CN104399523B - The preparation method of load type nano gold catalyst - Google Patents
The preparation method of load type nano gold catalyst Download PDFInfo
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- CN104399523B CN104399523B CN201410519661.5A CN201410519661A CN104399523B CN 104399523 B CN104399523 B CN 104399523B CN 201410519661 A CN201410519661 A CN 201410519661A CN 104399523 B CN104399523 B CN 104399523B
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Abstract
The preparation method that the present invention relates to a kind of load type nano gold catalyst, including step be: weigh polyoxyethylene polyoxypropylene copolymer solution be dissolved in deionized water formed muddiness solution A；The formalin that concentration is 37wt.% is mixed to get muddy solution B with deionized water, is subsequently adding tripolycyanamide and thiourea stirring obtains solution C；Solution A is poured into stirring in solution C and obtains solution D, waterglass is dissolved in deionized water and obtains solution E, solution D is quickly poured into glacial acetic acid, solution E is poured again in solution D, again with microwave heating and ethanol soxhlet type etc., obtain mesoporous organic-inorganic Acrylic Polymer Interpenetrating Polymer and be dispersed in deionized water, being then the HAuCl of 0.24M by concentration4Aqueous solution be added dropwise over, regulate pH value to 7-8 with NaOH that concentration is 1M, stir and be filtrated to get load type nano gold catalyst sample.Its advantage is: catalysis activity and good stability, it is possible to cheap chemical preparation load type nano gold catalyst, load type nano gold catalyst can be reused repeatedly.
Description
Technical field
The preparation method that the present invention relates to a kind of load type nano gold catalyst.
Background technology
Load type nano gold catalyst shows the catalytic performance of excellence in many important selective oxidation reactions, but the minimum gold particle of size has bigger surface free energy and relatively low fusing point, can occur quick self assemble that gold particle size is sharply increased when there is no space obstacle, thus losing catalysis activity.Therefore, the physicochemical properties of carrier in load type nano gold catalyst, as structure form, the catalysis Activity and stabill of final load type nano gold catalyst is played critical effect by interaction etc. between affinity and gold particle and carrier to gold species.With traditional load type nano gold catalyst carrier, as metal-oxide or activated carbon are compared, mesoporous material has relatively regular pore passage structure, and texture character is highly controllable, what is more important, mesoporous material have can the surface of cutting and structure, the material of task ad hoc type can be synthesized according to demand, this synthesizes load type nano gold catalyst carrier for appropriate design and provides possibility.
Inventor has synthesized a kind of bridge joint organosilicon precursor containing ionic liquid fragment and thioether before this and has been compound in mesoporous material, owing to sulfur organic component is uniformly distributed in the material, golden nanometer particle can high degree of dispersion wherein, gained nano catalyst is showing high catalysis activity and stability with hydrogen peroxide for the epoxidation reaction of olefines of oxidant；But, in above-mentioned catalyst, the bridge joint organosilicon precursor containing ionic liquid fragment and thioether synthesizes sufficiently complex and golden anchor point single property, and the catalysis activity of catalyst restricts mutually with catalyst stability.
Recently, the advantage that inventor separates at concentration of precious metal with mesoporous material in conjunction with chelating resin, synthesize carbamide-thiourea resin/SBA-15 composite that series of new is novel, 30oUnder C, the saturated extent of adsorption of Au (III) is reached 3.04mmol g by this composite, and this implies that this type of material is likely to be the carrier of good nano catalyst.
Summary of the invention
It is an object of the invention to overcome the deficiencies in the prior art to provide a kind of catalysis activity and good stability, it is possible to by the preparation method of the load type nano gold catalyst of cheap chemical preparation.
In order to achieve the above object, the present invention is achieved in that it is the preparation method of a kind of load type nano gold catalyst, it is characterised in that comprise the steps:
Step one
At 50-70oWhen C, weigh the polyoxyethylene polyoxypropylene copolymer solution of 15-23% and be dissolved in deionized water and form the solution A of muddiness；
Step 2
After the formaldehyde of 13-17% is prepared into the formalin that concentration is 37wt.%, the solution B of muddiness it is mixed to get again with deionized water, adjust the pH value of solution B to 8.5-9.0 with sodium hydrate aqueous solution again, be subsequently adding the tripolycyanamide of 8-14% and the thiourea of 5-9%, at 50-70oUnder C, stirring obtains solution C in 1-3 hour；
Step 3
Solution A is poured in solution C and stir 2-3 hour, obtain solution D, during solution D stirs, the waterglass of 35-45% is dissolved in deionized water, at room temperature stir about 25-35 minute, obtains solution E, solution D is quickly poured into the glacial acetic acid of 7-9%, it is stirred vigorously down, in solution D, pours solution E into, by gained mixed liquor in 50-70 at onceoAfter stirring 0.5-1.5 hour under C, then at 50-70oC microwave heating 5-7 hour, filters, dry, and namely ethanol soxhlet type 46-50 hour obtains nitrogenous and sulfur mesoporous organic-inorganic Acrylic Polymer Interpenetrating Polymer；
Step 4
Take the mesoporous organic-inorganic Acrylic Polymer Interpenetrating Polymer obtained in the step 3 of 90-98% to be dispersed in 3-5%ml deionized water and obtain material F, then by the HAuCl of 0.5-1.5%4It is diluted to the aqueous solution that concentration is 0.24M, at 25-35oIn material F, it has been added dropwise over HAuCl under C4Aqueous solution, regulate pH value to 7-8 with NaOH that concentration is 1M, stir 22-26 hour, filter, vacuum drying, obtain containing golden load type nano gold catalyst sample.
Present invention advantage compared with prior art is: catalysis activity and good stability, it is possible to cheap chemical preparation load type nano gold catalyst, load type nano gold catalyst can be reused repeatedly.
Accompanying drawing explanation
Fig. 1 is the catalyst (a) N with carrier (b) of the present invention2Adsorption-desorption isothermal (left side) and pore size distribution curve (right side)；
Fig. 2 is the FT-IR collection of illustrative plates of the tripolycyanamide of the present invention and carrier；
Fig. 3 be the present invention roasting after the N of carrier2Adsorption-desorption isothermal (left side) and pore size distribution curve (right side)；
Fig. 4 is the TEM figure of the load type nano gold catalyst of the present invention；
The load type nano gold catalyst of Fig. 5 present invention epoxidation of styrene react in reuse result.
Detailed description of the invention
Below in conjunction with accompanying drawing, the specific embodiment of the present invention is described further.At this it should be noted that be adapted to assist in for the explanation of these embodiments and understand the present invention, but it is not intended that limitation of the invention.As long as just can be combined with each other additionally, technical characteristic involved in each embodiment of invention described below does not constitute conflict each other.
Embodiment one
The preparation method of load type nano gold catalyst, comprises the steps:
Step one
60oWhen C, weigh the polyoxyethylene polyoxypropylene copolymer solution of 19% and be dissolved in deionized water and form the solution A of muddiness；
Step 2
After formaldehyde by 15% prepares into the formalin that concentration is 37wt.%, then it is mixed to get the solution B of muddiness with deionized water, then adjusts the pH value of solution B to 8.7 with sodium hydrate aqueous solution, be subsequently adding the tripolycyanamide of 11% and the thiourea of 7%, 60oUnder C, stirring obtains solution C in 2 hours；
Step 3
Solution A is poured in solution C and stir 2.5 hours, obtain solution D, during solution D stirs, waterglass by 40% is dissolved in deionized water, and at room temperature stir about 30 minutes, obtain solution E, solution D is quickly poured into the glacial acetic acid of 8%, it is stirred vigorously down, in solution D, pours solution E into, by gained mixed liquor in 60 at onceoAfter stirring 1 hour under C, then 60oC microwave heating 6 hours, filters, dry, and namely ethanol soxhlet type 48 hours obtains nitrogenous and sulfur mesoporous organic-inorganic Acrylic Polymer Interpenetrating Polymer；
Step 4
Take the mesoporous organic-inorganic Acrylic Polymer Interpenetrating Polymer obtained in the step 3 of 93% to be dispersed in 5%ml deionized water and obtain material F, then by the HAuCl of 2%4It is diluted to the aqueous solution that concentration is 0.24M, 30oIn material F, it has been added dropwise over HAuCl under C4Aqueous solution, regulate pH value to 7-8 with NaOH that concentration is 1M, stir 24 hours, filter, vacuum drying, obtain containing golden load type nano gold catalyst sample.
Embodiment two
The preparation method of load type nano gold catalyst, it is characterised in that comprise the steps:
Step one
70oWhen C, weigh the polyoxyethylene polyoxypropylene copolymer solution of 23% and be dissolved in deionized water and form the solution A of muddiness；
Step 2
After formaldehyde by 17% prepares into the formalin that concentration is 37wt.%, then it is mixed to get the solution B of muddiness with deionized water, then adjusts the pH value of solution B to 8.5-9.0 with sodium hydrate aqueous solution, be subsequently adding the tripolycyanamide of 9% and the thiourea of 6%, 50oUnder C, stirring obtains solution C in 3 hours；
Step 3
Solution A is poured in solution C and stir 3 hours, obtain solution D, during solution D stirs, waterglass by 38% is dissolved in deionized water, and at room temperature stir about 35 minutes, obtain solution E, solution D is quickly poured into the glacial acetic acid of 7%, it is stirred vigorously down, in solution D, pours solution E into, by gained mixed liquor in 70 at onceoAfter stirring 0.5 hour under C, then 70oC microwave heating 5 hours, filters, dry, and namely ethanol soxhlet type 50 hours obtains nitrogenous and sulfur mesoporous organic-inorganic Acrylic Polymer Interpenetrating Polymer；
Step 4
Take the mesoporous organic-inorganic Acrylic Polymer Interpenetrating Polymer obtained in the step 3 of 91% to be dispersed in 6%ml deionized water and obtain material F, then by the HAuCl of 3%4It is diluted to the aqueous solution that concentration is 0.24M, 35oIn material F, it has been added dropwise over HAuCl under C4Aqueous solution, regulate pH value to 7-8 with NaOH that concentration is 1M, stir 26 hours, filter, vacuum drying, obtain containing golden load type nano gold catalyst sample.
Embodiment three
The preparation method of load type nano gold catalyst, it is characterised in that comprise the steps:
Step one
50oWhen C, weigh the polyoxyethylene polyoxypropylene copolymer solution of 15% and be dissolved in deionized water and form the solution A of muddiness；
Step 2
After formaldehyde by 13% prepares into the formalin that concentration is 37wt.%, then it is mixed to get the solution B of muddiness with deionized water, then adjusts the pH value of solution B to 8.5-9.0 with sodium hydrate aqueous solution, be subsequently adding the tripolycyanamide of 13% and the thiourea of 8%, 70oUnder C, stirring obtains solution C in 1 hour；
Step 3
Solution A is poured in solution C and stir 2 hours, obtain solution D, during solution D stirs, waterglass by 42% is dissolved in deionized water, and at room temperature stir about 25 minutes, obtain solution E, solution D is quickly poured into the glacial acetic acid of 9%, it is stirred vigorously down, in solution D, pours solution E into, by gained mixed liquor in 50 at onceoAfter stirring 1.5 hours under C, then 70oC microwave heating 5 hours, filters, dry, and namely ethanol soxhlet type 46 hours obtains nitrogenous and sulfur mesoporous organic-inorganic Acrylic Polymer Interpenetrating Polymer；
Step 4
Take the mesoporous organic-inorganic Acrylic Polymer Interpenetrating Polymer obtained in the step 3 of 95% to be dispersed in 4%ml deionized water and obtain material F, then by the HAuCl of 1%4It is diluted to the aqueous solution that concentration is 0.24M, 25oIn material F, it has been added dropwise over HAuCl under C4Aqueous solution, regulate pH value to 7-8 with NaOH that concentration is 1M, stir 22 hours, filter, vacuum drying, obtain containing golden load type nano gold catalyst sample.
The sign of load type nano gold catalyst sample
By the infrared spectrogram of Avatar370FT-IR type determination of infrared spectroscopy sample, select wave-number range at 4000-400cm-1In, resolution is 4cm-1. with the specific surface area of MicromeriticsTristar3000 type physical adsorption appearance test sample and pore-size distribution, adsorption temp is liquid nitrogen temperature-196oC, sample specific surface area is calculated by BET method, calculated sample pore-size distribution by isothermal line absorption by BJH model, the catalyst synthesized by the present invention is observed on JEM-2010 type transmission electron microscope, to analyze size and the dispersion of catalytic active center golden nanometer particle；Measure, with ThermoICAP6300 type inductive coupling plasma emission spectrograph, the content that the metallic element in synthesized catalyst is golden, measure the content of N, S element in sample with VarioELCUBE type elemental analyser, as shown in Figure 1.
Fig. 1 is the N of load type nano gold catalyst and carrier thereof2Adsorption-desorption isothermal and pore size distribution curve, as seen from the figure, nano catalyst and carrier all have the IV type adsorption-desorption isothermal of typical mesoporous material feature, at N2Relative pressure p/p0There is an obvious capillary condensation hop at=0.7-0.85 place, and also possesses the H of SBA-15 type mesoporous material1Type hysteresis loop, these results show that catalyst and carrier have orderly meso-hole structure, the texture parameter (see table 1) of comparative catalyst and carrier, the specific surface area of catalyst and pore volume opposite carrier have obvious reduction, and, aperture has been reduced to 10.6nm from 11.0nm, these result explanations, golden nanometer particle be successfully introduced into carrier mesoporous in, the result according to ICP, in catalyst gold content be 2.1wt%.
The physico-chemical property of table 1 load type nano gold catalyst and carrier thereof
| Sample | Pore size(nm) | Surface area (m2/g) | Pore volume (cm3/g) |
| Catalyst | 10.6 | 277 | 0.58 |
| Support | 11.0 | 376 | 0.65 |
Fig. 2 is the infrared spectrum of tripolycyanamide and carrier.Can be seen that two spectrograms are all at 1531cm by comparing-1,1456cm-1There is belonging to the stretching vibration peak of C=N, 3380cm in tripolycyanamide-1-NH2Absworption peak disappears in the carrier, illustrates in the building-up process of carrier, and tripolycyanamide and formaldehyde there occurs polycondensation reaction, define organic network；In addition, carrier is at 3475cm-1Occur in that the absworption peak of-OH, at 1146cm-1Occur in that the absworption peak of Si-O-Si.
In order to further probe into organic network and the inorganic network of present invention synthesis by together with which kind of mode is entrained in, carrier having been carried out following process: weigh 0.5g carrier in 550oC calcines 1 hour in air atmosphere, thus completely removing the organic component of present invention synthesis, then remaining inorganic component is carried out N2Adsorption-desorption is tested, gained N2Adsorption-desorption isothermal and pore size distribution curve are shown in Fig. 3, and the inorganic component after carrier calcination has the IV type adsorption-desorption isothermal of typical mesoporous material feature, at N2Relative pressure p/p0There is an obvious capillary condensation hop at=0.7-0.9 place, and possesses the H of SBA-15 type mesoporous material1Type hysteresis loop, these results show, carrier still has orderly meso-hole structure after removing organic network；In addition, N2Adsorption-desorption result shows, after roasting, the specific surface area of carrier is 718m2/ g, pore volume is 1.25cm3/ g, has had before comparing roasting and has increased significantly；It is worthy of note, after roasting, the pore size of carrier is 11.0nm, it does not have change；Tem analysis shows that load type nano gold catalyst has the mesoporous space of prosperity, and does not observe organic aggregation dephasign (left hand view see Fig. 4)；In conjunction with N2In adsorption-desorption analysis, before and after carrier calcination, carrier aperture is constant, the result that specific surface area and pore volume increase, it can be inferred that in catalyst, organic network and inorganic network define interpenetrating networks.
It can also be seen that (left hand view of Fig. 4 is 110 crystal faces to load type nano gold catalyst tool well-regulated hexagonal hole road structure from Fig. 4, the right part of flg of Fig. 4 is 001 crystal face), golden nanometer particle is evenly distributed in the mesopore orbit of carrier (see Fig. 4 white circle place), and the diameter of golden nanometer particle is about 3nm；This shows the carrier of golden nanometer particle that our mesoporous organic-inorganic Acrylic Polymer Interpenetrating Polymer has been, and golden nanometer particle can high degree of dispersion thereon.
The catalyst of present invention synthesis obtains regeneration catalyzing agent with vacuum drying under three to four room temperatures of absolute ethanol washing by centrifugation afterwards, then carries out the examination of catalyst reusability.From Fig. 5 result it can be seen that, the first five time is basically unchanged along with the selectivity increasing cinnamic conversion ratio and Styryl oxide of reusable number of times, catalyst uses after five times, after the selectivity decline .ICP result display catalyst of cinnamic conversion ratio and Styryl oxide uses six times, its gold content be have decreased to 1.4wt% by 2.1wt%, thus the loss of golden nanometer particle result in catalyst decline of catalysis activity after using five times.In the preparation of mesoporous organic-inorganic interpenetrating networks carrier, the ratio of tripolycyanamide and the amount of substance of thiourea is 1:1, and the ratio of the tripolycyanamide that N, the S constituent content that organic element analyzer measures shows in final carrier and the amount of substance of thiourea is 5:1.This shows in mesoporous organic-inorganic interpenetrating networks carrier building-up process, and the amount that thiourea enters carrier is less.Owing to element S is for element N, gold species there is is higher affinity, thus in final carrier, relatively low S content is probably the catalyst reason that golden nanometer particle runs off after reusing 5 times.
Above in association with accompanying drawing, embodiments of the present invention are made detailed description, but the present invention is not limited to described embodiment.For the ordinary skill in the art, when without departing from principles of the invention and objective, these embodiments are carried out multiple change, amendment and replacement to still fall within protection scope of the present invention.
Claims (1)
1. the preparation method of a load type nano gold catalyst, it is characterised in that comprise the steps:
Step one
At 50-70oWhen C, weigh the polyoxyethylene polyoxypropylene copolymer solution of 15-23% and be dissolved in deionized water and form the solution A of muddiness；
Step 2
After the formaldehyde of 13-17% is prepared into the formalin that concentration is 37wt.%, the solution B of muddiness it is mixed to get again with deionized water, adjust the pH value of solution B to 8.5-9.0 with sodium hydrate aqueous solution again, be subsequently adding the tripolycyanamide of 8-14% and the thiourea of 5-9%, at 50-70oUnder C, stirring obtains solution C in 1-3 hour；
Step 3
Solution A is poured in solution C and stir 2-3 hour, obtain solution D, during solution D stirs, the waterglass of 35-45% is dissolved in deionized water, and at room temperature stirring 25-35 minute, obtains solution E, solution D is quickly poured into the glacial acetic acid of 7-9%, it is stirred vigorously down, in solution D, pours solution E into, by gained mixed liquor in 50-70 at onceoAfter stirring 0.5-1.5 hour under C, then at 50-70oC microwave heating 5-7 hour, filters, dry, and namely ethanol soxhlet type 46-50 hour obtains nitrogenous and sulfur mesoporous organic-inorganic Acrylic Polymer Interpenetrating Polymer；
Step 4
Take the mesoporous organic-inorganic Acrylic Polymer Interpenetrating Polymer obtained in the step 3 of 90-95% to be dispersed in 3-6%ml deionized water and obtain material F, then by the HAuCl of 1-3%4It is diluted to the aqueous solution that concentration is 0.24M, at 25-35oIn material F, it has been added dropwise over HAuCl under C4Aqueous solution, regulate pH value to 7-8 with NaOH that concentration is 1M, stir 22-26 hour, filter, vacuum drying, obtain containing golden load type nano gold catalyst sample.
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| CN107349960B (en) * | 2016-05-09 | 2020-02-07 | 中国科学院大连化学物理研究所 | Nitrogen-containing cross-linked polymer supported nano-gold catalyst, preparation thereof and application thereof in alcohol selective oxidation reaction in aqueous medium |
| CN106378188B (en) * | 2016-08-25 | 2018-12-07 | 中国科学院广州能源研究所 | A kind of polymer/mesoporous silicon composite loaded Cu-Fe-Co base catalyst, preparation method and its application |
| CN107589163B (en) * | 2017-09-06 | 2019-11-29 | 重庆医科大学 | A kind of electrochemical sensor preparation method for the detection of MECP2 mutated gene |
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| CN1304942A (en) * | 2000-05-12 | 2001-07-25 | 中国石油天然气股份有限公司兰州石化分公司 | Water-proof lower-aldehyde urea-formaldehyde resin and its preparing process |
| CN1865343A (en) * | 2005-05-20 | 2006-11-22 | 中国石油天然气股份有限公司 | Process for preparing urea-formaldehyde resin additive, preparation method and uses |
| CN102352006A (en) * | 2011-07-20 | 2012-02-15 | 合肥工业大学 | Ultrasonic preparation method of micron spherical melamine-formaldehyde-thiourea chelating resin |
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| CN1304942A (en) * | 2000-05-12 | 2001-07-25 | 中国石油天然气股份有限公司兰州石化分公司 | Water-proof lower-aldehyde urea-formaldehyde resin and its preparing process |
| CN1865343A (en) * | 2005-05-20 | 2006-11-22 | 中国石油天然气股份有限公司 | Process for preparing urea-formaldehyde resin additive, preparation method and uses |
| CN102352006A (en) * | 2011-07-20 | 2012-02-15 | 合肥工业大学 | Ultrasonic preparation method of micron spherical melamine-formaldehyde-thiourea chelating resin |
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