CN104147994B - Manufacturing method of metal ion-doped titanium dioxide plate-type photocatalytic microreactor - Google Patents
Manufacturing method of metal ion-doped titanium dioxide plate-type photocatalytic microreactor Download PDFInfo
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- CN104147994B CN104147994B CN201410415832.XA CN201410415832A CN104147994B CN 104147994 B CN104147994 B CN 104147994B CN 201410415832 A CN201410415832 A CN 201410415832A CN 104147994 B CN104147994 B CN 104147994B
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Abstract
The invention discloses a manufacturing method of a metal ion-doped titanium dioxide plate-type photocatalytic microreactor. The reactor includes a stainless steel plate base; a groove on the stainless steel plate base is used as a single-channel reaction region; an inlet and an outlet respectively communicated with an inlet and an outlet of the single-channel reaction region are arranged on the stainless steel plate base, the inlet is communicated with an inlet pipeline, and the outlet is communicated with an outlet pipeline; one face, having the groove, of the stainless steel plate base and one face of a light-penetrating surface are each loaded with the metal ion-doped TiO2 catalyst thin film; the face, loaded with the catalyst thin film, of the light-penetrating surface is in opposite arrangement with the face, having the groove, of the stainless steel plate base, and has the periphery edges bonded and fixed by a sealing adhesive; an incident light source is arranged above the light-penetrating surface opposite to the groove. By using the device and the method, the light utilization efficiency is higher, and the degradation rate is increased to 2 times of the original degradation rate of an undoped TiO2 catalyst.
Description
Technical field
The present invention relates to photocatalysis technology field, more particularly, to microreaction technology.
Background technology
tio2Catalysis material has the advantages that photocatalytic activity is high, oxidability is strong, stability is high, pollution-free, is mesh
One of catalysis material of front most popularization and application potentiality.But, when being applied to light-catalyzed reaction, there is spectrum and ring
Answer narrow range (below wavelength 387nm), photo-generate electron-hole is to easily compound, surface adsorption selectivity poor grade deficiency.Cause
This, domestic and international researcher is to tio2Photocatalyst carried out study on the modification (Gu Heng reaches, apply chemical industry, 2007,36 (2): 136-
139；Cattle new book etc., electronic component and material, 2004,23 (8): 39-44；Zhu Yuchan etc., Guangdong chemical industry, 2010,37 (12):
19-22), specifically include that semiconductors coupling, noble metal decorated, surface sensitization, metal ion mixing, nonmetallic ion-doped,
Codope, pattern modification etc..Modified catalyst or expanded spectral response range so as to there is catalysis in visible region
Activity, or stop the recombination process in electronics and hole etc., make photocatalysis effect and unmodified pure tio2Catalyst is compared into
Improve again.
Since the microreactor appearance nineties in 20th century, with its distinctive high-specific surface area, high mass transfer and heat transfer effect
Rate, reactant energy Quick uniform cause the advantages of mixing researcher concern (lu et al., lab on a chip, 2001,1
(1):22-28；gole et al.,advanced materials for energy conversion ii symposium,
2004,69-78；takei et al.,catal.commun.,2005,6(5):357-360；teekateerawe et al.,
adv.mater.res.,2006,11-12,303-306；lindstrom et al.,aiche j.,2007,53(3):695-
700；daniel et al.,electr-ochem.commun.,2007,9(3):522-528；matsushita et al.,
chem.eng.j.,2008,135(4):s303-s308；meng et al.,nanoscale,2013,5,4687-4690；Yin Xue
Peak etc., analytical chemistry, 2003,31 (1): 116-119；Leaf the U.S. and Britain etc., Hangzhou Pedagogic University's journal (natural science edition), 2009,8
(2):121-124；He Zhongyuan etc., Chinese Journal of Inorganic Chemistry, 2009,25 (11): 2021-2025；Leaf the U.S. and Britain etc., Hangzhou Pedagogic University
Journal (natural science edition), 2012,11 (1): 1-6).The photo catalysis reactor catalytic efficiency of macro-scale is relatively low, light attenuation
Ratio is more serious, and catalyst powder granule is easily reunited, and so that researcher is attempted should by microreaction technology
For photocatalysis field, and make some progress.In photocatalysis microreactor, some organic pollutants are in a few minutes
The time of staying within just can be completely degraded, catalytic efficiency greatly improves.But, how these photocatalysis microreactors are with micro-
Passage is its basic structure (such as Chinese patent 200910197401.x).This not only limit substrate flow, and single micro-
Effective illuminating area of passage is extremely limited, very low to the overall utilization of luminous energy, and parallel amplification control system is complicated.Therefore,
How to pass through technological invention, select suitable material and preparation technology, manufacture and design rational microreactor structure and size, make
Microreactor had both kept its feature and advantage, had larger effective illuminating area again, the higher efficiency of light energy utilization, improved it empty
Between and time utilization efficiency be urgent problem.
The Patents of photocatalysis microreactor have at present: Chinese patent 200910197401.x, it is characterized in that with quartz
Capillary tube (530-550 μm of internal diameter, length 100-200mm) as photocatalytic region microchannel, using the prefabricated nanosized seeds in surface
Liquid chemical method prepares zno coating, with the single quasiconductor of zno on the inner surface of microchannel for the vertical-growth, tio2Nano-particle
The zno couple semiconductor of cladding or pt metal-zno semiconductor composite nano rod array are as photocatalyst.To Organic substance methylene
The degradation rate of base indigo plant solution is more than 80%.
Chinese patent 201010148412.1, is characterized in that on silicon wafer, etching forms specific silicon miniflow groove pattern,
Appropriate high temperature bubble release agent is placed in its two ends or ad-hoc location local, by above-mentioned silicon wafer with glass wafer in air or vacuum
Anodic bonding makes silicon micro-flow groove form glass micro-channel seal cavity.By nanometer tio buied2Powder is first dissolved into suspension
Liquid, then this immersion is entered glass micro-channel, dry afterwards and high-temperature heat treatment fluid channel, repeatedly, by photocatalyst coating
On fluid channel inwall, form thermoforming glass photocatalytic microreactor.
Chinese patent 201210051512.1, is characterized in that in reactor, and optical fiber lower end passes through micropore glass piece to support
On cellular glass sand dividing plate, upper end is fixed with light transmission piece, and reactor bottom is provided with admission line, and light source incidence mode is by tradition
Out-shoot type penetrates formula in being changed to.Titanium is plated in optical fiber surface using cathode sputtering, then tio is obtained by anodic oxidation2Receive
Mitron photoreaction catalyst.
Said method all has some limitations, and industrialization is difficult.It is that a treating capacity is big that organic sewage is processed, energy consumption
Height, nothing very economic interests, but the engineering of environmental pollution can be reduced.Photocatalysis microreactor technology is applied at organic sewage ought to
When towards improving single microchannel treating capacity, efficient utilization sunlight develops as directions such as light source, reducing energy consumptions.Chinese patent
, all using circular microchannel as conversion zone, it is little not only exist light-receiving area for 200910197401.x and 201010148412.1,
Single microchannel treating capacity is low, and parallel amplification is difficult, and engineering issues are difficult to solve.Chinese patent
201210051512.1 provide a kind of mode of parallel amplification, but using optical fiber as the passage of light exist light have effect spread away from
From restriction (aiche j.2006,52 (6): 2271-2280), the direction of propagation of light with need by illumination catalyst surface not
Consistent the problems such as, simultaneous reactions device is intermittently operated.
Content of the invention
It is an object of the invention to overcoming the shortcoming of prior art, provide a kind of effective illumination that microreactor is greatly improved
Area and feed processing capacity, significantly improve that light-catalysed effect, technical maturity are simply ripe, with low cost has metal ion
The preparation method of the board-like photocatalysis microreactor of titanium dioxide of doping.
The board-like photocatalysis microreactor of titanium dioxide having metal ion mixing of the present invention, it includes corrosion resistant plate base
, there is a groove at bottom as single channel conversion zone, described recess width is 15- in described corrosion resistant plate substrate
50mm, depth is 250-500 μm, has the import and export phase respectively with single channel conversion zone in described corrosion resistant plate substrate
The entrance and exit of connection, entrance is connected with suction line, and outlet is connected with outlet line, in described corrosion resistant plate base
On bottom reeded and transparent surface while on be all loaded with the tio of metal ion mixing2Catalyst film, printing opacity
Being oppositely arranged and in edge while reeded with corrosion resistant plate substrate of catalyst film is loaded with face
Place's fluid sealant is adhesively fixed, and is provided with incident light source above the transparent surface described in relative with groove.
The preparation having catalyst film in the board-like photocatalysis microreactor of titanium dioxide of metal ion mixing of the present invention
Method, it comprises the following steps:
Step one: prepare sol-gel solution, concretely comprise the following steps:
A () sequentially adds butyl titanate, dehydrated alcohol and diethanolamine in the reactor, and electromagnetic agitation is to making mixture
Reach clear state, the wherein mol ratio of butyl titanate, dehydrated alcohol and diethanolamine is 1:(4-6): (1-8)；
B () sequentially adds dehydrated alcohol, distilled water and metal soluble-salt in a reservoir makes metal soluble-salt completely molten
Solution forms metal soluble salt solutions, and wherein in dehydrated alcohol, distilled water and metal soluble-salt and step (a), butyl titanate adds
The mol ratio entering amount is (2-4): (1-10): (0.0001-0.005): 1；
C (), by metal soluble salt solutions injecting reactor, after the completion of injection, stirring makes mixed solution mix homogeneously,
In clear shape, then under room temperature, stand aging 6-16h, obtain the tio having metal ion mixing2Sol-gel；
Step 2: plated film is lifted in corrosion resistant plate substrate and in the one side of transparent surface using sol-gel process, sinters shape
Become catalyst film, concretely comprise the following steps:
(1) corrosion resistant plate preparing substrate and transparent surface cleaning are removed the dirt on its surface；
(2) with adhesive tape, the one side of transparent surface is completely spread and be stained with, another side does not glue；Then use Best-Effort request coater to stainless
Steel panel substrate has a face plated film of reeded one side and the non-adhesive tape of transparent surface, and during plated film, dip time is 150-300s,
Pull rate is 1500-5000 μm/s；Take the adhesive tape on transparent surface after plated film off, corrosion resistant plate substrate and transparent surface are placed on horse
Not in stove, corrosion resistant plate substrate is heated to 400-700 DEG C, and transparent surface is heated to 400-500 DEG C, and is incubated 1-3h, makes amorphous
Tio2It is changed into Detitanium-ore-type, thus preparation has the tio of metal ion mixing in corrosion resistant plate substrate and transparent surface2Thin film.
Using the invention has the beneficial effects as follows:
(1) the microchannel grooves conversion zone that the present invention adopts, increased reaction volume and the Feedstock treating energy of reactor
Power, breaches the restriction of general microreactor, increased the light-receiving area of reactor simultaneously, be carried out using sunlight continuously big
The organic sewage of scale processes and provides probability, and parallel amplification is simple.
(2) using corrosion resistant plate is this light tight and reflective function is good material as substrate, light is thin from injecting catalyst
Film and all can excite electron transition when irradiating thin film again through stainless steel surfaces reflection, is directed through with quartz and the light such as glass
Material is compared, and the utilization ratio of light is higher.
(3) there iing the tio of metal ion mixing2In catalyst, metal ion can capture the electricity being excited transition by illumination
Son, stops the compound of electron-hole pair, light-catalysed effect is greatly improved, with plain tio2Catalyst phase specific degradation rate
Bring up to more than original 2 times.
(4) with the tio having metal ion mixing of sol-gel process preparation2Catalyst process is simple, with low cost, fits
For different substrates such as glass, quartz, common metal, pottery, monocrystal silicon etc., range of application is extremely wide.With Conventional nano powder
Shape catalyst is compared, and there is not catalyst agglomeration and catalyst reclaims problem.
Brief description
Fig. 1 is the structural representation of the board-like photocatalysis microreactor of titanium dioxide having metal ion mixing of the present invention；
Fig. 2 is the reaction unit schematic diagram of the reactor shown in Fig. 1 of the present invention；
Fig. 3-1 is the single channel groove conversion zone top view in the microreactor shown in Fig. 1 of the present invention；
Fig. 3-2 and Fig. 3-3 is existing multichannel groove conversion zone top view；
Fig. 4 (a) -1 is the tio of undoped p metal ion in corrosion resistant plate substrate2The overall pattern Flied emission scanning of thin film
Electron microscope；
Fig. 4 (a) -2 is the tio of undoped p metal ion in corrosion resistant plate substrate2The cracking area internal field emission scanning of thin film
Electron microscope；
Fig. 4 (b) -1 is the cu that adulterates in corrosion resistant plate substrate2+Molar concentration rate (cu2+With butyl titanate molar concentration rate, under
With) be 0.05% tio2The overall pattern field emission scanning electron microscope figure of thin film；
Fig. 4 (b) -2 is the cu that adulterates in corrosion resistant plate substrate2+Molar concentration rate is 0.05% tio2In the cracking area of thin film
Field emission scanning electron microscope figure；
Fig. 4 (c) -1 is the fe that adulterates in corrosion resistant plate substrate3+Molar concentration rate is 0.05% tio2The overall pattern of thin film
Field emission scanning electron microscope figure；
Fig. 4 (c) -2 is the fe that adulterates in corrosion resistant plate substrate3+Molar concentration rate is 0.05% tio2In the cracking area of thin film
Field emission scanning electron microscope figure；
Fig. 4 (d) -1 is the zn that adulterates in corrosion resistant plate substrate2+Molar concentration rate concentration ratio is 0.05% tio2Thin film whole
Bodily form looks field emission scanning electron microscope figure；
Fig. 4 (d) -2 is the zn that adulterates in corrosion resistant plate substrate2+Molar concentration rate is 0.05% tio2In the cracking area of thin film
Field emission scanning electron microscope figure；
Fig. 4 (e) -1 is the cu that adulterates on Pyrex glass2+Molar concentration rate is 0.01% tio2The overall pattern of thin film
Field emission scanning electron microscope figure；
Fig. 4 (e) -2 is the cu that adulterates on Pyrex glass2+Molar concentration rate is 0.01% tio2In the cracking area of thin film
Field emission scanning electron microscope figure；
Fig. 5 is doping cu2+Molar concentration rate is that 0.05% board-like photocatalysis microreactor is used for photocatalysis fall when 30 DEG C
Solution initial concentration is the graph of a relation of degradation rate during 20mg/l methylene blue solution and the time of staying in reactor for the solution；
Fig. 6 is doping cu2+Molar concentration rate is that 0.05% board-like photocatalysis microreactor is used for photocatalysis fall when 30 DEG C
Solution initial concentration is the graph of a relation of degradation rate during 10mg/l methyl orange solution and the time of staying in reactor for the solution；
Fig. 7 is to be coated with doping cu2+Molar concentration rate is 0.01% tio2The light transmittance of the Pyrex glass of thin film is bent
Line.
Specific embodiment
With specific embodiment, the present invention is described in detail below in conjunction with the accompanying drawings.
The board-like photocatalysis microreactor of titanium dioxide having metal ion mixing of the present invention as shown in Figure 1, it includes
Corrosion resistant plate substrate 3, has a groove as single channel conversion zone 4 in described corrosion resistant plate substrate, described groove
Width be 15-50mm, depth be 250-500 μm, described corrosion resistant plate substrate has respectively with single channel conversion zone
The entrance 1 that is connected of import and export and outlet 2, entrance is connected with suction line, exports and is connected with outlet line, described
Corrosion resistant plate substrate on reeded and transparent surface while on be all loaded with the tio of metal ion mixing2Urge
Agent thin film 5, transparent surface 6 is loaded with being oppositely arranged while reeded with corrosion resistant plate substrate of catalyst film
And fluid sealant is adhesively fixed in edge.It is provided with incident illumination above transparent surface described in relative with groove
Source 7.The horizontal cross sectional geometry of single channel groove is usually flat or rectangle.The forming method of passage includes chemical attack, machine
The method such as tool processing and galvano-cautery.
Preferably described transparent surface 6 is Pyrex glass or quartz, the thickness of described Pyrex glass or quartz
Degree≤1mm, advantage is both to have can guarantee that reactor had certain mechanical strength, can make again light particularly UV light permeability when decay
Less.
As the present invention preferred embodiment, tio2Catalyst film thickness is 300-350nm, and thickness is neither too
Thickness, is not too thin, and bind metal ion acts on to the capture of light induced electron, and advantage is that the catalyst for printing opacity surface side comes
Say, because light is injected from the catalyst back side, less thick thin film both can guarantee that there is a certain degree of absorption to ultraviolet light, produces
The light induced electron of q.s, also can make light induced electron migrate in shorter in the distance anti-to the interface of reactant and catalyst
Should, reduce and hole-recombination probability；Meanwhile, the light coming from transparent surface transmission is irradiated to the suprabasil catalyst of corrosion resistant plate
When, less thick thin film makes light be unlikely to be fully absorbed by thin film, and light is from injecting catalyst film and through stainless steel surfaces
Reflection all can excite electron transition when irradiating thin film again, and migration distance is short, low with hole-recombination probability, with quartz and glass
The material being directed through Deng light is compared, and the utilization ratio of light is higher.
In the present invention, incident light source can be using mercury lamp, xenon lamp or sunlight.
The metal ion of preferably doping is la3+、cu2+、mn2+、fe3+、zn2+Or ni2+One of.
As shown in Fig. 2 the board-like photocatalysis microreactor shown in Fig. 1 is in running, entrance pass through suction line with
Constant flow syringe pump 8 is connected, and methylene blue or methyl orange solution 9 enter groove 4 by suction line, the group relative with groove
Xenon lamp (can also be mercury lamp or sunlight) 7 is had to irradiate above Re Kesi glass or quartz 6, the power of the light source such as xenon lamp is
250w, outlet is connected with outlet line, and board-like microreactor is placed and kept 30 DEG C of constant temperature in water-bath 10.
The preparation having catalyst film in the board-like photocatalysis microreactor of titanium dioxide of metal ion mixing of the present invention
Method, it comprises the following steps:
Step one: prepare sol-gel solution, concretely comprise the following steps:
A () sequentially adds butyl titanate, dehydrated alcohol and diethanolamine in the reactor, and electromagnetic agitation is to making mixture
Reach clear state, the wherein mol ratio of butyl titanate, dehydrated alcohol and diethanolamine is 1:(4-6): (1-8)；
B () sequentially adds dehydrated alcohol, distilled water and metal soluble-salt in a reservoir makes metal soluble-salt completely molten
Solution forms metal soluble salt solutions, and wherein in dehydrated alcohol, distilled water and metal soluble-salt and step (a), butyl titanate adds
The mol ratio entering amount is (2-4): (1-10): (0.0001-0.005): 1；The metal ion of preferably doping is la3+、cu2+、mn2 +、fe3+、zn2+Or ni2+One of, soluble-salt is la (no respectively3)3、cu(no3)2、mn(ch3coo)2、fe(no3)3、zn
(ch3coo)2Or ni (no3)2One of；
C (), by metal soluble salt solutions injecting reactor, after the completion of injection, stirring makes mixed solution mix homogeneously,
In clear shape, then under room temperature, stand aging 6-16h, obtain the tio having metal ion mixing2Sol-gel；
Step 2: plated film is lifted in corrosion resistant plate substrate and in the one side of transparent surface using sol-gel process, sinters shape
Become catalyst film, concretely comprise the following steps:
(1) corrosion resistant plate preparing substrate and transparent surface cleaning are removed the dirt on its surface, common decontamination at present
Method is: respectively washes corrosion resistant plate substrate and transparent surface through the liquid detergent of 5-10min at 40-60 DEG C, alkali cleaning and alcohol are washed；
(2) with adhesive tape, the one side of transparent surface is completely spread and be stained with, it is therefore an objective to only give, another side does not glue treats that degraded solutions contact
A face plated film；Then Best-Effort request coater is used to have reeded one side and the non-adhesive tape of transparent surface to corrosion resistant plate substrate
A face plated film, during plated film dip time be 150-300s, pull rate be 1500-5000 μm/s；Transparent surface is taken off after plated film
On adhesive tape, corrosion resistant plate substrate and transparent surface are placed in Muffle furnace, corrosion resistant plate substrate is heated to 400-700 DEG C, printing opacity
Face is heated to 400-500 DEG C, and is incubated 1-3h, makes unbodied tio2It is changed into Detitanium-ore-type, thus in corrosion resistant plate substrate
There is the tio of metal ion mixing with preparation on transparent surface2Thin film.Preferably made not with the heating rate of 2 DEG C/min in this step
Rust steel panel substrate is heated to 400-700 DEG C, and transparent surface is heated to 400-500 DEG C.
Embodiment 1
The first step, forms single channel groove conversion zone by chemical attack on stainless steel.Described recess width
For 15mm, depth is 300 μm, opens and be connected with the import and export of single channel conversion zone respectively in described corrosion resistant plate substrate
Entrance 1 and outlet 2；
Second step, has the tio of metal ion mixing with sol-gel process preparation2Sol-gel.
A () sequentially adds butyl titanate, dehydrated alcohol and diethanolamine in the reactor, and electromagnetic agitation is to making mixture
Reach clear state, the wherein mol ratio of butyl titanate, dehydrated alcohol and diethanolamine is 1:4:5；
B () sequentially adds dehydrated alcohol, distilled water and metal soluble-salt in a reservoir, make metal soluble-salt completely molten
Solution forms metal soluble salt solutions, and wherein in dehydrated alcohol, distilled water and metal soluble-salt and step (a), butyl titanate adds
The mol ratio entering amount is 2:1:0.0005:1；
C (), by metal soluble salt solutions injecting reactor, after the completion of injection, stirring makes mixed solution mix homogeneously,
In clear shape, then under room temperature, stand aging 10h, obtain the tio having metal ion mixing2Sol-gel；
3rd step, lifts plated film, sintered catalyst
(1) corrosion resistant plate preparing substrate and transparent surface cleaning are removed the dirt on its surface；
(2) with adhesive tape, the one side of transparent surface is completely spread and be stained with, this simultaneously would not be contacted with sol-gel solution, another
Face is not glued；Then Best-Effort request coater is used to have the one of reeded one side and the non-adhesive tape of transparent surface to corrosion resistant plate substrate
Face plated film, during plated film, dip time is 180s, 1500 μm/s of pull rate；The adhesive tape on transparent surface is taken off after plated film, will be stainless
Steel panel substrate and transparent surface are placed in Muffle furnace, make corrosion resistant plate substrate with the heating rate of 2 DEG C/min, and transparent surface is all heated to
500 DEG C, and it is incubated 2h, make unbodied tio2It is changed into Detitanium-ore-type, thus preparing in corrosion resistant plate substrate and transparent surface
There is the tio of metal ion mixing2Thin film.
4th step, sealed light-transmitting face and gateway.
Entrance 12 is connected with suction line and outlet line respectively with outlet, suction line and constant flow syringe pump phase
Connection, transparent surface 6 is loaded with catalyst film be oppositely arranged while reeded with corrosion resistant plate substrate and
In edge, fluid sealant is adhesively fixed.Transparent surface is the Pyrex glass of 1mm for thickness.
The board-like photocatalysis microreactor of titanium dioxide having metal ion mixing being obtained using this method, tio2Thin film
Thickness is 300nm, and stainless steel surfaces thin film has different degrees of do not ftracture area and cracking area, and do not ftracture area tio2Particle diameter is more equal
Even, it is 15-20nm, ftracture area tio2Particle diameter is 15-200nm, as Fig. 4 (b) -1 arrives shown in Fig. 4 (d) -2.Wherein Detitanium-ore-type accounts for
75% about, rutile-type accounts for 25% about.
The metal ion mixing that has with different ions doping contents this method being obtained using the device shown in Fig. 2
The board-like smooth microreactor of titanium dioxide is tested respectively, wherein using xenon lamp as light source, vertical irradiation on microreactor, xenon
Lamp (simulated solar light source, ultraviolet light content accounts for 5%) power is 250w, and the bath temperature in thermostat water bath is 30 DEG C, light
Source is 25cm apart from the distance of board-like microreactor, and the liquid level in thermostat water bath did not had microreactor 2-3cm, and degraded is by constant current
The initial concentration of amount syringe pump 8 injection is respectively 20mg/l and 10mg/l methylene blue solution or methyl orange solution 9, uses cuvette
Connect a certain amount of reacted liquid, measure absorbance, calculate degradation rate.Ion doping molar concentration rate is (in the present embodiment
Butyl titanate molar concentration rate in metal ion in two step (b) steps and second step (a) step, similarly hereinafter) be 0.05% cu2 +, fe3+, zn2+, soluble-salt is cu (no respectively3)2, fe (no3)3, zn (ch3coo)2Shi Xiaoguo is preferable.When solution flow rate is
During 0.1ml/min (time of staying be 90s), the degradation rate of corresponding methylene blue and methyl orange be respectively 75% and 55% with
On.Ion doping concentration is 0.05%la3+, mn2+, ni2+, soluble-salt is la (no respectively3)3, mn (ch3coo)2, ni (no3)2
Shi Xiaoguo is slightly worse.When solution flow rate is for 0.1ml/min, the degradation rate of corresponding methylene blue and methyl orange be respectively 68% and
45% about.Doping cu2+Concentration be 0.05% board-like photocatalysis microreactor with this understanding be used for photocatalytic degradation this two
Plant relation such as Fig. 5 of degradation rate during solution and the time of staying in reactor for the solution, shown in Fig. 6, ultraviolet light in xenon lamp
Very high photocatalytic activity is shown in the case that content is so low.And the pure tio of undoped p metal ion2Catalysis dosage form
Looks such as shown in Fig. 4 (a) -1 and figure (a) -2, the pure tio of undoped p metal ion2Board-like photocatalysis microreactor is in the same terms
Under degradation rate be only 40% and 26% about.As can be seen here after the doping of metal ion, metal ion enters tio2Lattice, leads
Cause Lacking oxygen defect, form light induced electron adsorption site, prevention electronics is compound with hole, and photocatalytic activity is greatly improved.
Embodiment 2
The single pass reactor of the preparation present invention:
The first step, forms single channel groove conversion zone by galvano-cautery on stainless steel.Described recess width is
20mm, depth is 250 μm, opens and be connected with the import and export of single channel conversion zone respectively in described corrosion resistant plate substrate
Entrance 1 and outlet 2, channel wall area, passage inner bottom area, catalyst coat area, reaction volume, specific surface area parameter is divided
Not as follows: 26mm2, 727mm2, 753mm2, 0.15ml, 5.18mm2/mm3；
Second step, has cu with sol-gel process preparation2+The tio of doping2Sol-gel.
A () sequentially adds butyl titanate, dehydrated alcohol and diethanolamine in the reactor, and electromagnetic agitation is to making mixture
Reach clear state, the wherein mol ratio of butyl titanate, dehydrated alcohol and diethanolamine is 1:6:8；
B () sequentially adds dehydrated alcohol, distilled water and cu (no in a reservoir3)2, make cu (no3)2It is completely dissolved formation cu
(no3)2Solution, wherein dehydrated alcohol, distilled water and cu (no3)2Mol ratio with butyl titanate addition in step (a) is 3:
6:0.005:1；
C () is by cu (no3)2In solution injecting reactor, after the completion of injection, stirring makes mixed solution mix homogeneously, in clarification
Transparence, then stands aging 6h under room temperature, obtain there is cu2+The tio of doping2Sol-gel；
3rd step, lifts plated film, sintered catalyst
(1) corrosion resistant plate preparing substrate and transparent surface cleaning are removed the dirt on its surface；
(2) with adhesive tape, the one side of transparent surface is completely spread and be stained with, this simultaneously would not be contacted with sol-gel solution, another
Face is not glued；Then Best-Effort request coater is used to have the one of reeded one side and the non-adhesive tape of transparent surface to corrosion resistant plate substrate
Face plated film, during plated film, dip time is 150s, 5000 μm/s of pull rate；The adhesive tape on transparent surface is taken off after plated film, will be stainless
Steel panel substrate and transparent surface are placed in Muffle furnace, make corrosion resistant plate substrate be heated to 700 DEG C with the heating rate of 2 DEG C/min, thoroughly
Bright finish is heated to 400 DEG C, and is incubated 1h, makes unbodied tio2It is changed into Detitanium-ore-type, thus in corrosion resistant plate substrate and thoroughly
On bright finish, preparation has the tio of metal ion mixing2Thin film, film thickness is 350nm.
4th step, sealed light-transmitting face and gateway.
Entrance 12 is connected with suction line and outlet line respectively with outlet, suction line and constant flow syringe pump phase
Connection, transparent surface 6 is loaded with catalyst film be oppositely arranged while reeded with corrosion resistant plate substrate and
In edge, fluid sealant is adhesively fixed.Transparent surface is the Pyrex glass of 0.9mm for thickness.
Comparative example 1
As shown in figure 3-2, on stainless steel 9 MCA (each channel widths are formed by chemical attack
1.0mm, Channel spacing 0.5mm), channel wall area, passage inner bottom area, catalyst coat area, reaction volume, than
Surface area parameters are as follows respectively: 174mm2, 545mm2, 719mm2, 0.11ml, 6.59mm2/mm3；
Comparative example 2
As shown in Fig. 3-3, on stainless steel 19 MCA (each channel widths are formed by chemical attack
0.5mm, Channel spacing 0.2mm), channel wall area, passage inner bottom area, catalyst coat area, reaction volume, than
Surface area parameters are as follows respectively: 358mm2, 566mm2, 926mm2, 0.11ml, 8.16mm2/mm3；
Reactor in reactor in embodiment 2 and comparative example 1 and comparative example 2 is degraded under the same conditions initially dense
The methylene blue solution of degree 20mg/l, is tested: the reactor cu in embodiment 2 respectively2+Doping molar concentration rate be
0.5% microreactor, as solution flow rate 0.05ml/min, in reactor in embodiment 2, comparative example 1 and comparative example 2
The degradation rate of reactor is respectively 97.2%, 70.9%, 50.0%.Although multi-channel structure has bigger specific surface area,
Be its increase area more come from vertical walls, its catalyst coat is due to substantially parallel with irradiation light, received
Luminous energy extremely limited, catalytic efficiency is low.Therefore for board-like photocatalysis microreactor, single channel is than multiple microchannels
Advantageously.For photocatalysis microreactor, its effective illuminating area is particularly significant, with actual industrial production as application background
Microreactor research and development in it is impossible to pursue high conversion simply and continuous size reduction, and structure that should be reasonable in design and
Size, so as to the characteristic superiority of microreactor can either be kept, has big illuminating area and the efficiency of light energy utilization again, and higher
Space, time efficiency.
Embodiment 3
The first step, forms single channel groove conversion zone by machining on stainless steel.Described recess width
For 50mm, depth is 500 μm, opens and be connected with the import and export of single channel conversion zone respectively in described corrosion resistant plate substrate
Entrance 1 and outlet 2,
Second step, has cu with sol-gel process preparation2+The tio of doping2Sol-gel.
A () sequentially adds butyl titanate, dehydrated alcohol and diethanolamine in the reactor, and electromagnetic agitation is to making mixture
Reach clear state, the wherein mol ratio of butyl titanate, dehydrated alcohol and diethanolamine is 1:5:1；
B () sequentially adds dehydrated alcohol, distilled water and cu (no in a reservoir3)2, make cu (no3)2It is completely dissolved formation cu
(no3)2Solution, wherein dehydrated alcohol, distilled water and cu (no3)2Mol ratio with butyl titanate addition in step (a) is 4:
10:0.0001:1；
C () is by cu (no3)2In solution injecting reactor, after the completion of injection, stirring makes mixed solution mix homogeneously, in clarification
Transparence, then stands aging 16h under room temperature, obtain there is cu2+The tio of doping2Sol-gel；
3rd step, lifts plated film, sintered catalyst
(1) corrosion resistant plate preparing substrate and transparent surface cleaning are removed the dirt on its surface；
(2) with adhesive tape, the one side of transparent surface is completely spread and be stained with, this simultaneously would not be contacted with sol-gel solution, another
Face is not glued；Then Best-Effort request coater is used to have the one of reeded one side and the non-adhesive tape of transparent surface to corrosion resistant plate substrate
Face plated film, during plated film, dip time is 300s, 3000 μm/s of pull rate；The adhesive tape on transparent surface is taken off after plated film, will be stainless
Steel panel substrate and transparent surface are placed in Muffle furnace, make corrosion resistant plate substrate be heated to 400 DEG C with the heating rate of 2 DEG C/min, thoroughly
Bright finish is heated to 450 DEG C, and is incubated 3h, makes unbodied tio2It is changed into Detitanium-ore-type, thus in corrosion resistant plate substrate and thoroughly
On bright finish, preparation has the tio of metal ion mixing2Thin film, film thickness is 320nm.
4th step, sealed light-transmitting face and gateway.
Entrance 12 is connected with suction line and outlet line respectively with outlet, suction line and constant flow syringe pump phase
Connection, transparent surface 6 is loaded with catalyst film be oppositely arranged while reeded with corrosion resistant plate substrate and
In edge, fluid sealant is adhesively fixed.Transparent surface is the quartz of 0.9mm for thickness.
Comparative example 3
The first step: on Pyrex glass, rectangle single channel groove conversion zone is formed by chemical attack.Process is:
Hydrofluoric acid resistant protecting film carves and identical pattern on rustless steel in embodiment 3, protecting film is bonded at Pyrex glass
On, take quarter figuratum part off, be then placed in certain density hf corrosive liquid, maintain temperature to be 30-40 DEG C.Etch every time
Time is 10-15min, rinses salt tap water unreacted on glass well, place into corruption after glass is dried after taking-up
In erosion liquid.Repeat to etch and obtain final product the groove conversion zone that depth is 500 μm several times afterwards.Hydrofluoric acid resistant protecting film carves two
The circular hole of a diameter of 1.5mm, after being bonded on glass, etches under above-mentioned the same terms, and each time is 30-45min, and etching is several
Glass can be cut through after secondary, cut through part as gateway.
Second step, has cu with sol-gel process preparation2+The tio of doping2Sol-gel.
A () sequentially adds butyl titanate, dehydrated alcohol and diethanolamine in the reactor, and electromagnetic agitation is to making mixture
Reach clear state, the wherein mol ratio of butyl titanate, dehydrated alcohol and diethanolamine is 1:5:1；
B () sequentially adds dehydrated alcohol, distilled water and cu (no in a reservoir3)2, make cu (no3)2It is completely dissolved formation cu
(no3)2Solution, wherein dehydrated alcohol, distilled water and cu (no3)2Mol ratio with butyl titanate addition in step (a) is 4:
10:0.0001:1；
C () is by cu (no3)2In solution injecting reactor, marginal not enters side stirring, after the completion of injection, makes mixed solution continue to stir
Mix until solution mix homogeneously, in clear shape, then stand aging 16h under room temperature, obtain there is cu2+The tio of doping2Molten
Glue-gel；
3rd step, lifts plated film, sintered catalyst
(1) transparent surface preparing and the cleaning of Pyrex glass substrate are removed the dirt on its surface；
(2) with adhesive tape, the one side of transparent surface is completely spread and be stained with, this simultaneously would not be contacted with sol-gel solution, another
Face is not glued；Then Best-Effort request coater is used to have reeded one side and the non-adhesive tape of transparent surface to Pyrex glass substrate
A face plated film, during plated film dip time be 300s, 3000 μm/s of pull rate；The adhesive tape on transparent surface is taken off after plated film, will
Pyrex glass substrate and transparent surface are placed in Muffle furnace, so that Pyrex glass substrate is added with the heating rate of 2 DEG C/min
To 400 DEG C, transparent surface is heated to 450 DEG C to heat, and is incubated 3h, makes unbodied tio2It is changed into Detitanium-ore-type, thus in group's heat
In gram this substrate of glass and transparent surface, preparation has the tio of metal ion mixing2Thin film, film thickness is 320nm.
4th step, sealed light-transmitting face and gateway.
Entrance 12 is connected with suction line and outlet line respectively with outlet, suction line and constant flow syringe pump phase
Connection, transparent surface 6 is loaded with being oppositely arranged while reeded with Pyrex glass substrate of catalyst film
And fluid sealant is adhesively fixed in edge.Transparent surface is the quartz of 0.9mm for thickness.
In such scheme, corrosion resistant plate substrate catalyst pattern is close with Fig. 4 (b) -1 and Fig. 4 (b) -2, pyrex
Substrate of glass catalyst pattern such as shown in Fig. 4 (e) -1 and figure (e) -2, tio2Particle diameter difference is little.With embodiment 3 and comparative example 3
In two kinds of board-like photocatalysis microreactors degrade under the same conditions initial concentration be 10mg/l methyl orange solution, when solution stream
When speed is for 0.1ml/min, the board-like photocatalysis microreactor degradation rate with rustless steel as substrate is 55% about, and with Pai Reke
This glass is that the board-like photocatalysis microreactor degradation rate of substrate is only 22% about, and both have a long way to go.Its main cause is
It is good that rustless steel is unable to printing opacity and reflective function, and light is from injecting catalyst coat and irradiate coating again through stainless steel surfaces reflection
Be equivalent to coating to be irradiated twice, all can excite electron transition, the utilization ratio of light is higher.And Pyrex glass is printing opacity
Material, is coated with cu2+Doping molar concentration rate be 0.01% coating Pyrex glass light transmittance curve as shown in fig. 7, from
In figure can be seen that the also very high absorbance of the ultraviolet light for 350nm to 400nm for the wavelength, therefore also has quite a few purple
Just it is directed through Pyrex glass and is not used outward, so its degradation rate is relatively low.Thus with rustless steel is this can not
The printing opacity and good material of reflective function has more preferable photocatalysis effect as substrate than light transmissive material.
Claims (6)
1. have the preparation method of the board-like photocatalysis microreactor of titanium dioxide of metal ion mixing it is characterised in that it include with
Lower step:
The first step, forms single channel groove conversion zone by chemical attack on stainless steel, and described recess width is 15-
50mm, depth is 250-500 μm, opens up the import and export phase respectively with single channel conversion zone in the substrate of described corrosion resistant plate
The entrance and exit of connection；
Second step, has the tio of metal ion mixing with sol-gel process preparation2Sol-gel, concretely comprises the following steps:
A () sequentially adds butyl titanate, dehydrated alcohol and diethanolamine in the reactor, and electromagnetic agitation is to bringing the mixture to
The mol ratio of clear state, wherein butyl titanate, dehydrated alcohol and diethanolamine is 1:(4-6): (1-8)；
B () sequentially adds dehydrated alcohol, distilled water and metal soluble-salt in a reservoir makes metal soluble-salt be completely dissolved shape
Become metal soluble salt solutions, wherein butyl titanate addition in dehydrated alcohol, distilled water and metal soluble-salt and step (a)
Mol ratio be (2-4): (1-10): (0.0001-0.005): 1；
C (), by metal soluble salt solutions injecting reactor, after the completion of injection, stirring makes mixed solution mix homogeneously, in clear
Clear transparence, then stands aging 6-16h, obtains the tio having metal ion mixing under room temperature2Sol-gel；
3rd step, lifts plated film using sol-gel process in corrosion resistant plate substrate and in the one side of transparent surface, sintering formation is urged
Agent thin film, concretely comprises the following steps:
(1) corrosion resistant plate preparing substrate and transparent surface cleaning are removed the dirt on its surface；
(2) with adhesive tape, the one side of transparent surface is completely spread and be stained with, another side does not glue；Then use Best-Effort request coater to corrosion resistant plate
Substrate has a face plated film of reeded one side and the non-adhesive tape of transparent surface, and during plated film, dip time is 150-300s, lifting
Speed is 1500-5000 μm/s；Take the adhesive tape on transparent surface after plated film off, corrosion resistant plate substrate and transparent surface are placed on Muffle furnace
In, corrosion resistant plate substrate is heated to 400-700 DEG C, and transparent surface is heated to 400-500 DEG C, and is incubated 1-3h, makes unbodied
tio2It is changed into Detitanium-ore-type, thus preparation has the tio of metal ion mixing in corrosion resistant plate substrate and transparent surface2Thin film；
4th step, sealed light-transmitting face and gateway:
Entrance and exit is connected with suction line and outlet line respectively, and suction line is connected with constant flow syringe pump,
Being oppositely arranged and in surrounding while reeded with corrosion resistant plate substrate of catalyst film is loaded with transparent surface
Edge is adhesively fixed with fluid sealant.
2. the preparation side of the board-like photocatalysis microreactor of titanium dioxide having metal ion mixing according to claim 1
Method it is characterised in that: the metal ion of doping be la3+、cu2+、mn2+、fe3+、zn2+Or ni2+One of, soluble-salt is respectively
For la (no3)3、cu(no3)2、mn(ch3coo)2、fe(no3)3、zn(ch3coo)2Or ni (no3)2One of.
3. the preparation side of the board-like photocatalysis microreactor of titanium dioxide having metal ion mixing according to claim 1
Method it is characterised in that: the metal ion of doping and the molar concentration rate of butyl titanate are 0.05%.
4. the board-like photocatalysis microreactor of titanium dioxide having metal ion mixing according to one of claim 1-3
Preparation method it is characterised in that: make corrosion resistant plate substrate be heated to 400-700 DEG C with the heating rate of 2 DEG C/min, transparent surface adds
Heat arrives 400-500 DEG C.
5. the preparation side of the board-like photocatalysis microreactor of titanium dioxide having metal ion mixing according to claim 1
Method it is characterised in that: described transparent surface be Pyrex glass or quartz, the thickness of described Pyrex glass or quartz
≤1mm.
6. the preparation side of the board-like photocatalysis microreactor of titanium dioxide having metal ion mixing according to claim 1
Method it is characterised in that: tio2Catalyst film thickness is 300-350nm.
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| CN108371954A (en) * | 2018-03-30 | 2018-08-07 | 华南农业大学 | A kind of support type Ag-TiO2/Ti(NO2) film catalyst and its fruit storage in application |
| CN109589877A (en) * | 2018-12-26 | 2019-04-09 | 天津大学 | The small fluidized-bed reactor of airwater mist cooling photocatalysis |
| CN109991346A (en) * | 2019-04-18 | 2019-07-09 | 南京大学 | A kind of micro-fluidic Ultraviolet Oxidation device for organic nitrogen analysis |
| CN111041523B (en) * | 2020-01-02 | 2021-09-07 | 东莞理工学院 | Copper-doped titanium dioxide photoelectrode, preparation method thereof and application thereof in photoelectrocatalysis decomposition of water |
| CN111672502A (en) * | 2020-05-21 | 2020-09-18 | 哈尔滨学院 | Method for preparing lanthanum/manganese codoped titanium oxide nanotube with photocatalytic activity by anodic oxidation |
| CN112426986B (en) * | 2020-11-17 | 2022-08-12 | 清华大学深圳国际研究生院 | Chemical reactor and application thereof |
| CN115490435B (en) * | 2022-09-19 | 2023-11-21 | 蚌埠高华电子股份有限公司 | Vacuum coated glass supporting assembly and driving and controlling method |
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