CN105332050A - Palladium nanocrystals and synthesis method thereof - Google Patents
Palladium nanocrystals and synthesis method thereof Download PDFInfo
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- CN105332050A CN105332050A CN201510891010.3A CN201510891010A CN105332050A CN 105332050 A CN105332050 A CN 105332050A CN 201510891010 A CN201510891010 A CN 201510891010A CN 105332050 A CN105332050 A CN 105332050A
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Abstract
The invention provides a synthesis method of palladium nanocrystals. A palladium source compound, a ruthenium source compound and a surface modification reducer perform mixed reaction in a solvent to obtain the palladium nanocrystals. Ruthenium atoms are reduced on the surfaces of the palladium nanocrystals in the nucleation growth process of the palladium nanocrystals in a reducing under-potential deposition mode, accordingly the surface energy of the ruthenium atoms is affected, and formation of high-index crystal faces is prompted. The synthesis method can remarkably improve the reaction rate, has the advantages of being simple in process, moderate in condition, high in yield, good in purity and the like and is suitable for large-scale production. The irregular nanocrystals with the high-index crystal faces are obtained, have rich edge and corner sites, can widely meet the requirements on the catalysis aspect, especially have excellent light absorption characteristics, accordingly achieve the application on the solar energy aspect, can drive a variety of organic reactions under the light condition and achieve conversion from solar energy to chemical energy.
Description
Technical field
The invention belongs to metal catalyst technology field, particularly relate to a kind of palladium nano-crystal body and synthetic method thereof.
Background technology
Catalyzer is one of modal material in chemical reaction, it refers to and can change reactant chemical reaction rate and do not change chemical equilibrium in chemical reaction, and the material that the quality of itself and chemical property all do not change before and after chemical reaction is catalyzer, it is the same with the relation of key just as lock with the relation of reaction system, has the selectivity of height.According to statistics, about have in the commercial run of more than 90% and use catalyzer, as chemical industry, petrochemical industry, biochemistry, environmental protection etc.Thus, in field, the research of catalyzer is remain always to the concern of height.
Catalyst type is various, classify also a lot, usually homogeneous catalyst and heterogeneous catalyst is divided into by the phase of reaction system, and heterogeneous catalyst comprises solid acid catalyst, organic alkali catalyst, metal catalyst, metal oxide catalyst, complex compound catalyst, rare earth catalyst and nanocatalyst etc., this wherein metal catalyst be take metal as the solid catalyst of main active component, it is a kind of catalyzer being subject to widespread use at present, mainly be divided into precious metal and iron, cobalt, the transition element such as nickel, and noble metal catalyst is owing to having higher catalytic activity, more and more be widely used at industrial circle, it is the very important catalyzer of a class.
Nearly all precious metal all can be used as catalyzer, but conventional is platinum, palladium, rhodium, silver, ruthenium etc., wherein especially most widely used with platinum, rhodium and palladium, their d electronic orbit does not all fill up, and surface is absorption reaction thing easily, and moderate strength, be beneficial in the middle of being formed " active compound ", there is higher catalytic activity, also there is the comprehensive good characteristics such as high temperature resistant, anti-oxidant, corrosion-resistant simultaneously, thus become most important catalystic material.Wherein, palladium-based catalyst not only may be used for the multiple reaction systems such as hydrogenation reaction, linked reaction, oxidizing reaction, and has high catalytic activity, is therefore subject to the special concern of people.Owing to having good stability, be easy to reclaim and the advantage such as control measures are abundant, obtain in the last few years based on the palladium base catalyst system of nano material and develop fast, especially use it for the development and application field of various new forms of energy.
According to the data statistics of International Energy Agency, if can not reduce the energy consumption of human society now, the prospective oil that the earth has been verified can only maintain about 40 years.But in industrial system now, most catalyzed reaction is by heat-driven, and this needs in producing to consume a large amount of energy.Can from two aspect effort for reducing energy consumption: one is the performance improving catalyzer, make reaction can lesser temps, lower pressure, compared with the condition of low catalyst consumption under carry out efficiently; Two is seek the heat energy needed in novel energy alternative reaction, and utilizes Driven by Solar Energy chemical reaction to become to solve the scheme that of energy problem has bright prospects.
Therefore, how to improve the activity of palladium base catalyst system, can better combine with the energy of emerging Sustainable development again, become the problem that forward position scholar in the industry urgently opens up.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is the synthetic method providing palladium nano-crystal body, palladium nano-crystal body prepared by synthetic method provided by the invention, it is a kind of irregular nanocrystal with high miller index surface, there is higher catalytic activity, especially, in Driven by Solar Energy organic catalytic reaction process, its special crystalline structure obviously can increase photocatalytic activity.And synthetic method provided by the invention has increased considerably speed of reaction, there is the features such as the high and purity of mild condition, productive rate is good, be suitable for scale operation.
The invention provides a kind of synthetic method of palladium nano-crystal body, it is characterized in that, comprise the following steps:
A) by after palladium source compound, ruthenium source compound and finishing reductive agent in a solvent hybrid reaction, palladium nano-crystal body is obtained.
Preferably, described palladium source compound is the compound containing the sub-palladium acid group of chlorine;
Described ruthenium source compound is the compound containing trivalent ruthenium.
Preferably, the described compound containing the sub-palladium acid group of chlorine comprises one or more in potassium palladochloride, sodium chloropalladite and ammonium palladous chloride;
The described compound containing trivalent ruthenium comprise in ruthenium trichloride, methyl ethyl diketone ruthenium, iodate ruthenium and nitrosyl nitric acid ruthenium one or more.
Preferably, described finishing reductive agent comprises one or more in xitix, citric acid, letones and Potassium Bromide;
Described solvent is water and/or ethylene glycol.
Preferably, the temperature of described reaction is 60 ~ 120 DEG C; The time of described reaction is 5 ~ 120 minutes.
Preferably, the mol ratio of described palladium source compound and finishing reductive agent is 1:(28 ~ 48);
The mass ratio of described palladium source compound and solvent is 1:(85 ~ 105).
Preferably, described steps A) be specially,
A1), after being mixed in a solvent by finishing reductive agent, mixed solution is obtained;
A2) aqueous solution of the aqueous solution of palladium source compound and ruthenium source compound is added in mixed solution react, obtain palladium nano-crystal body.
The invention provides a kind of palladium nano-crystal body, it is characterized in that, described palladium nano-crystal body comprises the irregular nanocrystal with high miller index surface.
Preferably, described palladium nano-crystal body also comprises, and has the irregular nanocrystal containing arc-shaped curved surface of high miller index surface.
Preferably, described palladium nano-crystal body is of a size of 40 ~ 80nm.
The invention provides a kind of synthetic method of palladium nano-crystal body, it is characterized in that, comprise the following steps, after palladium source compound, ruthenium source compound and finishing reductive agent in a solvent hybrid reaction, obtain palladium nano-crystal body.Compared with prior art, the present invention is in the nucleating growth process of palladium nano-crystal body, and ruthenium atom reduces in nanocrystal surface to reduce the form of underpotential deposition, thus affects its surface energy, has impelled the formation of high miller index surface.But the ruthenium atom be reduced can react with the sub-palladium acid group of the chlorine in solution again, is oxidized to divalent ruthenium ion, is discharged in reaction system.Synthetic method provided by the invention can increase considerably speed of reaction, the feature such as have that technique is simple, mild condition, productive rate are high and purity is good, is suitable for scale operation.
The irregular nanocrystal of what the present invention obtained have high miller index surface, containing abundant corner angle site, extensively can meet the requirement of catalysis aspect, such as Heck linked reaction, Suzuki linked reaction, catalytic oxidation etc., be suitable for applying further in research and industrial production; There is the irregular palladium nano-crystal body of high miller index surface simultaneously, abundant corner angle site and Irregular Boundary Surface, light abstraction width can be made to cover from ultraviolet to infrared all zones, there is excellent optical absorption characteristics, thus realize the application of sun power aspect, the palladium nano-crystal body utilizing present method to be synthesized can drive various organic reactions under illumination condition, realizes sun power to chemical transformation of energy.Experimental result shows, palladium nano-crystal body prepared by the present invention, purity height inclusion-free, containing { 730} is with { 520} crystal face, particle diameter is about 40 ~ 80nm, has the irregular nanostructure of high miller index surface, can realize the reaction of photochemical catalysis organic hydrogenation.
Accompanying drawing explanation
Fig. 1 is the TEM photo with the irregular palladium nano-crystal body of high miller index surface prepared by the present invention, and scale is 20nm;
Fig. 2 is the TEM photo of palladium nano-crystal body prepared by the embodiment of the present invention 1, and scale is 10nm;
Fig. 3 is the TEM photo of palladium nano-crystal body prepared by the embodiment of the present invention 1, and scale is 20nm;
Fig. 4 is the TEM photo of palladium nano-crystal body prepared by the embodiment of the present invention 1, and scale is 40nm;
Fig. 5 is XRD (the turning target X-ray powder diffraction) analysis chart of palladium nano-crystal body prepared by the embodiment of the present invention 1;
Fig. 6 is UV-vis (UV, visible light extinction spectra) curve of palladium nano-crystal body prepared by the embodiment of the present invention 1;
Fig. 7 is the photochemical catalysis organic reaction productive rate of palladium nano-crystal body prepared by the embodiment of the present invention 1;
Fig. 8 is the TEM photo of palladium nano-crystal body prepared by the embodiment of the present invention 2, and scale is 20nm;
Fig. 9 is the TEM photo of palladium nano-crystal body prepared by the embodiment of the present invention 3, and scale is 100nm.
Embodiment
In order to understand the present invention further, below in conjunction with embodiment, the preferred embodiment of the invention is described, but should be appreciated that these describe just in order to further illustrate the features and advantages of the present invention, instead of the restriction to invention claim.
The all raw materials of the present invention, be not particularly limited its source, commercially buy or prepare according to ordinary method well known to those skilled in the art.
The all raw materials of the present invention, be not particularly limited its purity, the present invention preferably adopts analytical pure.
Equipment used of the present invention, is not particularly limited, and can be flask, beaker or reactor etc. conventional in this area, and other can meet the device of technical solution of the present invention.
The invention provides a kind of synthetic method of palladium nano-crystal body, comprise the following steps, after palladium source compound, ruthenium source compound and finishing reductive agent in a solvent hybrid reaction, obtain palladium nano-crystal body.
Palladium source compound of the present invention is preferably the compound containing the sub-palladium acid group of chlorine; Described ruthenium source compound is preferably the compound containing trivalent ruthenium.The present invention is not particularly limited the described compound containing the sub-palladium acid group of chlorine, with the compound containing the sub-palladium acid group of chlorine well known to those skilled in the art, the present invention preferably include in potassium palladochloride, sodium chloropalladite and ammonium palladous chloride one or more, be more preferably potassium palladochloride and/or sodium chloropalladite.The present invention is not particularly limited the described compound containing trivalent ruthenium, with the compound containing trivalent ruthenium well known to those skilled in the art, the present invention preferably include in ruthenium trichloride, methyl ethyl diketone ruthenium, iodate ruthenium and nitrosyl nitric acid ruthenium one or more, more preferably comprise in ruthenium trichloride, methyl ethyl diketone ruthenium and nitrosyl nitric acid ruthenium one or more, most preferably be ruthenium trichloride and/or nitrosyl nitric acid ruthenium.
The definition of finishing reductive agent of the present invention is not particularly limited, define with well known to those skilled in the art, the present invention refers to have the Surface Modification Effect, simultaneously or also have the reagent of reductive action, also can be understood as coating materials and/or reductive agent.Finishing reductive agent described in the present invention preferably include in xitix, citric acid, letones and Potassium Bromide one or more, more preferably comprise one or more of xitix, letones and Potassium Bromide; More preferably comprise in citric acid, letones and Potassium Bromide one or more, more preferably citric acid, letones and Potassium Bromide, most preferably is xitix, letones and Potassium Bromide; Described letones is preferably polyvinylpyrrolidone, being more preferably relative molecular mass is 10000,29000,40000, one or more in the polyvinylpyrrolidone of 55000 and 160000, most preferably are the polyvinylpyrrolidone that relative molecular weight is 55000.
If discuss with coating materials and reductive agent, described reductive agent preferably include in xitix, polyvinylpyrrolidone, citric acid and letones one or more, be more preferably in xitix, polyvinylpyrrolidone and citric acid one or more, be more preferably polyvinylpyrrolidone and citric acid, most preferably be xitix and polyvinylpyrrolidone; Described coating materials preferably include in xitix, polyvinylpyrrolidone, citric acid, letones and Potassium Bromide one or more, be more preferably in xitix, polyvinylpyrrolidone and Potassium Bromide one or more, be more preferably xitix, polyvinylpyrrolidone and Potassium Bromide, be more preferably citric acid, polyvinylpyrrolidone and Potassium Bromide, most preferably be Potassium Bromide.The present invention is not particularly limited described solvent, and with the conventional organic or inorganic solvent sent out well known to those skilled in the art, the present invention is preferably water and/or ethylene glycol, is more preferably water or ethylene glycol.
The mol ratio of palladium source compound of the present invention and finishing reductive agent is preferably 1:(28 ~ 48), be more preferably 1:(30 ~ 45), be more preferably 1:(35 ~ 40), most preferably be 1:38; The mass ratio of described palladium source compound and solvent is preferably 1:(85 ~ 105), be more preferably 1:(88 ~ 102), be more preferably 1:(90 ~ 100), most preferably be 1:95.If discuss with coating materials and reductive agent, the mol ratio of described palladium source compound and coating materials is preferably 1:(25 ~ 45), be more preferably 1:(30 ~ 40), be more preferably 1:(33 ~ 38), most preferably be 1:35; The mol ratio of described palladium source compound and reductive agent is preferably 1:(2 ~ 5), be more preferably 1:(2.4 ~ 4.4), be more preferably 1:(3.0 ~ 3.8), most preferably be 1:3.4.The ratio of the present invention to described ruthenium source compound and palladium source compound is not particularly limited, those skilled in the art can carry out from Row sum-equal matrix according to practical situation, product requirement and concrete purposes, the present invention is preferably by the ratio selecting different ruthenium sources and palladium source, the control of palladium nano-crystal body and pattern can be realized, the mol ratio of preferred ruthenium source compound and palladium source compound is more than or equal to 1 ‰, be more preferably 1 ‰ ~ 100%, be more preferably 3 ‰ ~ 1% or 1% ~ 100%, most preferably be 5 ‰ ~ 1% or 1% ~ 50%.In experimental system of the present invention, during mol ratio≤1% in the ruthenium source added and palladium source, the described palladium nano-crystal body now prepared is the irregular nanocrystal with high miller index surface; When in described experimental system, during mol ratio >=1% in the ruthenium source added and palladium source, now collecting the described palladium nano-crystal body obtained is the irregular nanocrystal containing arc-shaped curved surface with high miller index surface that structure is more complicated.
The temperature of reaction of the present invention is preferably 60 ~ 120 DEG C, is more preferably 70 ~ 110 DEG C, is more preferably 80 ~ 100 DEG C, most preferably is 85 ~ 95 DEG C.The present invention was not particularly limited the described reaction times, ruthenium source compound is introduced in the nucleating growth process of palladium nano-crystal body by the present invention, the process of growth of level time mutually little than ever, the present invention shortens to a minute level, significantly accelerates the nucleating growth process of palladium nano-crystal body, add speed of reaction, reduce the reaction times, the time of described reaction is preferably 5 ~ 120 minutes, is more preferably 6 ~ 100 minutes, be more preferably 7 ~ 80 minutes, most preferably be 8 ~ 59 minutes.
Above-mentioned steps, for improving reaction efficiency and final product quality, also preferably to be carried out with reference to following concrete scheme by the present invention, after first being mixed in a solvent by finishing reductive agent, obtains mixed solution; Again the aqueous solution of the aqueous solution of palladium source compound and ruthenium source compound is added in mixed solution and react, obtain palladium nano-crystal body; Described adding preferably adds rapidly.Also, after can first being mixed in a solvent by the aqueous solution of finishing reductive agent and palladium source compound, mixed solution is obtained; Again the aqueous solution of ruthenium source compound is added in mixed solution and react, obtain palladium nano-crystal body.The concentration of the present invention to the aqueous solution of described palladium source compound and the aqueous solution of ruthenium source compound is not particularly limited, with the normal concentration of respective compound well known to those skilled in the art, also can carry out from Row sum-equal matrix according to practical situation, product requirement and concrete purposes.
Above-mentioned preparation method provided by the invention, speed of reaction can be increased considerably, adopt the method for low-temperature atmosphere-pressure synthesis, can not need in main equipment and severe condition situation, the high efficiency formation large-size of single stage method, there is palladium nano-crystal body compared with wide spectral respective range.With two-step synthetic method ratio in the past, there is the advantage that technique is simple, productive rate is high, system is clean and be easy to amplify batch production.
The present invention is in the nucleating growth process of palladium nano-crystal body, and ruthenium atom reduces in nanocrystal surface to reduce the form of underpotential deposition, thus affects its surface energy, has impelled the formation of high miller index surface.And the ruthenium atom be reduced can react with the sub-palladium acid group of the chlorine in solution again, is oxidized to divalent ruthenium ion, is discharged in reaction system, by selecting the ratio in different ruthenium sources and palladium source, can also can realize the control of palladium nano-crystal body and pattern.In building-up process of the present invention, adding of ruthenium source is one of successful key, if do not add ruthenium source compound in reaction process, larger-size nanocrystal can not be formed, especially the irregular nanocrystal of 50nm is more than or equal to, if add other metal in reaction process, such as copper, cobalt, silver etc., can not form the nanocrystal that this size has more greatly high miller index surface.In addition, in preparation method provided by the present invention, temperature of reaction, reaction times have good adaptability, do not have a significant effect in very wide scope to the quality of product.
The present invention also provides a kind of palladium nano-crystal body, it is characterized in that, described palladium nano-crystal body comprises the irregular nanocrystal with high miller index surface; Described palladium nano-crystal body is preferably dimensioned to be 40 ~ 80nm, is more preferably 45 ~ 80nm, is more preferably 51 ~ 79nm, most preferably be 55 ~ 78nm; The present invention is by improving the additional proportion of ruthenium source compound, and when mol ratio >=1% in ruthenium source and palladium source, described palladium nano-crystal body preferably also comprises the irregular nanocrystal containing arc-shaped curved surface with high miller index surface.Be the TEM photo with the irregular palladium nano-crystal body of high miller index surface prepared by the present invention see Fig. 1, Fig. 1, scale is 20nm.As shown in Figure 1, palladium nano-crystal body of the present invention has the irregular nanocrystal containing arc-shaped curved surface of high miller index surface.
Palladium nano-crystal body provided by the invention has the irregular nanocrystal of high miller index surface, containing abundant corner angle site, extensively can meet the requirement of catalysis aspect, there is higher catalytic activity, such as Heck linked reaction, Suzuki linked reaction, catalytic oxidation etc., be suitable for applying further in research and industrial production; There is the irregular palladium nano-crystal body of high miller index surface simultaneously, abundant corner angle site and Irregular Boundary Surface, light abstraction width can be made to cover from ultraviolet to infrared all zones, there is excellent optical absorption characteristics, thus realize the application of sun power aspect, especially, in Driven by Solar Energy organic catalytic reaction process, its special random crystal structure obviously can increase photocatalytic activity.Realize sun power to chemical transformation of energy.Experimental result shows, palladium nano-crystal body prepared by the present invention, purity height inclusion-free, containing { 730} is with { 520} crystal face, particle diameter is about 40 ~ 80nm, has the irregular nanostructure of high miller index surface, can realize the reaction of photochemical catalysis organic hydrogenation.
In order to further illustrate the present invention, be described in detail to palladium nano-crystal body provided by the invention and synthetic method thereof below in conjunction with embodiment, protection scope of the present invention is not limited by the following examples.
Embodiment 1
There is the irregular palladium nano-crystal body of high miller index surface
210 milligrams of PVP (polyvinylpyrrolidone), 120 milligrams of AA (xitix) and 600 milligrams of KBr are dissolved in 16 ml distilled waters.Being positioned over volume is in the there-necked flask of 50 milliliters, is heated to 80 DEG C, and constant temperature 5 minutes, obtain mixed solution.
By 63 milligrams of K
2pdCl
4be dissolved in 3 ml distilled waters, then by the ruthenium chloride (RuCl of 5 milligrams
3) be dissolved in 1 ml distilled water.Respectively by K
2pdCl
4solution and RuCl
3solution promptly injects mixed solution and reacts, and isothermal reaction, after 10 minutes, by centrifugal and distilled water wash, is removed PVP, AA and KBr, obtained the irregular palladium nano-crystal body with high miller index surface.
Detect the irregular palladium nano-crystal body with high miller index surface prepared by aforesaid method, detected result shows, be the TEM photo of palladium nano-crystal body prepared by the embodiment of the present invention 1 see Fig. 2, Fig. 2, scale is 10nm.See the TEM photo that Fig. 3, Fig. 3 are palladium nano-crystal body prepared by the embodiment of the present invention 1, scale is 20nm.See the TEM photo that Fig. 4, Fig. 4 are palladium nano-crystal body prepared by the embodiment of the present invention 1, scale is 40nm.From Fig. 2 ~ 4, palladium nano-crystal body prepared by the present invention has the irregularly shaped of high miller index surface, containing { 730} is with { 520} crystal face, particle diameter is about 40 ~ 80nm.
See XRD (the turning target X-ray powder diffraction) analysis chart that Fig. 5, Fig. 5 are palladium nano-crystal body prepared by the embodiment of the present invention 1.As shown in Figure 5, all X-ray powder diffraction peaks index can be palladium nano-crystal body and do not have other impurity peaks to occur, the powder body material of therefore present method synthesis is highly purified palladium nano-crystal body material.
See UV-vis (UV, visible light extinction spectra) curve that Fig. 6, Fig. 6 are palladium nano-crystal body prepared by the embodiment of the present invention 1.As shown in Figure 6, palladium nano-crystal body prepared by the present invention, spectral absorption is had at ultraviolet-visible-near-infrared band, illustrate that this product has the Extinction Characteristic of very wide region, therefore the palladium nano-crystal body obtained according to method provided by the present invention has very superior absorbing properties, can meet the application demand in photochemical catalysis organic reaction.
Embodiment 2
210 milligrams of PVP (polyvinylpyrrolidone), 120 milligrams of AA (xitix) and 600 milligrams of KBr are dissolved in 16 ml distilled waters.Being positioned over volume is in the there-necked flask of 50 milliliters, is heated to (100) DEG C, and constant temperature 5 minutes, obtain mixed solution.
63 milligrams of K2PdCl4 are dissolved in 3 ml distilled waters, then the ruthenium chloride (RuCl3) of 5 milligrams is dissolved in 1 ml distilled water.Respectively K2PdCl4 solution and RuCl3 solution are promptly injected mixed solution to react, isothermal reaction, after 10 minutes, by centrifugal and distilled water wash, is removed PVP, AA and KBr, is obtained the irregular palladium nano-crystal body with high miller index surface.
See the TEM photo that Fig. 8, Fig. 8 are palladium nano-crystal body prepared by the embodiment of the present invention 2, scale is 20nm.As shown in Figure 8, palladium nano-crystal body prepared by the present invention has the irregularly shaped of high miller index surface, and particle diameter is about 40 ~ 80nm.
Embodiment 3
210 milligrams of PVP (polyvinylpyrrolidone), 120 milligrams of AA (xitix) and 600 milligrams of KBr are dissolved in 16 ml distilled waters.Being positioned over volume is in the there-necked flask of 50 milliliters, is heated to (80) DEG C, and constant temperature 5 minutes, obtain mixed solution.
63 milligrams of K2PdCl4 are dissolved in 3 ml distilled waters, then the ruthenium chloride (RuCl3) of 20 milligrams is dissolved in 1 ml distilled water.Respectively K2PdCl4 solution and RuCl3 solution are promptly injected mixed solution to react, isothermal reaction, after 5 minutes, by centrifugal and distilled water wash, is removed PVP, AA and KBr, is obtained the irregular palladium nano-crystal body with high miller index surface.
See the TEM photo that Fig. 9, Fig. 9 are palladium nano-crystal body prepared by the embodiment of the present invention 3, scale is 100nm.As shown in Figure 9, palladium nano-crystal body prepared by the present invention has the irregularly shaped of high miller index surface, and particle diameter is about 40 ~ 80nm.
Embodiment 4
Optical drive organic reaction
The palladium nano-crystal body 2 milligrams of embodiments 2 prepared, 2 mmole vinylbenzene are dispersed in 1 ml distilled water.Being positioned over solvent is in the silica tube of 20 milliliters, reaction atmosphere is replaced into 10% hydrogen.Introduce the incident light of varying strength at ambient temperature, thus drive the carrying out of hydrogenation reaction.The photochemical catalysis organic reaction productive rate of the palladium nano-crystal body of Fig. 9 prepared by the embodiment of the present invention 1.
As shown in Figure 7, irregular palladium nano-crystal body prepared by the embodiment of the present invention 1 has excellent optical absorption characteristics, in Driven by Solar Energy organic catalytic reaction process, has photocatalytic activity, can drive the carrying out of hydrogenation reaction, realize sun power to chemical transformation of energy.
Above a kind of palladium nano-crystal body provided by the present invention and synthetic method thereof are described in detail.Apply a concrete example herein to set forth principle of the present invention and embodiment, the explanation of above embodiment just understands method of the present invention and core concept thereof for helping.It should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention, can also carry out some improvement and modification to the present invention, these improve and modify and also fall in the protection domain of the claims in the present invention.
Claims (10)
1. a synthetic method for palladium nano-crystal body, is characterized in that, comprises the following steps:
A) by after palladium source compound, ruthenium source compound and finishing reductive agent in a solvent hybrid reaction, palladium nano-crystal body is obtained.
2. synthetic method according to claim 1, is characterized in that, described palladium source compound is the compound containing the sub-palladium acid group of chlorine;
Described ruthenium source compound is the compound containing trivalent ruthenium.
3. synthetic method according to claim 2, is characterized in that, the described compound containing the sub-palladium acid group of chlorine comprise in potassium palladochloride, sodium chloropalladite and ammonium palladous chloride one or more;
The described compound containing trivalent ruthenium comprise in ruthenium trichloride, methyl ethyl diketone ruthenium, iodate ruthenium and nitrosyl nitric acid ruthenium one or more.
4. synthetic method according to claim 1, is characterized in that, described finishing reductive agent comprise in xitix, citric acid, letones and Potassium Bromide one or more;
Described solvent is water and/or ethylene glycol.
5. synthetic method according to claim 1, is characterized in that, the temperature of described reaction is 60 ~ 120 DEG C; The time of described reaction is 5 ~ 120 minutes.
6. synthetic method according to claim 1, is characterized in that, the mol ratio of described palladium source compound and finishing reductive agent is 1:(28 ~ 48);
The mass ratio of described palladium source compound and solvent is 1:(85 ~ 105).
7. synthetic method according to claim 1, is characterized in that, described steps A) be specially,
A1), after being mixed in a solvent by finishing reductive agent, mixed solution is obtained;
A2) aqueous solution of the aqueous solution of palladium source compound and ruthenium source compound is added in mixed solution react, obtain palladium nano-crystal body.
8. a palladium nano-crystal body, is characterized in that, described palladium nano-crystal body comprises the irregular nanocrystal with high miller index surface.
9. palladium nano-crystal body according to claim 8, is characterized in that, described palladium nano-crystal body also comprises, and has the irregular nanocrystal containing arc-shaped curved surface of high miller index surface.
10. palladium nano-crystal body according to claim 8, is characterized in that, described palladium nano-crystal body is of a size of 40 ~ 80nm.
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| CN109833835A (en) * | 2019-02-26 | 2019-06-04 | 杭州师范大学 | A kind of preparation method of the hollow platinum palladium nano-crystal body of inner concave shape, the hollow platinum palladium nano-crystal body of inner concave shape and its application |
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| CN106914238B (en) * | 2017-03-27 | 2019-10-25 | 中国科学技术大学 | A kind of palladium-silver double metallic composite material and preparation method thereof |
| CN107930625A (en) * | 2017-11-16 | 2018-04-20 | 江西省科学院应用化学研究所 | A kind of BiVO of ruthenium load4The preparation method of@C composite material of core-shell structure |
| CN107855123A (en) * | 2017-11-23 | 2018-03-30 | 中国科学技术大学 | A kind of Pd/SiO2@Al2O3Nanocrystalline material and preparation method thereof, application |
| CN107855123B (en) * | 2017-11-23 | 2020-04-10 | 中国科学技术大学 | Pd/SiO2@Al2O3Nanocrystalline material and preparation method and application thereof |
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| CN108054391B (en) * | 2017-12-11 | 2021-03-30 | 贵州大学 | Synthesis method and application of dendritic Pd nanocrystal catalyst |
| CN108273563A (en) * | 2018-02-02 | 2018-07-13 | 江西省科学院应用化学研究所 | A kind of embedded precious metals pd/BiVO4@RuIIIThe preparation method of-TA nuclear-shell structured nano-composite materials |
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| CN109833835A (en) * | 2019-02-26 | 2019-06-04 | 杭州师范大学 | A kind of preparation method of the hollow platinum palladium nano-crystal body of inner concave shape, the hollow platinum palladium nano-crystal body of inner concave shape and its application |
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