CN102286185A - Temperature sensitive composite gold nano particles and preparation method and catalytic application thereof - Google Patents
Temperature sensitive composite gold nano particles and preparation method and catalytic application thereof Download PDFInfo
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- CN102286185A CN102286185A CN201110177820A CN201110177820A CN102286185A CN 102286185 A CN102286185 A CN 102286185A CN 201110177820 A CN201110177820 A CN 201110177820A CN 201110177820 A CN201110177820 A CN 201110177820A CN 102286185 A CN102286185 A CN 102286185A
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Abstract
The invention relates to temperature sensitive composite gold nano particles and a preparation method and catalytic application thereof. The temperature sensitive composite gold nano particles are compounded by using nano gold particles and poly (N-isopropyl acrylamide) (PNIPAM) grafted glucan polymer, and the diameter of the particles is 1 to 20 nanometers; the preparation method comprises the following process of: mixing and shaking chloroauric acid serving as a precursor, the PNIPAM grafted glucan polymer serving as a nucleating agent and a stabilizing agent and sodium borohydride serving as a reducing agent to obtain a product; and the temperature sensitive composite gold nano particles serving as a catalyst are used for regulating and controlling the temperature of the nitrophenol reduction reaction process to control the process and the stop of the reaction. The invention has the advantages that: the preparation process is simple; and the prepared temperature sensitive composite gold nano particles have high dispersion, good stability and temperature sensitivity, and are used as the catalyst for controlling the nitrophenol reduction reaction process.
Description
Technical field
The present invention relates to compound gold nano grain of a kind of temperature sensitive property and preparation method thereof and catalytic applications, belong to the gold nano-material technical field.
Background technology
Nano material has the special property that many traditional materials do not have, and causes extensive concern both domestic and external.Wherein, gold nano grain since its good bio-compatibility, special optical property, electrical properties and catalytic performance all be widely used at aspects such as useful for drug delivery, medical diagnosis on disease, optics, electronic machine and microreactors.Gold nano grain also has good catalytic performance, and Au is the highest metal of inertia, is considered to not have catalytic activity usually.But size reaches the Au nano particle of nanoscale and high dispersing has good catalytic activity (M.Haruta, Nature, 2005,437,1098～1099).
An important research direction of gold nano grain is given gold nano grain external environment stimulating responsive exactly, promptly to realizing the response of gold nano grain to external stimuluss such as temperature, pH value, ionic strength, light, electric fields.The gold nano grain of wherein temperature sensitive property is subjected to extensive concern, and it has good using value on making nanometer reactive switches and warning.Because many chemical reactions need carry out in certain temperature range, temperature is too high may to produce by product, reduces productive rate, perhaps blasts, and causes security incident.Temperature sensitive property gold nano grain has catalytic activity in certain temperature range, surpass this scope nanometer gold and can lose catalytic activity with regard to particle, causes reaction no longer to be carried out, thereby realizes temperature controlled chemical reaction.
But in research before, two-step approach is adopted in the gold nano grain preparation usually, needs the reaction of several hrs and the dialysis of a couple of days, and preparation process is complicated; The gold nano grain that makes is at extreme pH, high salt concentration solution, and coagulation, less stable take place under the hot conditions easily; And can not be when temperature be too high complete termination reaction, temperature sensitivity is relatively poor.
Summary of the invention
The objective of the invention is to be to provide compound gold nano grain of a kind of temperature sensitive property and preparation method thereof and catalytic applications.The compound gold nano grain of described temperature sensitive property has the characteristics of high degree of dispersion, good stability and temperature sensitive property; Its preparation method is simple and efficient; Use function with speed of reaction under Indicator Reaction temperature and the control differing temps as catalyzer.
The present invention is realized by following technical proposals: the compound gold nano grain of a kind of temperature sensitive property, it is characterized in that the compound gold nano grain of this temperature sensitive property is by gold nano grain and PNIPAM grafting dextran, (DexPNI) polymkeric substance is composited, wherein, the mass ratio of gold and PNIPAM grafting dextran polymer is 1:, (9～400), the compound gold nano grain particle diameter of temperature sensitive property is 1～11nm, the molecular formula of described PNIPAM grafting dextran polymer is as follows, under 25 ℃ and 40 ℃, have the thermal stimulus response property
Formula 1
In the formula: R
1, R
2, R
3, R
4, R
5, R
6H or be respectively does for oneself
In the formula: n is 40～100;
M is 5～50;
In the polymkeric substance, the massfraction of N-isopropylacrylamide group in each macromole is 7%～45%, and molecular weight is 8.08 * 10
4～1.29 * 10
5
The preparation method of the above-mentioned compound gold nano grain of temperature sensitive property is characterized in that comprising following process: with hydrochloro-auric acid (HAuCl
4) be presoma, be nucleator and stablizer with PNIPAM grafting dextran polymer, with sodium borohydride (NaBH
4) as reductive agent, by hydrochloro-auric acid and sodium borohydride mol ratio is 1: (5～10), by hydrochloro-auric acid and PNIPAM grafting dextran polymer mass ratio is 1: (17～680), PNIPAM grafting dextran polymer is mixed the compound gold nano grain of temperature sensitive property that under 0～32 ℃ temperature, vibrates and promptly obtained particle diameter 1-20nm in 1～2 minute with hydrochloro-auric acid and sodium borohydride.
The prepared compound gold nano grain of temperature sensitive property of the above-mentioned compound gold nano grain of temperature sensitive property or the method for having stated is used as catalyzer; in p-NP reduction reaction process; when regulating and controlling temperature reacted in time below 35 ℃, when regulating and controlling temperature stopped reaction more than 35 ℃ the time.
The invention has the advantages that and developed gold nano grain strong by single stage method synthetic stability and that have good temperature sensitivity.The preparation method is simple and convenient fast.The gold nano grain that makes has satisfactory stability, descends can keep stable in the salts solution and the different PH (PH=2～13) of high density, and can preserve with solid form by the freeze-drying means.Gold nano grain has good temperature sensitivity.When temperature surpasses critical temperature, gold nano grain generation coagulation, particle diameter increases.Particle diameter is less than gold nano grain catalytic activity difference under differing temps of 3nm, uses this gold nano grain can control speed of reaction under the differing temps, prevents to be reflected under the excessive temperature and carries out.
Description of drawings
Fig. 1 is projection electron microscope (TEM) figure of the compound gold nano grain colloidal solution of temperature sensitive property of embodiment 1 preparation.
Fig. 2 is the ultraviolet-visible spectrum of the compound gold nano grain of temperature sensitive property under differing temps of embodiment 1 preparation.
Fig. 3 is the temperature variant graphic representation of particle diameter of the compound gold nano grain of temperature sensitive property of embodiment 1 preparation.The grain diameter value of the compound gold nano grain of temperature sensitive property is recorded by dynamic light scattering among the figure.
Fig. 4 is used for the change curve of the reaction rate constant of catalyzed reaction with temperature change for the compound gold nano grain of temperature sensitive property of embodiment 1 preparation.
Embodiment
With reference to the following examples the present invention will be described in more detail.The following examples are the purposes that are used to explain, are not that intention limits the scope of the invention.
Embodiment 1
(1) PNIPAM grafting dextran polymer (DexPNI) is synthetic:
12mL Dodecyl Mercaptan, 40mL acetone and 0.8mL tri-n-octyl methyl ammonium chloride are added in the 150mL there-necked flask, at N
2Protection is cooled to 10 ℃ down.Dropwise 5 0% sodium hydroxide solution 4mL in 20min dropwises back restir 15min.Drip the mixing solutions of 3mL dithiocarbonic anhydride and 8mL acetone, this moment, solution became redness gradually, continued stirring reaction 30min.Dropwise 5 0% sodium hydroxide 13mL afterwards, stirring at normal temperature 12h.Add 65mL water, the acidifying of 33mL concentrated hydrochloric acid finally obtains yellow solid.Normal hexane recrystallization 8 times of this yellow solid, the gained yellow crystal is 2-dodecyl trithio carbonyl-2 Methylpropionic acid (DTM).At N
2Protection is dissolved in 0.55g DTM in the 5mL methylene dichloride down.At room temperature stir, drip 1.2mL oxalyl chloride solution, elevated temperature to 50 ℃ then, reaction 2h, this moment the solution becomes laking.1g dextran, 0.38g dimethyl aminopyridine and 0.4g triethylamine are dissolved in the 10mL anhydrous dimethyl sulfoxide, join in the reaction solution after mixing.Be warming up to 80 ℃, react and add ethanol after 24 hours, separate out precipitation and be the DexDTM crude product.With molecular weight cut-off (MWCO) is 3 days purifying of 3500 dialysis tubing dialysis.Lyophilize promptly gets DexDTM.At N
2Under the protection, ice bath is dissolved in 0.62g NIPAAm and 0.6g DexDTM in the 120mL deionized water.Feed 30min nitrogen, behind the excluding air, add 0.18g water soluble starter VA-044, elevated temperature to 80 ℃, reaction 4h.Is 14000 dialysis tubing dialysis 3 days with reaction solution with molecular weight cut-off (MWCO), removes small molecular weight impurity and salt, promptly gets DexPNI.
(2) the compound gold nano grain of temperature sensitive property is synthetic:
(1mL is 10mg/mL) with hydrochloro-auric acid (HAuCl with polymkeric substance (DexPNI) solution
4) (0.2mL 10mmol/L) mixes, and adds excessive sodium borohydride (NaBH again
4) (1mL, 10mmol/mL), color no longer changes (about 1min) to reacting also in vibration, generates gold nano grain.The ultraviolet-visible spectrophotometric spectra analysis revealed of product at 25 ℃, obvious crest do not occur and is increased to 40 ℃ when temperature, and absorbancy obviously increases.
Product (gold nano grain colloidal solution) is brown, and the TEM (transmission electron microscope) analysis of product shows that its particle diameter is about 1.8 ± 0.7nm, and is spherical in shape, do not have tangible agglomeration.
(3) catalytic performance of the compound gold nano grain of temperature sensitive property test:
Under 25 ℃, with the gold nano grain colloidal solution (1mL) that makes among the embodiment 1, with p-nitrophenyl phenol solution (1.5mL, 0.2mmol/L), (1mL 10mmol/L) mixes sodium borohydride solution, by ultraviolet-visible pectrophotometer the ultraviolet-visible spectrum of its mixing solutions is measured, through after a while, the crest at 400nm place fades away, and new crest appears in the 293nm place.Do not add gold nano grain, only add the p-nitrophenyl phenol solution and sodium borohydride solution ultraviolet-visible spectrum does not have considerable change, prove that gold nano grain has katalysis with the reduction reaction of p-NP.Test gold nano grain respectively 15,20,25,30,33,35, the catalytic performance under 38,40 ℃.At 15～30 ℃, reaction rate constant raises with the rising of temperature, meets general reaction rule.Near critical temperature (32～33 ℃), reaction rate constant raises with temperature and descends, and more than 35 ℃, reaction rate constant is reduced to 0, and reaction stops, and gold nano grain loses catalytic activity.When temperature is reduced to 30 ℃ again, gold nano grain recovers catalytic activity, and reaction can be proceeded.
Embodiment 2
Present embodiment step (1) is identical with embodiment 1 step (1).
(2) the compound gold nano grain of temperature sensitive property is synthetic:
(1mL is 10mg/mL) with hydrochloro-auric acid (HAuCl with polymkeric substance (DexPNI) solution
4) (1mL 10mmol/L) mixes, and adds excessive sodium borohydride (NaBH again
4) (5mL, 10mmol/mL), color no longer changes (about 1min) to reacting also in vibration, generates gold nano grain.
Gold nano grain colloidal solution is brown, and the TEM (transmission electron microscope) analysis of product shows that its particle diameter is about 3.4 ± 0.9nm, and is spherical in shape, do not have tangible agglomeration, the ultraviolet-visible spectrophotometric spectra analysis revealed of product is at 25 ℃, crest is 513nm, is the characteristic peak of particle diameter greater than the gold nano grain of 3nm.When temperature is increased to 40 ℃, absorbancy obviously increases, and the crest red shift is to 526nm.
Embodiment 3
Present embodiment step (1) is identical with embodiment 1 step (1).
(2) the compound gold nano grain of temperature sensitive property is synthetic:
(1mL is 10mg/mL) with hydrochloro-auric acid (HAuCl with polymkeric substance (DexPNI) solution
4) (2mL 10mmol/L) mixes, and adds excessive sodium borohydride (NaBH again
4) (10mL, 10mmol/mL), color no longer changes (about 1min) to reacting also in vibration, generates gold nano grain.
Gold nano grain colloidal solution takes on a red color, and the TEM (transmission electron microscope) analysis of product shows that its particle diameter is about 10 ± 1nm, and shape has circle, trilateral and Polygons.
Claims (3)
1. compound gold nano grain of temperature sensitive property, it is characterized in that, the compound gold nano grain of this temperature sensitive property is to be composited by nm gold particles and PNIPAM grafting dextran polymer, wherein, the mass ratio of gold and PNIPAM grafting dextran polymer is 1: (9～400), and the particle diameter of the compound gold nano grain of temperature sensitive property is 1～20nm; The molecular formula of described PNIPAM grafting dextran polymer is as follows, under 25 ℃ and 40 ℃, has temperature and the sensitive response property of redox,
Formula 1
In the formula: R
1, R
2, R
3, R
4, R
5, R
6H or be respectively does for oneself
In the formula: n is 40～100;
M is 5～50;
In the polymkeric substance, the massfraction of N-isopropylacrylamide group in each macromole is 7%～45%, and molecular weight is 8.08 * 10
4～1.29 * 10
5
2. method for preparing the compound gold nano grain of the described temperature sensitive property of claim 1, it is characterized in that comprising following process: be presoma with the hydrochloro-auric acid, with PNIPAM grafting dextran polymer is nucleator and stablizer, with sodium borohydride (NaBH
4) as reductive agent, by hydrochloro-auric acid and sodium borohydride mol ratio is 1: (5～10), by hydrochloro-auric acid and PNIPAM grafting dextran polymer mass ratio is 1: (17～680), PNIPAM grafting dextran polymer is mixed the compound gold nano grain of temperature sensitive property that under 0～32 ℃ temperature, vibrates and promptly obtained particle diameter 1-20nm in 1～2 minute with hydrochloro-auric acid and sodium borohydride.
3. use as catalyzer by the described compound gold nano grain of temperature sensitive property of claim 1 or with the compound gold nano grain of temperature sensitive property of the described method of claim 2 preparation for one kind; in p-NP reduction reaction process; when regulating and controlling temperature reacted in time below 35 ℃, when regulating and controlling temperature stopped reaction more than 35 ℃ the time.
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| CN104399534A (en) * | 2014-11-11 | 2015-03-11 | 无锡江南电缆有限公司 | Intelligent controllable catalytic material containing metal nano particle catalyst and preparation method thereof |
| CN104497237A (en) * | 2014-12-16 | 2015-04-08 | 湖南科技大学 | Temperature/light double-response gold nanocluster hybrid microgel and preparation method thereof |
| CN104826656A (en) * | 2015-04-30 | 2015-08-12 | 天津大学 | Temperature sensitive graphene-based gold-platinum core-shell bimetallic catalyst and preparation method thereof |
| CN105860089A (en) * | 2016-06-20 | 2016-08-17 | 东华大学 | Method for synthesizing thermosensitive sugar-containing polymer grafted nanogold micelle |
| CN106546749A (en) * | 2016-10-26 | 2017-03-29 | 首都师范大学 | Method of protein is detected based on nanometer gold DNA composites |
| CN106670497A (en) * | 2015-11-11 | 2017-05-17 | 中国科学院苏州纳米技术与纳米仿生研究所 | Temperature sensitive nano material and preparing method and application thereof |
| ES2637035A1 (en) * | 2017-03-31 | 2017-10-10 | Universidade De Santiago De Compostela | Sanitary product for antimicrobial treatment through photothermia (Machine-translation by Google Translate, not legally binding) |
| CN111450824A (en) * | 2020-05-14 | 2020-07-28 | 河北大学 | Preparation method and application of gold nano-catalyst with temperature response catalysis performance |
| CN111889137A (en) * | 2020-07-03 | 2020-11-06 | 湖北科技学院 | Full-solar-spectrum response type double-network hydrogel-based photocatalyst and preparation method thereof |
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| CN104399534A (en) * | 2014-11-11 | 2015-03-11 | 无锡江南电缆有限公司 | Intelligent controllable catalytic material containing metal nano particle catalyst and preparation method thereof |
| CN104497237A (en) * | 2014-12-16 | 2015-04-08 | 湖南科技大学 | Temperature/light double-response gold nanocluster hybrid microgel and preparation method thereof |
| CN104497237B (en) * | 2014-12-16 | 2017-02-01 | 湖南科技大学 | Temperature/light double-response gold nanocluster hybrid microgel and preparation method thereof |
| CN104826656B (en) * | 2015-04-30 | 2017-07-04 | 天津大学 | Temperature sensitive type Graphene fund platinum nucleocapsid bimetallic catalyst and preparation method thereof |
| CN104826656A (en) * | 2015-04-30 | 2015-08-12 | 天津大学 | Temperature sensitive graphene-based gold-platinum core-shell bimetallic catalyst and preparation method thereof |
| CN106670497B (en) * | 2015-11-11 | 2018-08-10 | 中国科学院苏州纳米技术与纳米仿生研究所 | Temperature sensitive nano material and its preparation method and application |
| CN106670497A (en) * | 2015-11-11 | 2017-05-17 | 中国科学院苏州纳米技术与纳米仿生研究所 | Temperature sensitive nano material and preparing method and application thereof |
| CN105860089A (en) * | 2016-06-20 | 2016-08-17 | 东华大学 | Method for synthesizing thermosensitive sugar-containing polymer grafted nanogold micelle |
| CN106546749A (en) * | 2016-10-26 | 2017-03-29 | 首都师范大学 | Method of protein is detected based on nanometer gold DNA composites |
| ES2637035A1 (en) * | 2017-03-31 | 2017-10-10 | Universidade De Santiago De Compostela | Sanitary product for antimicrobial treatment through photothermia (Machine-translation by Google Translate, not legally binding) |
| CN111450824A (en) * | 2020-05-14 | 2020-07-28 | 河北大学 | Preparation method and application of gold nano-catalyst with temperature response catalysis performance |
| CN111889137A (en) * | 2020-07-03 | 2020-11-06 | 湖北科技学院 | Full-solar-spectrum response type double-network hydrogel-based photocatalyst and preparation method thereof |
| CN111889137B (en) * | 2020-07-03 | 2023-08-04 | 湖北科技学院 | Full solar spectrum response type double-network hydrogel-based photocatalyst and preparation method thereof |
| CN114858733A (en) * | 2022-07-07 | 2022-08-05 | 江苏满星测评信息技术有限公司 | System and method for testing and analyzing optical performance of temperature-controlled film material |
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Application publication date: 20111221 |