CN101947448A - Nano-gold catalyst supported on combined metal oxide, preparation method and application thereof - Google Patents
Nano-gold catalyst supported on combined metal oxide, preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a nano-gold catalyst supported on combined metal oxide, a preparation method and an application thereof. The preparation method comprises the following steps: preparing layered double hydroxides (LDH) precursor crystal nucleus and dispersing the LDH precursor crystal nucleus into sucrose solution; then adding chloroauric acid solution in the obtained mixture so as to reduce Au3+ in HAuCl4 to Au single substances by using the reduction of glucose and fructose produced by sucrose hydrolysis; in the process of reduction, crystallizing the LDHs so as to obtain solid LDH supported on nano-gold; and carrying out high-temperature roasting on the solid LDH supported on the nano-gold so as to obtain the nano-gold catalyst supported on the combined metal oxide. The combined oxide of the catalyst is taken as a carrier on which the nanosize gold particles is supported, wherein the combined oxide refers to MgO or compound of ZnO and Al2O3, and the mole ratio of the MgO to the compound of ZnO and Al2O3 is 2-6:1; the gold capacity is 0.5 to 3 percent, the size of the gold particle is 8 to 15nm, and the gold particle is ellipsoidal or polyhedral. When the catalyst is used in the catalytic hydrogenation reaction of unsaturated aldehydes, the conversion rate of reactants reaches 60 to 97 percent, and the selectivity of cinnamyl alcohol is 40 to 75 percent.
Description
Technical field
The invention belongs to composite metal oxide nano material and preparation field thereof, be specifically related to load type gold catalyst and preparation method thereof, and used as the catalytic hydrogenation catalyst of unsaturated aldehyde.
Background technology
It is chemically inert that gold always is considered to, active far away from the platinum group metal aspect catalytic performance.But load on the nano catalyst on the transition metal oxide and be used for the carbon monoxide oxidation reaction since employing coprecipitations such as Haruta have prepared, show excellent catalytic performance [Haruta M, Yamada N, Kobayashi T, Iijima S.Journal of Catalysis, 1989,115 (2), 301-309], this discovery has been broken and has been thought that gold does not have the traditional concept of catalytic activity, causes people that the catalysis characteristics of gold has been produced very big interest and concern.After this, the research and development of relevant Au catalyst becomes increasingly active.Along with deepening continuously to Au catalyst research, the factor that it is found that the golden catalytic performance of influence mainly contains following three aspects: the interfacial structure between the size of nano Au particle, the character of carrier and gold grain and carrier, more than three factors all substantial connection is arranged with the preparation method of Au catalyst.Preparation method's difference can cause act between the difference of gold grain size and gold and carrier different, thus the catalytic performance of influence gold greatly.
The method for preparing load type gold catalyst of bibliographical information has at present: infusion process, coprecipitation, the deposition-precipitation method, ion-exchange.The Au catalyst dispersiveness that infusion process makes is bad, load capacity is little, the gold grain particle diameter is big, and its catalytic performance is relatively poor.The auri catalyst of coprecipitation preparation is wrapped in the inside of carrier because of considerable gold grain, and the particle that is wrapped in carrier inside can not participate in catalytic reaction, thereby golden utilization rate [Mamiko Yamashita, Hironori Ohashi, YasuhiroKobayashi have been reduced, Yoshihiro Okaue, Tsutomu Kurisaki, Hisanobu Wakita, Takushi Yokoyama.Journal ofColloid and Interface Science 2008,319,25-29].Deposition-the precipitation method are a kind of than effective method, and the key of this method is to control suitable pH value by the amount that drips alkali, thereby gold hydroxide is deposited on the carrier, obtain the catalyst that load capacity is low, granularity is little, activity is high, but cross low pH value gold hydroxide can't be deposited, so this method only just is suitable for [X.Yang, A.Wang to specific carrier, X.Wang, T.Zhang, K.Han, J.Li.J.Phys.Chem.C 2009,113,20918-20926.].Utilize hydroxyl on the carrier surface and the chlorion generation exchange reaction in the gold chloride, also can prepare load type gold catalyst [G.Riahi, D.Guillemot, M.Polisset-Thfoin, A.A.Khodadadi, J.Fraissar d, Catalysis Today 2002,72,115-121], but preparation process is wayward.
Summary of the invention
The purpose of this invention is to provide a kind of composite metal oxide nano catalyst and preparation thereof, and used as the catalytic hydrogenation reaction catalyst of unsaturated aldehyde.
Preparation method of the present invention is: at first utilize full back-mixing liquid film reactor (referring to patent CN1358691) to obtain layered double hydroxide precursor nucleus, the layered double hydroxide nucleus is dispersed in the aqueous sucrose solution, under proper temperature, add HAuCl
4The aqueous solution utilizes the glucose of sucrose hydrolysis generation and the reduction of fructose, with HAuCl
4In Au
3+Be reduced into Au simple substance, stratiform double-metal hydroxide crystallization simultaneously between reduction period obtains the layered double hydroxide solid of supported nano-gold, obtains the nano catalyst of composite metal oxide load through high-temperature roasting.
Composite metal oxide supported nanometer gold catalyst provided by the present invention: this catalyst is that nanogold particle is carried on the composite metal oxide carrier; Composite oxides are M
IIO and Al
2O
3Compound, M
IIO and Al
2O
3Molar ratio be 2-6: 1; Wherein Jin load capacity is 0.5-3%, and gold grain is of a size of 8-15nm, and gold grain is elliposoidal or polyhedron-shaped; Described M
IIO is MgO or ZnO.
The concrete preparation process of this composite metal oxide supported nanometer gold catalyst is as follows:
A. with solubility divalent salts and aluminum soluble salt preparation mixing salt solution, wherein aluminum ions molar concentration is 0.1-0.3mol/L, and the molar concentration of bivalent metal ion is Al
3+The 1-3 of molar concentration doubly; Described solubility divalent salts is a magnesium nitrate, magnesium chloride, and magnesium sulfate, zinc nitrate, a kind of in the zinc chloride, aluminum soluble salt is an aluminum nitrate, a kind of in the aluminium chloride.
Preparation NaOH and Na
2CO
3Mixed ammonium/alkali solutions, make its satisfy the NaOH molar concentration be metal ion molar concentration sum in the above-mentioned mixing salt solution 1-2 doubly, Na
2CO
3Concentration is 2-3 times of its aluminium ion molar concentration;
Mixing salt solution and mixed ammonium/alkali solutions are joined in the full back-mixing liquid film reactor simultaneously, mix 3-5min through rotating at a high speed, obtain layered double hydroxide suspension, to neutral, the sediment that obtains is standby with the suspension centrifuge washing; Wherein the rotating speed of liquid film reactor is 4000-4500r/min, and stator and gap between rotor are of a size of 15-18 μ m;
B. the layered double hydroxide precipitation adding mass concentration with steps A is in the sucrose solution of 2.5-10g/L, and wherein the mass ratio of layered double hydroxide and sucrose is 0.7-3, and more excellent mass ratio is 1.4-2.5; Ultrasonic 5-30min transfers in the reactor of band stirring, stirs, and temperature is heated to 80-95 ℃ from room temperature; With concentration is the chlorauric acid solution of 5-15mg/ml, is 10-80 according to sucrose solution and chlorauric acid solution mol ratio: 1, and more excellent mol ratio is 20-40: 1; Slowly be added drop-wise in the reactor of band stirring, reacted 0.5-6 hour; Question response is cooled to room temperature after finishing, centrifugal, washing; Descended dry 6-24 hour at 60-80 ℃, again in 50-70ml/min flow N
2Under the atmosphere,, obtain the composite Nano Au catalyst in 300-600 ℃ of roasting.
Adopt day island proper Tianjin XRD-6000 type x-ray powder diffraction instrument (XRD) to characterize product structure, the results are shown in Figure 1; Contain golden simple substance in this catalyst as seen from Figure 1.Adopt JEOL JEM-2100 type high power transmission electron microscope (HRTEM) to observe the pattern and the particle size of catalyst, the results are shown in Figure 2; The gold grain diameter of institute's load is at 8-15nm as seen from Figure 2, and particle is elliposoidal or polyhedron-shaped.Adopting the actual negative carrying capacity of gold on the Z-8000 type atomic absorption spectrometry catalyst is 0.5%-3%.
The present invention can be used as the unsaturated aldehyde hydrogenation catalyst, hydrogenation reaction with cinnamic acid is an example, cinnamic acid is a kind of typical unsaturated aldehyde, the product of its liquid-phase hydrogenatin reaction has many kinds, hydrogenation products cinnamyl alcohol wherein is a kind of important chemical intermediate feed, be widely used in industries such as spices, medicine, but the cinnamyl alcohol that traditional catalyst hydrogenation on cinnamic aldehyde obtains not that conversion ratio is low, is exactly poor selectivity.Catalyst of the present invention can improve the catalytic effect of this reaction.Concrete evaluation test is as follows: take by weighing the 0.2g catalyst, in the ultrasonic absolute ethyl alcohol that is dispersed in 60ml, transfer in the autoclave that volume is 100ml, the cinnamic acid of measuring 0.8mmol adds reactor, reactor is airtight, fill, put the air in 10 displacement stills of hydrogen, behind the air in the emptying still, reactor is put into after oil bath is heated to 120 ℃, charge into the hydrogen of 1MPa, keep temperature-resistant reaction 6 hours, after question response is finished, take out the liquid in the reactor, utilize the gas chromatographic analysis product to form and content.The result shows: the conversion ratio of reactant reaches 60-97%, and the selectivity of cinnamyl alcohol is 40-75%.
The present invention has following remarkable result:
(1) be reducing agent with sucrose, the golden salt of reduction prepares load type gold catalyst under relatively mild condition, is a kind of eco-friendly green method, the reaction condition gentleness, and energy consumption is low.
(2) reduction process of the crystallization of layered double hydroxide precursor and golden salt is carried out simultaneously, helps pay(useful) load and the high degree of dispersion of gold at carrier surface, thereby obtains the little gold nano grain of size.
(3) size of gold nano grain modulation flexibly, catalyst has high activity to the hydrogenation of unsaturated aldehyde (cinnamic acid), and hydrogenation selectivity is controlled.
Description of drawings
Fig. 1 is the XRD spectra of the catalyst of embodiment 2 preparations
Fig. 2 is the HRTEM image of the catalyst of embodiment 2 preparations, and wherein a figure is the Electronic Speculum spectrogram under the 50K; B figure is the Electronic Speculum spectrogram under the 300K.
The specific embodiment
Embodiment 1
Take by weighing 1.5382gMg (NO
3)
26H
2O and 2.2510gAl (NO
3)
39H
2O is dissolved in the 30ml deionized water and prepares mixing salt solution, wherein Al
3+Molar concentration is 0.2mol/L, Mg
2+Molar concentration be Al
3+1 times of molar concentration; With 0.768gNaOH and 1.2718gNa
2CO
3Preparation mixed ammonium/alkali solutions 30ml, wherein the NaOH molar concentration is (Mg
2++ Al
3+) 1.6 times of concentration, Na
2CO
3Concentration is Al
3+2 times of concentration.
The mixing salt solution and the mixed ammonium/alkali solutions that prepare are at room temperature poured in the full back-mixing liquid film reactor, rotating speed at liquid film reactor is 4200r/min, stator and gap between rotor are of a size of under the 16 μ m conditions, 3min is stirred in violent rotation, the suspension centrifuge washing that obtains to pH=7, is obtained sediment.
The sucrose that takes by weighing 0.5g is dissolved in the deionized water of 100ml, it is in the sucrose solution of 5g/L that the layered double hydroxide precipitation that obtains is added mass concentration, ultrasonic reaction 10min, again mixture is transferred in the four-hole bottle, be heated with stirring to 95 ℃, pipette the chlorauric acid solution that 3ml concentration is 10mg/ml with pipette, speed with 1ml/min is added drop-wise in the flask, under this temperature, reaction 2h, question response is cooled to room temperature, centrifuge washing after finishing, in 70 ℃ dry 12 hours down, with dried product at N
2The following 500 ℃ of roasting 3h of atmosphere.
The XRD characterization result shows the catalyst of product load type gold, and the average diameter of observing the gold grain of catalyst cupport by HRTEM is 10.8nm, and the actual negative carrying capacity of gold is 2.09% on the atomic absorption spectrometry catalyst.
The catalytically active assessment result shows: the conversion ratio of reactant is 66%, and the selectivity of cinnamyl alcohol is 58%.
Embodiment 2
Take by weighing 2.3077gMg (NO
3)
26H
2O and 1.1254gAl (NO
3)
39H
2O is dissolved in the 30ml deionized water and prepares mixing salt solution, wherein Al
3+Molar concentration is 0.1mol/L, Mg
2+Molar concentration be Al
3+3 times of molar concentration; With taking by weighing 0.768gNaOH and 0.636gNa
2CO
3Preparation mixed ammonium/alkali solutions 30ml, wherein the NaOH molar concentration is (Mg
2++ Al
3+) 1.6 times of concentration, Na
2CO
3Concentration is Al
3+2 times of concentration, the mixing salt solution and the mixed ammonium/alkali solutions that prepare are at room temperature poured in the full back-mixing liquid film reactor, rotating speed at liquid film reactor is 4200r/min, stator and gap between rotor are of a size of under the 16 μ m conditions, 3min is stirred in violent rotation, the suspension centrifuge washing that obtains to pH=7, is obtained sediment.The sucrose that takes by weighing 0.5g is dissolved in the deionized water of 100ml, it is in the sucrose solution of 5g/L that the layered double hydroxide precipitation that obtains is added mass concentration, ultrasonic reaction 10min, again mixture is transferred in the four-hole bottle, be heated with stirring to 95 ℃, pipetting 3ml concentration with pipette is the 10mg/ml chlorauric acid solution, speed with 1ml/min is added drop-wise in the flask, under this temperature, reaction 2h, question response is cooled to room temperature, centrifuge washing after finishing, in 70 ℃ dry 12 hours down, with dried product at N
2The following 500 ℃ of roasting 3h of atmosphere.
The XRD characterization result shows the catalyst of product load type gold, and the average diameter of observing the gold grain of catalyst cupport by HRTEM is 10.2nm, and the actual negative carrying capacity of gold is 2.30% on the atomic absorption spectrometry catalyst.
The catalytically active assessment result shows: the conversion ratio of reactant is 92%, and the selectivity of cinnamyl alcohol is 53%.
Embodiment 3
Take by weighing 2.3077gMg (NO
3)
26H
2O and 1.1254gAl (NO
3)
39H
2O is dissolved in the 30ml deionized water and prepares mixing salt solution, wherein Al
3+Molar concentration is 0.1mol/L, Mg
2+Molar concentration be Al
3+3 times of molar concentration; With taking by weighing 0.768gNaOH and 0.636gNa
2CO
3Preparation mixed ammonium/alkali solutions 30ml, wherein the NaOH molar concentration is (Mg
2++ Al
3+) 1.6 times of concentration, Na
2CO
3Concentration is Al
3+2 times of concentration, the mixing salt solution and the mixed ammonium/alkali solutions that prepare are at room temperature poured in the full back-mixing liquid film reactor, rotating speed at liquid film reactor is 4200r/min, stator and gap between rotor are of a size of under the 16 μ m conditions, 3min is stirred in violent rotation, the suspension centrifuge washing that obtains to pH=7, is obtained sediment.The sucrose that takes by weighing 1g is dissolved in the deionized water of 100ml, it is in the sucrose solution of 10g/L that the layered double hydroxide precipitation that obtains is added mass concentration, ultrasonic reaction 10min, again mixture is transferred in the four-hole bottle, be heated with stirring to 95 ℃, pipetting 3ml concentration with pipette is the 10mg/ml chlorauric acid solution, speed with 1ml/min is added drop-wise in the flask, under this temperature, reaction 2h, question response is cooled to room temperature, centrifuge washing after finishing, in 70 ℃ dry 12 hours down, with dried product at N
2The following 500 ℃ of roasting 3h of atmosphere.
The XRD characterization result shows the catalyst of product load type gold, and the average diameter of observing the gold grain of catalyst cupport by HRTEM is 11.6nm, and the actual negative carrying capacity of gold is 2.21% on the atomic absorption spectrometry catalyst.The catalytically active assessment result shows: the conversion ratio of reactant is 75%, and the selectivity of cinnamyl alcohol is 68%.
Embodiment 4
Take by weighing 3.0771gMg (NO
3)
26H
2O and 2.2512gAl (NO
3)
39H
2O is dissolved in the 30ml deionized water and prepares mixing salt solution, wherein Al
3+Molar concentration is 0.2mol/L, Mg
2+Molar concentration be Al
3+2 times of molar concentration; With taking by weighing 1.1526gNaOH and 1.2713gNa
2CO
3Preparation mixed ammonium/alkali solutions 30ml, wherein the NaOH molar concentration is (Mg
2++ Al
3+) 1.6 times of concentration, Na
2CO
3Concentration is Al
3+2 times of concentration, the mixing salt solution and the mixed ammonium/alkali solutions that prepare are at room temperature poured in the full back-mixing liquid film reactor, rotating speed at liquid film reactor is 4200r/min, stator and gap between rotor are of a size of under the 16 μ m conditions, 3min is stirred in violent rotation, the suspension centrifuge washing that obtains to pH=7, is obtained sediment.The sucrose that takes by weighing 0.87g is dissolved in the deionized water of 100ml, it is in the sucrose solution of 8.7g/L that the layered double hydroxide precipitation that obtains is added mass concentration, ultrasonic reaction 10min, again mixture is transferred in the four-hole bottle, be heated with stirring to 95 ℃, pipetting 5.1ml concentration with pipette is the 10mg/ml chlorauric acid solution, speed with 1ml/min is added drop-wise in the flask, under this temperature, reaction 2h, question response is cooled to room temperature, centrifuge washing after finishing, in 70 ℃ dry 12 hours down, with dried product at N
2The following 500 ℃ of roasting 3h of atmosphere.
The XRD characterization result shows the catalyst of product load type gold, and the average diameter of observing the gold grain of catalyst cupport by HRTEM is 10.5nm, and the actual negative carrying capacity of gold is 2.17% on the atomic absorption spectrometry catalyst.The catalytically active assessment result shows: the conversion ratio of reactant is 86%, and the selectivity of cinnamyl alcohol is 52%.
Embodiment 5
Take by weighing 2.3077gMg (NO
3)
26H
2O and 1.1254gAl (NO
3)
39H
2O is dissolved in the 30ml deionized water and prepares mixing salt solution, wherein Al
3+Molar concentration is 0.1mol/L, Mg
2+Molar concentration be Al
3+3 times of molar concentration; With taking by weighing 0.768gNaOH and 0.636gNa
2CO
3Preparation mixed ammonium/alkali solutions 30ml, wherein the NaOH molar concentration is (Mg
2++ Al
3+) 1.6 times of concentration, Na
2CO
3Concentration is Al
3+2 times of concentration, the mixing salt solution and the mixed ammonium/alkali solutions that prepare are at room temperature poured in the full back-mixing liquid film reactor, rotating speed at liquid film reactor is 4200r/min, stator and gap between rotor are of a size of under the 16 μ m conditions, 3min is stirred in violent rotation, the suspension centrifuge washing that obtains to pH=7, is obtained sediment.The sucrose that takes by weighing 0.5g is dissolved in the deionized water of 100ml, it is in the sucrose solution of 5g/L that the layered double hydroxide precipitation that obtains is added mass concentration, ultrasonic reaction 10min, again mixture is transferred in the four-hole bottle, be heated with stirring to 95 ℃, pipetting 3ml concentration with pipette is the 10mg/ml chlorauric acid solution, speed with 1ml/min is added drop-wise in the flask, under this temperature, reaction 4h, question response is cooled to room temperature, centrifuge washing after finishing, in 70 ℃ dry 12 hours down, with dried product at N
2The following 500 ℃ of roasting 3h of atmosphere.
The XRD characterization result shows the catalyst of product load type gold, and the average diameter of observing the gold grain of catalyst cupport by HRTEM is 10.3nm, and the actual negative carrying capacity of gold is 2.35% on the atomic absorption spectrometry catalyst.The catalytically active assessment result shows: the conversion ratio of reactant is 91%, and the selectivity of cinnamyl alcohol is 51%.
Embodiment 6
Take by weighing 2.3077gMg (NO
3)
26H
2O and 1.1254gAl (NO
3)
39H
2O is dissolved in the 30ml deionized water and prepares mixing salt solution, wherein Al
3+Molar concentration is 0.1mol/L, Mg
2+Molar concentration be Al
3+3 times of molar concentration; With taking by weighing 0.768gNaOH and 0.636gNa
2CO
3Preparation mixed ammonium/alkali solutions 30ml, wherein the NaOH molar concentration is (Mg
2++ Al
3+) 1.6 times of concentration, Na
2CO
3Concentration is Al
3+2 times of concentration, the mixing salt solution and the mixed ammonium/alkali solutions that prepare are at room temperature poured in the full back-mixing liquid film reactor, rotating speed at liquid film reactor is 4200r/min, stator and gap between rotor are of a size of under the 16 μ m conditions, 3min is stirred in violent rotation, the suspension centrifuge washing that obtains to pH=7, is obtained sediment.The sucrose that takes by weighing 0.25g is dissolved in the deionized water of 100ml, it is in the sucrose solution of 5g/L that the layered double hydroxide precipitation that obtains is added mass concentration, ultrasonic reaction 10min, again mixture is transferred in the four-hole bottle, be heated with stirring to 95 ℃, pipetting 1.5ml concentration with pipette is the 10mg/ml chlorauric acid solution, speed with 1ml/min is added drop-wise in the flask, under this temperature, reaction 2h, question response is cooled to room temperature, centrifuge washing after finishing, in 70 ℃ dry 12 hours down, with dried product at N
2The following 500 ℃ of roasting 3h of atmosphere.
The XRD characterization result shows the catalyst of product load type gold, and the average diameter of observing the gold grain of catalyst cupport by HRTEM is 8.9nm, and the actual negative carrying capacity of gold is 1.08% on the atomic absorption spectrometry catalyst.The catalytically active assessment result shows: the conversion ratio of reactant is 65%, and the selectivity of cinnamyl alcohol is 58%.
Claims (3)
1. the preparation method of a composite metal oxide supported nanometer gold catalyst, concrete preparation process is as follows:
A. with solubility divalent salts and aluminum soluble salt preparation mixing salt solution, wherein aluminum ions molar concentration is 0.1-0.3mol/L, and the molar concentration of bivalent metal ion is Al
3+The 1-3 of molar concentration doubly; Described solubility divalent salts is a magnesium nitrate, magnesium chloride, and magnesium sulfate, zinc nitrate, a kind of in the zinc chloride, aluminum soluble salt is an aluminum nitrate, a kind of in the aluminium chloride.
Preparation NaOH and Na
2CO
3Mixed ammonium/alkali solutions, make its satisfy the NaOH molar concentration be metal ion molar concentration sum in the above-mentioned mixing salt solution 1-2 doubly, Na
2CO
3Concentration is 2-3 times of its aluminium ion molar concentration;
Mixing salt solution and mixed ammonium/alkali solutions are joined in the full back-mixing liquid film reactor simultaneously, mix 3-5min through rotating at a high speed, obtain layered double hydroxide suspension, to neutral, the sediment that obtains is standby with the suspension centrifuge washing; Wherein the rotating speed of liquid film reactor is 4000-4500r/min, and stator and gap between rotor are of a size of 15-18 μ m;
B. the layered double hydroxide precipitation adding mass concentration with steps A is in the sucrose solution of 2.5-10g/L, wherein the mass ratio of layered double hydroxide and sucrose is 0.7-3, ultrasonic 5-30min, transfer in the reactor of band stirring, stir, temperature is heated to 80-95 ℃ from room temperature; With concentration is the chlorauric acid solution of 5-15mg/ml, is 10-80 according to sucrose solution and chlorauric acid solution mol ratio: 1, slowly be added drop-wise in the reactor of band stirring, and reacted 0.5-6 hour; Question response is cooled to room temperature after finishing, centrifugal, washing; Descended dry 6-24 hour at 60-80 ℃, again in 50-70ml/min flow N
2Under the atmosphere,, obtain the composite Nano Au catalyst in 300-600 ℃ of roasting.
2. according to the preparation method of claims 1 described composite metal oxide supported nanometer gold catalyst, the mass ratio that it is characterized in that layered double hydroxide and sucrose is 1.4-2.5, and sucrose solution and chlorauric acid solution mol ratio are 20-40: 1.
3. composite metal oxide supported nanometer gold catalyst by claim 1 and 2 described preparation methods preparation, this catalyst is that nanogold particle is carried on the composite metal oxide carrier; Composite oxides are M
IIO and Al
2O
3Compound, M
IIO and Al
2O
3Molar ratio be 2-6: 1; Wherein Jin load capacity is 0.5-3%, and gold grain is of a size of 8-15nm, and gold grain is elliposoidal or polyhedron-shaped; Described M
IIO is MgO or ZnO.
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