CN105289735A - Pd/UiO-66-NH2 material having high stability as well as preparation method and application of Pd/UiO-66-NH2 material - Google Patents
Pd/UiO-66-NH2 material having high stability as well as preparation method and application of Pd/UiO-66-NH2 material Download PDFInfo
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Abstract
The invention relates to a Pd/UiO-66-NH2 material having the high stability as well as a preparation method and application of the Pd/UiO-66-NH2 material. According to the Pd/UiO-66-NH2 material, a carrier is a Zr6O32 secondary structure unit and has a carrier molecular formula being [Zr6O4(OH)4(O2C-C6NH3-CO2)6], and loaded noble metal is Pd. The preparation method is as follows: weighing UiO-66-NH2 and Pd(acac), performing ultrasonic dissolving on UiO-66-NH2 and Pd(acac) in a DMF solution, simultaneously dropwise adding a Pd(acac)2DMF solution in a UiO-66-NH2 solution, mixing, performing ultrasound operation to obtain a mixed solution, transferring the mixed solution into a round-bottom flask for stirring, dropwise adding NaBH4 solution for reducing, stirring, filtering, washing, and drying to obtain powder Pd/UiO-66-NH2. Pd/UiO-66-NH2 particles related in the invention are uniform in distribution, have the sizes of about 4nm, have a high-stability carbon monoxide oxidation performance, are high in stability and are reusable.
Description
Technical field
The invention belongs to catalyst preparation technical field, be specifically related to a kind of Pd/UiO-66-NH2 material with high stability and its preparation method and application.
Background technology
Recent two decades, MOFs material because of its special structure with adsorbing, be separated, catalysis, luminescence, magnetic and the potential of nonlinear optics quote the concern causing everybody.He is also widely used in homogeneous catalysis.Precious metals pt, Pd, Au etc. are because of its good catalytic effect, but noble metal nano particles is easily reunited, and there is the shortcomings such as expensive, difficult separation, inhibit it further to develop.The crystallite of MOFs and nanocrystalline structure are the carriers of extraordinary fixing noble metal granule.
XuQ reports ZIF-8 load Au nano particle catalysis CO oxidation reaction, and be the participation gas-phase reaction reporting MOF carried noble metal first, XuQ seminar has reported again a series of MOF carried noble metal catalysis CO oxidation reaction subsequently.
Chang-JunLiu etc. have reported a series of MOF framework (as Cu (BTB) 3, the COP-4) catalytic effect of carried noble metal in CO catalytic oxidation, and experiment shows, Pd/MOF is a kind of CO oxidation catalyst efficiently.
ThomasE.Reichbb912012b report is by adopting different microwave method, can by Pd particulate load in MIL-101 surface even duct, research shows, Pd nanoparticle size is at 4-6nm, and what the result of its CO catalytic oxidation had shown catalytic effect is mainly embedded in Pd nano particle in duct.
Since Pd/MOF-5 is in the news, MOF-74, ZIF-8, MIL-101, MOF-177 is by as study on the carrier, the MOFs of Zr base, because its good heat endurance and chemical stability, improves their potentiality in industrial applications, adopts a kind of MOFs load granule Pd of stable Zr base and applied to CO oxidation to be of great significance.
Summary of the invention
For the above-mentioned problems in the prior art, the object of the present invention is to provide a kind of Pd/UiO-66-NH2 material with high stability and its preparation method and application, UiO-66-NH
2have good heat endurance and chemical stability, Pd particle at about 4nm, and is evenly distributed, and under low catalytic amount, have good CO catalytic oxidation effect, catalyst 100% conversion ratio can maintain more than 100h.
Described a kind of Pd/UiO-66-NH with high stability
2material, is characterized in that carrier is Zr
6o
32secondary structure unit, its carrier molecule formula is [Zr
6o
4(OH)
4(O
2c – C
6nH
3– CO
2)
6], the noble metal of load is Pd.
Described a kind of Pd/UiO-66-NH with high stability
2material, is characterized in that the granular size of the Pd of load is 2-6nm, is preferably 4nm.
The described Pd/UiO-66-NH with high stability
2the preparation method of material, is characterized in that concrete steps are as follows:
1) be dissolved in DMF by amino for 5-terephthalic acid (TPA) and zirconium chloride, carry out hydro-thermal reaction, filter, washing, vacuum drying obtains UiO-66-NH
2;
2) by Pd (acac)
2the DMF solution of (palladium acetylacetonate) is added drop-wise to UiO-66-NH
2dMF solution in, mix ultrasonic after be transferred to round-bottomed flask stir, drip NaBH
4solution reduction, stirring, filtration, washing, drying, obtain powder-product Pd/UiO-66-NH
2material.
The described Pd/UiO-66-NH with high stability
2the preparation method of material, it is characterized in that in step 1), hydrothermal temperature is 110-130 DEG C, the reaction time is 2860-2900min.
The described Pd/UiO-66-NH with high stability
2the preparation method of material, it is characterized in that in step 1), hydrothermal temperature is 120 DEG C, the reaction time is 2880min.
The described Pd/UiO-66-NH with high stability
2the preparation method of material, is characterized in that step 2) middle NaBH
4with Pd (acac)
2molar ratio be 8-12:1, be preferably 10:1.
The described Pd/UiO-66-NH with high stability
2the preparation method of material, is characterized in that step 2) in cleaning solvent be DMF and the ether mixtures of any ratio.
The described Pd/UiO-66-NH with high stability
2the preparation method of material, is characterized in that step 1) and step 2) in vacuum drying chamber temperature be 75-85 DEG C, drying time is 2.5-3.5h.
Described a kind of Pd/UiO-66-NH with high stability
2material in Oxidation of Carbon Monoxide reaction as the application of catalyst.
Pd/UiO-66-NH of the present invention
2material, as the application of carbon monoxide oxidation catalyst, specifically comprises the steps: at Pd/UiO-66-NH
2under material exists, first by catalyst P d/UiO-66-NH
2material is loaded in the quartz ampoule that internal diameter is 4mm, connects to continue to pass into CO, O that volume ratio is 1:20:79 with the speed of 100ml/min in this quartz ampoule
2react with Ar mist, the temperature in quartz ampoule is with 0.5 DEG C of min
-1from room temperature temperature programming to the temperature making CO change completely, under its CO oxidation reaches 100% conversion ratio, 1%Pd/UiO-66-NH
2material even can continue and use more than 100h, and reacted gas passes through chromatogram on-line checkingi,
Wherein, X
0for reacting the percentage composition of front CO in mist, x is the percentage composition of CO in gaseous mixture after reaction, and α is correction factor.
By adopting above-mentioned technology, compared with prior art, advantage of the present invention is as follows: the present invention makes full use of UiO-66-NH
2there is the advantage of good heat endurance and chemical stability, by UiO-66-NH
2as carrier, granular size is that the precious metals pd load of about 4nm is at UiO-66-NH
2on carrier, obtain even particle size, the noble metal catalyst Pd/UiO-66-NH of nano-grade size that Pd is highly dispersed at carrier surface
2material, this Pd/UiO-66-NH
2the oxidation of material to CO has good catalytic effect, experiment proves, along with the increase of Pd load capacity, temperature when the T50(CO conversion ratio of reaction is 50%) reduce, this is because along with the increase of Pd load capacity, the CO adsorption potential exposed to the open air on surface increases, and under low catalytic amount, uses Pd/UiO-66-NH of the present invention
2material is as catalyst, and its CO catalytic oxidation effect is better than other catalyst similar, and its long service life, and catalyst 100% conversion ratio can maintain more than 100h, Pd/UiO-66-NH
2it is a kind of economical and practical effective catalyst.
Accompanying drawing explanation
Fig. 1 is 1%Pd/UiO-66-NH
2transmission electron microscope picture under 50nm;
Fig. 2 is 1%Pd/UiO-66-NH
2transmission electron microscope picture under 10nm;
Fig. 3 is 1%Pd/UiO-66-NH
2transmission electron microscope picture under 5nm;
Fig. 4 is 1%Pd/UiO-66-NH
2in Pd particle size distribution figure; Pd granular size is about 4nm.
Fig. 5 is 1%Pd/UiO-66-NH
2and UiO-66-NH
2thermal multigraph; The composition lost before 100 DEG C is as we can see from the figure low boiling point solvent molecule ether, and between 100 DEG C to 326 DEG C, such as the DMF of the solvent molecule in framework evaporates.When temperature continues to rise, the hurried decline of thermogravimetric curve, now MOF framework starts to cave in, and 491 DEG C time, framework complete collapse is ZrO
2.
Fig. 6 is Pd/UiO-66-NH
2n
2absorption figure; UiO-66-NH
2, 0.3%Pd/UiO-66-NH
2, 0.5%Pd/UiO-66-NH
2, 1.0%Pd/UiO-66-NH
2specific area be followed successively by 659m2/g, 461m2/g, 438m2/g and 377m2/g, along with load capacity increase, specific area reduces successively, this is because some Pd plugs UiO-66-NH
2duct.
Fig. 7 is with Pd/UiO-66-NH
2for the CO conversion ratio figure of catalyst; Load capacity is 0.3%, 0.5%, the temperature when T50(CO conversion ratio of UiO-66-NH2 to CO of 1.0% is 50%) be 160,165, and170 DEG C respectively, the temperature of 100% conversion ratio is all 180 DEG C, and the catalytic effect of 1.0% is best.
Fig. 8 is 1%Pd/UiO-66-NH
2xRD(X x ray diffration pattern x before and after reaction) figure; Before and after CO oxidation, our UiO-66-NH
2framework remains intact.
Fig. 9 is 1%Pd/UiO-66-NH
2life-span at 180 DEG C and time chart.At 120 DEG C, 1%Pd/UiO-66-NH
2cO oxidation 100% conversion ratio can be kept at more than 100h.
Detailed description of the invention
With specific embodiment, technical scheme of the present invention is described further below, but protection scope of the present invention is not limited thereto:
Embodiment 10.3%Pd/UiO-66-NH
2preparation
1) UiO-66-NH
2preparation: the zirconium chloride of the amino terephthalic acid (TPA) of 5-and 0.0261g that take 0.0706g is dissolved in 5mlN, and in N-dimethylformamide, hydro-thermal reaction 2880min at 120 DEG C, filters, and washing, vacuum drying obtains UiO-66-NH
2;
2) 0.3%Pd/UiO-66-NH
2preparation take the UiO-66-NH that 0.1g embodiment 1 obtains
2ultrasonic dissolution, in 8mlDMF solution, meanwhile, measures the Pd (acac) of 1.12mg
2dMF solution is added drop-wise in above-mentioned solution, under the condition of room temperature, is transferred to 25ml round-bottomed flask and stirs 4h, make Pd ion fully adsorb and can be uniformly dispersed in UiO-66-NH after ultrasonic 1h
2carrier surface, the NaBH now joined
4solution slowly drops to above-mentioned mixed solution, by Pd
2+be reduced to Pd atom, can see that solution colour is black from yellow mutation, aging half an hour, makes Pd in this process
2+after thorough reduction, filter in sand core funnel, after filter cake DMF washs three times, then use washed with diethylether three times, filter cake after dry 4h, is obtained the 0.3%Pd/UiO-66-NH of powder under vacuum, the condition of 80 DEG C
2;
3) Pd/UiO-66-NH
2application
CO oxidation reaction is carried out in the fixed bed device assembled voluntarily (namely diameter is the quartz ampoule of 4mm), takes 0.05g step 2) 0.3%Pd/UiO-66-NH that obtains
2catalyst is loaded in the quartz ampoule that diameter is 4mm, and reaction gas is CO, O
2with the gaseous mixture of Ar, with volume basis, CO:O
2: Ar=1:20:79, be that 100ml/min passes in this quartz ampoule with flow, flow is controlled by spinner flowmeter, experiment is investigated certain in other condition, the conversion ratio (as Fig. 7) of CO at from 30 DEG C to 180 DEG C, by temperature controller, experimental temperature with 0.5 DEG C of min-1 from room temperature temperature programming to the temperature making CO change completely.Tail gas is by gas chromatograph on-line analysis, and its chromatographic column is the TDX-01 packed column of 3m, and with argon gas as carrier, post case temperature is 80 DEG C, and injector temperature is 150 DEG C, and conductance cell temperature is 110 DEG C, and bridge electric current is 80mA.CO conversion ratio is calculated by formula (1).
Wherein, x
0for reacting the percentage composition of front CO in mist, x is the percentage composition of CO in gaseous mixture after reaction, and α is correction factor.
Embodiment 20.5%Pd/UiO-66-NH
2preparation
Take 0.1gUiO-66-NH
2ultrasonic dissolution, in 8mlDMF solution, meanwhile, measures the Pd (acac) of 1.88mg
2dMF solution is added drop-wise in above-mentioned solution, under the condition of room temperature, is transferred to 25ml round-bottomed flask and stirs 4h, make Pd ion fully adsorb and can be uniformly dispersed in carrier surface after ultrasonic 1h.The NaBH now joined
4solution slowly drops to above-mentioned mixed solution, by Pd
2+be reduced to Pd atom, can see that solution colour is black from yellow mutation, aging half an hour, makes Pd in this process
2+after thorough reduction, filter in sand core funnel, after filter cake DMF washs three times, then use washed with diethylether three times, in order to replace the DMF molecule in MOF duct, filter cake after dry 4h, is obtained the 0.5%Pd/UiO-66-NH of powder under vacuum, the condition of 80 DEG C
2.
UiO-66-NH
2synthesis is in the same manner as in Example 1 with CO catalytic reaction test condition.
Embodiment 31.0%Pd/UiO-66-NH
2preparation
Take 0.1gUiO-66-NH
2ultrasonic dissolution, in 8mlDMF solution, meanwhile, measures the Pd (acac) of 3.77mg
2dMF solution is added drop-wise in above-mentioned solution, under the condition of room temperature, is transferred to 25ml round-bottomed flask and stirs 4h, make Pd ion fully adsorb and can be uniformly dispersed in carrier surface after ultrasonic 1h.The NaBH now joined
4solution slowly drops to above-mentioned mixed solution, by Pd
2+be reduced to Pd atom, can see that solution colour is black from yellow mutation, aging half an hour, makes Pd in this process
2+after thorough reduction, filter in sand core funnel, after filter cake DMF washs three times, then use washed with diethylether three times, in order to replace the DMF molecule in MOF duct, filter cake after dry 4h, is obtained the 1.0%Pd/UiO-66-NH of powder under vacuum, the condition of 80 DEG C
2.
This 1%Pd/UiO-66-NH in the present embodiment
2transmission electron microscope picture under 50nm as shown in Figure 1,1%Pd/UiO-66-NH
2transmission electron microscope picture under 10nm as shown in Figure 2; 1%Pd/UiO-66-NH
2transmission electron microscope picture under 5nm as shown in Figure 3; 1%Pd/UiO-66-NH
2in Pd particle size distribution figure as shown in Figure 4, can 1%Pd/UiO-66-NH be found out from Fig. 1-3
2middle Pd is at UiO-66-NH
2be evenly distributed in carrier; Fig. 4 is 1%Pd/UiO-66-NH
2in Pd particle size distribution figure, as we can see from the figure, the Pd granular size of load is about 4nm.
1%Pd/UiO-66-NH
2and UiO-66-NH
2thermal multigraph as shown in Figure 5; Fig. 5 is 1%Pd/UiO-66-NH
2and UiO-66-NH
2thermal multigraph; The composition lost before 100 DEG C is as we can see from the figure low boiling point solvent molecule ether, and between 100 DEG C to 326 DEG C, such as the DMF of the solvent molecule in framework evaporates.When temperature continues to rise, the hurried decline of thermogravimetric curve, now MOF framework starts to cave in, and 491 DEG C time, framework complete collapse is ZrO
2.
Fig. 6 is Pd/UiO-66-NH
2n
2absorption figure; Fig. 6 can find out, UiO-66-NH
2, 0.3%Pd/UiO-66-NH
2, 0.5%Pd/UiO-66-NH
2, 1.0%Pd/UiO-66-NH
2specific area be followed successively by 659m2/g, 461m2/g, 438m2/g and 377m2/g, along with load capacity increase, specific area reduces successively, this is because some Pd plugs UiO-66-NH
2duct;
Fig. 7 is the Pd/UiO-66-NH with different content
2for the CO conversion ratio figure of catalyst; Load capacity is 0.3%, 0.5%, the temperature when T50(CO conversion ratio of UiO-66-NH2 to CO of 1.0% is 50%) be 160,165, and170 DEG C respectively, the temperature of 100% conversion ratio is all 180 DEG C, and the catalytic effect of 1.0% is best.
Fig. 8 is 1%Pd/UiO-66-NH
2xRD(X x ray diffration pattern x before and after reaction) figure; Before and after CO oxidation, our UiO-66-NH
2framework remains intact, and the good stability of this catalyst is described, long service life;
Fig. 9 is 1%Pd/UiO-66-NH
2life-span at 180 DEG C and time chart, using the temperature of CO100% conversion ratio as reaction condition, namely 180 DEG C, as can be seen from the figure, at 180 DEG C, 1%Pd/UiO-66-NH
2cO oxidation 100% conversion ratio can be kept at more than 100h.
The foregoing is only section Example of the present invention, be not used for limiting the present invention.In every case the equalization done according to content of the present invention changes and modifies, and is all within protection scope of the present invention.
Claims (9)
1. one kind has the Pd/UiO-66-NH of high stability
2material, is characterized in that carrier is Zr
6o
32secondary structure unit, its carrier molecule formula is [Zr
6o
4(OH)
4(O
2c – C
6nH
3– CO
2)
6], the noble metal of load is Pd.
2. a kind of Pd/UiO-66-NH with high stability according to claim 1
2material, is characterized in that the granular size of the Pd of load is 2-6nm, is preferably 4nm.
3. a Pd/UiO-66-NH with high stability according to claim 1
2the preparation method of material, is characterized in that concrete steps are as follows:
1) be dissolved in DMF by amino for 5-terephthalic acid (TPA) and zirconium chloride, carry out hydro-thermal reaction, filter, washing, vacuum drying obtains UiO-66-NH
2;
2) by Pd (acac)
2dMF solution be added drop-wise to UiO-66-NH
2dMF solution in, mix ultrasonic after be transferred to round-bottomed flask stir, drip NaBH
4solution reduction, stirring, filtration, washing, drying, obtain powder-product Pd/UiO-66-NH
2material.
4. the Pd/UiO-66-NH with high stability according to claim 3
2the preparation method of material, it is characterized in that in step 1), hydrothermal temperature is 110-130 DEG C, the reaction time is 2860-2900min.
5. the Pd/UiO-66-NH with high stability according to claim 3
2the preparation method of material, it is characterized in that in step 1), hydrothermal temperature is 120 DEG C, the reaction time is 2880min.
6. the Pd/UiO-66-NH with high stability according to claim 3
2the preparation method of material, is characterized in that step 2) middle NaBH
4with Pd (acac)
2molar ratio be 8-12:1, be preferably 10:1.
7. the Pd/UiO-66-NH with high stability according to claim 3
2the preparation method of material, is characterized in that step 2) in cleaning solvent be DMF and the ether mixtures of any ratio.
8. the Pd/UiO-66-NH with high stability according to claim 3
2the preparation method of material, is characterized in that step 1) and step 2) in vacuum drying chamber temperature be 75-85 DEG C, drying time is 2.5-3.5h.
9. one kind has the Pd/UiO-66-NH of high stability
2material in Oxidation of Carbon Monoxide reaction as the application of catalyst.
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