CN103962162B - A kind of composite micro-nano rice material and its preparation method and application - Google Patents
A kind of composite micro-nano rice material and its preparation method and application Download PDFInfo
- Publication number
- CN103962162B CN103962162B CN201410188196.1A CN201410188196A CN103962162B CN 103962162 B CN103962162 B CN 103962162B CN 201410188196 A CN201410188196 A CN 201410188196A CN 103962162 B CN103962162 B CN 103962162B
- Authority
- CN
- China
- Prior art keywords
- composite
- rice material
- sea urchin
- nano
- micro
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Abstract
The invention discloses a kind of composite micro-nano rice material, is sea urchin shape Ni-Co-P metallic composite, is characterized determine that its structure is Ni@Ni by XRD
3p@CoP
2@P.The invention discloses another kind of composite micro-nano rice material, Technique of Nano Pd is introduced on the basis of described Ni-Co-P metallic composite, form sea urchin shape Ni-Co-Pd-P metallic composite.The invention also discloses described two kinds of preparation method and application thereof meeting micro Nano material.The present invention is by one step hydro thermal method synthesis Ni@Ni
3p@CoP
2@P, the basis of Ni-Co-P composite is adsorbed palladium salt, adds reducing agent, introduces Technique of Nano Pd, and the Ni-Co-Pd-P of synthesis has good catalytic effect and circulating effect in reduction paranitrophenol.
Description
Technical field
The present invention relates to inorganic material preparation and application field, particularly relate to that a kind of synthesis is 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 making hemoglobin be converted into ferrihemoglobin, nitrophenol exists in water body can reduce its self-purification capacity, except can as several antalgesic 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 made from catalysis/electrochemical reduction nitrobenzene, therefore, paranitrophenol catalytic reduction is the excellent catalyst of para-aminophenol by exploration is necessary, the catalytic hydrogenation of some metallic composite p-nitrophenols is extensively studied, but the heterogeneous noble metal catalyst of tradition application needs extreme reaction condition usually in the hydrogenation reaction of aromatic hydrocarbons.At present, still be in the starting stage to the catalyticing research of aromatic hydrogenation, and develop the effective catalyst that can aromatic hydrocarbons be promoted in a mild condition to reduce and significant challenge is still to researcher, metal micro-/ nano catalyst has different architectures, as Ju He Wu ﹑ Shu Zhi Zhuan ﹑ micella and mesoporous material, recently in specific reaction compartment, the interest that it is studied is increased 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 the substituting group building multi-functional micro-/ nano catalyst, the catalyst of gained not only has the composite performance of the individuality composition of oneself, and go out new features and function due to the interaction display of the cooperative information between parts, from the angle of the materials chemistry of sustainable chemistry and green syt, an urgent demand development composite, go out in the strategy of different surfaces modification at nearest multi-functional micro-/ nano catalyst preparation, microstructure receives maximum concerns with the synthesis increasing catalytic effect.
Summary of the invention
The technical problem to be solved in the present invention is to provide that a kind of synthesis is easy, magnetic good and have high catalytic performance composite micro-nano rice material.
The preparation method and the described micro Nano material that meets that present invention also offers a kind of described composite micro-nano rice material are reducing the application in paranitrophenol as catalyst.
A kind of composite micro-nano rice material, it is sea urchin shape Ni-C
o-P metallic composite, is characterized by XRD and determines that its structure is Ni@Ni
3p@CoP
2@P.
A kind of composite micro-nano rice material, Technique of Nano Pd is introduced 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 by XRD determines that its structure is Ni@Ni
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
2mix in water, then add organic solvent mixing, obtain mixed solution;
(2) described mixed solution is placed in the autoclave that liner is polytetrafluoroethylene (PTFE), at the temperature of 120 DEG C ~ 180 DEG C, heats 14h ~ 16h, synthesis 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 20ml water-soluble solution to mix 2mmol NiCl
2, 2mmol CoCl
2with 1mmol NaH
2pO
2, add 20mlDMF under stirring, 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 of acquisition and PdCl
2mix and blend spends the night, and adds sodium borohydride;
(B) collect product with magnet and spend deionized water repeatedly, 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 as the application of catalyst in reduction paranitrophenol.
Application of the present invention, keep 10min at the method for the composite micro-nano rice material catalyzes reduction paranitrophenol described in employing comprises the steps: to adopt the sodium borohydride of 30ml freshly prepd 0.264mol/L and 20ml2.5mmol/L paranitrophenol to be blended in 45 DEG C, 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 the bottom of beaker with quick separating mixture, repeatedly can 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: the fine structure material of composite micro-nano rice material of the present invention to Ni-P is slightly modified, prepare nickeliferous by a simple one-step method hydro-thermal method, cobalt, and the sea urchin shape material of P, and determine that its structure is Ni@Ni by XRD sign
3p@CoP
2@P.In order to obtain high catalytic activity, at NaBH
4there is lower palladium ion absorbed by sea urchin shape material and be reduced into Pd nano particle, this catalyst is for reducing paranitrophenol than containing nickel separately, the catalyst of cobalt or P demonstrates stronger catalytic capability, will containing nickel, cobalt, phosphorus, be filled into a micro-/ nano reactor with the multifunctional material of Pd and be applied in hydrogenation nitrophenol, produce a kind of new catalyst of p-nitrophenol hydrogenation, for reduce paranitrophenol and the catalytic activity of improvement of nickel-cobalt-palladium-P composite prepared by being easy to be separated from reactant mixture, achieve the catalytic activity of raising reduction p-nitrophenol simultaneously and be easy to from reactant mixture, be separated prepared nickel-cobalt-palladium-P composite.The composite of synthesis has good magnetic, makes to be easy to realize effectively being separated of catalyst and degradation product in application process, and carrying out easily and effectively repeatedly recycles.After the present invention modifies protocorm material, when reducing paranitrophenol, Ni – Co – Pd – P composite shows good catalytic capability and good cycle performance.
The present invention is by one step hydro thermal method synthesis Ni@Ni
3p@CoP
2@P, the basis of Ni-Co-P composite is adsorbed palladium salt, adds reducing agent, introduces Technique of Nano Pd, and the Ni-Co-Pd-P of synthesis has good catalytic effect and circulating effect in reduction paranitrophenol.
The microcomposite of transition metal phosphide has with low cost and catalytic activity is a little high, therefore very concerned at catalytic field.But, high temperature and poisonous phosphorus source (such as, trictylphosphine) 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 and the impact of output is carried out smoothly.Except cost is low, of nickel (Ni) is important be advantage it have and give the ability of ferromagnetic behavior to another kind of material.Magnetic catalyst is collected easily by Magnetic Isolation from different reaction systems, thus when 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 by a simple water and the synthesis of DMF solvent heat path, and this microstructure can promptly heavy-metal ion removal from water.
Consider its excellent catalytic capability 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 partly can be replaced by cobalt, and not lose the catalytic capability of whole material.Many catalyst containing Co, as platinum-cobalt and molybdenum-cobalt, are exploited recently.These reports show, the microstructure containing Ni and Co composite can be exploitation effective catalyst, and reduce the use amount of noble metal, 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.
Accompanying drawing explanation
Fig. 1 is the thing phasor of the composite Ni – Co – P that the present invention synthesizes;
The ultraviolet figure of Fig. 2 to be micro Nano material Ni – Co – P of the present invention to p-nitrophenol carry out solution after catalytic reduction;
The ultraviolet figure of Fig. 3 to be micro Nano material Ni – Co – Pd – P of the present invention to p-nitrophenol carry out solution after catalytic reduction;
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 determine that its structure is Ni@Ni by XRD
3p@CoP
2@P.
A kind of composite micro-nano rice material, Technique of Nano Pd is introduced on the basis of described Ni-Co-P metallic composite, forms sea urchin shape Ni-Co-Pd-P metallic composite, is characterized determine 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) the water-soluble solution of 20ml is adopted to mix 2mmol NiCl
2, 2mmol CoCl
2with 1mmol NaH
2pO
2, add 20mlDMF under stirring, form the mixed solution of 40ml altogether;
(2) described mixed solution is placed in the autoclave that liner is polytetrafluoroethylene (PTFE), the inner bag volume of described autoclave is 50ml, at the temperature of 160 DEG C, heat 15h, synthesis Ni-Co-P metallic composite.
A preparation method for sea urchin shape Ni-Co-Pd-P metallic composite, comprises the steps:
(A) 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;
(B) collect product with magnet and spend deionized water repeatedly, 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, keep 10min at the method for the composite micro-nano rice material catalyzes reduction paranitrophenol described in employing comprises the steps: to adopt the sodium borohydride of 30ml freshly prepd 0.264mol/L and 20ml2.5mmol/L paranitrophenol to be blended in 45 DEG C, 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 extract with magnet, and being diluted to 5ml with liquid-transfering gun, carrying out ultraviolet-visible light adsorption analysis within the interval time of regulation.
Reduction paranitrophenol process in, bottom magnet being placed on beaker with quick separating mixture, by washed with de-ionized water, to remove the Pd being adsorbed on Pd NPs
2+, repeatedly can 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 created them and studied interest widely in the last few years.These phosphides are used for hydrodesulfurization and hydrodenitrogeneration as the high-activity hydrogenation catalyst that a class is new, and instead of general catalyst.The hydrogenation of p-nitrophenol is for evaluating the catalytic capability of synthesized sea urchin shape composite.In order to study the impact of Co and Pd on reduction paranitrophenol, synthesized Ni – Co – P and Ni – Co – Pd – P two kinds of sea urchin shape composites respectively, as shown in Fig. 2 ~ Fig. 5, ultraviolet-visible spectrum is in order to illustrate the reduction process of paranitrophenol.
Fig. 1 represents that 19.7,32.3,37.5 and 58.3 ° of place's diffraction maximums are 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.When the mixed liquor of Ni-Co-P composite and paranitrophenol and NaBH4 is mixed, 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, thus 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 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 evaluates by measuring the catalytic performance after using 7 times 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 only be described the preferred embodiment of the present invention; not scope of the present invention is limited; under not departing from the present invention and designing the prerequisite of spirit; the various distortion that those of ordinary skill in the art make technical scheme of the present invention and improvement, all should fall in protection domain that claims of the present invention determines.
Claims (9)
1. a composite micro-nano rice material, is characterized in that: be sea urchin shape Ni-Co-P metallic composite, is characterized determine 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 Ni-Co-P metallic composite according to claim 1, introduce Technique of Nano Pd, forms 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 by XRD determines that its structure is Ni@Ni
3p@CoP
2@P@Pd.
4. a preparation method for composite micro-nano rice material according to claim 1, is characterized in that: comprise the steps:
(1) by NiCl
2, CoCl
2and NaH
2pO
2mix in water, then add organic solvent mixing, obtain mixed solution;
(2) described mixed solution is placed in the autoclave that liner is polytetrafluoroethylene (PTFE), at the temperature of 120 DEG C ~ 180 DEG C, heats 14h ~ 16h, synthesis Ni-Co-P metallic composite;
NiCl described in step (1)
2, CoCl
2and NaH
2pO
2mol ratio be 2:2:1, described organic solvent is DMF, adopts 20ml water-soluble solution to mix 2mmol NiCl
2, 2mmol CoCl
2with 1mmol NaH
2pO
2, add 20mlDMF under stirring, form the mixed solution of 40ml altogether.
5. the preparation method of composite micro-nano rice material according to claim 4, is characterized in that: 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 Claims 2 or 3, is characterized in that: comprise the steps:
(A) Ni-Co-P metallic composite claim 4 or 5 obtained and PdCl
2mix and blend spends the night, and adds sodium borohydride;
(B) collect product with magnet and spend deionized water repeatedly, drying grinding and obtain Ni-Co-Pd-P metallic composite;
Step (A) is specially: with the composite of Ni-Co-P and the PdCl of 1ml 2.8mmol/L of 25mg
2solution mixing is spent the night, and adds the NaBH of 5mL 8mol/L
4.
7. claim 1 or the composite micro-nano rice material described in 2 or 3 are as the application of catalyst in reduction paranitrophenol.
8. application according to claim 7, it is characterized in that: keep 10min at adopting the method for claim 1 or the reduction of the composite micro-nano rice material catalyzes described in 2 or 3 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 in 45 DEG C, add 25mg sea urchin shape Ni – P-Co metallic composite or sea urchin shape Ni-Co-Pd-P metallic composite.
9. application according to claim 8, it is characterized in that: in the process of reduction paranitrophenol, magnet is placed on the bottom of beaker with quick separating mixture, repeatedly can 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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410188196.1A CN103962162B (en) | 2014-05-06 | 2014-05-06 | A kind of composite micro-nano rice material and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410188196.1A CN103962162B (en) | 2014-05-06 | 2014-05-06 | A kind of composite micro-nano rice material and its preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103962162A CN103962162A (en) | 2014-08-06 |
| CN103962162B true CN103962162B (en) | 2015-09-23 |
Family
ID=51232448
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410188196.1A Expired - Fee Related CN103962162B (en) | 2014-05-06 | 2014-05-06 | A kind of composite micro-nano rice material and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103962162B (en) |
Cited By (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 |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105836720B (en) * | 2016-03-25 | 2017-08-25 | 上海理工大学 | A kind of cross nickel cobalt phosphorus compound and its synthetic method |
| 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 |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU883017A1 (en) * | 1980-02-18 | 1981-11-23 | Предприятие П/Я В-8469 | Method of preparing aminophenols |
| 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 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6032619B2 (en) * | 1976-09-06 | 1985-07-29 | 日本化薬株式会社 | Method for producing aminophenols |
-
2014
- 2014-05-06 CN CN201410188196.1A patent/CN103962162B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU883017A1 (en) * | 1980-02-18 | 1981-11-23 | Предприятие П/Я В-8469 | Method of preparing aminophenols |
| 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 |
Cited By (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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103962162A (en) | 2014-08-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Veerakumar et al. | Biomass-derived activated carbon supported Fe3O4 nanoparticles as recyclable catalysts for reduction of nitroarenes | |
| Şen et al. | A novel thiocarbamide functionalized graphene oxide supported bimetallic monodisperse Rh-Pt nanoparticles (RhPt/TC@ GO NPs) for Knoevenagel condensation of aryl aldehydes together with malononitrile | |
| Lu et al. | Decoration of Pd nanoparticles with N and S doped carbon quantum dots as a robust catalyst for the chemoselective hydrogenation reaction | |
| She et al. | High catalytic performance of a CeO2-supported Ni catalyst for hydrogenation of nitroarenes, fabricated via coordination-assisted strategy | |
| Olveira et al. | Nanocatalysis: academic discipline and industrial realities | |
| Ai et al. | Amorphous flowerlike goethite FeOOH hierarchical supraparticles: Superior capability for catalytic hydrogenation of nitroaromatics in water | |
| Yan et al. | One-step seeding growth of magnetically recyclable Au@ Co core− shell nanoparticles: highly efficient catalyst for hydrolytic dehydrogenation of ammonia borane | |
| Xu et al. | Cobalt nanoparticles encapsulated in nitrogen-doped carbon shells: efficient and stable catalyst for nitrobenzene reduction | |
| Zhao et al. | Monodisperse metal–organic framework nanospheres with encapsulated core–shell nanoparticles Pt/Au@ Pd@{Co2 (oba) 4 (3-bpdh) 2} 4H2O for the highly selective conversion of CO2 to CO | |
| Zhuang et al. | One-step rapid and facile synthesis of subnanometer-sized Pd6 (C12H25S) 11 clusters with ultra-high catalytic activity for 4-nitrophenol reduction | |
| Kang et al. | Efficient catalytic hydrolytic dehydrogenation of ammonia borane over surfactant-free bimetallic nanoparticles immobilized on amine-functionalized carbon nanotubes | |
| Sánchez-Delgado et al. | Hydrogenation of quinoline by ruthenium nanoparticles immobilized on poly (4-vinylpyridine) | |
| Hu et al. | Cobalt with porous carbon architecture: Towards of 4-nitrophenol degradation and reduction | |
| Wu et al. | Magnetic cobaltic nanoparticle-anchored carbon nanocomposite derived from cobalt-dipicolinic acid coordination polymer: An enhanced catalyst for environmental oxidative and reductive reactions | |
| Cho et al. | Synthesis of cobalt-impregnated carbon composite derived from a renewable resource: Characterization and catalytic performance evaluation | |
| CN103962162B (en) | A kind of composite micro-nano rice material and its preparation method and application | |
| Wu et al. | Nano-pyramid-type Co-ZnO/NC for hydrogen transfer cascade reaction between alcohols and nitrobenzene | |
| Ashik et al. | Nanomaterials as catalysts | |
| Lian et al. | Template-regulated bimetallic sulfide nanozymes with high specificity and activity for visual colorimetric detection of cellular H2O2 | |
| Lu et al. | In situ synthesis of cobalt alginate/ammonium perchlorate composite and its low temperature decomposition performance | |
| Feng et al. | Controllable synthesis of cobalt-containing nanosheet array-like ternary CuCoAl-LDH/rGO hybrids to boost the catalytic efficiency for 4-nitrophenol reduction | |
| Liu et al. | Transforming cobalt hydroxide nanowires into single atom site catalysts | |
| Yang et al. | Record-high catalytic hydrogenated activity in nitroarenes reduction derived from in-situ nascent active metals enabled by constructing bimetallic phosphate | |
| Wang et al. | Ultrasmall Ni–ZnO/SiO2 synergistic catalyst for highly efficient hydrogenation of NaHCO3 to formic acid | |
| Bagheri et al. | A quasi-metal–organic framework based on cobalt for improved catalytic conversion of aquatic pollutant 4-nitrophenol |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150923 Termination date: 20160506 |