbon and the application of fluorin-doped titanium dioxide optical catalyst, it is characterised in that: use
Dielectric barrier discharge plasma generator, mixes the titanium deoxide catalyst of pretreatment with carbon tetrafluoride for discharge gas
Live together reason, carbon and fluorine element are mixed titanium dioxide lattice with activated form；
Described carbon and fluorin-doped titanium dioxide optical catalyst are applied in TCP degradation reaction；
In described degradation reaction, TCP concentration is 60 × 10-6g·mL-1, catalyst amount is 1g every liter TCP solution, and light source is
110W high-pressure mercury lamp, filters off the ultraviolet light of below wavelength 400nm with optical filter, and reaction condition is 30 DEG C, normal atmosphere, reaction
Time is 4h；The mensuration of TCP concentration uses high performance liquid chromatograph Jasco LC2000, and detached dowel is ODS-C18Reversed phase chromatographic column
250mm × 4.6mm, 5 μm, flow velocity is 1mL/min, and ultraviolet detection wavelength is 210nm, and flowing is methanol/water=90:10 mutually, post
Temperature is room temperature, and sampling volume is 20 μ L.
2. the efficient visible light as described in claim 1 excites carbon and the application of fluorin-doped titanium dioxide optical catalyst, its
It is characterised by: during the electric discharge of described doping treatment, discharge frequency is 8～12kHz, and pressure regulator input voltage is 60～80V, tetrafluoride
Carbon flow velocity is 60～80mL/min, and discharge time is 5～30min.
3. the efficient visible light as described in claim 1 excites carbon and the application of fluorin-doped titanium dioxide optical catalyst, its
It is characterised by: the pretreatment of described titanium dioxide is by titanium deoxide catalyst roasting 1～4h at 350～450 DEG C, to remove
The material of surface adsorption.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US4574177A (en) * | 1982-02-01 | 1986-03-04 | Texas Instruments Incorporated | Plasma etch method for TiO2 |
| CN101528976A (en) * | 2006-11-02 | 2009-09-09 | 旭硝子株式会社 | Ethylene-tetrafluoroethylene copolymer molded product and method for producing the same |
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| US4574177A (en) * | 1982-02-01 | 1986-03-04 | Texas Instruments Incorporated | Plasma etch method for TiO2 |
| CN101528976A (en) * | 2006-11-02 | 2009-09-09 | 旭硝子株式会社 | Ethylene-tetrafluoroethylene copolymer molded product and method for producing the same |
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