Method for preparing titanium dioxide nanosphere by titanocene dichloride cracking

The technical field of

[0001] the invention belongs to nanometer material technique field especially claims a method of using second dichloro titanocene cracking to prepare titanium dioxide nanometer sphere method for.

Background technology

[0002] early 1955 life of the literature report it the two dichloro titanocene synthesis of; 1979 grade hartmunt ko printing f *** keopf maier and it has certain anti-cancer properties. As a new type organic metal anticancer medicine second dichloro titanocene the anticancer activity is high the drug effect is high toxicity is less than the molybdenum along the solid tumor it has strong inhibiting effect. Other two dichloro titanocene is a high efficiency the hydrogenation catalyst can be widely used in alkene polymerization and hydrogenation reaction in. Such as the high temperature and the upper and lower two dichloro titanocene the light bow character stroke the invention claims diphenyl ethylene polymerization to obtain crystal degree is 95 percent of a second benzene acetylene.

[0003] titanium dioxide normal of anatase and rutile phase. In the rutile phase the band gap 3 oev when it is anatase phase band gap when 3 2ev. The nanometre rutile phase titanium dioxide because it has very high the stability of the particle on the surface of the superfine high activity in many fields such as high quality of fine ceramics coating material sunscreen cosmetic composition has extensive use. The nanometer anatase it has high photo-catalytic activity normally used in organic substance in sewage decomposition of mineralized water for catalytic decomposition of photovoltaic battery field.

[0004] zeng the front of the subject is set report for chemical gas phase deposition preparation method of tic material by the started the invention uses hydro-thermal method to prepare the amorphous state of the nanometer titanium dioxide material. Through the different temperature roasting amorphous state according to needs to be converted into the anatase and rutile phase. Photocatalysis degrading rhodamine b is methyl blue solution experiment shows that preparing the anatase titanium dioxide with high light catalytic capability.

The content of invention

[0005] the purpose of this invention is to overcome above of the existing technology defect the invention claims a low cost simple technology condition is mild and it is easy to realize the use of the second dichloro titanocene cracking to prepare titanium dioxide nanometer sphere method for.

[0006] the purpose of this invention can be obtained through following technical proposal to realize:

[0007] using a second dichloro titanocene cracking to prepare titanium dioxide nanometer sphere method wherein the method comprises the following steps:

[0008] accurate weighing second dichloro titanocene is dissolved in deionized water to control concentration is 2 mg per ml under the condition of stirring to drop add the ethylene diamine control the ph value of the solution is the 9 the solution by ultrasonic wave oscillation 10-15 min;

[0009] using the solution turns into polyfluortetraethylene hydro-thermal reaction kettle inner container of stainless steel sleeve sealed and set in oven to control the temperature is the temperature for 24 hours l c 120-160°;

[0010] said hot water after the reaction naturally cooling to room temperature then using deionized water dehydrated alcohol respectively centrifugal washing sample 3 times and the sample obtained by drying case drying;

[0011] the drying of the sample is put in ceramic boat to control temperature rising rate is 5-10° c r/min in tubular furnace to increase the temperature to 400-500° c heat preservation reacting for 2 hours so as to obtain the product.

Between 0012 on the centrifugal washing in centrifugal machine of the rotating speed is 1500_3000 rpm.

0013 ] and [ compared with existing technology this invention has following advantages:

[0014] because the reaction of the invention does not need to use organic solvent relates to a solvent only one side of water can be greatly reduced the manufacturing cost of the other side opposite to the environment will not cause pollution it meets international environment requirement trend;

[0015] the invention relates to the water heating has simple technics condition is mild and it is easy to realize and it is convenient to industrialization production;

[0016] this invention the prepared product has good photocatalysis degrading organic substance in water the performance of the to be relaxed in the field of environmental protection and has important applied;

[0017] by this method can be prepared the invention claims a with flower shape structure with nanometer structure of ultra structure controlling the different temperature and time to obtain the shape of various structure.

Specification attached drawing

[0018] image i is an embodiment of the water in heated i the get sample of sem diagram;

[0019] 2 is an embodiment of the water in heat and the get sample of sem image;

[0020] 3 is an embodiment 3 water in heat and the get sample of sem image;

[0021] 4 is an embodiment of i *** 3 water in heated and the sample obtained by using xrd image;

[0022] 5 as an example in water after heating and the sample obtained by sem image;

[0023] 6 as an example 5 is water after heating and the sample obtained by sem image;

[0024] an embodiment of 6 7 is in the water after heating and the sample obtained by sem image;

[0025] picture 7 8 are taken as the embodiment of the water after heating and the sample obtained by sem image;

[0026] 9 is an embodiment 4***7 in the water after heating and the sample obtained by using xrd image;

[0027] 10 is an embodiment of the product i water heat 400° c after roasting the get sample of sem diagram;

[0028] 11 is an embodiment of i water heating product at 500 0 c after roasting the get sample of sem diagram;

[0029] 12 is an embodiment of i water heating product at 500 400° c v after roasting the product image using xrd;

[0030] an 13 is a embodiment i water heating product obtained after drying and roasting of the sample of the ultraviolet light irradiation of the methylene blue and ultraviolet absorption spectrum image.

Specific implementing manner

[0031] a lower surface of the attached drawing and the embodiment of this invention to detailed explain.

[0032] embodiment i

[0033] using a second dichloro titanocene cracking to prepare titanium dioxide nanometer sphere method comprises the following steps:

0034 [ ] accurate weighing second dichloro titanocene 20mg put into 20ml capacity of polytetrafluoroethylene inner container adding the deionized water into 10 ml of ethylene diamine 2 dripping control the ph value is the 9.

[0035] the putting the mixed solution of polytetrafluoroethylene inner container into ultrasonic apparatus ultrasonic lomin into the stainless steel kettle to seal.

[0036] are sealed by the stainless steel kettle is put in drying box to carry out hot water to react for half an hour the temperature to 120 degree c keeps temperature for 6 hours. Naturally cooling to room temperature water heat and the get sample of sem picture as picture i show xrd image such as drawing 4 the.

[0037] head burette with glue the reaction product of the suction centrifugal tube in order to 1500-2000 and rotating speed of centrifugally separating time is 5 minutes. The obtained precipitate with deionized water and absolute ethyl alcohol are respectively centrifugal washing by 3 times 80 degrees c dried in oven. To obtain the needed sample.

[0038] and the product tubular furnace in the air atmosphere to 5-10° c centigrade/min speed in tubular furnace to increase the temperature to 400-5000 c and then preserve heat for 2 hours. To obtain with good crystallization degree the titanium dioxide 400° c after roasting and the sample obtained by sem picture as picture displayed in the 10 500° c after roasting and the sample obtained by sem picture as picture 1 which is displayed on the 400° 500° c and c after roasting the product using xrd image is shown as fig 12 the.

[0039] 400° c ] of the temperature of the roasting of the sample of the ultraviolet light irradiation of the methylene blue and ultraviolet absorption spectrum image as image 13 the.

[0040] embodiment 2

[0041] using a second dichloro titanocene cracking to prepare titanium dioxide nanometer sphere method comprises the following steps:

[0042] accurate weighing second dichloro titanocene 20mg put into 20ml capacity of polytetrafluoroethylene inner container in. Adding de-ionized water 10 ml of triethylamine 2 dripping control the ph value is the 9.

[0043] the putting the mixed solution of polytetrafluoroethylene inner container into ultrasonic apparatus ultrasonic lomin into the stainless steel kettle to seal.

[0044] are sealed by the stainless steel kettle is put in drying box to carry out hot water to react for half an hour the heating up to 140 degrees c keeps temperature for 6 hours. Naturally cooling to room temperature water heat and the get sample of sem picture as picture 2 1 the displaying image using xrd shows as drawing 4 the.

[0045] head burette with glue the reaction product of the suction centrifugal tube in order to 1500-2000 and rotating speed of centrifugally separating time is 5 minutes. The obtained precipitate with deionized water and absolute ethyl alcohol are respectively centrifugal washing by 3 times 80 degrees c dried in oven. To obtain the needed sample.

[0046] embodiment 3

[0047] using a second dichloro titanocene cracking to prepare titanium dioxide nanometer sphere method comprises the following steps:

[0048] accurate weighing second dichloro titanocene 20mg put into 20ml capacity of polytetrafluoroethylene inner container in. Adding de-ionized water 10 ml of ethanolamine 2 dripping control the ph value is the 9.

[0049] the putting the mixed solution of polytetrafluoroethylene inner container into ultrasonic apparatus ultrasonic lomin into the stainless steel kettle to seal.

[0050] are sealed by the stainless steel kettle is put in drying box to carry out hot water to react for half an hour the temperature to 160° c keeps temperature for 6 hours. Naturally cooling to room temperature water heat and the get sample of sem picture as picture the image displaying using xrd shows as drawing 4 the.

[0051] head burette with glue the reaction product of the suction centrifugal tube in order to 1500-2000 and rotating speed of centrifugally separating time is 5 minutes. The obtained precipitate with deionized water and absolute ethyl alcohol are respectively centrifugal washing by 3 times 80 degrees c dried in oven. To obtain the needed sample.

[0052] embodiment 4

[0053] using a second dichloro titanocene cracking to prepare titanium dioxide nanometer sphere method comprises the following steps:

[0054] accurate weighing second dichloro titanocene 20mg put into 20ml capacity of polytetrafluoroethylene inner container in. Adding de-ionized water 10 ml of ethylene diamine 2 dripping control the ph value is the 9.

[0055] the putting the mixed solution of polytetrafluoroethylene inner container into ultrasonic apparatus ultrasonic lomin into the stainless steel kettle to seal.

[0056] are sealed by the stainless steel kettle is put in drying box to carry out hot water to react for half an hour the temperature to 120 degree c keeping warm for 3 hours. Naturally cooling to room temperature water heat and the get sample of sem picture as picture 5 the xrd image picture displayed 9.

[0057] head burette with glue the reaction product of the suction centrifugal tube in order to 1500-2000 and rotating speed of centrifugally separating time is 5 minutes. The obtained precipitate with deionized water and absolute ethyl alcohol are respectively centrifugal washing by 3 times 80 degrees c dried in oven. To obtain the needed sample.

[0058] 5 embodiment

[0059] using a second dichloro titanocene cracking to prepare titanium dioxide nanometer sphere method comprises the following steps:

[0060] accurate weighing second dichloro titanocene 20mg put into 20ml capacity of polytetrafluoroethylene inner container in. Adding de-ionized water 10 ml of ethylene diamine 2 dripping control the ph value is the 9.

[0061] the putting the mixed solution of polytetrafluoroethylene inner container into ultrasonic apparatus ultrasonic lomin into the stainless steel kettle to seal.

[0062] are sealed by the stainless steel kettle is put in drying box to carry out hot water to react for half an hour the temperature to 120 degree c keep warm 12 hours. Naturally cooling to room temperature water heat and the get sample of sem picture as picture 6 the xrd image picture displayed 9.

[0063] head burette with glue the reaction product of the suction centrifugal tube in order to 1500-2000 and rotating speed of centrifugally separating time is 5 minutes. The obtained precipitate with deionized water and absolute ethyl alcohol are respectively centrifugal washing by 3 times 80 degrees c dried in oven. To obtain the needed sample.

[0064] embodiment 6

[0065] using a second dichloro titanocene cracking to prepare titanium dioxide nanometer sphere method comprises the following steps:

[0066] accurate weighing second dichloro titanocene 20mg put into 20ml capacity of polytetrafluoroethylene inner container in. Adding de-ionized water 10 ml of ethylene diamine 2 dripping control the ph value is the 9.

[0067] the putting the mixed solution of polytetrafluoroethylene inner container into ultrasonic apparatus ultrasonic lomin into the stainless steel kettle to seal.

[0068] are sealed by the stainless steel kettle is put in drying box to carry out hot water to react for half an hour the temperature to 120 degree and temperature for 24 hours c. Naturally cooling to room temperature water heat and the get sample of sem picture as picture 7 the xrd image picture displayed 9.

[0069] head burette with glue the reaction product of the suction centrifugal tube in order to 1500-2000 and rotating speed of centrifugally separating time is 5 minutes. The obtained precipitate with deionized water and absolute ethyl alcohol are respectively centrifugal washing by 3 times 80 degrees c dried in oven. To obtain the needed sample.

[0070] embodiment 7

[0071] using a second dichloro titanocene cracking to prepare titanium dioxide nanometer sphere method comprises the following steps:

[0072] accurate weighing second dichloro titanocene 20mg put into 20ml capacity of polytetrafluoroethylene inner container in. Adding de-ionized water 10 ml of ethylene diamine 2 dripping control the ph value is the 9.

[0073] the putting the mixed solution of polytetrafluoroethylene inner container into ultrasonic apparatus ultrasonic lomin into the stainless steel kettle to seal.

[0074] are sealed by the stainless steel kettle is put in drying box to carry out hot water to react for half an hour the temperature to 120 degree c keep warm for 48 hours. Naturally cooling to room temperature water heat and the get sample of sem picture as picture 8 the xrd image picture displayed 9.

[0075] head burette with glue the reaction product of the suction centrifugal tube in order to 1500-2000 and rotating speed of centrifugally separating time is 5 minutes. The obtained precipitate with deionized water and absolute ethyl alcohol are respectively centrifugal washing by 3 times 80 degrees c dried in oven. To obtain the needed sample.

[0076] embodiment 8

[0077] using second dichloro titanocene cracking to prepare titanium dioxide nanometer sphere method comprises the following steps:

[0078] accurate weighing second dichloro titanocene is dissolved in deionized water to control concentration is 2 mg per ml under the condition of stirring to drop add the ethylene diamine control the ph value of the solution is the 9 the solution by ultrasonic wave oscillation iomin;

[0079] using the solution turns into polyfluortetraethylene hydro-thermal reaction kettle inner container of stainless steel sleeve sealed and set in oven to control the temperature is 120 degrees the temperature for 24 hours c;

[0080] said hot water after the reaction naturally cooling to room temperature then using deionized water dehydrated alcohol respectively centrifugal washing sample 3 times of centrifuge is rotating speed of 1500 rpm and the sample obtained by drying case drying;

[0081] the drying of the sample is put in ceramic boat to control temperature rising rate is from 5 degree c r/min in tubular furnace to increase the temperature to 400° c heat preservation reacting for 2 hours so as to obtain the product.

[0082] the centrifugal washing in.

Embodiments 0083 ] [ 9

[0084] using a second dichloro titanocene cracking to prepare titanium dioxide nanometer sphere method comprises the following steps:

[0085] accurate weighing second dichloro titanocene is dissolved in deionized water to control concentration is 2 mg per ml under the condition of stirring to drop add the ethylene diamine control the ph value of the solution is the 9 the solution by ultrasonic wave oscillation 15min at medium baking temperature;

[0086] using the solution turns into polyfluortetraethylene hydro-thermal reaction kettle inner container of stainless steel sleeve sealed and set in oven to control the temperature is 160° c heat preservation ih;

[0087] said hot water after the reaction naturally cooling to room temperature then using deionized water dehydrated alcohol respectively centrifugal washing sample 3 times of centrifuge is rotating speed is 3000 rpm- and the sample obtained by drying case drying;

[0088] the drying of the sample is put in ceramic boat to control temperature rising rate of 10 centigrade/min c in tubular furnace to increase the temperature to 500° c heat preservation reacting for 2 hours so as to obtain the product.