CN104525178A - Preparation process of sulfur and rare-earth element doped nano titanium dioxide three-element photocatalyst - Google Patents
Preparation process of sulfur and rare-earth element doped nano titanium dioxide three-element photocatalyst Download PDFInfo
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Abstract
The invention relates to a preparation process of a sulfur and rare-earth element doped nano titanium dioxide three-element photocatalyst, which comprises the following steps: respectively preparing a rare-earth salt water solution, a titanium tetrachloride anhydrous ethanol solution and a thiocarbamide solution; dropwisely adding the rare-earth salt solution into a mixed solution, uniformly stirring, then simultaneously dropwisely adding the titanium tetrachloride anhydrous ethanol solution and the thiocarbamide solution, and uniformly stirring; adding activated carbon, and further uniformly stirring; and finally, aging at room temperature, drying to obtain a solid, grinding, and calcining to obtain the sulfur and rare-earth element doped nano titanium dioxide three-element photocatalyst. The sulfur and rare-earth element doped nano titanium dioxide three-element photocatalyst prepared by the invention has efficient photocatalytic degradation effect on pollutants, especially organic pollutants.
Description
Technical field
The present invention relates to a kind of preparation technology of catalyst, be specifically related to the preparation technology of a kind of sulphur and rare earth doped nano titanium oxide ternary photochemical catalyst.
Background technology
Photocatalyst is a kind of emerging pollutant treatment technology, has wide market prospects.And nano titanium oxide is a kind of excellent, photochemical catalyst that application potential is best, it has the features such as nontoxic, active high, cheap, the resistance to strong acid of ultraviolet resistance burn into, resistance to highly basic and powerful oxidation corrosion resistance agent.But it is very low to the utilization rate of sunshine, ultraviolet light can only be absorbed.In research in the past, although doping carbon is improved the effect of catalyst photoresponse scope, it can not improve catalytic efficiency.
Summary of the invention
The object of the present invention is to provide the preparation technology of a kind of nano titanium oxide, sulphur and rear-earth-doped ternary photochemical catalyst, the ternary photochemical catalyst that this technique obtains can not only improve the effect of catalyst photoresponse scope, also and can also improve the photocatalysis performance of nano titanium oxide.
In order to achieve the above object, the technical solution used in the present invention comprises the following steps:
1) rare-earth salts is dissolved in distilled water, is mixed with rare earth salt aqueous solution; Titanium tetrachloride is added drop-wise in absolute ethyl alcohol, is mixed with titanium tetrachloride ethanol solution; Thiocarbamide is added in ethanol, be mixed with thiourea solution; Wherein, every 20-50 ml distilled water adds the rare-earth salts of 0.2-5 gram; 5-10g titanium tetrachloride is dripped in every 30-60 milliliter absolute ethyl alcohol; The thiourea solution of 1-50 gram is added in the distilled water of every 5-300 milliliter; Rare-earth salts is the inorganic salts of nonmetalloid, Main Group Metal Elements, lanthanide series, actinides or transition metal;
2) rare earths salt is added drop-wise to be made up of in mixed solution absolute ethyl alcohol, acetic acid and distilled water and stirs, then drip titanium tetrachloride ethanol solution and thiourea solution simultaneously, stir after being added dropwise to complete, add active carbon more wherein to continue to stir, last room temperature ageing is also dried, the solid obtained in 300-600 DEG C of calcining 1-5 hour, obtains sulphur and rare earth doped nano titanium oxide ternary photochemical catalyst after grinding; Wherein, in mixed solution, the volume ratio of absolute ethyl alcohol, acetic acid and distilled water is (30-60): (5-30): (5-20); And the volume ratio of absolute ethyl alcohol is (2-15) in rare earths salt and mixed solution: (30-60); The volume ratio of rare earths salt, titanium tetrachloride ethanol solution and thiourea solution is (2-15): (30-60): (5-30); The mass ratio of the titanium tetrachloride in active carbon and titanium tetrachloride ethanol solution is (2-8): (5-10).
Step 1) middle rare earth salt adopts and obtains with the following method: concentrated acid joined in rare earth oxide, then under 40-70 DEG C of condition, is stirred to dissolving, make rare-earth salts acid solution, rare-earth salts acid solution is dried at 40-60 DEG C, namely obtains rare-earth salts.
Described concentrated acid is one or more in dense hydracid, red fuming nitric acid (RFNA), the concentrated sulfuric acid, SPA.
Described dense hydracid is one or more in concentrated hydrochloric acid, concentrated hydrobromic acid, dense hydroiodic acid, dense hydrofluoric acid.
Step 1) in the compound method of titanium tetrachloride ethanol solution be:
Titanium tetrachloride is poured in constant pressure funnel, then under agitation with 7-12 second/rate of addition that drips drips titanium tetrachloride, obtained titanium tetrachloride ethanol solution in absolute ethyl alcohol; Wherein, in dropping process, the temperature of absolute ethyl alcohol is controlled in room temperature to 30 DEG C.
Described nonmetalloid is boron, silicon, phosphorus, arsenic or selenium; Main Group Metal Elements comprises magnesium, aluminium, gallium, germanium, arsenic, selenium, indium, tin, antimony, tellurium, thallium, lead, bismuth or polonium; Transition metal comprises scandium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, yttrium, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, silver, cadmium, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum or gold.
Described lanthanide series comprises lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium or lutetium; Actinides comprises actinium, thorium, protactinium, uranium, neptunium, plutonium, americium, curium, berkelium, californium, einsteinium, fermium, mendelevium, nobelium or lawrencium.
Described step 2) in bake out temperature be 40-60 DEG C.
Compared with prior art, beneficial effect of the present invention is:
Be doped with sulphur and rare earth element in three-way catalyst prepared by the present invention, the present invention adulterates after sulphur and rare earth element simultaneously, proves through test, can improve catalyst to the response range of light and the photocatalysis efficiency improving it simultaneously.
Accompanying drawing explanation
Fig. 1 is nano titanium oxide, sulphur and rare earth doped three-way catalyst degraded comparison diagram prepared by commercially available titanium dioxide and embodiment 16; Wherein, a is embodiment 16, b is commercially available nano titanium oxide;
Detailed description of the invention
The preparation technology of sulphur of the present invention and rare earth doped nano titanium oxide ternary photochemical catalyst comprises the following steps:
1) take rare earth oxide 1-8 gram with electronics Libra and be placed in beaker, take concentrated acid 2-10 gram again and slowly pour the beaker filling rare earth oxide into, constantly dissolving is stirred under 40-70 DEG C of condition, make rare-earth salts acid solution, rare-earth salts acid solution is dried in drying box in 40-60 DEG C, obtains rare-earth salts solid; Wherein, concentrated acid to be mass concentration be 37.5% concentrated hydrochloric acid, the mass concentration hydrobromic acid that is 40%, the mass concentration hydroiodic acid that is 57%, mass concentration be 40% hydrofluoric acid, the mass concentration red fuming nitric acid (RFNA) that is 65%, the mass concentration concentrated sulfuric acid that is 98%, mass concentration be one or more in the SPA of 85%; Rare-earth salts is the inorganic salts of nonmetalloid, Main Group Metal Elements, lanthanide series, actinides or transition metal; And nonmetalloid is boron, silicon, phosphorus, arsenic or selenium; Main Group Metal Elements comprises magnesium, aluminium, gallium, germanium, indium, tin, antimony, tellurium, thallium, lead, bismuth or polonium; Transition metal comprises scandium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, yttrium, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, silver, cadmium, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum or gold; Lanthanide series comprises lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium or lutetium; Actinides comprises actinium, thorium, protactinium, uranium, neptunium, plutonium, americium, curium, berkelium, californium, einsteinium, fermium, mendelevium, nobelium or lawrencium.
2) take 0.2-5 gram of rare-earth salts solid to add in the distilled water of 20-50 milliliter and make rare earth salt aqueous solution; Get 5-10 gram of titanium tetrachloride carefully to pour in constant pressure funnel, then under agitation with 7-12 second/drip rate of addition be added drop-wise in the conical flask filling 30-60 milliliter absolute ethyl alcohol, in dropping process, control temperature is at 20-30 DEG C, makes transparent titanium tetrachloride ethanol solution; Taking thiocarbamide 1-50 gram adds in 5-300 ml distilled water, and stirring and dissolving, obtains thiourea solution;
3) measure 2-15 milliliter rare earth salt aqueous solution and be placed in constant pressure funnel, slowly being added drop-wise to while stirring fills in the there-necked flask of mixed solution, dropwising rear continuation stirring makes evenly for 30 minutes, then respectively all titanium tetrachloride ethanol solutions prepared and thiourea solution are placed in constant pressure funnel, and be slowly added drop-wise in there-necked flask, drip rear stirring 0.5-3 hour, add 2-8 gram of active carbon more wherein to continue to stir 0.5-3 hour, ambient temperatare to be put after ageing in drying box in 40-60 DEG C of oven dry, in Muffle furnace, 1-5 hour is calcined in 300-600 DEG C after grinding, obtain sulphur and rare earth doped nano titanium oxide ternary photochemical catalyst, wherein, mixed solution is made up of 30-60 milliliter absolute ethyl alcohol, 5-30 milliliter acetic acid and 5-20 ml distilled water.
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further details, but does not get rid of other elements do not provided.
Embodiment 1:
1) take lanthana 2.5 grams with electronics Libra and be placed in beaker, take again mass concentration be 65% red fuming nitric acid (RFNA) 3.5 grams slowly pour the beaker filling lanthana into, constantly dissolving is stirred under 50 DEG C of conditions, make lanthanum nitrate hexahydrate, then by lanthanum nitrate hexahydrate in drying box in 55 DEG C of oven dry, namely obtain lanthanum nitrate solid;
2) take 0.5 gram of lanthanum nitrate solid to add in 25 ml distilled waters and make lanthanum nitrate aqueous solution; Take 7.5 grams of titanium tetrachlorides carefully to pour in constant pressure funnel, then be added drop-wise in the conical flask filling 30 milliliters of absolute ethyl alcohols with the rate of addition of 7 seconds/under agitation, in dropping process, control temperature is at 20 DEG C, makes transparent titanium tetrachloride ethanol solution; Taking thiocarbamide 1.5 grams adds in 6 ml distilled waters, and stirring and dissolving, obtains thiourea solution;
3) measure 2 milliliters of lanthanum nitrate aqueous solutions and be placed in constant pressure funnel, slowly being added drop-wise to while stirring fills in the there-necked flask of mixed solution, dropwising rear continuation stirring makes evenly for 30 minutes, then respectively all titanium tetrachloride ethanol solutions prepared and thiourea solution be placed in constant pressure funnel and be slowly added drop-wise to there-necked flask, drip stirring 0.5 hour, add 2 grams of active carbons more wherein and continue stirring 0.5 hour, ambient temperatare to be put after ageing in drying box in 55 DEG C of oven dry, calcine 1 hour in 300 DEG C in Muffle furnace after grinding, obtain sulphur and rare earth doped nano titanium oxide ternary photochemical catalyst, wherein, mixed solution is made up of 30 milliliters of absolute ethyl alcohols, 5 milliliters of acetic acid and 6 ml distilled waters.
Embodiment 2:
1) take yittrium oxide 4.5 grams with electronics Libra and be placed in beaker, take again mass concentration be 65% red fuming nitric acid (RFNA) 3.25 grams slowly pour the beaker filling yittrium oxide into, constantly dissolving is stirred under 50 DEG C of conditions, make yttrium nitrate solution, then by yttrium nitrate solution in drying box in 55 DEG C of oven dry, namely obtain yttrium nitrate solid;
2) take 0.35 gram of yttrium nitrate solid to add in 25 ml distilled waters and make yttrium nitrate aqueous solution; Take 8.5 grams of titanium tetrachlorides carefully to pour in constant pressure funnel, then be added drop-wise in the conical flask filling 30 milliliters of absolute ethyl alcohols with the rate of addition of 7 seconds/under agitation, in dropping process, control temperature is at 20 DEG C, makes transparent titanium tetrachloride ethanol solution; Taking thiocarbamide 1.35 grams adds in 6 ml distilled waters, and stirring and dissolving, obtains thiourea solution;
3) measure 2 milliliters of yttrium nitrate aqueous solutions and be placed in constant pressure funnel, slowly being added drop-wise to while stirring fills in the there-necked flask of mixed solution, dropwising rear continuation stirring makes evenly for 30 minutes, then respectively all titanium tetrachloride ethanol solutions prepared and thiourea solution be placed in constant pressure funnel and be slowly added drop-wise to there-necked flask, drip stirring 0.5 hour, add 2.5 grams of active carbons more wherein and continue stirring 0.5 hour, ambient temperatare to be put after ageing in drying box in 55 DEG C of oven dry, calcine 1 hour in 300 DEG C in Muffle furnace after grinding, obtain sulphur and rare earth doped nano titanium oxide ternary photochemical catalyst, wherein, mixed solution is made up of 30 milliliters of absolute ethyl alcohols, 5 milliliters of acetic acid and 6 ml distilled waters.
Embodiment 3:
1) take europium oxide 3.5 grams with electronics Libra and be placed in beaker, take again mass concentration be 65% red fuming nitric acid (RFNA) 2.75 grams slowly pour the beaker filling europium oxide into, constantly dissolving is stirred under 50 DEG C of conditions, make europium nitrate solution, then by europium nitrate solution in drying box in 40 DEG C of oven dry, namely obtain europium nitrate solid;
2) take 0.4 gram of europium nitrate solid to add in 30 ml distilled waters and make the europium nitrate aqueous solution; Take 9.5 grams of titanium tetrachlorides carefully to pour in constant pressure funnel, then be added drop-wise in the conical flask filling 30 milliliters of absolute ethyl alcohols with the rate of addition of 10 seconds/under agitation, in dropping process, control temperature is at 25 DEG C, makes transparent titanium tetrachloride ethanol solution; Taking thiocarbamide 5 grams adds in 20 ml distilled waters, and stirring and dissolving, obtains thiourea solution;
3) measure 3 milliliters of europium nitrate aqueous solution and be placed in constant pressure funnel, slowly being added drop-wise to while stirring fills in the there-necked flask of mixed solution, dropwising rear continuation stirring makes evenly for 30 minutes, then respectively all titanium tetrachloride ethanol solutions prepared and thiourea solution be placed in constant pressure funnel and be slowly added drop-wise to there-necked flask, drip stirring 1 hour, add 5 grams of active carbons more wherein and continue stirring 1.5 hours, ambient temperatare to be put after ageing in drying box in 40 DEG C of oven dry, calcine 2 hours in 400 DEG C in Muffle furnace after grinding, obtain sulphur and rare earth doped nano titanium oxide ternary photochemical catalyst, wherein, mixed solution is made up of 40 milliliters of absolute ethyl alcohols, 10 milliliters of acetic acid and 8 ml distilled waters.
Embodiment 4:
1) take niobium oxide 5.5 grams with electronics Libra and be placed in beaker, take again mass concentration be 65% red fuming nitric acid (RFNA) 4.5 grams slowly pour the beaker filling niobium oxide into, constantly dissolving is stirred under 50 DEG C of conditions, make nitric acid niobium solution, then by nitric acid niobium solution in drying box in 55 DEG C of oven dry, namely obtain nitric acid niobium solid;
2) take 3.5 grams of nitric acid niobium solids to add in 40 ml distilled waters and make the nitric acid niobium aqueous solution; Take 7.5 grams of titanium tetrachlorides carefully to pour in constant pressure funnel, then be added drop-wise in the conical flask filling 45 milliliters of absolute ethyl alcohols with the rate of addition of 9 seconds/under agitation, in dropping process, control temperature is at 25 DEG C, drop rate, makes transparent titanium tetrachloride ethanol solution; Taking thiocarbamide 4.5 grams adds in 20 ml distilled waters, and stirring and dissolving is placed on stirring and dissolving in constant pressure funnel, obtains thiourea solution;
3) measure 8 milliliters of nitric acid niobium aqueous solution and be placed in constant pressure funnel, slowly being added drop-wise to while stirring fills in the there-necked flask of mixed solution, dropwising rear continuation stirring makes evenly for 30 minutes, then respectively all titanium tetrachloride ethanol solutions prepared and thiourea solution be placed in constant pressure funnel and be slowly added drop-wise to there-necked flask, drip stirring 2 hours, add 4 grams of active carbons more wherein and continue stirring 1 hour, ambient temperatare to be put after ageing in drying box in 55 DEG C of oven dry, calcine 3 hours in 500 DEG C in Muffle furnace after grinding, obtain sulphur and rare earth doped nano titanium oxide ternary photochemical catalyst, wherein, mixed solution is made up of 30 milliliters of absolute ethyl alcohols, 10 milliliters of acetic acid and 15 ml distilled waters.
Embodiment 5:
1) take cerium oxide 1 gram with electronics Libra and be placed in beaker, take again mass concentration be 65% red fuming nitric acid (RFNA) 1.5 grams and mass concentration be 37.5% concentrated hydrochloric acid 0.5 gram slowly pour the beaker filling cerium oxide into, constantly dissolving is stirred under 40 DEG C of conditions, make cerium hydrochloric acid solution, then by cerium hydrochloric acid solution in drying box in 60 DEG C of oven dry, namely obtain cerium salt solid;
2) take 0.2 gram of cerium salt solid to add in 20 ml distilled waters and make cerium salt solution; Take 5 grams of titanium tetrachlorides carefully to pour in constant pressure funnel, then be added drop-wise in the conical flask filling 40 milliliters of absolute ethyl alcohols with the rate of addition of 12 seconds/under agitation, in dropping process, control temperature is at 25 DEG C, drop rate, makes transparent titanium tetrachloride ethanol solution; Taking thiocarbamide 1 gram adds in 5 ml distilled waters, and stirring and dissolving is placed on stirring and dissolving in constant pressure funnel, obtains thiourea solution;
3) measure 10 milliliters of cerium salt solutions and be placed in constant pressure funnel, slowly being added drop-wise to while stirring fills in the there-necked flask of mixed solution, dropwising rear continuation stirring makes all for 30 minutes, then respectively all titanium tetrachloride ethanol solutions prepared and thiourea solution be placed in constant pressure funnel and be slowly added drop-wise to there-necked flask, drip stirring 3 hours, add 3 grams of active carbons more wherein and continue stirring 2 hours, ambient temperatare to be put after ageing in drying box in 60 DEG C of oven dry, calcine 5 hours in 350 DEG C in Muffle furnace after grinding, obtain sulphur and rare earth doped nano titanium oxide ternary photochemical catalyst, wherein, mixed solution is made up of 60 milliliters of absolute ethyl alcohols, 15 milliliters of acetic acid and 5 ml distilled waters.
By step 1 in embodiment 5) in cerium oxide replace with oxide in table 1, red fuming nitric acid (RFNA) and concentrated hydrochloric acid replace with the concentrated acid in table 1, and other conditions are identical, obtain embodiment 6-10.
The rare earth oxide that table 1 embodiment 6-10 adopts and concentrated acid
Embodiment 11:
1) take silica 8 grams with electronics Libra and be placed in beaker, take again mass concentration be 40% 10 grams, hydrofluoric acid slowly pour the beaker filling silica into, constantly dissolving is stirred under 70 DEG C of conditions, make ocratation acid solution, then by ocratation acid solution in drying box in 40 DEG C of oven dry, namely obtain ocratation solid;
2) take 5 grams of silicon fluoride solids to add in 50 ml distilled waters and make the ocratation aqueous solution; Take 10 grams of titanium tetrachlorides carefully to pour in constant pressure funnel, then be added drop-wise in the conical flask filling 60 milliliters of absolute ethyl alcohols with the rate of addition of 10 seconds/under agitation, in dropping process, control temperature is at 25 DEG C, drop rate, makes transparent titanium tetrachloride ethanol solution; Taking thiocarbamide 5 grams adds in 30 ml distilled waters, and stirring and dissolving is placed on stirring and dissolving in constant pressure funnel, obtains thiourea solution;
3) measure 15 milliliters of ocratation aqueous solution and be placed in constant pressure funnel, slowly being added drop-wise to while stirring fills in the there-necked flask of mixed solution, dropwising rear continuation stirring makes all for 30 minutes, then respectively all titanium tetrachloride ethanol solutions prepared and carbon thiourea solution be placed in constant pressure funnel and be slowly added drop-wise to there-necked flask, drip stirring 3 hours, add 3 grams of active carbons more wherein and continue stirring 2 hours, ambient temperatare to be put after ageing in drying box in 60 DEG C of oven dry, calcine 5 hours in 350 DEG C in Muffle furnace after grinding, obtain sulphur and rare earth doped nano titanium oxide ternary photochemical catalyst, wherein, mixed solution is made up of 50 milliliters of absolute ethyl alcohols, 30 milliliters of acetic acid and 20 ml distilled waters.
Embodiment 12:
1) take 6 grams, magnesia with electronics Libra and be placed in beaker, take again mass concentration be 57% hydroiodic acid 10 grams slowly pour into and fill magnesian beaker, constantly dissolving is stirred under 50 DEG C of conditions, make magnesium iodide acid solution, then by magnesium iodide acid solution in drying box in 40 DEG C of oven dry, namely obtain magnesium iodide solid;
2) take 5 grams of magnesium iodide solids to add in 50 ml distilled waters and make the magnesium iodide aqueous solution; Take 10 grams of titanium tetrachlorides carefully to pour in constant pressure funnel, then be added drop-wise in the conical flask filling 60 milliliters of absolute ethyl alcohols with the rate of addition of 10 seconds/under agitation, in dropping process, control temperature is at 25 DEG C, drop rate, makes transparent titanium tetrachloride ethanol solution; Taking thiocarbamide 5 grams adds in 30 ml distilled waters, and stirring and dissolving is placed on stirring and dissolving in constant pressure funnel, obtains thiourea solution;
3) measure 15 milliliters of magnesium iodide aqueous solution and be placed in constant pressure funnel, slowly being added drop-wise to while stirring fills in the there-necked flask of mixed solution, dropwising rear continuation stirring makes all for 30 minutes, then respectively all titanium tetrachloride ethanol solutions prepared and thiourea solution be placed in constant pressure funnel and be slowly added drop-wise to there-necked flask, drip stirring 3 hours, add 3 grams of active carbons more wherein and continue stirring 2 hours, ambient temperatare to be put after ageing in drying box in 60 DEG C of oven dry, calcine 5 hours in 350 DEG C in Muffle furnace after grinding, obtain sulphur and rare earth doped nano titanium oxide ternary photochemical catalyst, wherein, mixed solution is by 50 milliliters of absolute ethyl alcohols, 30 milliliters of acetic acid with 20 ml distilled waters are even forms.
Embodiment 13:
1) take 6 grams, aluminium oxide with electronics Libra and be placed in beaker, take again mass concentration be 37% hydrochloric acid 5 grams and mass concentration be 98% lane phosphoric acid 7g slowly pour the beaker filling aluminium oxide into, constantly dissolving is stirred under 50 DEG C of conditions, make aluminium chlorhydrate solution, then by aluminium chlorhydrate solution in drying box in 40 DEG C of oven dry, namely obtain aluminium salt solid;
2) take 5 grams of aluminium salt solids to add in 50 ml distilled waters and make aluminum saline solution; Take 10 grams of titanium tetrachlorides carefully to pour in constant pressure funnel, then be added drop-wise in the conical flask filling 60 milliliters of absolute ethyl alcohols with the rate of addition of 10 seconds/under agitation, in dropping process, control temperature is at 25 DEG C, drop rate, makes transparent titanium tetrachloride ethanol solution; Taking thiocarbamide 5 grams adds in 30 ml distilled waters, and stirring and dissolving is placed on stirring and dissolving in constant pressure funnel, obtains thiourea solution;
3) measure 15 ml aluminium saline solutions and be placed in constant pressure funnel, slowly being added drop-wise to while stirring fills in the there-necked flask of mixed solution, dropwising rear continuation stirring makes all for 30 minutes, then respectively all titanium tetrachloride ethanol solutions prepared and thiourea solution be placed in constant pressure funnel and be slowly added drop-wise to there-necked flask, drip stirring 3 hours, add 3 grams of active carbons more wherein and continue stirring 2 hours, ambient temperatare to be put after ageing in drying box in 60 DEG C of oven dry, calcine 5 hours in 350 DEG C in Muffle furnace after grinding, obtain sulphur and rare earth doped nano titanium oxide ternary photochemical catalyst, wherein, mixed solution is by 50 milliliters of absolute ethyl alcohols, 30 milliliters of acetic acid with 20 ml distilled waters are even forms.
Embodiment 14:
1) take diphosphorus trioxide 2 grams with electronics Libra and be placed in beaker, take again mass concentration be 57% hydroiodic acid 5 grams and mass concentration be 40% hydrobromic acid 1g slowly pour into and fill magnesian beaker, constantly dissolving is stirred under 40 DEG C of conditions, make phosphorus trihalide acid solution, then by phosphorus trihalide acid solution in drying box in 40 DEG C of oven dry, namely obtain phosphorus trihalide solid;
2) take 1 gram of phosphorus trihalide solid to add in 20 ml distilled waters and make the phosphorus trihalide aqueous solution; Take 10 grams of titanium tetrachlorides carefully to pour in constant pressure funnel, then be added drop-wise in the conical flask filling 60 milliliters of absolute ethyl alcohols with the rate of addition of 10 seconds/under agitation, in dropping process, control temperature is at 25 DEG C, drop rate, makes transparent titanium tetrachloride ethanol solution; Taking thiocarbamide 5 grams adds in 30 ml distilled waters, and stirring and dissolving is placed on stirring and dissolving in constant pressure funnel, obtains thiourea solution;
3) measure 15 milliliters of phosphorus trihalide aqueous solution and be placed in constant pressure funnel, slowly being added drop-wise to while stirring fills in the there-necked flask of mixed solution, dropwising rear continuation stirring makes all for 30 minutes, then respectively all titanium tetrachloride ethanol solutions prepared and thiourea solution be placed in constant pressure funnel and be slowly added drop-wise to there-necked flask, drip stirring 3 hours, add 3 grams of active carbons more wherein and continue stirring 2 hours, ambient temperatare to be put after ageing in drying box in 60 DEG C of oven dry, calcine 5 hours in 350 DEG C in Muffle furnace after grinding, obtain sulphur and rare earth doped nano titanium oxide ternary photochemical catalyst, wherein, mixed solution is by 50 milliliters of absolute ethyl alcohols, 30 milliliters of acetic acid with 20 ml distilled waters are even forms.
Embodiment 15:
1) take manganese dioxide 6 grams with electronics Libra and be placed in beaker, take again mass concentration be 98% the concentrated sulfuric acid 2 grams and mass concentration be 65% red fuming nitric acid (RFNA) slowly pour the beaker filling manganese dioxide into, constantly dissolving is stirred under 50 DEG C of conditions, make manganese hydrochloric acid solution, then by manganese hydrochloric acid solution in drying box in 60 DEG C of oven dry, namely obtain manganese salt solid;
2) take 5 grams of manganese salt solids to add in 50 ml distilled waters and make manganese salt solution; Take 10 grams of titanium tetrachlorides carefully to pour in constant pressure funnel, then be added drop-wise in the conical flask filling 60 milliliters of absolute ethyl alcohols with the rate of addition of 10 seconds/under agitation, in dropping process, control temperature is at 25 DEG C, drop rate, makes transparent titanium tetrachloride ethanol solution; Taking thiocarbamide 5 grams adds in 30 ml distilled waters, and stirring and dissolving is placed on stirring and dissolving in constant pressure funnel, obtains thiourea solution;
3) measure 15 milliliters of manganese salt solutions and be placed in constant pressure funnel, slowly being added drop-wise to while stirring fills in the there-necked flask of mixed solution, dropwising rear continuation stirring makes all for 30 minutes, then respectively all titanium tetrachloride ethanol solutions prepared and thiourea solution be placed in constant pressure funnel and be slowly added drop-wise to there-necked flask, drip stirring 3 hours, add 3 grams of active carbons more wherein and continue stirring 2 hours, ambient temperatare to be put after ageing in drying box in 60 DEG C of oven dry, calcine 5 hours in 350 DEG C in Muffle furnace after grinding, obtain sulphur and rare earth doped nano titanium oxide ternary photochemical catalyst, wherein, mixed solution is made up of 50 milliliters of absolute ethyl alcohols, 30 milliliters of acetic acid and 20 ml distilled waters.
Embodiment 16:
1) take cerium oxide 1 gram with electronics Libra and be placed in beaker, take again mass concentration be 65% red fuming nitric acid (RFNA) 1.5 grams and mass concentration be 37.5% concentrated hydrochloric acid 0.5 gram slowly pour the beaker filling cerium oxide into, constantly dissolving is stirred under 40 DEG C of conditions, make cerium hydrochloric acid solution, then by cerium hydrochloric acid solution in drying box in 60 DEG C of oven dry, namely obtain cerium salt solid;
2) take 0.2 gram of cerium salt solid to add in 20 ml distilled waters and make cerium salt solution; Take 5 grams of titanium tetrachlorides carefully to pour in constant pressure funnel, then be added drop-wise in the conical flask filling 40 milliliters of absolute ethyl alcohols with the rate of addition of 12 seconds/under agitation, in dropping process, control temperature is at 25 DEG C, drop rate, makes transparent titanium tetrachloride ethanol solution; Taking thiocarbamide 1 gram adds in 5 ml distilled waters, and stirring and dissolving is placed on stirring and dissolving in constant pressure funnel, obtains thiourea solution;
3) measure 10 milliliters of cerium salt solutions and be placed in constant pressure funnel, slowly being added drop-wise to while stirring fills in the there-necked flask of mixed solution, dropwising rear continuation stirring makes all for 30 minutes, then respectively all titanium tetrachloride ethanol solutions prepared and thiourea solution be placed in constant pressure funnel and be slowly added drop-wise to there-necked flask, drip stirring 3 hours, add 3 grams of active carbons more wherein and continue stirring 2 hours, ambient temperatare to be put after ageing in drying box in 60 DEG C of oven dry, calcine 2 hours in 600 DEG C in Muffle furnace after grinding, obtain sulphur and rare earth doped nano titanium oxide ternary photochemical catalyst, wherein, mixed solution is made up of 40 milliliters of absolute ethyl alcohols, 10 milliliters of acetic acid and 9 ml distilled waters.
Light degradation is tested: the methyl orange aqueous solution configuring 50mg/L in the volumetric flask of 250mL.The catalyst taking 0.10g-0.50g adds in the quartz beaker filling 100mL methyl orange solution, then carries out light degradation experiment.Take out sample, after high speed centrifugation twice, test its absorbance with ultraviolet-visual spectrometer immediately.As seen from Figure 1, methyl orange is 60min (see 1b figure) in the time of the degradable methyl orange of commercially available nano titanium oxide; And time shorten degradable under the effect of the nano titanium oxide that methyl orange is prepared at the present embodiment, sulphur and rare earth doped three-way catalyst be 30min (see Fig. 1 a); This can show, cerium, sulphur, to the doping of nano titanium oxide, not only change the crystalline phase of nano titanium oxide, has expanded the response range of light, and be reactivity by the Conversion of Energy of photoresponse, large increase its to the degradation efficiency of methyl orange.
Claims (8)
1. a preparation technology for sulphur and rare earth doped nano titanium oxide ternary photochemical catalyst, is characterized in that, comprise the following steps:
1) rare-earth salts is dissolved in distilled water, is mixed with rare earth salt aqueous solution; Titanium tetrachloride is added drop-wise in absolute ethyl alcohol, is mixed with titanium tetrachloride ethanol solution; Thiocarbamide is added in ethanol, be mixed with thiourea solution; Wherein, every 20-50 ml distilled water adds the rare-earth salts of 0.2-5 gram; 5-10g titanium tetrachloride is dripped in every 30-60 milliliter absolute ethyl alcohol; The thiourea solution of 1-50 gram is added in the distilled water of every 5-300 milliliter; Rare-earth salts is the inorganic salts of nonmetalloid, Main Group Metal Elements, lanthanide series, actinides or transition metal;
2) rare earths salt is added drop-wise to be made up of in mixed solution absolute ethyl alcohol, acetic acid and distilled water and stirs, then drip titanium tetrachloride ethanol solution and thiourea solution simultaneously, stir after being added dropwise to complete, add active carbon more wherein to continue to stir, last room temperature ageing is also dried, the solid obtained in 300-600 DEG C of calcining 1-5 hour, obtains sulphur and rare earth doped nano titanium oxide ternary photochemical catalyst after grinding; Wherein, in mixed solution, the volume ratio of absolute ethyl alcohol, acetic acid and distilled water is (30-60): (5-30): (5-20); And the volume ratio of absolute ethyl alcohol is (2-15) in rare earths salt and mixed solution: (30-60); The volume ratio of rare earths salt, titanium tetrachloride ethanol solution and thiourea solution is (2-15): (30-60): (5-30); The mass ratio of the titanium tetrachloride in active carbon and titanium tetrachloride ethanol solution is (2-8): (5-10).
2. the preparation technology of sulphur according to claim 1 and rare earth doped nano titanium oxide ternary photochemical catalyst, it is characterized in that, step 1) middle rare earth salt adopts and obtains with the following method: concentrated acid joined in rare earth oxide, then under 40-70 DEG C of condition, dissolving is stirred to, make rare-earth salts acid solution, rare-earth salts acid solution is dried at 40-60 DEG C, namely obtains rare-earth salts.
3. the preparation technology of sulphur according to claim 2 and rare earth doped nano titanium oxide ternary photochemical catalyst, is characterized in that: described concentrated acid is one or more in dense hydracid, red fuming nitric acid (RFNA), the concentrated sulfuric acid, SPA.
4. the preparation technology of sulphur according to claim 3 and rare earth doped nano titanium oxide ternary photochemical catalyst, is characterized in that: described dense hydracid is one or more in concentrated hydrochloric acid, concentrated hydrobromic acid, dense hydroiodic acid, dense hydrogen carbonic acid.
5. the preparation technology of sulphur according to claim 1 and rare earth doped nano titanium oxide ternary photochemical catalyst, is characterized in that, step 1) in the compound method of titanium tetrachloride ethanol solution be:
Titanium tetrachloride is poured in constant pressure funnel, then under agitation with 7-12 second/rate of addition that drips drips titanium tetrachloride, obtained titanium tetrachloride ethanol solution in absolute ethyl alcohol; Wherein, in dropping process, the temperature of absolute ethyl alcohol is controlled in room temperature to 30 DEG C.
6. the preparation technology of sulphur according to claim 1 and rare earth doped nano titanium oxide ternary photochemical catalyst, is characterized in that: described nonmetalloid is boron, silicon, phosphorus, arsenic or selenium; Main Group Metal Elements comprises magnesium, aluminium, gallium, germanium, arsenic, selenium, indium, tin, antimony, tellurium, thallium, lead, bismuth or polonium; Transition metal comprises scandium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, yttrium, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, silver, cadmium, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum or gold.
7. the preparation technology of nano titanium oxide according to claim 1, sulphur and rear-earth-doped ternary photochemical catalyst, is characterized in that: described lanthanide series comprises lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium or lutetium; Actinides comprises actinium, thorium, protactinium, uranium, neptunium, plutonium, americium, curium, berkelium, californium, einsteinium, fermium, mendelevium, nobelium or lawrencium.
8. the preparation technology of nano titanium oxide according to claim 1, sulphur and rear-earth-doped ternary photochemical catalyst, is characterized in that: described step 2) in bake out temperature be 40-60 DEG C.
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