CN106268947A - A kind of preparation method of nanometer starch crystal load gold nano grain effective catalyst - Google Patents
A kind of preparation method of nanometer starch crystal load gold nano grain effective catalyst Download PDFInfo
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- 229920002472 Starch Polymers 0.000 title claims abstract description 81
- 239000008107 starch Substances 0.000 title claims abstract description 81
- 235000019698 starch Nutrition 0.000 title claims abstract description 81
- 239000013078 crystal Substances 0.000 title claims abstract description 59
- 239000010931 gold Substances 0.000 title claims abstract description 53
- 229910052737 gold Inorganic materials 0.000 title claims abstract description 50
- 239000003054 catalyst Substances 0.000 title claims abstract description 49
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 230000003197 catalytic effect Effects 0.000 claims abstract description 16
- 239000002245 particle Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 40
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 27
- 235000013339 cereals Nutrition 0.000 claims description 26
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000002202 Polyethylene glycol Substances 0.000 claims description 14
- 229920001223 polyethylene glycol Polymers 0.000 claims description 14
- 229910004042 HAuCl4 Inorganic materials 0.000 claims description 11
- 238000006555 catalytic reaction Methods 0.000 claims description 10
- 229920002261 Corn starch Polymers 0.000 claims description 9
- 239000008120 corn starch Substances 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 239000002270 dispersing agent Substances 0.000 claims description 8
- 238000012360 testing method Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 238000006479 redox reaction Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 6
- 240000003183 Manihot esculenta Species 0.000 claims description 5
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 229940100486 rice starch Drugs 0.000 claims description 5
- 230000007062 hydrolysis Effects 0.000 claims description 4
- 238000006460 hydrolysis reaction Methods 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 238000010531 catalytic reduction reaction Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000008346 aqueous phase Substances 0.000 claims description 2
- 238000007710 freezing Methods 0.000 claims description 2
- 230000008014 freezing Effects 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 230000004044 response Effects 0.000 claims description 2
- 235000011149 sulphuric acid Nutrition 0.000 claims 1
- 239000001117 sulphuric acid Substances 0.000 claims 1
- 230000004048 modification Effects 0.000 abstract description 3
- 238000012986 modification Methods 0.000 abstract description 3
- 230000002829 reductive effect Effects 0.000 abstract description 3
- 239000000463 material Substances 0.000 description 8
- 229920002678 cellulose Polymers 0.000 description 7
- 239000001913 cellulose Substances 0.000 description 7
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 239000002159 nanocrystal Substances 0.000 description 6
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 5
- 238000004108 freeze drying Methods 0.000 description 5
- 239000008187 granular material Substances 0.000 description 5
- 239000002105 nanoparticle Substances 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 239000011943 nanocatalyst Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229920000881 Modified starch Polymers 0.000 description 1
- 239000004368 Modified starch Substances 0.000 description 1
- 229920001046 Nanocellulose Polymers 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- NJSSICCENMLTKO-HRCBOCMUSA-N [(1r,2s,4r,5r)-3-hydroxy-4-(4-methylphenyl)sulfonyloxy-6,8-dioxabicyclo[3.2.1]octan-2-yl] 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)O[C@H]1C(O)[C@@H](OS(=O)(=O)C=2C=CC(C)=CC=2)[C@@H]2OC[C@H]1O2 NJSSICCENMLTKO-HRCBOCMUSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 235000019426 modified starch Nutrition 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/068—Polyalkylene glycols
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0063—Granulating
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to the preparation method of a kind of nanometer starch crystal load gold nano grain effective catalyst, including preparation and nanometer starch crystal load gold nano grain two parts content of nanometer starch crystal.The nanometer starch crystal load gold nano grain effective catalyst of the present invention is mainly carried out in solwution method modification environment.The nanometer starch crystal particle diameter of preparation is 20 ~ 300 nm, and the particle diameter of gold nano grain is 1 ~ 10 nm；The catalyst of the nanocrystalline load gold nano grain of novel starch of preparation has the catalysed reductive energy of excellence, and its observed rate constant k is 3 ~ 3.22 × 10−2s−1, catalytic cycle frequency TOF is 650 ~ 670 h−1。
Description
Technical field
The present invention relates to the preparation method of a kind of bio-based nanocatalyst, especially relate to a kind of nanometer starch crystal load
The preparation method of gold nano grain effective catalyst, belongs to modified starch processing technique field.
Background technology
In recent years, gold nano grain had caused interest widely as a kind of novel catalyst.It is known that macroscopic view gold
Belonging to gold is a kind of inert material, and its nano-particle has the reactivity of height and can optionally participate in a series of heavy
The catalytic reaction wanted.Experiment finds, only just has stronger reactivity when gold grain size reaches a few nanometer, and when height
When 10 nm, this activity the most gradually weakens, until disappearing.Owing to having the biggest specific surface area, gold nano grain is with other
Nano material is the same, and dispersion is unstable and easily reunites and becomes larger particles, and then the activity needed for reducing as catalyst.
Therefore, supported gold nanoparticles just arises at the historic moment.With bigger organic or inorganic granule (such as nano-sized carbon, silicon, metal-oxide
Or polymer etc.) as carrier, gold nano grain being connected on carrier surface, this modified catalyst is the most organic
Reaction shows good catalytic effect.
Along with being rooted in the hearts of the people of environmental consciousness and sustainable application idea, researchers are sought for using biomass material
Expect the carrier as gold nano grain catalyst, but the achievement of this respect is the most little.Starch is as nature content very
High pure biomass macromolecular material, but be the most always mainly used in food service industry, the most minimal amount of starch application in
Material Field.In the growth course of nature, the strand of starch, through regular accumulation, defines crystal-amorphous
The starch granules that district is arranged alternately.It is demonstrated experimentally that the amorphous domain in starch granules can be degraded under the corrosion of acid, and brilliant
The chemical resistance that Qu Zeyou is the strongest, therefore the hydrolysis through strong acid can realize the separation of crystalline region and amorphous area.Separate
After the starch crystal grain that obtains present the round pie of nanoscale, and substantial amounts of oh group is contained on its surface, and this is starch
Nanocrystalline surface modification provides possibility.
With nanometer starch crystal similarly, Cellulose nanocrystal is also used as the carrier of gold nano grain, and research
Personnel have carried out substantial amounts of work around this field, and have prepared the preferable loaded catalyst of catalytic performance.But,
In some preparation methoies, commonly used chemical reagent toxicity is big, the synthesis mode of operational hazards.Research afterwards proves, boron hydrogen
Change sodium and can be effectively reduced the particle size of gold so that it is reach nanoscale.(Wu X, Lu C, Zhou Z, the et al. such as Wu
Green synthesis and formation mechanism of cellulose nanocrystal-supported
gold nanoparticles with enhanced catalytic performance[J]. Environmental
Science:Nano, 2014,1 (1): 71-79.) by Cellulose nanocrystal and HAuCl4Together it is scattered in aqueous solution, and
Under the conditions of 120 DEG C, react 10 h, obtain the hybrid material of Cellulose nanocrystal load gold nano grain, this hydridization material
The particle diameter of material at about 20 nm, and n nonylphenol to carry out effect be to show that to answer observed rate constant k be 2.06 × 10−3 s−1,
Catalytic cycle frequency TOF is 109 h−1.And Lam et al. (Lam E, Hrapovic S, Majid E, et al.
Catalysis using gold nanoparticles decorated on nanocrystalline cellulose[J].
Nanoscale, 2012,4 (3): 997-1002.) using the modified Cellulose nanocrystal of diallyldimethylammonium chloride as
The same n nonylphenol of nano catalyst prepared by carrier carries out catalysis reduction, and reaction k value is 5.1 × 10−3 s−1, catalytic cycle
Frequency TOF is 212 h−1.And, surface more smaller than Cellulose nanocrystal is had hydroxyl structure equally, bear as catalyst
The bigger nanometer starch crystal of load advantage is but rarely reported as the trial of nanometer gold carrier.
Summary of the invention
The present invention's is exactly on the basis of using for reference conventional staff's experience, and the carrier of nanometer gold is changed to granule more
Little, load effect more preferably nanometer starch crystal, change reaction condition so that the preparation process of hybrid catalyst more preferably ring simultaneously
Guarantor, gentleness, reach the purpose of environmental protection while improving catalyst efficiency.The invention provides one is to be with nanometer starch crystal
Carrier, realizes the preparation of the new catalyst that gold nano grain is loaded by nanometer starch crystal in a mild condition.
The preparation method of a kind of nanometer starch crystal load gold nano grain effective catalyst of the present invention: pass through sulfuric acid solution
Starch is processed by method, obtains the nanometer starch crystal that particle diameter is nanoscale, then by nanometer starch crystal and HAuCl4, poly-second
Glycol is mix homogeneously in aqueous phase, has reacted the synthesis of efficient catalyst in a mild condition.
Further, described sulfuric acid solution method processes starch and prepares nanometer starch crystal, uses and is pressed with sulfuric acid solution by starch
Mix according to certain proportion, at a certain temperature stirring hydrolysis 6 ~ 8 hours, be then passed through deionized water centrifuge washing thoroughly after carry out
Lyophilization obtains nanometer starch crystal.
Preferably, described starch includes corn starch, tapioca, rice starch, wheaten starch；
Described sulfuric acid solution concentration is 3 ~ 4mol/L, and starch concentration in reaction system is 0.05 ~ 0.15 g/mL；
Described reaction temperature is 60 ~ 80 DEG C；
Described nanometer starch crystal particle size is distributed as 20 ~ 300 nm.
Further, in the synthetic reaction condition of described efficient catalyst, with deionized water as dispersant, add certain
Nanometer starch crystal, Polyethylene Glycol and the HAuCl of amount4, mixed system reacts at a certain temperature until synthetic reaction terminates, then
Nanometer starch crystal supported nanometer gold catalyst is obtained after separating, washing, drying.
Preferably, described nanometer starch crystal consumption is 0.02 ~ 0.5 %, and Polyethylene Glycol consumption is 20 (v/v) %,
HAuCl4Consumption is 170 ~ 190 μm ol/L；Described molecular weight polyethylene glycol is 300 ~ 500 g/mol；Described reaction temperature
Being 75 ~ 85 DEG C, the response time is 0.8 ~ 1.5 h.
Further, described nanometer starch crystal supported nanometer gold catalyst has the highest catalytic reduction efficiency, through test
Test, during its participation redox reaction, the apparent rate constants k of reaction through catalysis is 3 ~ 3.22 × 10−2s−1, catalytic cycle frequency
Rate TOF is 650 ~ 670 h−1。
Compared with prior art, beneficial effects of the present invention:
(1) compared with prior art, present invention introduces the nanometer starch crystal carrier as gold nano grain catalyst, due to starch
Nanocrystalline granule is less than the particle size of Cellulose nanocrystal, and has substantial amounts of surface hydroxyl structure equally, therefore,
On the basis of keeping gold nano grain high capacity rate, it is possible to increase the catalytic effect of catalyst, give full play to gold nano grain
Catalytic action.
(2) present invention uses deionized water as dispersant, has carried out nanometer starch crystal at normal temperatures to gold nano grain
Load-reaction.Compared with existing technology, on the one hand reaction does not use any chemical reagent to environmental toxic, fully
Embodying the friendly of environment, still further aspect, gentle reaction condition will be substantially reduced enterprise's production cost, avoid simultaneously
Danger in technological operation, has the strongest practicality.
(3) present invention introduces the Polyethylene Glycol of low-molecular-weight in loaded catalyst so that catalyst was unlikely to
Subpackage is covered and while loss of activity, it is possible to make catalyst be easily applied to medical treatment, change under homodisperse state
Etc. field, has good organic, biocompatibility.
(4) the nanometer starch crystal supported nanometer gold catalyst that prepared by the present invention has the highest catalytic reduction efficiency, through examination
Test tries, and during its participation nonyl phenol redox reaction, the apparent rate constants k of reaction through catalysis is 3 ~ 3.22 × 10−2s−1, urge
Changing period frequency TOF is 650 ~ 670 h−1, higher than the catalytic efficiency of similar catalyst in existing report.
Detailed description of the invention
Face combines detailed description of the invention, and the present invention is expanded on further.Should be understood that these embodiments are merely to illustrate the present invention
Rather than restriction the scope of the present invention.In addition, it is to be understood that after having read the content that the present invention lectures, people in the art
The present invention can be made various changes or modifications by member, and these equivalent form of values fall within the application appended claims equally and limited
Scope.
A kind of preparation method of the nanometer starch crystal load gold nano grain effective catalyst of the present invention, concrete technology step
For:
(1) hydrolysis of nanometer starch crystal
Sulfuric acid concentration is configured to 3.16 mol/L, adds the starch of 0.1 g/mL, be warming up to 60 ~ 80 DEG C after stirring and open
Begin to hydrolyze.Duration of the reaction is 6 ~ 8 h.Final reacting product is centrifugal through deionized water, it is freezing dry to carry out after washing thoroughly
Dry, obtain nanometer starch crystal powder.The particle diameter of gained nanometer starch crystal product is 20 ~ 300 nm.
(2) preparation of nanometer starch crystal load gold nano grain hybrid material
Using deionized water as dispersant, by the poly-second that nanometer starch crystal (0.02 ~ 0.5 %), molecular weight are 300 ~ 500 g/mol
Glycol (20 (v/v) %), HAuCl4(170 ~ 190 μm ol/L) is sequentially added into, and rises high-temperature and starts reaction to 75 ~ 85 DEG C, instead
Answer stopped reaction after 0.8 ~ 1.5 h.Carry out reacted mixed system separating, wash, obtain nanometer starch crystal after drying and bear
Carried nano-gold catalyst synthetic products.
In the present invention, reaction do not participated in by Polyethylene Glycol.The effect introducing Polyethylene Glycol is to bear for nanometer starch crystal
Carried nano-gold hybrid catalyst provides an organic carrier, enables this catalyst to be applied to body medical, organically-modified more easily
System.
Embodiment 1
Sulfuric acid concentration is configured to 3.16 mol/L, adds the corn starch of 0.1 g/mL, be warming up to 60 DEG C after stirring and open
Begin to hydrolyze.Duration of the reaction is 8 h.Final reacting product is centrifugal through deionized water, carry out lyophilization after washing thoroughly,
Obtain nanometer starch crystal powder.The particle diameter of gained nanometer starch crystal product is 300 nm.
Again using deionized water as dispersant, it is 500 by worth corn starch nanocrystalline (0.02 %), molecular weight
The Polyethylene Glycol (20 (v/v) %) of g/mol, HAuCl4(170 μm ol/L) is sequentially added into, and rises high-temperature and starts to 85 DEG C anti-
Should, react stopped reaction after 1.5 h.Carry out reacted mixed system separating, wash, obtain nanometer starch crystal after drying and bear
Carried nano-gold catalyst synthetic products.
Through experimental test, corn starch nanocrystalline load gold nano grain catalyst prepared by the present embodiment participates in nonyl phenol
During redox reaction, the apparent rate constants k of reaction through catalysis is 3 × 10−2s−1, catalytic cycle frequency TOF is 650 h−1。
Embodiment 2
Sulfuric acid concentration is configured to 3.16 mol/L, adds the corn starch of 0.1 g/mL, be warming up to 80 DEG C after stirring and open
Begin to hydrolyze.Duration of the reaction is 6 h.Final reacting product is centrifugal through deionized water, carry out lyophilization after washing thoroughly,
Obtain corn starch manocrystalline powders.The particle diameter of gained nanometer starch crystal product is 20 nm.
Again using deionized water as dispersant, it is 500 g/mol's by nanocrystalline for corn starch (0.5 %), molecular weight
Polyethylene Glycol (20 (v/v) %), HAuCl4(170 μm ol/L) is sequentially added into, and rises high-temperature and starts reaction, reaction to 75 DEG C
Stopped reaction after 1.5 h.Carry out reacted mixed system separating, wash, obtain nanometer starch crystal load nanometer after drying
Au catalyst synthetic products.
Through experimental test, corn starch nanocrystalline load gold nano grain catalyst prepared by the present embodiment participates in nonyl phenol
During redox reaction, the apparent rate constants k of reaction through catalysis is 3.22 × 10−2s−1, catalytic cycle frequency TOF is 670 h−1, higher than the catalytic efficiency of catalyst in embodiment 1.
Embodiment 3
Sulfuric acid concentration is configured to 3.16 mol/L, adds the tapioca of 0.1 g/mL, be warming up to 80 DEG C after stirring and open
Begin to hydrolyze.Duration of the reaction is 8 h.Final reacting product is centrifugal through deionized water, carry out lyophilization after washing thoroughly,
Obtain tapioca manocrystalline powders.The particle diameter of gained nanometer starch crystal product is 138 nm.
Again using deionized water as dispersant, it is 300 g/mol's by nanocrystalline for tapioca (0.45 %), molecular weight
Polyethylene Glycol (20 (v/v) %), HAuCl4(190 μm ol/L) is sequentially added into, and rises high-temperature and starts reaction, reaction to 85 DEG C
Stopped reaction after 0.8 h.Carry out reacted mixed system separating, wash, obtain nanometer starch crystal load nanometer after drying
Au catalyst synthetic products.
Through experimental test, when hydridization gold nano catalyst prepared by the present embodiment participates in nonyl phenol redox reaction, warp
The apparent rate constants k of reaction of catalysis is 3.01 × 10−2s−1, catalytic cycle frequency TOF is 663 h−1。
Embodiment 4
Sulfuric acid concentration is configured to 3.16 mol/L, adds the rice starch of 0.1 g/mL, be warming up to 80 DEG C after stirring and open
Begin to hydrolyze.Duration of the reaction is 8 h.Final reacting product is centrifugal through deionized water, carry out lyophilization after washing thoroughly,
Obtain rice starch manocrystalline powders.The particle diameter of gained nanometer starch crystal product is 30 nm.
Again using deionized water as dispersant, it is 410 g/mol's by nanocrystalline for rice starch (0.45 %), molecular weight
Polyethylene Glycol (20 (v/v) %), HAuCl4(190 μm ol/L) is sequentially added into, and rises high-temperature and starts reaction, reaction to 76 DEG C
Stopped reaction after 1.0 h.Carry out reacted mixed system separating, wash, obtain nanometer starch crystal load nanometer after drying
Au catalyst synthetic products.
Through experimental test, when hydridization gold nano catalyst prepared by the present embodiment participates in nonyl phenol redox reaction, warp
The apparent rate constants k of reaction of catalysis is 3.14 × 10−2s−1, catalytic cycle frequency TOF is 692 h−1。
Claims (7)
1. the preparation method of a nanometer starch crystal load gold nano grain effective catalyst, it is characterised in that by sulphuric acid acid
Starch is processed by solution, obtains the nanometer starch crystal that particle diameter is nanoscale, then by nanometer starch crystal and HAuCl4, poly-
Ethylene glycol is mix homogeneously in aqueous phase, has reacted the synthesis of efficient catalyst in a mild condition.
The preparation method of a kind of nanometer starch crystal load gold nano grain effective catalyst the most according to claim 1, its
Being characterised by, described sulfuric acid solution method processes starch and prepares nanometer starch crystal, uses starch with sulfuric acid solution according to necessarily
Ratio mixes, at a certain temperature stirring hydrolysis 6 ~ 8 hours, be then passed through deionized water centrifuge washing thoroughly after carry out freezing dry
Dry obtain nanometer starch crystal.
The preparation method of a kind of nanometer starch crystal load gold nano grain effective catalyst the most according to claim 2, its
Being characterised by, described starch includes corn starch, tapioca, rice starch, wheaten starch；
Described sulfuric acid solution concentration is 3 ~ 4mol/L, and starch concentration in reaction system is 0.05 ~ 0.15 g/mL；
Described reaction temperature is 60 ~ 80 DEG C；
Described nanometer starch crystal particle size is distributed as 20 ~ 300 nm.
The preparation method of a kind of nanometer starch crystal load gold nano grain effective catalyst the most according to claim 1, its
It is characterised by, in the synthetic reaction condition of described efficient catalyst, with deionized water as dispersant, adds a certain amount of shallow lake
Powder is nanocrystalline, Polyethylene Glycol and HAuCl4, mixed system reacts at a certain temperature until synthetic reaction terminates, then through dividing
From, washing, obtain nanometer starch crystal supported nanometer gold catalyst after drying.
The preparation method of a kind of nanometer starch crystal load gold nano grain effective catalyst the most according to claim 4, its
Being characterised by, described nanometer starch crystal consumption is 0.02 ~ 0.5 %, and Polyethylene Glycol consumption is 20 (v/v) %, HAuCl4Consumption
It is 170 ~ 190 μm ol/L；Described molecular weight polyethylene glycol is 300 ~ 500 g/mol；Described reaction temperature is 75 ~ 85
DEG C, the response time is 0.8 ~ 1.5 h.
The preparation method of a kind of nanometer starch crystal load gold nano grain effective catalyst the most according to claim 1, its
Being characterised by, described nanometer starch crystal supported nanometer gold catalyst has the highest catalytic reduction efficiency, through experimental test, its
During participation redox reaction, the apparent rate constants k of reaction through catalysis is 3 ~ 3.22 × 10−2s−1, catalytic cycle frequency TOF is
650~670 h−1。
The preparation method of a kind of nanometer starch crystal load gold nano grain effective catalyst the most according to claim 2, its
Being characterised by, described sulfuric acid concentration is configured to 3.16 mol/L, adds the starch of 0.1 g/mL.
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