CN103962162A - Micro-nanometer composite, preparing method and application thereof - Google Patents
Micro-nanometer composite, preparing method and application thereof Download PDFInfo
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- CN103962162A CN103962162A CN201410188196.1A CN201410188196A CN103962162A CN 103962162 A CN103962162 A CN 103962162A CN 201410188196 A CN201410188196 A CN 201410188196A CN 103962162 A CN103962162 A CN 103962162A
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Abstract
The invention discloses a micro-nanometer composite. The micro-nanometer composite is an urchin-like Ni-Co-P metallic composite, and the structure of the micro-nanometer composite is determined as Ni@Ni3P@CoP2@P through XRD (X-Ray Diffraction) representation. The invention discloses another micro-nanometer composite. An urchin-like Ni-Co-Pd-P metallic composite is formed through introducing nanometer palladium on the basis of the Ni-Co-P metallic composite. The invention further discloses a preparing method and application thereof for the two micro-nanometer materials. The Ni@Ni3P@CoP2@P is synthesized through a one-step hydrothermal method, palladium salt is absorbed on the basis of the Ni-Co-P composite, a reductant is added, and nanometer palladium is introduced. The synthesized Ni-Co-Pd-P has great catalytic and circulating effects on the reduction of para-nitrophenol.
Description
Technical field
The present invention relates to inorganic material preparation and application field, particularly relate to a kind of synthetic easy, magnetic good and have high catalytic performance composite micro-nano rice material.
Background technology
As aromatic hydrocarbons, nitrophenol has severe toxicity, and can inhale in Xi Tong ﹑ digestive system and skin intrusive body by Hu, nitrophenol mainly has bad reaction to Xue Ye ﹑ liver and central nervous system, nitrophenol has the ability that makes hemoglobin be converted into ferrihemoglobin, nitrophenol exists and can reduce its self-purification capacity in water body, except can be used as several antalgesics and alexipyretic (such as paracetamol, antifebrin and phenacetin) important intermediate, para-aminophenol also can be used as photo development, corrosion inhibitor, anti corrosion lubricant and hair dye etc.
Paranitrophenol is mainly to make from catalysis/electrochemical reduction nitrobenzene, therefore, it is necessary exploring the good catalyst that is para-aminophenol by paranitrophenol catalytic reduction, the catalytic hydrogenation of some metallic composite p-nitrophenols broad research, but the heterogeneous noble metal catalyst of tradition application needs extreme reaction condition conventionally in the hydrogenation reaction of aromatic hydrocarbons.At present, to the catalyticing research of aromatic hydrogenation still in the starting stage, and exploitation can promote the effective catalyst of aromatic hydrocarbons reduction to be still significant challenge to researcher under temperate condition, metal micro-/ nano catalyst has different architectures, as Ju He Wu ﹑ Shu Zhi Zhuan ﹑ micella and mesoporous material, the interest of recently in specific reaction compartment, it being studied increases to some extent.Micro/nano material function of surface can allow them be processed into catalyst carrier, sensor and drug delivering material, consider its economical advantage, some nonmetallic materials, as carbon and phosphorus (P), be used as building the substituting group of multi-functional micro-/ nano catalyst, the catalyst of gained not only has the composite performance of the individuality composition of oneself, and because the interaction display of the cooperative information between parts goes out new features and function, from the angle of sustainable chemistry and green synthetic materials chemistry, an urgent demand development composite, go out in the strategy of different surfaces modification at nearest multi-functional micro-/ nano catalyst preparation, microstructure with increase catalytic effect synthetic and received maximum concerns.
Summary of the invention
The technical problem to be solved in the present invention be to provide a kind of synthetic easy, magnetic good and have high catalytic performance composite micro-nano rice material.
The present invention also provide a kind of described composite micro-nano rice material preparation method and described in meet micro Nano material as catalyst application in paranitrophenol in reduction.
A kind of composite micro-nano rice material, it is sea urchin shape Ni-C
o-P metallic composite, is characterized and is determined that its structure is Ni@Ni by XRD
3p@CoP
2@P.
A kind of composite micro-nano rice material is introduced Technique of Nano Pd on the basis of described Ni-Co-P metallic composite, forms sea urchin shape Ni-Co-Pd-P metallic composite.
Composite micro-nano rice material of the present invention, wherein said sea urchin shape Ni-Co-Pd-P metallic composite is characterized and is determined that its structure is Ni@Ni by XRD
3p@CoP
2@P@Pd.
A preparation method for sea urchin shape Ni-Co-P metallic composite, comprises the steps:
(1) by NiCl
2, CoCl
2and NaH
2pO
2in water, mix, then add organic solvent to mix, obtain mixed solution;
(2) described mixed solution is placed in to the autoclave that liner is polytetrafluoroethylene (PTFE), at the temperature of 120 DEG C～180 DEG C, heats 14h～16h, synthetic Ni-Co-P metallic composite.
The preparation method of composite micro-nano rice material of the present invention, wherein, NiCl described in step (1)
2, CoCl
2and NaH
2pO
2mol ratio be 2:2:1, described organic solvent is DMF, adopts the mixed 2mmol NiCl of 20ml water-soluble solution
2, 2mmol CoCl
2with 1mmol NaH
2pO
2, under stirring action, add 20mlDMF, form the mixed solution of 40ml altogether, described in step (2), the inner bag volume of autoclave is 50ml.
A preparation method for sea urchin shape Ni-Co-Pd-P metallic composite, comprises the steps:
(A) by the Ni-Co-P metallic composite and the PdCl that obtain
2mix and blend spends the night, and adds sodium borohydride;
(B) collect product with magnet and wash repeatedly by deionized water, drying grinding and obtain Ni-Co-Pd-P metallic composite.
The preparation method of composite micro-nano rice material of the present invention, wherein, step (A) is specially: with the composite of Ni-Co-P and the PdCl of 1ml2.8mmol/L of 25mg
2solution mixing is spent the night, and adds the NaBH of 5mL8mol/L
4.
Composite micro-nano rice material of the present invention is the application in reduction paranitrophenol as catalyst.
Application of the present invention, adopt the method for described composite micro-nano rice material catalytic reduction paranitrophenol to comprise the steps: to adopt the sodium borohydride of the freshly prepd 0.264mol/L of 30ml and 20ml2.5mmol/L paranitrophenol to be blended at 45 DEG C and keep 10min, add 25mg sea urchin shape Ni – P-Co metallic composite or sea urchin shape Ni-Co-Pd-P metallic composite.
Application of the present invention, wherein, in the process of reduction paranitrophenol, magnet is placed on to the bottom of beaker with quick separating mixture, can repeatedly recycle described sea urchin shape Ni – P-Co metallic composite and sea urchin shape Ni-Co-Pd-P metallic composite, described recycling number of times is 7 times.
Composite micro-nano rice material difference from prior art of the present invention is: composite micro-nano rice material of the present invention is slightly modified the fine structure material of Ni-P, prepare nickeliferous by a simple one-step method hydro-thermal method, cobalt, and the sea urchin shape material of P, and characterize and determine that its structure is Ni@Ni by XRD
3p@CoP
2@P.In order to obtain high catalytic activity, at NaBH
4exist lower palladium ion to be absorbed by sea urchin shape material and be reduced into Pd nano particle, this catalyst is used for reducing paranitrophenol than containing separately nickel, the catalyst of cobalt or P demonstrates stronger catalytic capability, to contain nickel, cobalt, phosphorus, be filled into a micro-/ nano reactor and be applied in hydrogenation nitrophenol with the multifunctional material of Pd, produce a kind of new catalyst of p-nitrophenol hydrogenation, for reduce paranitrophenol with the improved catalytic activity that is easy to separate nickel-cobalt-palladium prepared from reactant mixture-P composite, realize simultaneously and improved the catalytic activity of reduction p-nitrophenol and be easy to separate prepared nickel-cobalt-palladium-P composite from reactant mixture.Synthetic composite has good magnetic, makes to be easy to realize catalyst in application process and separates with the effective of degradation product, and carrying out easily and effectively repeatedly recycles.After the present invention modifies protocorm material, in the time of reduction paranitrophenol, Ni – Co – Pd – P composite shows good catalytic capability and good cycle performance.
The present invention synthesizes Ni@Ni by one step hydro thermal method
3p@CoP
2@P adsorbs palladium salt on the basis of Ni-Co-P composite, adds reducing agent, introduces Technique of Nano Pd, and synthetic Ni-Co-Pd-P has good catalytic effect and circulating effect in reduction paranitrophenol.
The microcosmic composite of transition metal phosphide has with low cost and catalytic activity is a little high, therefore very concerned at catalytic field.For example, but high temperature and poisonous phosphorus source (, trictylphosphine) be often for the synthesis of at some transition metal phosphide nanocrystal, as FEP, Fe
2p, Ni
2p, Co
2p and MNP.In the preparation process of transition metal phosphide composite, make great efforts the condition of investigating the impact of output is carried out smoothly.Except cost is low, of nickel (Ni) is important be advantage it there is the ability of ferromagnetic behavior to another kind of material of giving.Magnetic catalyst can be collected easily by Magnetic Isolation from different reaction systems, thereby in the time that recovery experiment completes, catalyst and noble metal consumption is minimized.Except high catalytic rate and ferromagnetic advantage, the micro-structural of porous sea urchin shape Ni-P is synthetic by a simple water and DMF solvent heat path, and promptly heavy-metal ion removal from water of this microstructure.
Consider catalytic capability that it is good and availability widely, cobalt (Co) becomes just rapidly the welcome material of a synthesizing new catalyst.Some noble metals, as Jin ﹑ palladium (Pd)/platinum (Pt) and Rh etc., also can partly be replaced by cobalt, and do not lose the catalytic capability of whole material.Many catalyst containing Co, as platinum-cobalt and molybdenum-cobalt, are exploited recently.These reports show, can be exploitation effective catalyst containing the microstructure of Ni and Co composite, reduce the use amount of noble metal, and keep even improving catalytic performance provides capital chance simultaneously.
Below in conjunction with accompanying drawing, composite micro-nano rice material of the present invention is described further.
Brief description of the drawings
Fig. 1 is the thing phasor of the synthetic composite Ni – Co – P of the present invention;
To be micro Nano material Ni – Co – P of the present invention carry out the ultraviolet figure of solution after catalytic reduction to p-nitrophenol to Fig. 2;
To be micro Nano material Ni – Co – Pd – P of the present invention carry out the ultraviolet figure of solution after catalytic reduction to p-nitrophenol to Fig. 3;
Fig. 4 is the design sketch that in the present invention, Ni – Co – Pd – P micro Nano material carries out catalytic reduction to p-nitrophenol;
Fig. 5 is that in the present invention, Ni – Co – Pd – P micro Nano material carries out solution ultraviolet figure after catalytic reduction the 7th time to p-nitrophenol.
Detailed description of the invention
Embodiment 1
A kind of composite micro-nano rice material, it is sea urchin shape Ni-Co-P metallic composite, as shown in Figure 1, is characterized and is determined that its structure is Ni@Ni by XRD
3p@CoP
2@P.
A kind of composite micro-nano rice material is introduced Technique of Nano Pd on the basis of described Ni-Co-P metallic composite, forms sea urchin shape Ni-Co-Pd-P metallic composite, is characterized and is determined that its structure is Ni@Ni by XRD
3p@CoP
2@P@Pd.
A preparation method for sea urchin shape Ni-Co-P metallic composite, comprises the steps:
(1) adopt the mixed 2mmol NiCl of the water-soluble solution of 20ml
2, 2mmol CoCl
2with 1mmol NaH
2pO
2, under stirring action, add 20mlDMF, form the mixed solution of 40ml altogether;
(2) described mixed solution is placed in to the autoclave that liner is polytetrafluoroethylene (PTFE), the inner bag volume of described autoclave is 50ml, at the temperature of 160 DEG C, heats 15h, synthetic Ni-Co-P metallic composite.
A preparation method for sea urchin shape Ni-Co-Pd-P metallic composite, comprises the steps:
(A) composite of Ni-Co-P and the PdCl of 1ml2.8mmol/L of use 25mg
2solution mixing is spent the night, and adds the NaBH of 5mL8mol/L
4;
(B) collect product with magnet and wash repeatedly by deionized water, to remove unreacted reagent and impurity, drying grinding and obtain Ni-Co-Pd-P metallic composite.
Composite micro-nano rice material of the present invention is applied in reduction paranitrophenol as catalyst, adopt the method for described composite micro-nano rice material catalytic reduction paranitrophenol to comprise the steps: to adopt the sodium borohydride of the freshly prepd 0.264mol/L of 30ml and 20ml2.5mmol/L paranitrophenol to be blended at 45 DEG C and keep 10min, add 25mg sea urchin shape Ni – P-Co metallic composite or sea urchin shape Ni-Co-Pd-P metallic composite.Get this solution of 0.5ml and with magnet extraction, and be diluted to 5ml with liquid-transfering gun, for carry out ultraviolet-visible light adsorption analysis within the interval time of regulation.
In the process of reduction paranitrophenol, magnet is placed on to the bottom of beaker with quick separating mixture, by washed with de-ionized water, to remove the Pd that is adsorbed on Pd NPs
2+, can repeatedly recycle described sea urchin shape Ni – P-Co metallic composite and sea urchin shape Ni-Co-Pd-P metallic composite, described recycling number of times is 7 times.
Because transition metal phosphide has the hot and semiconductive of unique Cuiization ﹑ Ci ﹑ magnetic, people had produced and had studied widely interest them in the last few years.These phosphides are used for hydrodesulfurization and hydrodenitrogeneration as the new high-activity hydrogenation catalyst of a class, and have replaced general catalyst.The hydrogenation of p-nitrophenol is for evaluating the catalytic capability of synthesized sea urchin shape composite.In order to study Co and the Pd impact on reduction paranitrophenol, synthesize respectively Ni – Co – P and two kinds of sea urchin shape composites of Ni – Co – Pd – P, as shown in Fig. 2～Fig. 5, ultraviolet-visible spectrum is in order to illustrate the reduction process of paranitrophenol.
Fig. 1 represents 19.7,32.3, locates diffraction maximum for 37.5 and 58.3 ° and is respectively Ni
3(200) face and CoP in P
2(JCPDS77-0263) in (020), (121), the diffraction maximum of (131), other diffraction maximums are attributable to P (JCPDS75-0577).
Fig. 2 represents that paranitrophenol has obvious absworption peak at 400nm place.In the time that Ni-Co-P composite is mixed with the mixed liquor of paranitrophenol and NaBH4, As time goes on, the peak at 40nm place weakens gradually, and 295nm place occur new peak and As time goes on its intensity increase gradually, this shows, under the catalytic action of Ni-Co-P composite, paranitrophenol gradates as p-aminophenol; After 30s, reaction rate shows gradually, and paranitrophenol can be converted into p-aminophenol completely in 15min, thereby Co plays a very important role in the process of reduction paranitrophenol.
Fig. 3 represents when sea urchin shape Ni – Co – Pd – P composite is immersed to paranitrophenol and NaBH
4mixed liquor mixed liquor 50s time, the original yellow of solution is taken off, and more what is interesting is, when adding Pd NPs time ratio to add Ni – Co – P reaction rate faster.
Fig. 4 represents that sea urchin shape Ni – Co – Pd – P composite participates in the effect actual conditions of reaction, and solution is finally become colorless by yellow; Because it has ferromagnetism, therefore available magnet is collected.
Fig. 5 represents that the cycle performance of Ni – Co – Pd – P composite is to evaluate with the catalytic performance after 7 times by measuring in its 15min, uses 7 rear catalysts to demonstrate the catalytic efficiency similar to primary catalyst.
Embodiment 2
Be with the difference of embodiment 1: in step (2), in autoclave, at the temperature of 120 DEG C, heat 16h.
Embodiment 3
Be with the difference of embodiment 1: in step (2), in autoclave, at the temperature of 180 DEG C, heat 14h.
Above-described embodiment is described the preferred embodiment of the present invention; not scope of the present invention is limited; design under the prerequisite of spirit not departing from the present invention; various distortion and improvement that those of ordinary skill in the art make technical scheme of the present invention, all should fall in the definite protection domain of the claims in the present invention book.
Claims (10)
1. a composite micro-nano rice material, is characterized in that: be sea urchin shape Ni-Co-P metallic composite, characterized and determined that its structure is Ni Ni by XRD
3p@CoP
2@P.
2. a composite micro-nano rice material, is characterized in that: on the basis of the Ni-Co-P metallic composite described in claims 1, introduce Technique of Nano Pd, form sea urchin shape Ni-Co-Pd-P metallic composite.
3. composite micro-nano rice material according to claim 2, is characterized in that: described sea urchin shape Ni-Co-Pd-P metallic composite is characterized and determined that its structure is Ni@Ni by XRD
3p@CoP
2@P@Pd.
4. a preparation method for composite micro-nano rice material claimed in claim 1, is characterized in that: comprise the steps:
(1) by NiCl
2, CoCl
2and NaH
2pO
2in water, mix, then add organic solvent to mix, obtain mixed solution;
(2) described mixed solution is placed in to the autoclave that liner is polytetrafluoroethylene (PTFE), at the temperature of 120 DEG C～180 DEG C, heats 14h～16h, synthetic Ni-Co-P metallic composite.
5. the preparation method of composite micro-nano rice material according to claim 4, is characterized in that: NiCl described in step (1)
2, CoCl
2and NaH
2pO
2mol ratio be 2:2:1, described organic solvent is DMF, adopts the mixed 2mmolNiCl of 20ml water-soluble solution
2, 2mmol CoCl
2with 1mmol NaH
2pO
2, under stirring action, add 20ml DMF, form the mixed solution of 40ml altogether, described in step (2), the inner bag volume of autoclave is 50ml.
6. a preparation method for the composite micro-nano rice material described in claim 2 or 3, is characterized in that: comprise the steps:
(A) the Ni-Co-P metallic composite and the PdCl that claim 4 or 5 are obtained
2mix and blend spends the night, and adds sodium borohydride;
(B) collect product with magnet and wash repeatedly by deionized water, drying grinding and obtain Ni-Co-Pd-P metallic composite.
7. the preparation method of composite micro-nano rice material according to claim 6, is characterized in that: step (A) is specially: with the composite of Ni-Co-P and the PdCl of 1ml2.8mmol/L of 25mg
2solution mixing is spent the night, and adds the NaBH of 5mL8mol/L
4.
8. the application in reduction paranitrophenol as catalyst of the composite micro-nano rice material described in claim 1 or 2 or 3.
9. application according to claim 8, it is characterized in that: adopt the method for the composite micro-nano rice material catalytic reduction paranitrophenol described in claim 1 or 2 or 3 to comprise the steps: to adopt the sodium borohydride of the freshly prepd 0.264mol/L of 30ml and 20ml2.5mmol/L paranitrophenol to be blended at 45 DEG C and keep 10min, add 25mg sea urchin shape Ni – P-Co metallic composite or sea urchin shape Ni-Co-Pd-P metallic composite.
10. application according to claim 9, it is characterized in that: in the process of reduction paranitrophenol, magnet is placed on to the bottom of beaker with quick separating mixture, can repeatedly recycle described sea urchin shape Ni – P-Co metallic composite and sea urchin shape Ni-Co-Pd-P metallic composite, described recycling number of times is 7 times.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105836720A (en) * | 2016-03-25 | 2016-08-10 | 上海理工大学 | Cross-shaped nickel-cobalt-phosphorus compound and synthesis method of same |
| CN110297025A (en) * | 2019-07-26 | 2019-10-01 | 衡阳师范学院 | A kind of application of the Prussian blue similar object material of nanoscale Ni-Fe and preparation method thereof with Electrochemical Detection ortho-nitrophenol |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106784899A (en) * | 2015-11-24 | 2017-05-31 | 天津大学 | A kind of three-dimensional Pd-P alloy nanoparticles network structure material and its preparation method and application |
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| JPS5331632A (en) * | 1976-09-06 | 1978-03-25 | Nippon Kayaku Co Ltd | Preparation of amionphenols |
| CN101734726A (en) * | 2009-12-15 | 2010-06-16 | 浙江师范大学 | Method for preparing urchin-shaped hydroxyferric oxide and urchin-shaped ferric oxide nano material |
| CN102641736A (en) * | 2012-03-19 | 2012-08-22 | 中国科学院过程工程研究所 | Sea urchin shaped copper oxide catalyst, as well as preparation method and application thereof |
| CN103357891A (en) * | 2013-05-25 | 2013-10-23 | 北京化工大学 | Preparation method and application of nickel and cobalt multi-level branching structure |
| CN103566956A (en) * | 2013-11-22 | 2014-02-12 | 安徽师范大学 | Micron-size nickel phosphide material as well as preparation method and application of micron-size nickel phosphide material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| SU883017A1 (en) * | 1980-02-18 | 1981-11-23 | Предприятие П/Я В-8469 | Method of preparing aminophenols |
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2014
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| JPS5331632A (en) * | 1976-09-06 | 1978-03-25 | Nippon Kayaku Co Ltd | Preparation of amionphenols |
| CN101734726A (en) * | 2009-12-15 | 2010-06-16 | 浙江师范大学 | Method for preparing urchin-shaped hydroxyferric oxide and urchin-shaped ferric oxide nano material |
| CN102641736A (en) * | 2012-03-19 | 2012-08-22 | 中国科学院过程工程研究所 | Sea urchin shaped copper oxide catalyst, as well as preparation method and application thereof |
| CN103357891A (en) * | 2013-05-25 | 2013-10-23 | 北京化工大学 | Preparation method and application of nickel and cobalt multi-level branching structure |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105836720A (en) * | 2016-03-25 | 2016-08-10 | 上海理工大学 | Cross-shaped nickel-cobalt-phosphorus compound and synthesis method of same |
| CN110297025A (en) * | 2019-07-26 | 2019-10-01 | 衡阳师范学院 | A kind of application of the Prussian blue similar object material of nanoscale Ni-Fe and preparation method thereof with Electrochemical Detection ortho-nitrophenol |
| CN110297025B (en) * | 2019-07-26 | 2021-05-28 | 衡阳师范学院 | Nano-scale Ni-Fe Prussian blue analogue material, preparation method thereof and application of nano-scale Ni-Fe Prussian blue analogue material in electrochemical detection of o-nitrophenol |
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