CN103433058B - Au-Cu/TiO 2-NBs bimetal nanostructure integral catalyzer, preparation method and application thereof - Google Patents

Au-Cu/TiO 2-NBs bimetal nanostructure integral catalyzer, preparation method and application thereof Download PDF

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CN103433058B
CN103433058B CN201310392577.7A CN201310392577A CN103433058B CN 103433058 B CN103433058 B CN 103433058B CN 201310392577 A CN201310392577 A CN 201310392577A CN 103433058 B CN103433058 B CN 103433058B
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许效红
贾琴琴
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Shandong University
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Abstract

The present invention relates to Au-Cu/TiO 2-NBs bimetal nanostructure integral catalyzer, preparation method and application thereof, this catalyst is at TiO by light deposition 2the area load Cu nano particle of nanobelt, then load is had the TiO of Cu nano particle 2nanobelt and AuCl 4 -reaction load Au nano particle, forms Au-Cu/TiO 2-NBs bimetal nanostructure integral catalyzer.The invention still further relates to the preparation method and application of this catalyst.Au-Cu/TiO of the present invention 2-NBs bimetal nanostructure integral catalyzer catalytic activity and stability high, selective good; Preparation technology is simple, easy to operate, favorable repeatability.

Description

Au-Cu/TiO 2-NBs bimetal nanostructure integral catalyzer, preparation method and application thereof
Technical field
The present invention relates to a kind of TiO 2nanobelt (TiO 2-NBs i.e. TiO 2nanobelt) load Au-Cu duplex metal nano granule integral catalyzer and preparation method thereof, and the application of this catalyst in the processes such as phenmethylol, methyl alcohol selective oxidation and CO are oxidized, belong to chemical catalyst technical field.
Background technology
Bimetal nanostructure material, due to intermetallic synergy, has far above the excellent catalytic activity of single metal, selective and stability, therefore, in recent years bimetallic catalytic material synthesis and be applied in order to one of chemical material area research focus.In order to improve catalytic activity and the stability of metal nanoparticle, avoid reuniting between particle, metal nanoparticle needs the immobilized surface to catalyst carrier of high degree of dispersion usually.For auri metallic catalyst, TiO 2a kind of conventional carrier material, the TiO of various structures kenel 2(such as grain structure, meso-hole structure, membrane structure etc.) are often used as the carrier of metallic particles.Research shows, the structure, pattern, size etc. of carrier all have a significant impact the performance of catalyst.Monodimension nanometer material is (as TiO 2nanobelt) there is integration, by the paper technology of simple improvement, a kind of nanometer paper can be formed.This nanometer paper has the three-dimensional porous structure of intersection, this structure gives catalyst high chemical stability and heat endurance, high porosity and specific area, good permeability and low-density, and the adjustable controllability of shape and size, therefore this material is suitable as the carrier of metal nanoparticle very much, form catalyst material, be applied to heterogeneous catalysis process.
Light deposition is that one is widely used at semiconductor light-catalyst (as TiO 2) method of surface deposition metal nanoparticle.The method is under the condition having semiconductor substance existence and illumination, is the process of metal simple-substance by reducing metal ions in metal salt solution.Such as, 2005, Mark A.Barteau etc. successfully prepared finely dispersed Ag/TiO by the method for light deposition 2and Au/TiO 2catalyst (Langmuir200521:5588-5595); 2009, the people such as Eilidh Morrison utilized the method for light deposition to prepare Cu/TiO 2catalyst (Thin Solid Films2009517:5621-5624); 2013, the people such as the Ruey-an Doong Cu particle that utilized the method for light deposition at titanate nanotube surface deposition, successfully prepared Cu-deposited TiO 2/ TNTs catalyst (Applied Catalysis B:Environmental2013129:48-55).In addition, in-situ oxidation reduction replacement process has been proved to be a kind of method of effective synthesis duplex metal nano granule.Such as, 2007, the method that the people such as Xiaomao Lu utilize original position to replace successfully prepared high activity Au-Ag bimetallic catalyst with core-casing structure (J.AM.CHEM.SOC.2007129:1733-1742); 2011, the method that the people such as Melinda Mohl utilize original position to replace prepared CuPd and CuPt bimetallic catalyst, and shows good catalytic activity (J.Phys, Chem.C2011115:9403-9409).
At present, Au-Cu/TiO is prepared at titanium dioxide nano-belts area load bimetal Au-Cu nano particle 2there is not been reported for-NBs nanometer paper catalyst.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of Au-Cu/TiO 2-NBs bimetal nanostructure integral catalyzer, preparation method and application thereof.This catalyst is used for the processes such as catalytic oxidation of benzyl alcohol produces benzaldehyde, methanol catalytic oxidation produces formaldehyde, CO oxidation, and conversion ratio is high, selective good, and recyclable recycling, be applicable to large-scale industrial production.
Technical scheme of the present invention is as follows:
Au-Cu/TiO 2-NBs bimetal nanostructure integral catalyzer, this catalyst is at TiO by light deposition 2nanobelt (TiO 2-NBs i.e. TiO 2nanobelt) area load Cu nano particle, then load is had the TiO of Cu nano particle 2nanobelt and AuCl 4 -reaction load Au nano particle, forms Au-Cu/TiO 2-NBs bimetal nanostructure integral catalyzer; Described TiO 2nanometer belt length 0.05 ~ 20 μm, wide 10 ~ 500nm, thick 5 ~ 100nm, described Cu nano particle is with Cu 2the form of O exists, and particle diameter is 1 ~ 3nm; Described Au nano particle diameter is 1 ~ 3nm.
According to the present invention, preferably, the load capacity of Cu nano particle is the load capacity of 1 ~ 10wt%, Au nano particle is 1 ~ 5wt%.
Au-Cu/TiO of the present invention 2the preparation method of-NBs bimetal nanostructure integral catalyzer, step is as follows:
(1) TiO 2the preparation of nanobelt
By TiO 2being dispersed in concentration is in the strong base solution of 5 ~ 20mol/L, and in 180 ~ 220 DEG C of thermostatic drying chambers, heating in water bath for reaction 48 ~ 72 hours, obtains banded titanate; Then being placed in concentration is that the acid solution of 0.01 ~ 0.2mol/L carries out acidifying, obtains banded metatitanic acid; Finally metatitanic acid is calcined 1 ~ 5 hour in 550 ~ 650 DEG C of high-temperature electric resistance furnaces, obtain TiO 2nanobelt;
Described nano-TiO 2be 1:(70 ~ 100 with the mass ratio of highly basic);
(2) Cu/TiO 2the preparation of-NBs
By TiO prepared by step (1) 2nanobelt is distributed in ethanol, adds copper nitrate solution, is 7 ~ 9 with aqueous slkali adjust pH, logical N 2, irradiate 5 ~ 30min with the xenon lamp of 20 ~ 1000W, obtain Cu/TiO 2-NBs solution;
Described TiO 2the mass volume ratio of nanometer and ethanol is (0.05 ~ 0.1): (10 ~ 50) g/ml; Described TiO 2the mass ratio of nanobelt and copper nitrate is 1:(0.5 ~ 1);
(3) Au-Cu/TiO 2the preparation of-NBs
By Cu/TiO prepared by step (2) 2-NBs solution joins 1 ~ 20g/L HAuCl 4in solution, logical N 2, reaction 5 ~ 30min, suction filtration, washing, dries, obtains Au-Cu/TiO 2-NBs bimetal nanostructure integral catalyzer;
Described Cu/TiO 2-NBs solution joins HAuCl 4cu after in solution 2+with Au 3+mol ratio be (1 ~ 30): 1.
In step of the present invention (1), preferably, described strong base solution is sodium hydroxide solution or potassium hydroxide solution;
Preferably, described acid solution is hydrochloric acid solution or salpeter solution.
In step of the present invention (2), preferably, described TiO 2the mass ratio of nanobelt and copper nitrate is 1:(0.6 ~ 0.7);
Preferably, described aqueous slkali is sodium hydroxide solution or potassium hydroxide solution;
Preferably, described TiO 2the mass volume ratio of nanometer and ethanol is (0.05 ~ 0.1): (10 ~ 20) g/ml;
Preferably, described Xenon light shining is for irradiating 10 ~ 20min with 20 ~ 500W xenon lamp.
In step of the present invention (3), preferably, described Cu/TiO 2-NBs joins HAuCl 4cu after in solution 2+with Au 3+mol ratio be (5 ~ 15): 1;
Preferably, the described reaction time is 10 ~ 20min;
Preferably, described washing is for wash with ultra-pure water.
Au-Cu/TiO of the present invention 2-NBs bimetal nanostructure integral catalyzer is applied to that catalytic oxidation of benzyl alcohol produces benzaldehyde, methanol catalytic oxidation produces formaldehyde and CO oxidizing process.
The invention provides a kind of light deposition-original position displacement synthesis Au-Cu/TiO 2the method of-NBs nano-structured calalyst, the method mainly comprises two parts: TiO 2the preparation of nanobelt and the load of bimetal granule.TiO 2nanobelt is by TiO 2adopt hydro-thermal method to grow formation in high temperature strong base solution, then utilize the method for light deposition at TiO 2the area load Cu nano particle of nanobelt, and by original position displacement method by itself and AuCl 4 -reaction forms bimetal Au-Cu nano particle, thus obtained Au-Cu/TiO 2-NBs nanostructured integral catalyzer material, then takes out film film-making and obtains integral catalyzer by catalyst material; On each face that Cu nano particle and Au nano particle are evenly distributed on titanium dioxide nano-belts and each rib; This bimetallic catalyst improves single metal A u/TiO 2the shortcoming of the low poor stability of-NBs catalyst activity.Catalytic oxidation of benzyl alcohol (molecular oxygen) is converted into the process of benzaldehyde, Au-Cu/TiO 2nanocomposite catalytic shows high catalytic activity, high selectivity and high stability.
The present invention has the following advantages:
(1) the present invention obtains the Au-Cu/TiO of noble metal surface even particle distribution by light deposition-original position displacement legal system 2-NBs bimetal nanostructure integral catalyzer, technique is simple, easy to operate, favorable repeatability.
(2) the inventive method prepare Au-Cu/TiO 2-NBs bimetal nanostructure integral catalyzer, its surface metal particle size, that load capacity is adjustable is controlled, can improve catalytic activity and the stability of catalyst simply by changing Au, Cu proportion of composing in solution;
(3) Au-Cu/TiO for preparing of the present invention 2-NBs bimetal nanostructure, is through suction filtration press mold, obtained overall nanometer paper catalyst, macroscopic view independently can exist, and is easy to recycle and reuse.
(4) Au-Cu/TiO of the present invention 2-NBs bimetal nanostructure integral catalyzer catalytic activity and stability high, selective good.
Accompanying drawing explanation
Fig. 1 is the Au-Cu/TiO that the embodiment of the present invention 1 obtains 2sEM (SEM) photo of-NBs bimetal nanostructure integral catalyzer.
Fig. 2 is the Au-Cu/TiO that the embodiment of the present invention 1 obtains 2high resolution transmission electron microscopy (HRTEM) photo before the catalysis of-NBs bimetal nanostructure integral catalyzer.
Fig. 3 is the Au-Cu/TiO that the embodiment of the present invention 1 obtains 2high resolution transmission electron microscopy (HRTEM) photo after-NBs catalysis.
Fig. 4 is the Au-Cu/TiO that the embodiment of the present invention 1 obtains 2-NBs nanobelt bimetallic catalyst XRD picture.
Fig. 5 is the Au-Cu/TiO that the embodiment of the present invention 1 obtains 2the optical photograph of-NBs bimetal nanostructure integral catalyzer.
Fig. 6 is the Au-Cu/TiO that the embodiment of the present invention 1 obtains 2the optical photograph of-NBs bimetal nanostructure integral catalyzer in vertical quartz pipe reactor.
Fig. 7 is the blank TiO of the present invention 2the catalyst Oxybenzene methyl alcohol Comparison of experiment results figure that nanobelt, embodiment 1, comparative example 1, comparative example 2 are obtained.
Fig. 8 is the Au-Cu/TiO that the embodiment of the present invention 1 obtains 2-NBs bimetal nanostructure integral catalyzer is to the result curve of phenmethylol catalytic gas phase oxidation.
Detailed description of the invention
Below in conjunction with embodiment and Figure of description, technical scheme of the present invention is described further, but institute of the present invention protection domain is not limited thereto.
Raw materials usedly in embodiment be conventional reagent, commercial products.
Embodiment 1
Au-Cu/TiO 2the preparation method of-NBs bimetal nanostructure integral catalyzer, step is as follows:
(1) TiO 2the preparation of nanobelt
By 1.75g nano-TiO 2it is in 10mol/L sodium hydroxide solution that P25 is dispersed in 350ml concentration, 200 DEG C of heating in water bath for reaction 72 hours in thermostatic drying chamber, obtain banded sodium titanate, then banded sodium titanate sample being placed in 800mL concentration is that 0.1mol/L hydrochloric acid solution carries out acidifying, obtain banded metatitanic acid, finally banded metatitanic acid is put into 600 DEG C of electric furnaces and calcine 2h, and then obtain TiO 2nanobelt;
(2) Cu/TiO 2the preparation of-NBs
Get TiO prepared by step (1) 2nanobelt 0.1g, in the beaker containing 50mL ethanol, adds 3mL0.1mol/LNaOH solution adjust pH, ultrasonic disperse, logical N 2, obtain solution 1-1;
Get the copper nitrate solution of 5mL0.1mol/L in the beaker containing 50mL ethanol, ultrasonic disperse, logical N 2, obtain solution 1-2;
N is led on limit 2under the condition of limit magnetic agitation, solution 1-2 is poured in solution 1-1, and irradiate 10min with 500W xenon lamp immediately, obtain Cu/TiO 2-NBs solution;
(3) Au-Cu/TiO 2the preparation of-NBs
Get 3mL10g/L HAuCl 4solution, in beaker, with ultra-pure water dilution, leads to N 2, obtain solution 1-3;
N is led on limit 2under the condition of limit magnetic agitation, solution 1-3 pours the obtained Cu/TiO of step (2) into 2in-NBs solution, after lucifuge reaction 10min, suction filtration, washing, dry, obtain Au-Cu/TiO 2-NBs bimetal nanostructure integral catalyzer;
Described Cu/TiO 2-NBs solution joins Cu after in solution 1-3 2+with Au 3+mol ratio be 10:1;
Described Cu nano particle is with Cu 2the form of O exists, and particle diameter is 1 ~ 3nm; Described Au nano particle diameter is 1 ~ 3nm.
Au-Cu/TiO prepared by the present embodiment 2sEM (SEM) photo of-NBs bimetal nanostructure integral catalyzer as shown in Figure 1, the high resolution transmission electron microscopy of catalyst before catalysis (HRTEM) photo as shown in Figure 2, as can be seen from Figure 2 TiO 2the metal nanoparticle that is evenly distributed of the nanobelt successful load in surface; As shown in Figure 3, can find out reaction from Fig. 2,3 before and after, granule-morphology does not change the high resolution transmission electron microscopy of catalyst after catalysis (HRTEM) photo substantially.
Au-Cu/TiO prepared by the present embodiment 2as shown in Figure 4, as can be seen from Figure 4 Au, Cu success load is at TiO for the XRD picture of-NBs bimetal nanostructure integral catalyzer 2nanobelt surface, but Cu is with Cu 2the form of O exists.
Comparative example 1
Cu/TiO 2the preparation of-NBs metal Nano structure catalyst, step is as follows:
(1) TiO 2the preparation of nanobelt
By 1.75g nano-TiO 2it is in 10mol/L sodium hydroxide solution that P25 is dispersed in 350ml concentration, 200 DEG C of heating in water bath for reaction 72 hours in thermostatic drying chamber, obtain banded sodium titanate, then banded sodium titanate sample being placed in 800mL concentration is that 0.1mol/L hydrochloric acid solution carries out acidifying, obtain banded metatitanic acid, finally banded metatitanic acid is put into 600 DEG C of electric furnaces and calcine 2h, and then obtain TiO 2nanobelt;
(2) Cu/TiO 2the preparation of-NBs
Get TiO prepared by step (1) 2nanobelt 0.1g, in the beaker containing 50mL ethanol, adds 3mL0.1mol/LNaOH solution adjust pH, ultrasonic disperse, logical N 2, obtain solution 2-1;
Get 5mL0.1mol/L copper nitrate solution in the beaker containing 50mL ethanol, ultrasonic disperse, logical N 2, obtain solution 2-2;
N is led on limit 2under the condition of limit magnetic agitation, poured in solution 1-1 by solution 1-2, and irradiate 10min with 500W xenon lamp immediately, after illumination, suction filtration, washing, oven dry, obtain Cu/TiO 2-NBs metal Nano structure catalyst.
Comparative example 2
Au/TiO 2the preparation of-NBs metal Nano structure catalyst, step is as follows:
(1) TiO 2the preparation of nanobelt
By 1.75g nano-TiO 2it is in 10mol/L sodium hydroxide solution that P25 is dispersed in 350ml concentration, 200 DEG C of heating in water bath for reaction 72 hours in thermostatic drying chamber, obtain banded sodium titanate, then banded sodium titanate sample being placed in 800mL concentration is that 0.1mol/L hydrochloric acid solution carries out acidifying, obtain banded metatitanic acid, finally banded metatitanic acid is put into 600 DEG C of electric furnaces and calcine 2h, and then obtain TiO 2nanobelt;
(2) Au/TiO 2the preparation of-NBs
Get TiO prepared by step (1) 2nanobelt 0.1g, in the beaker containing 50mL0.1mol/L NaOH solution, adds 10mL10g/L HAuCl 4solution, drip 2mL0.02mol/L sodium citrate solution, under 500W xenon lamp, irradiate 3min after ultrasonic disperse, after illumination, suction filtration, washing, oven dry, obtain Au/TiO 2-NBs metal Nano structure catalyst.
Application examples
By Au-Cu/TiO prepared by embodiment 1 2-NBs bimetal nanostructure integral catalyzer is used for catalytic oxidation of benzyl alcohol and prepares benzaldehyde, and catalyst prepared by comparative example 1, comparative example 2 is used for catalytic oxidation of benzyl alcohol and prepares benzaldehyde and compare, and concrete steps are as follows:
Catalytic oxidation of benzyl alcohol is prepared benzaldehyde reaction and is carried out in small-sized gas phase catalytic reaction device, prepares the yield of the conversion ratio of benzaldehyde, the selective of benzaldehyde and benzaldehyde for standard with catalytic oxidation of benzyl alcohol;
Under normal pressure, phenmethylol to be entered in 220 DEG C of preheating furnaces by syringe pump with the speed of 20 μ L/min and vaporizes; O simultaneously 2with 7.9mL/min, N 2enter preheating furnace with the speed of 43.5mL/min and carry out preheating.After fully vaporization, mixing, three kinds of gases enter 240 DEG C and are equipped with in the reacting furnace of 20mg catalyst; After reaction, mixture carries out condensation recovery by cold-trap, detects by gas-chromatography.Catalytic result is as shown in accompanying drawing 7,8.
Accompanying drawing 7 is blank TiO 2the catalytic performance of the catalyst of nanobelt, comparative example 2, comparative example 1, embodiment 1 preparation compares, and above-mentioned catalyst is respectively blank TiO 2nanobelt, TiO 2nanobelt load gold catalyst, TiO 2nanobelt copper-loading catalyst and TiO 2nanobelt load Au, Cu bimetallic catalyst, at 240 DEG C, under normal pressure, the selective and benzaldehyde productive rate of the phenmethylol conversion ratio of reaction 6h gained, benzaldehyde.
As can be seen from data in Fig. 7: compared with other catalyst, Au-Cu/TiO 2the conversion ratio of-NBs bimetal nanostructure integral catalyzer catalytic reaction and selective all higher, reaches more than 93% and 98% respectively; Showing excellent catalytic performance, is a kind of new catalyst having application prospect.
Accompanying drawing 8 is the Au-Cu/TiO that embodiment 1 obtains 2the long-time reaction experiment result of-NBs bimetal nanostructure integral catalyzer catalytic oxidation phenmethylol, as can be seen from Fig. 8, long-time catalytic reaction phenmethylol conversion ratio and the selective all quite stables of benzaldehyde, show Au-Cu/TiO thus 2-NBs bimetal nanostructure integral catalyzer has higher stability.
Embodiment 2
Au-Cu/TiO 2the preparation method of-NBs bimetal nanostructure integral catalyzer, step is as follows:
(1) TiO 2the preparation of nanobelt
By nano-TiO 2being dispersed in concentration is in the sodium hydroxide solution of 5mol/L, and in 180 DEG C of thermostatic drying chambers, heating in water bath for reaction 48 hours, obtains banded sodium titanate; Then being placed in concentration is that the hydrochloric acid solution of 0.01mol/L carries out acidifying, obtains banded metatitanic acid; Finally metatitanic acid is calcined 1 hour in 550 DEG C of high-temperature electric resistance furnaces, obtain TiO 2nanobelt;
Described nano-TiO 2be 1:70 with NaOH mass ratio;
(2) Cu/TiO 2the preparation of-NBs
By TiO prepared by step (1) 2nanobelt is distributed in ethanol, adds copper nitrate solution, is 7 with NaOH solution adjust pH, logical N 2, irradiate 30min with the xenon lamp of 20W, obtain Cu/TiO 2-NBs solution;
Described TiO 2the mass volume ratio of nanometer and ethanol is 0.05:10g/ml; Described TiO 2the mass ratio of nanobelt and copper nitrate is 1:1;
(3) Au-Cu/TiO 2the preparation of-NBs
By Cu/TiO prepared by step (2) 2-NBs solution joins 1g/L HAuCl 4in solution, logical N 2, reaction 30min, suction filtration, washing, dries, obtains Au-Cu/TiO 2-NBs bimetal nanostructure integral catalyzer;
Described Cu/TiO 2-NBs solution joins HAuCl 4cu after in solution 2+with Au 3+mol ratio be 1:1.
Embodiment 3
Au-Cu/TiO 2the preparation method of-NBs bimetal nanostructure integral catalyzer, step is as follows:
(1) TiO 2the preparation of nanobelt
By nano-TiO 2being dispersed in concentration is in the sodium hydroxide solution of 20mol/L, and in 180 DEG C of thermostatic drying chambers, heating in water bath for reaction 48 hours, obtains banded sodium titanate; Then being placed in concentration is that the hydrochloric acid solution of 0.2mol/L carries out acidifying, obtains banded metatitanic acid; Finally metatitanic acid is calcined 5 hours in 650 DEG C of high-temperature electric resistance furnaces, obtain TiO 2nanobelt;
Described nano-TiO 2be 1:100 with NaOH mass ratio;
(2) Cu/TiO 2the preparation of-NBs
By TiO prepared by step (1) 2nanobelt is distributed in ethanol, adds copper nitrate solution, is 9 with NaOH solution adjust pH, logical N 2, irradiate 5min with the xenon lamp of 1000W, obtain Cu/TiO 2-NBs solution;
Described TiO 2the mass volume ratio of nanometer and ethanol is 0.1:10g/ml; Described TiO 2the mass ratio of nanobelt and copper nitrate is 1:0.7;
(3) Au-Cu/TiO 2the preparation of-NBs
By Cu/TiO prepared by step (2) 2-NBs solution joins 20g/L HAuCl 4in solution, logical N 2, reaction 5min, suction filtration, washing, dries, obtains Au-Cu/TiO 2-NBs bimetal nanostructure integral catalyzer;
Described Cu/TiO 2-NBs solution joins HAuCl 4cu after in solution 2+with Au 3+mol ratio be 30:1.
Embodiment 4
Au-Cu/TiO 2the preparation method of-NBs bimetal nanostructure integral catalyzer, step is as follows:
(1) TiO 2the preparation of nanobelt
By nano-TiO 2being dispersed in concentration is in the potassium hydroxide solution of 10mol/L, and in 200 DEG C of thermostatic drying chambers, heating in water bath for reaction 48 hours, obtains banded potassium titanate; Then being placed in concentration is that the hydrochloric acid solution of 0.1mol/L carries out acidifying, obtains banded metatitanic acid; Finally metatitanic acid is calcined 3 hours in 600 DEG C of high-temperature electric resistance furnaces, obtain TiO 2nanobelt;
Described nano-TiO 2be 1:80 with potassium hydroxide mass ratio;
(2) Cu/TiO 2the preparation of-NBs
By TiO prepared by step (1) 2nanobelt is distributed in ethanol, adds copper nitrate solution, is 8 with KOH solution adjust pH, logical N 2, irradiate 20min with the xenon lamp of 500W, obtain Cu/TiO 2-NBs solution;
Described TiO 2the mass volume ratio of nanometer and ethanol is 0.1:40g/ml; Described TiO 2the mass ratio of nanobelt and copper nitrate is 1:0.8;
(3) Au-Cu/TiO 2the preparation of-NBs
By Cu/TiO prepared by step (2) 2-NBs solution joins 10g/L HAuCl 4in solution, logical N 2, reaction 30min, suction filtration, washing, dries, obtains Au-Cu/TiO 2-NBs bimetal nanostructure integral catalyzer;
Described Cu/TiO 2-NBs solution joins HAuCl 4cu after in solution 2+with Au 3+mol ratio be 10:1.
Embodiment 5
Au-Cu/TiO 2the preparation method of-NBs bimetal nanostructure integral catalyzer, step is as follows:
(1) TiO 2the preparation of nanobelt
By nano-TiO 2being dispersed in concentration is in the potassium hydroxide solution of 15mol/L, and in 220 DEG C of thermostatic drying chambers, heating in water bath for reaction 72 hours, obtains banded potassium titanate; Then being placed in concentration is that the hydrochloric acid solution of 0.1mol/L carries out acidifying, obtains banded metatitanic acid; Finally metatitanic acid is calcined 5 hours in 600 DEG C of high-temperature electric resistance furnaces, obtain TiO 2nanobelt;
Described nano-TiO 2be 1:90 with potassium hydroxide mass ratio;
(2) Cu/TiO 2the preparation of-NBs
By TiO prepared by step (1) 2nanobelt is distributed in ethanol, adds copper nitrate solution, is 9 with KOH solution adjust pH, logical N 2, irradiate 10min with the xenon lamp of 800W, obtain Cu/TiO 2-NBs solution;
Described TiO 2the mass volume ratio of nanometer and ethanol is 0.1:30g/ml; Described TiO 2the mass ratio of nanobelt and copper nitrate is 1:0.6;
(3) Au-Cu/TiO 2the preparation of-NBs
By Cu/TiO prepared by step (2) 2-NBs solution joins 15g/L HAuCl 4in solution, logical N 2, reaction 20min, suction filtration, washing, dries, obtains Au-Cu/TiO 2-NBs bimetal nanostructure integral catalyzer;
Described Cu/TiO 2-NBs solution joins HAuCl 4cu after in solution 2+with Au 3+mol ratio be 15:1.

Claims (9)

1.Au-Cu/TiO 2-NBs bimetal nanostructure integral catalyzer, is characterized in that, this catalyst is at TiO by light deposition 2nanobelt (TiO 2-NBs i.e. TiO 2nanobelt) area load Cu nano particle, then load is had the TiO of Cu nano particle 2nanobelt and AuCl 4 -reaction load Au nano particle, forms Au-Cu/TiO 2-NBs bimetal nanostructure integral catalyzer; Described TiO 2nanometer belt length 0.05 ~ 20 μm, wide 10 ~ 500 nm, thick 5 ~ 100 nm, described Cu nano particle is with Cu 2the form of O exists, and particle diameter is 1 ~ 3nm; Described Au nano particle diameter is 1 ~ 3nm; The load capacity of described Cu nano particle is the load capacity of 1 ~ 10 wt%, Au nano particle is 1 ~ 5 wt%.
2.Au-Cu/TiO 2the preparation method of-NBs bimetal nanostructure integral catalyzer, step is as follows:
(1) TiO 2the preparation of nanobelt
By TiO 2being dispersed in concentration is in the strong base solution of 5 ~ 20mol/L, and in 180 ~ 220 DEG C of thermostatic drying chambers, heating in water bath for reaction 48 ~ 72 hours, obtains banded titanate; Then being placed in concentration is that the acid solution of 0.01 ~ 0.2 mol/L carries out acidifying, obtains banded metatitanic acid; Finally metatitanic acid is calcined 1 ~ 5 hour in 550 ~ 650 DEG C of high-temperature electric resistance furnaces, obtain TiO 2nanobelt;
Described nano-TiO 2be 1:(70 ~ 100 with the mass ratio of highly basic);
(2) Cu/TiO 2the preparation of-NBs
By TiO prepared by step (1) 2nanobelt is distributed in ethanol, adds copper nitrate solution, is 7 ~ 9 with aqueous slkali adjust pH, logical N 2, irradiate 5 ~ 30min with the xenon lamp of 20 ~ 1000 W, obtain Cu/TiO 2-NBs solution;
Described TiO 2the mass volume ratio of nanometer and ethanol is (0.05 ~ 0.1): (10 ~ 50) g/ml; Described TiO 2the mass ratio of nanobelt and copper nitrate is 1:(0.5 ~ 1);
(3) Au-Cu/TiO 2the preparation of-NBs
By Cu/TiO prepared by step (2) 2-NBs solution joins 1 ~ 20g/L HAuCl 4in solution, logical N 2, reaction 5 ~ 30 min, suction filtration, washing, dries, obtains Au-Cu/TiO 2-NBs bimetal nanostructure integral catalyzer;
Described Cu/TiO 2-NBs solution joins HAuCl 4cu after in solution 2+with Au 3+mol ratio be (1 ~ 30): 1.
3. Au-Cu/TiO according to claim 2 2the preparation method of-NBs bimetal nanostructure integral catalyzer, is characterized in that, the strong base solution described in step (1) is sodium hydroxide solution or potassium hydroxide solution.
4. Au-Cu/TiO according to claim 2 2the preparation method of-NBs bimetal nanostructure integral catalyzer, is characterized in that, the acid solution described in step (1) is hydrochloric acid solution or salpeter solution.
5. Au-Cu/TiO according to claim 2 2the preparation method of-NBs bimetal nanostructure integral catalyzer, is characterized in that, the TiO described in step (2) 2the mass ratio of nanobelt and copper nitrate is 1:(0.6 ~ 0.7); Described aqueous slkali is sodium hydroxide solution or potassium hydroxide solution.
6. Au-Cu/TiO according to claim 2 2the preparation method of-NBs bimetal nanostructure integral catalyzer, is characterized in that, the TiO described in step (2) 2the mass volume ratio of nanometer and ethanol is (0.05 ~ 0.1): (10 ~ 20) g/ml, and described Xenon light shining is for irradiating 10 ~ 20 min with 20 ~ 500W xenon lamp.
7. Au-Cu/TiO according to claim 2 2the preparation method of-NBs bimetal nanostructure integral catalyzer, is characterized in that, the Cu/TiO described in step (3) 2-NBs joins HAuCl 4cu after in solution 2+with Au 3+mol ratio be (5 ~ 15): 1; The described reaction time is 10 ~ 20 min.
8. Au-Cu/TiO according to claim 2 2the preparation method of-NBs bimetal nanostructure integral catalyzer, is characterized in that, the washing described in step (3) is for wash with ultra-pure water.
9. Au-Cu/TiO according to claim 1 2-NBs bimetal nanostructure integral catalyzer is applied to that catalytic oxidation of benzyl alcohol produces benzaldehyde, methanol catalytic oxidation produces formaldehyde and catalysis CO oxidizing process.
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