CN105664834A - Silane coupling agent modified titanium dioxide nanotube array material as well as preparation method and application thereof - Google Patents

Silane coupling agent modified titanium dioxide nanotube array material as well as preparation method and application thereof Download PDF

Info

Publication number
CN105664834A
CN105664834A CN201610062344.4A CN201610062344A CN105664834A CN 105664834 A CN105664834 A CN 105664834A CN 201610062344 A CN201610062344 A CN 201610062344A CN 105664834 A CN105664834 A CN 105664834A
Authority
CN
China
Prior art keywords
silane coupling
coupling agent
tio
array material
preparation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201610062344.4A
Other languages
Chinese (zh)
Inventor
晏铭
赖萃
曾光明
李小明
陶林暄
张鹏
张海波
王菡
常慧敏
陈晨
杨光
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hunan University
Original Assignee
Hunan University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hunan University filed Critical Hunan University
Priority to CN201610062344.4A priority Critical patent/CN105664834A/en
Publication of CN105664834A publication Critical patent/CN105664834A/en
Pending legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
    • B01J20/0251—Compounds of Si, Ge, Sn, Pb
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/42—Materials comprising a mixture of inorganic materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/30—Wastewater or sewage treatment systems using renewable energies
    • Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy

Landscapes

  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Hydrology & Water Resources (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Catalysts (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

The invention discloses a silane coupling agent modified titanium dioxide nanotube array material as well as a preparation method and an application thereof. The silane coupling agent modified titanium dioxide nanotube array material is mainly prepared from titanium dioxide nanotube arrays, a silane coupling agent, an organic solvent and glacial acetic acid through a reaction after mixing, and can be applied to treatment of wastewater containing organic pollutants and/or heavy metal pollutants. The redox capacity of the silane coupling agent modified titanium dioxide nanotube array material is high, the organic pollutants and the heavy metal pollutants can be removed simultaneously, the removing effect is good, and the material can be repeatedly used.

Description

TiO 2 nanotubes modified array material of silane coupling agent and its preparation method and application
Technical field
The invention belongs to nanometer-material-modified and water-treatment technology field, it is specifically related to the TiO 2 nanotubes modified array material of silane coupling agent and its preparation method and is removing containing the application in organic pollutant and/or heavy metal contaminants waste water.
Background technology
TiO2Photocatalysis technology is the novel method of the removal environmental pollutant got most of the attention at present. TiO2Light produces electron-hole pair after irradiating, and electronics has stronger reducing power, and hole has relatively Strong oxdiative ability. Utilize the synergy in electronics-hole, remove the organic pollutant in environment and reducing heavy metal simultaneously, become a focus in current catalysis and environmental protection research. But due to TiO2Surface has a large amount of hydroxyls, therefore that the binding ability of the persistence organic pollutant of parent's lipid is more weak.
TiO2The most frequently used nano shape comprises powder body, film and forms matrix material with carrier. What research was maximum at present is powder morphology. Exist when but powder body material is applied in engineering and not easily disperse, easily reunite, difficult recycle and easily cause secondary pollution problems, limit its application in environmental pollutant are removed. Within 2001, Grimes the first in the group time reports preparation TiO2The method of nano-tube array, nano-tube array prepared by the method owing to easily reclaiming, the characteristic of preparation method's simplicity substantially increase TiO2The application of photocatalyst in environmental pollution is removed. But, still can not solve with parent lipid organic pollutant in conjunction with problem. Therefore, seek a kind of catalyzer that simultaneously can effectively remove the organic pollutant in environment and reducing heavy metal and become the task of top priority.
Summary of the invention
The technical problem to be solved in the present invention overcomes the deficiencies in the prior art, there is provided a kind of redox ability strong, organic pollutant and heavy metal contaminants can be removed, and the good TiO 2 nanotubes modified array material of silane coupling agent of removal effect and its preparation method and application simultaneously.
For solving the problems of the technologies described above, the present invention by the following technical solutions:
A kind of TiO 2 nanotubes modified array material of silane coupling agent, the TiO 2 nanotubes modified array material of described silane coupling agent is obtained by reacting after mixing primarily of Nano tube array of titanium dioxide, silane coupling agent, organic solvent and Glacial acetic acid.
As a total invention design, present invention also offers the preparation method of the TiO 2 nanotubes modified array material of a kind of silane coupling agent, comprise the following steps: by Nano tube array of titanium dioxide, silane coupling agent, organic solvent and Glacial acetic acid mixing, after reaction, obtain the TiO 2 nanotubes modified array material of silane coupling agent.
In the preparation method of the TiO 2 nanotubes modified array material of above-mentioned silane coupling agent, it is preferable that, the quality of described silane coupling agent accounts for the 0.1%～20% of described silane coupling agent and organic solvent quality sum.
In the preparation method of the TiO 2 nanotubes modified array material of above-mentioned silane coupling agent, it is preferable that, described organic solvent is toluene.
In the preparation method of the TiO 2 nanotubes modified array material of above-mentioned silane coupling agent, it is preferable that, the temperature of described reaction is 50 DEG C～80 DEG C, and the time of described reaction is 0.5h～8h.
In the preparation method of the TiO 2 nanotubes modified array material of above-mentioned silane coupling agent, it is preferable that, described silane coupling agent is Silane coupling reagent KH-570.
As a total invention design, the TiO 2 nanotubes modified array material of silane coupling agent that the TiO 2 nanotubes modified array material of the silane coupling agent that the present invention also provides above-mentioned or above-mentioned preparation method obtain is in the application processed in the waste water containing organic pollutant and/or heavy metal contaminants.
In above-mentioned application, it is preferable that, described application comprises the following steps: is added by TiO 2 nanotubes modified for silane coupling agent array material in the waste water containing organic pollutant and/or heavy metal contaminants and carries out light-catalyzed reaction, completes the process to waste water.
In above-mentioned application, it is preferable that, the pH value in described light-catalyzed reaction process is 3～6.
Silane coupling agent is the silicoorganic compound that a class contains two kinds of different chemical character groups in the molecule simultaneously, and its classical product can use general formula YSiX3Represent. In formula, Y is non-hydrolytic group, comprises alkenyl (being mainly vinyl), and end is with Cl, NH2, SH, ring oxygen, N3, alkyl such as functional group such as (methyl) acryloxy or isocyanate group etc., be also exactly carbon functional group; X is hydrolysable group, comprises Cl, OMe, OEt, OC2H4OCH3、OSiMe3Or OAc etc. Due to this special construction, there is the reactive group of energy with inanimate matter material (such as glass, silica sand, metal etc.) Chemical bond and the reactive group with organic material (synthetic resins etc.) Chemical bond in the molecule thereof simultaneously, it is possible to for surface treatment.
The present invention is intended to find out the method that a set of effective silane coupling agent modifies Nano tube array of titanium dioxide material surface, and finds out the parameters optimization that it modifies system on this basis. for KH-570, KH-570 has 3 silicone hydroxyl after being hydrolyzed, usually one of them silicone hydroxyl can be combined in catalyst surface with the hydroxyl generation dehydration reaction of catalyst surface with the form of chemical bond, all the other two silicone hydroxyl or with between silicone hydroxyl dehydration reaction generate reticulated structure, or exist with free state form, therefore the KH-570 on modifying can as a kind of hole trapping agents being well fixed on material surface, improve the hole-electronics separation efficiency of catalyzer, unsaturated olefin on KH-570 has strong parent's ester simultaneously, parent's Ester is had good absorption and Degradation by the material after therefore modifying.
Owing to reaction is comparatively complicated, the catalytic performance for catalyzer can be had bigger impact by the scion grafting form of silane coupling agent and scion grafting amount. It is not obvious that scion grafting amount brings performance to improve compared with I haven't seen you for ages, scion grafting amount relatively conference bring the reaction times excessively long, silane coupling agent consumption increases, the polymkeric substance that silane coupling agent generates simultaneously can cover surface in a large number affects catalyzer to the absorption of photon, and part silane coupling agent likely can enter the inside of titania nanotube, cause nanotube to block, affect pollutent and enter titania nanotube inside. In order to find good processing method and parameter, the technical solution used in the present invention is that research silane coupling agent, in suitable system, hydrolysis reaction occurs, and the hydroxyl generation hydrolysis reaction on the nano-tube array surface simultaneously and in system, by-SiX3Group scion grafting is to the surface of Nano tube array of titanium dioxide.
About hole trapping agents: hole trapping agents to improve the additive with reductibility of catalyst system efficiency, very fast the reacting with-OH in the hole that it produces under-OH can be provided in photochemical catalysis system to make illumination, therefore improves the hole-electronics separation efficiency of system.
Compared with prior art, it is an advantage of the current invention that:
1, the TiO 2 nanotubes modified array material of the silane coupling agent of the present invention has stronger redox ability, not only can significantly improve this material to the absorption of hydrophobic organic compound and degradation effect, the excellent absorption to wetting ability pollutent and Degradation can also be kept simultaneously.
2, silane coupling agent is successfully disperseed and modifies the surface of Nano tube array of titanium dioxide by the present invention, the silicone hydroxyl of its free state improves the both hole and electron separation efficiency of nano material as hole trapping agents, it is to increase the efficiency of its degradable organic pollutant and reducing heavy metal ion.
3, silane coupling agent is successfully disperseed and modifies the surface of Nano tube array of titanium dioxide by the present invention, the unsaturated olefin of silane coupling agent has strong parent's ester, greatly strengthen it to the absorption of hydrophobic organic compound and degradation effect, and the material after modifying, the part surface of all the other non-scion grafting silane coupling agents contains a large amount of hydroxyls, and wetting ability pollutent still has absorption and Degradation preferably.
4, the TiO 2 nanotubes modified array material of the silane coupling agent of the present invention can be used for processing the combined pollution waste water simultaneously containing organic pollutant and heavy metal contaminants, has very strong soil removability, and can Reusability.
Accompanying drawing explanation
Fig. 1 is the stereoscan photograph of the TiO 2 nanotubes modified array material of silane coupling agent in the embodiment of the present invention 4.
Fig. 2 is the EDS collection of illustrative plates of the TiO 2 nanotubes modified array material of silane coupling agent in the embodiment of the present invention 4.
Embodiment
Below in conjunction with Figure of description and concrete preferred embodiment, the invention will be further described, but protection domain not thereby limiting the invention.
The material adopted in following examples and instrument are commercially available.
Embodiment 1: probing into of temperature of reaction
A preparation method for the TiO 2 nanotubes modified array material of the silane coupling agent of the present invention, gets 4 Nano tube array of titanium dioxide, is cut into 4cm2Square, move in the beaker of 4 50ml respectively, add 20ml toluene, Silane coupling reagent KH-570 and 1ml Glacial acetic acid, 5%(and KH-570 that the quality of Silane coupling reagent KH-570 accounts for KH-570 and toluene quality sum forms the KH-570 solution that massfraction is 5wt% in 20ml toluene), it is adjusted to pH=4 with the acetic acid of w=5%, shake even after, it is placed in water bath heating device, temperature of reaction system is accurately measured with thermometer, temperature is regulated to be 50 DEG C respectively, 60 DEG C, 70 DEG C, 80 DEG C, after reaction 6h, take out titanium sheet, three times are cleaned again with acetone, be used for degrading four bromo biphenyl ethers and reduction Cu(II by the catalyzer of modification) during ion tests, get degradation efficiency the highest for optimal conditions.
In the present invention, the toluene solution that with the addition of silane coupling agent of reaction can submergence Nano tube array of titanium dioxide.
Above-mentioned preparation finds, when temperature of reaction is 50 DEG C, modified TiO2-NT due to hydrolysis reaction slower, the self-polymerization product being not easy to produce a large amount of KH-570 covers the surface of titanium dioxide, catalyzer can not be affected and accept the efficiency of photon and the efficiency of pollutent exchange, when more than 70 DEG C, owing to speed of reaction is very fast, easily there is self polycondensation of silane coupling agent, lose metalluster, therefore, 50 DEG C time create good scion grafting effect.This is modified with certain difference with other powder catalysts of research. Being tested by catalysis, the present embodiment selects T=50 DEG C for the optimization reaction times.
In above-mentioned the present embodiment, Nano tube array of titanium dioxide can adopt electrochemistry anodic oxidation to be prepared (other ordinary method also can be adopted to prepare), and preparation process is as follows:
(1) get 2cm × 2cm titanium sheet, soak 1～2s with dilute concentration HF, rapid deionized water rinsing after taking out, with cotton swab wiping repeatedly, repeat aforesaid operations, until titanium plate surface is bright and clean seamless. The preparation of electrolytic solution: get 2.77gNaHSO4, 0.168gNaF, be mixed with 40mL solution, repeatedly stir with glass stick, until solid dissolves completely. DC voltage-stabilizing power supply (ARRAY3646A) circuit is used to connect. Taking platinum electrode as negative electrode, titanium sheet is anode, and voltage is set to 15V, treats circuit stability, and electric current is 1A, treats that electrode reaction carries out 2h, and powered-down, takes off titanium sheet, first does with deionized water rinsing after-blow.
(2) above-mentioned gained titania nanotube is put into electric tube furnace to calcine.
Temperature program
First paragraph: time t1=20min temperature c2=40 DEG C
2nd section: time t2=10min temperature c3=50 DEG C
3rd section: time t3=200min temperature c4=500 DEG C
4th section: time t4=180min temperature c5=500 DEG C
5th section: time t5=-121min temperature c6=0 DEG C (end program).
Embodiment 2: probing into of reaction times
Adopt the preparation method of the TiO 2 nanotubes modified array material of silane coupling agent of the present invention, get 6 Nano tube array of titanium dioxide (method of embodiment 1 can be adopted to prepare), be cut into 4cm2Square, move in the beaker of 6 50ml respectively, add 20ml toluene, KH-570 and 1ml Glacial acetic acid, the quality of KH-570 accounts for the 5% of KH-570 and toluene quality sum, it is adjusted to pH=4 with the acetic acid of w=5%, shake even after, it is placed in water bath heating device, temperature is regulated to be 50 DEG C, after reacting 0.5h, 1h, 2h, 4h, 6h, 8h respectively, take out titanium sheet, then clean three times with acetone, be used for degrading four bromo biphenyl ethers and reduction Cu(II by the catalyzer of modification) during ion tests, get degradation efficiency the highest be optimal conditions.
Above-mentioned preparation finds, when experimental period is below 2h, TiO2There is not obvious change in-NT surface, after measured along with the increase in reaction times, the silane coupling agent white sample of scion grafting increases gradually, reach maximum when the time is 6h, reduce to some extent during 8h, this is because after silane coupling agent is combined completely with nano-tube array, can in conjunction with formation polymkeric substance between silane coupling agent. Being tested by its catalysis, selecting t=8h is the optimization reaction times.
Embodiment 3: probing into of silane coupling agent dosage
Adopt the preparation method of the TiO 2 nanotubes modified array material of silane coupling agent of the present invention, get 5 Nano tube array of titanium dioxide (method of embodiment 1 can be adopted to prepare), be cut into 4cm2Square, move in the beaker of 5 50ml respectively, after adding the Glacial acetic acid of 20ml toluene and 1ml, respectively to the KH-570 adding different amount in 5 beakers, make KH-570 form massfraction in 20ml toluene and it is respectively 0.1%, 1%, 5%, 10%, the KH-570 solution of 20%, it is adjusted to pH=4 with the acetic acid of w=5%, shake even after, it is placed in hot-plate, regulate temperature 50 DEG C, after reaction 8h, take out titanium sheet, three times are cleaned again with acetone, be used for degrading four bromo biphenyl ethers and reduction Cu(II by the catalyzer of modification) during ion tests, get degradation efficiency the highest for optimal conditions.
Finding in above-mentioned preparation, by adding the amount of the silane coupling agent of different concns, by the efficiency size of its degraded BDE47, when selecting the dosage of wt%=5%, modification effect is best.
Embodiment 4
A preparation method for the TiO 2 nanotubes modified array material of the silane coupling agent of the present invention, comprises the following steps:
Nano tube array of titanium dioxide is cut into 4cm2Square (nano-tube array can adopt the method for embodiment 1 to prepare), move in the beaker of 100ml, add 20ml toluene, KH-570 and 1ml Glacial acetic acid, the quality of KH-570 accounts for the 5% of KH-570 and toluene quality sum, the acetic acid being 5% with massfraction is adjusted to pH=4, shake even after, it is heated to 50 DEG C, after reaction 8h, take out titanium sheet, then clean three times with acetone, be placed in 80 DEG C of loft drier and be dried, obtaining the TiO 2 nanotubes modified array material of silane coupling agent, its stereoscan photograph is as shown in Figure 1. Fig. 2 is the EDS collection of illustrative plates of the TiO 2 nanotubes modified array material of this silane coupling agent, and as seen from the figure, there is the existence of Si element on the Nano tube array of titanium dioxide surface of modification, represents that silane coupling agent is successfully surperficial to Nano tube array of titanium dioxide by modification.
Embodiment 5
The application of the TiO 2 nanotubes modified array material of the silane coupling agent of the present invention in process phenol, the TiO 2 nanotubes modified array material of the silane coupling agent that specifically embodiment 4 can be adopted to prepare, comprises the following steps:
Through the TiO that silane coupling agent is modified2Nano-tube array material light catalysis degradation of phenol, irradiates 240min under ultraviolet lamp, leaves standstill after 15min at 0min(respectively), 30min, 60min, 120min, 180min and 240min time sampling, utilize gas chromatograph-mass spectrometer to detect its concentration. Adopt not modified titania nanotube (TiO simultaneously2-NT) array do blank experiment. Experimental result shows that four hours efficiency of post treatment bring up to 94% by 89%.
Embodiment 6
The TiO 2 nanotubes modified array material of the silane coupling agent of the present invention is in the application processed in four bromo biphenyl ether BDE47, and the TiO 2 nanotubes modified array material of the silane coupling agent that specifically embodiment 4 can be adopted to prepare, comprises the following steps:
Through the TiO that silane coupling agent is modified2Nano-tube array material light catalysis is degraded four bromo biphenyl ether BDE47, irradiates 240min under ultraviolet lamp, respectively after 0min(leaves standstill 15min), 30min, 60min, 120min, 180min and 240min time sampling, utilize gas chromatograph-mass spectrometer to detect its concentration. Adopt not modified Nano tube array of titanium dioxide to do blank experiment simultaneously. Experimental result shows that four hours efficiency of post treatment are by 87%(blank) bring up to 99%(the present embodiment).
Embodiment 7
The TiO 2 nanotubes modified array material of the silane coupling agent of a kind of the present invention is at process heavy metal ion Pb2+In application, the TiO 2 nanotubes modified array material of the silane coupling agent that specifically embodiment 4 can be adopted to prepare, comprises the following steps:
Through the TiO that silane coupling agent is modified2Nano-tube array material light catalysis reduces with Pb2+For the heavy metal ion of example, under ultraviolet lamp, irradiate 240min, leave standstill after 15min at 0min(respectively), 30min, 60min, 120min, 180min and 240min time sampling, utilize in Atomic Absorption Spectroscopy AAS detection system and remain concentration of heavy metal ion. Under UV-light, make catalyzer with the Nano tube array of titanium dioxide material modified through KH-570, to Pb2+Carry out light-catalyzed reaction, under the condition of pH=3,5,6, Pb2+Four hours clearances be respectively 87.9%, 81.9%, 80.5%.Under UV-light, make catalyzer with ordinary titanium dioxide, to Pb2+Carry out light-catalyzed reaction, under the condition of pH=3,5,6, Pb2+Four hours clearances be respectively 72.5%, 71.4%, 69.4%.
Embodiment 8
The TiO 2 nanotubes modified array material of the silane coupling agent of a kind of the present invention contains Cu in process2+、Pb2+、Cr6+Application in combined pollution waste water, the TiO 2 nanotubes modified array material of the silane coupling agent that specifically embodiment 4 can be adopted to prepare, comprises the following steps:
Get 50ml beaker adds Nano tube array of titanium dioxide catalyzer (2 × 2cm, 0.18g) and KH-570 modifies Nano tube array of titanium dioxide catalyzer (2 × 2cm, 0.18g) respectively, add respectively containing Cu2+、Pb2+、Cr6+Compound heavy metal ion solution (simulated wastewater) 20ml, wherein Cu2+、Pb2+、Cr6+Concentration be 10mg/L. Leaving standstill after 15 minutes in dark, (Japan MUA-165,365nm, keeps light intensity to be 88.8 μ W/cm to open UV irradiation equipment2); Uniform irradiation sample system reacts 4 hours, and per half an hour samples 0.5ml and is settled to 4ml, measure heavy metal ion concentration. The ionic concn of residual solution is measured, to investigate the accuracy of system at the end of experiment. Change system pH (getting pH=3,5,6) and repeat above experiment.
The result that above reduction experiment obtains is: when illumination condition, pH condition are identical, three heavy metal species ions have better removal efficiency in the catalysis of the Nano tube array of titanium dioxide modified through KH-570 is tested, and this rule embodies more obvious under ultraviolet light conditions. Although absorption spectrum is not almost expanded effect by KH-570, but in reducing heavy metal is tested, pure TiO2-NT is in the sunlight to Cu(II) reduction efficiency is only 10%, and KH-570-TiO2-NT is in the sunlight to Cu(II) reduction efficiency rises to 30%, to Cr(VI) reduction efficiency double, to Pb(II) reduction efficiency also improve.
Embodiment 9
The TiO 2 nanotubes modified array material of the silane coupling agent of the present invention is in process containing the application in BDE47 waste water, and the TiO 2 nanotubes modified array material of the silane coupling agent that specifically embodiment 4 can be adopted to prepare, comprises the following steps:
Get that 50ml beaker adds the 10mg/L being dissolved in methylene dichloride respectively 2,2,4,4-TETRABDE(is hereinafter referred to as BDE47) storing solution 20ml, and add Nano tube array of titanium dioxide catalyzer (2 × 2cm, 0.18g) that KH-570 modifies and P25 titania nanoparticles as a reference. Leaving standstill after 15 minutes in dark, (light intensity is 88.8 μ W/cm to open UV irradiation equipment2) uniform irradiation sample system reacts four hours, per half an hour adopts SIM pattern to measure residue BDE47 concentration with gas chromatograph-mass spectrometer.
Experimental result shows that the catalyzer do not modified compared by the catalyzer after modifying, and rises to rise in 92%, 4h from 72% in 60%, 2h from 50% in the degradation efficiency 1h of BDE47 and rises to 99% from 92%.
The above is only the better embodiment of the present invention, and the present invention not does any restriction in form. Although the present invention discloses as above with better embodiment, but and it is not used to limit the present invention. Any those of ordinary skill in the art, when not departing from spirit and the technical scheme of the present invention, all can utilize the Method and Technology content of above-mentioned announcement that technical solution of the present invention is made many possible variations and modification, or be revised as the equivalent embodiment of equivalent variations.Therefore, every content not departing from technical solution of the present invention, to any simple modification made for any of the above embodiments, equivalent replacement, equivalence change and modifies according to the technical spirit of the present invention, all still belongs in the scope of technical solution of the present invention protection.

Claims (9)

1. the TiO 2 nanotubes modified array material of silane coupling agent, it is characterized in that, the TiO 2 nanotubes modified array material of described silane coupling agent is obtained by reacting after mixing primarily of Nano tube array of titanium dioxide, silane coupling agent, organic solvent and Glacial acetic acid.
2. the preparation method of the TiO 2 nanotubes modified array material of silane coupling agent, it is characterized in that, comprise the following steps: by Nano tube array of titanium dioxide, silane coupling agent, organic solvent and Glacial acetic acid mixing, after reaction, obtain the TiO 2 nanotubes modified array material of silane coupling agent.
3. the preparation method of the TiO 2 nanotubes modified array material of silane coupling agent according to claim 2, it is characterised in that, the quality of described silane coupling agent accounts for the 0.1%～20% of described silane coupling agent and organic solvent quality sum.
4. the preparation method of the TiO 2 nanotubes modified array material of silane coupling agent according to Claims 2 or 3, it is characterised in that, described organic solvent is toluene.
5. the preparation method of the TiO 2 nanotubes modified array material of silane coupling agent according to Claims 2 or 3, it is characterised in that, the temperature of described reaction is 50 DEG C～80 DEG C, and the time of described reaction is 0.5h～8h.
6. the preparation method of the TiO 2 nanotubes modified array material of silane coupling agent according to Claims 2 or 3, it is characterised in that, described silane coupling agent is Silane coupling reagent KH-570.
7. the application of the TiO 2 nanotubes modified array material of silane coupling agent that preparation method according to any one of the TiO 2 nanotubes modified array material of silane coupling agent as claimed in claim 1 or claim 2～6 obtains in the waste water of process containing organic pollutant and/or heavy metal contaminants.
8. application according to claim 7, it is characterized in that, described application comprises the following steps: is added by TiO 2 nanotubes modified for silane coupling agent array material in the waste water containing organic pollutant and/or heavy metal contaminants and carries out light-catalyzed reaction, completes the process to waste water.
9. application according to claim 8, it is characterised in that, the pH value in described light-catalyzed reaction process is 3～6.
CN201610062344.4A 2016-01-29 2016-01-29 Silane coupling agent modified titanium dioxide nanotube array material as well as preparation method and application thereof Pending CN105664834A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610062344.4A CN105664834A (en) 2016-01-29 2016-01-29 Silane coupling agent modified titanium dioxide nanotube array material as well as preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610062344.4A CN105664834A (en) 2016-01-29 2016-01-29 Silane coupling agent modified titanium dioxide nanotube array material as well as preparation method and application thereof

Publications (1)

Publication Number Publication Date
CN105664834A true CN105664834A (en) 2016-06-15

Family

ID=56303158

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610062344.4A Pending CN105664834A (en) 2016-01-29 2016-01-29 Silane coupling agent modified titanium dioxide nanotube array material as well as preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN105664834A (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107383420A (en) * 2017-07-14 2017-11-24 中钛化工集团有限公司 The special titanium dioxide process of rubber
CN107961803A (en) * 2017-12-12 2018-04-27 成都育芽科技有限公司 A kind of organo-mineral complexing photochemical catalyst for environmental pollution purification
CN112973437A (en) * 2021-02-20 2021-06-18 武汉绿知行环保科技有限公司 Formaldehyde removal master batch for air purification device and preparation method thereof
CN114570424A (en) * 2022-03-30 2022-06-03 东北石油大学 Double-modified carbon nitride and preparation method and application thereof
CN115920871A (en) * 2022-10-28 2023-04-07 浙江工业大学 Adsorption and photocatalytic degradation functional material, and preparation method and application thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002083297A1 (en) * 2001-04-16 2002-10-24 Ims Llc Adsorbent materials for treating biodegradable waste and process for their preparation
CN101016642A (en) * 2006-12-31 2007-08-15 厦门大学 Construction method of titanium surface micrometre-grade pattern based on ultra-hydrophilic/ultra-hydrophobic characteristic
CN102031022A (en) * 2010-10-27 2011-04-27 华南理工大学 Method for modifying nano titanium dioxide sol by utilizing silane coupling agent

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002083297A1 (en) * 2001-04-16 2002-10-24 Ims Llc Adsorbent materials for treating biodegradable waste and process for their preparation
CN101016642A (en) * 2006-12-31 2007-08-15 厦门大学 Construction method of titanium surface micrometre-grade pattern based on ultra-hydrophilic/ultra-hydrophobic characteristic
CN102031022A (en) * 2010-10-27 2011-04-27 华南理工大学 Method for modifying nano titanium dioxide sol by utilizing silane coupling agent

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
周亚民等: "硅烷偶联剂改性超细TiO2的研究", 《东莞理工学院学报》 *
黄运瑞等: "二氧化钛纳米管阵列的应用研究进展", 《材料导报Ａ：综述篇》 *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107383420A (en) * 2017-07-14 2017-11-24 中钛化工集团有限公司 The special titanium dioxide process of rubber
CN107961803A (en) * 2017-12-12 2018-04-27 成都育芽科技有限公司 A kind of organo-mineral complexing photochemical catalyst for environmental pollution purification
CN107961803B (en) * 2017-12-12 2020-10-09 北京众智创新科技开发有限公司 Organic-inorganic composite photocatalyst for purifying environmental pollution
CN112973437A (en) * 2021-02-20 2021-06-18 武汉绿知行环保科技有限公司 Formaldehyde removal master batch for air purification device and preparation method thereof
CN112973437B (en) * 2021-02-20 2022-08-26 武汉绿知行环保科技有限公司 Formaldehyde removal master batch for air purification device and preparation method thereof
CN114570424A (en) * 2022-03-30 2022-06-03 东北石油大学 Double-modified carbon nitride and preparation method and application thereof
CN114570424B (en) * 2022-03-30 2024-02-09 东北石油大学 Double-modified carbon nitride and preparation method and application thereof
CN115920871A (en) * 2022-10-28 2023-04-07 浙江工业大学 Adsorption and photocatalytic degradation functional material, and preparation method and application thereof

Similar Documents

Publication Publication Date Title
CN105664834A (en) Silane coupling agent modified titanium dioxide nanotube array material as well as preparation method and application thereof
CN103285891B (en) Preparation method of bismuth oxide halide-titanium oxide nanotube array composite photo-catalytic membrane
CN108585106B (en) Method for removing nonyl phenol through selective photocatalytic oxidation based on hydrophobic effect
CN103464122B (en) A kind of preparation method of graphene/chitosan adsorbent resin
CN110152702A (en) Derivative nitrogen carbon nanomaterial of a kind of organic backbone and its preparation method and application
CN108532290A (en) A kind of preparation method and applications of photocatalytic functional fabric
CN101698155A (en) Method for preparing floating type composite photocatalyst
CN102071449A (en) Environmental-function nano material Cu-Fe/TiO2 nanotube array, and preparation and application thereof
CN104437551B (en) Preparation method and use method of CuS modified immobilized TiO2 nanoribbon photocatalyst
CN102276023A (en) Method for treating organic dyestuff in wastewater
Shaban Effective photocatalytic reduction of Cr (VI) by carbon modified (CM)-n-TiO2 nanoparticles under solar irradiation
CN109078647A (en) A kind of Mn3O4/g-C3N4Photo-thermal concerted catalysis composite material and preparation method and application
CN109675547A (en) A kind of preparation method and applications of hollow cube type zinc stannate photochemical catalyst
CN110756163A (en) Nano CoFe2O4Carbon fiber felt composite material and preparation method and application thereof
CN105668711A (en) Sponge electrode for pollutant degradation as well as preparation and application thereof
CN104549400A (en) Visible light response type TiO2 nanotube array, as well as preparation method and applications thereof
CN102553649B (en) 17beta-estradiol molecular imprinted silver-doped TiO2 nanotube and preparation method thereof
CN110182888A (en) A kind of photocatalytic reaction device and technique handling rose red b high-salt wastewater
CN107955523B (en) A kind of environmental-protecting self visible light catalytic coating and its preparation and application
CN102941129B (en) Supported photocatalyst as well as preparation method and application thereof
CN107803185A (en) A kind of magnetic oil absorption material based on biomass template and preparation method thereof
Ge et al. Hierarchical carbon fiber cloth (CFC)/Co3O4 composite with efficient photo-electrocatalytic performance towards water purification
CN103922608A (en) Preparation method and application of titanium dioxide heterojunction photoanode
CN102826631B (en) Hydrodynamic impeller disk reactor for efficiently evaluating efficiency of photoelectric catalytic reaction
CN109939697A (en) A kind of CdS/TOC photochemical catalyst, Pd/CdS/TOC photochemical catalyst and its preparation method and application

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication

Application publication date: 20160615

RJ01 Rejection of invention patent application after publication