CN103435813B - A kind of ligand polymer microballoon and preparation method and use for storing hydrogen - Google Patents
A kind of ligand polymer microballoon and preparation method and use for storing hydrogen Download PDFInfo
- Publication number
- CN103435813B CN103435813B CN201310372985.6A CN201310372985A CN103435813B CN 103435813 B CN103435813 B CN 103435813B CN 201310372985 A CN201310372985 A CN 201310372985A CN 103435813 B CN103435813 B CN 103435813B
- Authority
- CN
- China
- Prior art keywords
- ligand polymer
- polymer microballoon
- dicarboxylic acid
- cpm
- ferrocene dicarboxylic
- 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.)
- Active
Links
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a kind of ligand polymer microballoon and preparation method and use for storing hydrogen, with 1,1 '-ferrocene dicarboxylic acid and 4,4 '-dipyridyl as part, by its according to mol ratio 1:1 mixed dissolution at N, in N '-dimethyl methane amide, add metal-salt mixing, metal-salt and 1, the mol ratio of 1 '-ferrocene dicarboxylic acid is 1:1, is heated to 120-180 DEG C of reaction 12h; After question response terminates, by reactor cool to room temperature, then obtained the reaction solution on upper strata by centrifugation, then by obtaining solid product after rotary evaporation, vacuum-drying obtains ligand polymer microballoon; This ligand polymer microballoon has great utility in Chu Qing; The present invention is by using with 1,1 '-ferrocene dicarboxylic acid and 4,4'-Bipyridine as part, and make them more with the binding site of metal, coordination power more by force, can increase the stability of material.
Description
Technical field
The present invention relates to a kind of technology of preparing comprising the ligand polymer of metal and organic ligand, particularly a kind of ligand polymer microballoon and preparation method and use for storing hydrogen.
Background technology
Ligand polymer owing to having unique constitutional features, have morphology controllable, high-sequential porousness, high-specific surface area, be easy to modified, be thus subject to extensive concern.And ferrocene is because have high heat stability and unique performance such as redox, electricity, light, magnetic, so based on 1,1 '-ferrocene dicarboxylic acid ligand polymer as the important material of a class gas storage be separated, selective catalysis, drug release, electroluminescent, molecular recognition and light/magnetic device preparation in have important application.
Summary of the invention
In order to overcome the not high problem of the thermostability that causes of ligand polymer that builds based on 1,1 '-ferrocene dicarboxylic acid, the invention provides a kind of ligand polymer microballoon and preparation method and use for storing hydrogen.The present invention is by using with 1,1 '-ferrocene dicarboxylic acid and 4,4'-Bipyridine as part, and make them more with the binding site of metal, coordination power more by force, can increase the stability of material.Thus the present invention utilizes simple synthesis technique to obtain the high ligand polymer of thermostability to have important using value.
The object of the invention is to be achieved through the following technical solutions: a kind of ligand polymer microballoon, is characterized in that, its structural formula is:
；
Wherein, M is Mn, Co or Zn.Molecular weight ranges is 200-800.
A kind of preparation method of ligand polymer microballoon, the method is: with 1,1 '-ferrocene dicarboxylic acid and 4,4 '-dipyridyl as part, by its according to mol ratio 1:1 mixed dissolution at N, in N '-dimethyl methane amide, add metal-salt mixing, metal-salt and 1, the mol ratio of 1 '-ferrocene dicarboxylic acid is 1:1, is placed in air dry oven and is heated to 120-180 DEG C of reaction 12h; After question response terminates, by reactor cool to room temperature, then obtained the reaction solution on upper strata by centrifugation, by the reaction solution obtained by obtaining solid product after rotary evaporation, being placed on vacuum drying oven and carrying out drying, obtaining ligand polymer microballoon.
A kind of use for storing hydrogen of ligand polymer microballoon.
The invention has the beneficial effects as follows,
1, the preparation technology of this ligand polymer is simple, only needs part and metal-salt to join in polytetrafluoroethyllining lining, then liner is placed on heated sealed in stainless steel still, just can obtain target product by single step reaction.
2, owing to adopting solvent-thermal method, thus there is the general advantage of solvent-thermal method: energy consumption is low, granule-morphology is controlled, reaction conditions is easy to control.
3, the pattern of this product is better, and in regular spherical particle, and spherome surface is coarse, is conducive to increasing specific surface area.
4, the part owing to adopting has the rigid structure of phenyl ring and so on, and the thermostability of the microballoon thus obtained is high.
Accompanying drawing explanation
Fig. 1 is the SEM picture of three kinds of ligand polymer microballoons of synthesis, and wherein, (A) is the scanning electron microscope (SEM) photograph of Mn-CPM, and (B) is the Electronic Speculum figure of the partial enlargement of (A); (C) be the scanning electron microscope (SEM) photograph of Co-CPM, (D) is the Electronic Speculum figure of the partial enlargement of (C); (E) be the Electronic Speculum figure of Zn-CPM, (F) is the partial enlarged drawing of (E);
Fig. 2 is the particle size distribution figure of the Mn-CPM of the polymer microballoon of synthesis;
Fig. 3 is the particle size distribution figure of the Co-CPM of the polymer microballoon of synthesis;
Fig. 4 is the particle size distribution figure of the Zn-CPM of the polymer microballoon of synthesis;
Fig. 5 is the material infrared spectrum that the present invention obtains, and wherein, (a) is 1, the infrared spectrum of 1 '-ferrocene dicarboxylic acid, and (b) is the infrared spectrum of Mn-CPM, and (c) is the infrared spectrum of Co-CPM, and (d) is the infrared spectrum of Co-CPM;
Fig. 6 is the PXRD spectrogram of three kinds of polymer materialss that the present invention obtains;
Fig. 7 is the N of the Mn-CPM that the present invention obtains
2adsorption desorption graphic representation;
Fig. 8 is the graph of pore diameter distribution of the Mn-CPM that the present invention obtains;
Fig. 9 is the N of the Co-CPM that the present invention obtains
2adsorption desorption graphic representation;
Figure 10 is the graph of pore diameter distribution of the Co-CPM that the present invention obtains;
Figure 11 is the N of the Zn-CPM that the present invention obtains
2adsorption desorption graphic representation;
Figure 12 is the graph of pore diameter distribution of the Zn-CPM that the present invention obtains;
Figure 13 is thermogravimetric curve and the differential curve figure of the Mn-CPM that the present invention obtains;
Figure 14 is thermogravimetric curve and the differential curve figure of the Co-CPM that the present invention obtains;
Figure 15 is thermogravimetric curve and the differential curve figure of the Zn-CPM that the present invention obtains;
Figure 16 be three kinds of materials obtaining of the present invention under 163 K, the hydrogen adsorption curve within the scope of-0.1-5.0 MPa.
Embodiment
Principle of the present invention is:
The preparation method of ligand polymer microballoon of the present invention is: with 1,1 '-ferrocene dicarboxylic acid and 4,4 '-dipyridyl is as part, by its according to mol ratio 1:1 mixed dissolution at N, in N '-dimethyl methane amide (DMF), add metal-salt mixing, metal-salt and 1, the mol ratio of 1 '-ferrocene dicarboxylic acid is 1:1, is placed in air dry oven and heats 120-180 DEG C of reaction 12h.After question response terminates, by reactor cool to room temperature, then obtained the reaction solution on upper strata by centrifugation, by the reaction solution obtained by obtaining solid product after rotary evaporation, being placed on vacuum drying oven and carrying out drying, obtaining ligand polymer microballoon.
The ligand polymer microballoon that the present invention prepares, its structural formula is:
；
Wherein, M is Mn, Co or Zn.Molecular weight ranges is 200-800.
The ligand polymer microballoon that the present invention is based on two kinds of parts structures adopts multiple various test to characterize its correlated performance, and concrete characterization test step is as follows:
(1) infrared spectra
Infrared spectra (FT-IR) measures (KBr compressing tablet) on Nicolet5700 type infrared spectrometer.
Testing method: get a certain amount of sample powder and dry KBr powder, be ground in agate crucible, gained powder is measured after (~ 30 MPa) film-making of colding pressing.
Visible through test: 1 of the present invention's use, the carboxyl of 1 '-ferrocene dicarboxylic acid generates ligand polymer with metal ion by coordination reaction after de-proton.
(2) scanning electronic microscope
Scanning electron microscope (Scanning electron microscopy, SEM) photo is in SIRION scanning electron microscope instrument photographs, and subsidiary GENESIS-4000 type X-ray energy dispersive spectrometer (Energy dispersive X-ray spectroscopy, EDX).
Testing method: take a morsel powder dispersion in ethanol, microsyringe is used to extract the alcohol dispersion liquid of 2 μ L containing sample, drop in be placed in and be bonded at the suprabasil silicon chip surface of copper with conductive resin, until solvent naturally volatilize dry after, Jiang Tongtai puts into SEM cavity and tests.
Visible through test: ligand polymer prepared by the present invention presents spherical, and all particle diameters are in micro-meter scale, and the diameter of ball is within the scope of 200nm-9 μm, and its diameter Distribution is also uneven, and has reunion in various degree.
(3) thermogravimetic analysis (TGA)
The test of thermogravimetic analysis (TGA) (Thermogravimetry analysis, the TGA) curve of sample is carried out on Perkin-Elmer Pyris 1 TGA thermogravimetric analyzer.
Testing method: the sample of about 2 mg is placed in crucible, thermogravimetric analyzer is tested, test condition is: under nitrogen or air atmosphere, temperature rise rate is 10
oc/min, temperature test scope is 50-800 DEG C.
Visible through test: ligand polymer microballoon prepared by the present invention has different thermal stabilities, and its heat decomposition temperature, from 200 DEG C to 450 DEG C, all there will be decomposition in various degree and structure collapse.Finally just decompose completely at 600 DEG C, generate the oxide compound of metal, show that such material has good thermostability.
(4) powder x-ray diffraction
Powder x-ray diffraction (Powder X-ray diffraction, the PXRD) spectrum of sample is at X'Pert PRO(CuK
α , λ=1.54) X-ray diffractometer is tested.
Testing method: be laid in sample table by the powdered sample of about 20 mg, puts into X-ray diffractometer and tests.
Visible through test: ligand polymer microballoon prepared by the present invention is in 2 θ=7
.there is sharp-pointed diffraction peak, 10
.-20
。there are many bunches of charateristic avsorption bands, 30
.-40
。have short broad peak to occur, show this material crystalline performance and bad, but the almost identical peak position that goes out of three kinds of materials shows that three class materials have the structural similarity of height.
(5) nitrogen adsorption desorption
Specific surface area, the pore size distribution of sample are tested on AUTOSORB-1-C type gas adsorption instrument.
Testing method: get a certain amount of powdered sample and add in sample hose, under 160 oC after vacuum-drying 2 h, tests.
Visible through test: the specific surface area of Mn-CPM, Co-CPM and Zn-CPM is 137.5,123.8 and 36.30 m respectively
2g
-1.
(6) hydrogen storage property test
High pressure (about 5MPa) the hydrogen storage property test of sample carries out on the Sievert type storage hydrogen test set of designed, designed.By the sample of accurate weighing (about 0.3 g) put into sample chamber after, sealed sample room.The resistance to air loss checking hydrogen storage property test set is immersed in water after being filled with the hydrogen of certain pressure (about 4 MPa) in sample chamber, vacuumize 30 min again and remove hydrogen, then sample chamber is put into vertical retort furnace and be slowly heated to about 160 DEG C, stop after vacuum-drying 6 h heating and naturally cooling to room temperature, sample chamber is moved in cryogenic thermostat reactive bath technique, after system stability 30 min, open computer, computer expert's excess pressure sensor and Chu Qing test set are coupled together, then the data logging software M400 on computer is opened, then in device, be filled with the hydrogen of certain pressure, the pressure change recording this process after balance is reached until sample adsorption hydrogen, progressively hydrogen pressure is raised until reach 5 MPa with the speed of each 0.5 MPa.Chu Qing test progressively reduces the dehydrogenation of the pressure test sample of system after finishing, until final pressure drops to 0.1 MPa, finally all data importing origin 8.5 obtained are carried out processing the adsorption desorption curve obtaining hydrogen.
Visible through test: ligand polymer microballoon prepared by the present invention has good hydrogen storage property, the Mn-CPM of preparation, Co-CPM, Zn-CPM 163K and 5 MPa can storage of hydrogen according to weight hydrogen-storage amount calculate be respectively 1.60 wt %, 2.12 wt % and 1.22 wt %, wherein wt% represents that the weight of material storage hydrogen accounts for the per-cent of material own wt.
Obtained all kinds of physical propertiess of material by above characterization test, comprise microscopic appearance, thermostability and specific surface area pore size distribution etc., be finally applied in hydrogen storage aspect.
Below by embodiment, the present invention is specifically described; only be used to further illustrate the present invention; can not be interpreted as limiting the scope of the present invention, the technician in this field can make some nonessential improvement and adjustment according to the content of foregoing invention to the present invention.
Embodiment 1:
For Mn-CPM, its concrete preparation method is as follows: by 0.3981 g (2 mmol) MnCl
24H
2o, 0.5480 g (2 mmol) 1,1 '-ferrocene dicarboxylic acid (Fc(COOH)
2) and 0.3120 g (2 mmol) 4,4 '-dipyridyl is dissolved in 8 mL N, in the mixed solvent of N '-dimethyl methane amide (DMF) and 8 mL deionized waters, again solution is joined and be equipped with in 23 mL teflon-lined stainless steel cauldrons, mix, baking oven is put into, first with 2 after being sealed by reactor
oc/min is warming up to 120
oc, after isothermal reaction 12 h, naturally cools to room temperature.Centrifugation is precipitated, then uses DMF and CHCl
3repetitive scrubbing is (each first ultrasonic 10 min, then centrifugation under 3000 r/min and 2000 r/min conditions respectively) for several times, to supernatant liquid is clear liquid, are deposited in 40 after removing clear liquid by what obtain
ovacuum-drying 24 h under C.
Can find out that this Mn-CPM presents from the A-B of Fig. 1 complete spherical, have the microballoon of part to reunite.Its grain size distribution can as can be seen from Figure 2 come, and maximum particle diameter is 7 μm, and minimum is 1 μm, and median size is 3.62 μm.In Figure 5, a curve is have neither part nor lot in coordination 1, the infrared spectrum of 1 '-ferrocene dicarboxylic acid, and b is the infrared spectrum of Mn-CPM, solid vertical line perpendicular to X-coordinate in figure represents 1, and in 1 '-ferrocene dicarboxylic acid, carboxyl charateristic avsorption band disappears after sloughing proton participation coordination, and vertical dotted line represents the appearance of the charateristic avsorption band of new ligand polymer, the two common this carboxylic acid of explanation participates in coordination reaction, generates title complex.This product X ray diffraction peaks is relatively more sharp-pointed as can be seen from Figure 6, has good crystal property.Its specific surface area is 137.5 m as can be drawn from Figure 7
2g
-1, mean pore size measured by the pore size distribution of Fig. 8 is 224.9nm.Can find out that this product is more stable from the TGA curve of Figure 13, be heated to 400 DEG C and just can decompose.The ability of its adsorbed hydrogen increases along with pressure and increases as can be seen from Figure 16, the maximum hydrogen adsorptive capacity 1.60 wt % by weight percentage under 5MPa, 163K.
Embodiment 2:
For Co-CPM, its concrete preparation method is as follows: by 0.4278 g (1.8 mmol) CoCl
24H
2o, 0.4938 g (2 mmol) 1,1 '-ferrocene dicarboxylic acid (Fc(COOH)
2) and 0.2813 g (1.8 mmol) 4,4 '-dipyridyl is dissolved in 8 mL N, in the mixed solvent of N '-dimethyl methane amide (DMF) and 8 mL deionized waters, again solution is joined and be equipped with in 23 mL teflon-lined stainless steel cauldrons, mix, baking oven is put into, first with 2 after being sealed by reactor
oc/min is warming up to 125
oc, after isothermal reaction 12 h, naturally cools to room temperature.Centrifugation is precipitated, then uses DMF and CHCl
3repetitive scrubbing is (each first ultrasonic 10 min, then centrifugation under 3000 r/min and 2000 r/min conditions respectively) for several times, to supernatant liquid is clear liquid, are deposited in 40 after removing clear liquid by what obtain
ovacuum-drying 24 h under C.
Can find out that this Co-CPM presents from the C-D of Fig. 1 complete spherical, reunite less, ball dispersion very well, its surface irregularity.Its grain size distribution can as can be seen from Figure 3 come, and size distribution is wider, and median size is 3.67 μm.In Figure 5, a curve is have neither part nor lot in coordination 1, the infrared spectrum of 1 '-ferrocene dicarboxylic acid, and c is the infrared spectrum of Co-CPM, solid vertical line perpendicular to X-coordinate in figure represents 1, and in 1 '-ferrocene dicarboxylic acid, carboxyl charateristic avsorption band disappears after sloughing proton participation coordination, and vertical dotted line represents the appearance of the charateristic avsorption band of new ligand polymer, the two common this carboxylic acid of explanation participates in coordination reaction, generates title complex.This product X ray diffraction peaks is relatively more sharp-pointed as can be seen from Figure 6, but diffraction peak broadens to some extent, and oriented crystalline performance declines to some extent.Its specific surface area is 123.8 m as can be drawn from Figure 9
2g
-1, mean pore size measured by the pore size distribution of Figure 10 is 252.4nm.Can find out that this product presents multistep weightlessness from the TGA curve of Figure 14.All have more violent weightlessness 200 DEG C and 350 DEG C, more than 400 DEG C weightless obviously, title complex structure collapse, the finally oxide compound of only remaining metal.The ability of its adsorbed hydrogen increases along with pressure and increases as can be seen from Figure 16, the maximum hydrogen adsorptive capacity 2.12 wt % by weight percentage under 5MPa, 163K.
Embodiment 3:
For Zn-CPM, its concrete preparation method is as follows: by 0.1775 g (0.6 mmol) Zn(NO
3)
26H
2o, 0.1653 g (0.6mmol) 1,1 '-ferrocene dicarboxylic acid (Fc(COOH)
2) and 0.9410 g (0.6 mmol) 4,4 '-dipyridyl is dissolved in 8 mL N, in the mixed solvent of N '-dimethyl methane amide (DMF) and 8 mL deionized waters, again solution is joined and be equipped with in 23 mL teflon-lined stainless steel cauldrons, mix, baking oven is put into, first with 2 after being sealed by reactor
oc/min is warming up to 180
oc, after isothermal reaction 12 h, naturally cools to room temperature.Centrifugation is precipitated, then uses DMF and CHCl
3repetitive scrubbing is (each first ultrasonic 10 min, then centrifugation under 3000 r/min and 2000 r/min conditions respectively) for several times, to supernatant liquid is clear liquid, are deposited in 40 after removing clear liquid by what obtain
ovacuum-drying 24 h under C.
Can find out that this Zn-CPM presents from the E-F of Fig. 1 spherical, but it is severe to reunite, sphere diameter is less, and its surface has a lot of unbodied fragment to link together.Its grain size distribution can as can be seen from Figure 4 come, and size distribution is comparatively even, and median size is 1.37 μm.In Figure 5, a curve is have neither part nor lot in coordination 1, the infrared spectrum of 1 '-ferrocene dicarboxylic acid, and d is the infrared spectrum of Zn-CPM, solid vertical line perpendicular to X-coordinate in figure represents 1, and in 1 '-ferrocene dicarboxylic acid, carboxyl charateristic avsorption band disappears after sloughing proton participation coordination, and vertical dotted line represents the appearance of the charateristic avsorption band of new ligand polymer, the two common this carboxylic acid of explanation participates in coordination reaction, generates title complex.This product X ray diffraction peaks is less as can be seen from Figure 6, and intensity reduces and peak shape broadens, and illustrate that this spheroidal particle crystal property declines to some extent, this has direct relation with its serious particle aggregation phenomenon.Its specific surface area is less as can be drawn from Figure 11, is 36.30 m
2g
-1, mean pore size measured by the pore size distribution of Figure 12 is 211.4nm.Can find out that this product thermostability is fine from the TGA curve of Figure 15.Below 300 DEG C, the quality of Zn-CPM has almost no change, and all has more violent weightlessness at 350 DEG C to 550 DEG C, title complex structure collapse, finally the oxide compound of only remaining metal.The ability of its adsorbed hydrogen increases along with pressure and increases as can be seen from Figure 16, the maximum hydrogen adsorptive capacity 1.22 wt %. by weight percentage under 5MPa, 163K
Above-described embodiment is used for explaining and the present invention is described, instead of limits the invention, and in the protection domain of spirit of the present invention and claim, any amendment make the present invention and change, all fall into protection scope of the present invention.
Claims (3)
1. a ligand polymer microballoon, is characterized in that, its structural formula is:
Wherein, M is Mn, Co or Zn; Molecular weight ranges is 200-800.
2. the preparation method of ligand polymer microballoon described in a claim 1, it is characterized in that, the method is: with 1,1 '-ferrocene dicarboxylic acid and 4,4'-Bipyridine as part, by its according to mol ratio 1:1 mixed dissolution at N, in N '-dimethyl methane amide, add metal-salt mixing, metal-salt and 1, the mol ratio of 1 '-ferrocene dicarboxylic acid is 1:1, is placed in air dry oven and is heated to 120-180 DEG C of reaction 12h; After question response terminates, by reactor cool to room temperature, then obtained the reaction solution on upper strata by centrifugation, by the reaction solution obtained by obtaining solid product after rotary evaporation, being placed on vacuum drying oven and carrying out drying, obtaining ligand polymer microballoon.
3. the use for storing hydrogen of ligand polymer microballoon described in a claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310372985.6A CN103435813B (en) | 2013-08-25 | 2013-08-25 | A kind of ligand polymer microballoon and preparation method and use for storing hydrogen |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310372985.6A CN103435813B (en) | 2013-08-25 | 2013-08-25 | A kind of ligand polymer microballoon and preparation method and use for storing hydrogen |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103435813A CN103435813A (en) | 2013-12-11 |
| CN103435813B true CN103435813B (en) | 2015-08-19 |
Family
ID=49689540
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310372985.6A Active CN103435813B (en) | 2013-08-25 | 2013-08-25 | A kind of ligand polymer microballoon and preparation method and use for storing hydrogen |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103435813B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107312164B (en) * | 2017-06-09 | 2019-08-20 | 浙江华纯有机光电材料有限公司 | Conjugated polymer and its polymerization and application based on ferrocene and phenanthroline derivative |
| CN107619468B (en) * | 2017-09-18 | 2020-04-07 | 浙江工业大学义乌科学技术研究院有限公司 | Conjugated polymer of ferrocene and phenanthroline derivative and polymerization method and application thereof |
| CN110127763B (en) * | 2019-05-14 | 2021-06-01 | 南京科技职业学院 | Three-dimensional inorganic high-molecular polymer and preparation method thereof |
| RU2741301C1 (en) * | 2019-11-13 | 2021-01-25 | федеральное государственное бюджетное образовательное учреждение высшего образования "Самарский государственный технический университет" | Diphenylferrocene as liquid organic hydrogen carrier, as well as hydrogen cycle based thereon |
| CN112058236B (en) * | 2020-09-01 | 2021-09-03 | 浙江大学 | Preparation of ferrocenyl metal-organic framework microspheres and application of ferrocenyl metal-organic framework microspheres in gold recovery |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102002071A (en) * | 2010-10-21 | 2011-04-06 | 聊城大学 | Ferrocenedicarboxylic acid trialkyl tin chloride coordination compound as well as preparation method and application thereof |
| CN102424693A (en) * | 2011-10-10 | 2012-04-25 | 聊城大学 | Tetra-2,6-dipicolinic acid-di-(ferrocenedicarboxylic acid)triphenyl tin complex, and its preparation method and application |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7871748B2 (en) * | 2007-07-31 | 2011-01-18 | Xerox Corporation | Iron containing hole blocking layer containing photoconductors |
-
2013
- 2013-08-25 CN CN201310372985.6A patent/CN103435813B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102002071A (en) * | 2010-10-21 | 2011-04-06 | 聊城大学 | Ferrocenedicarboxylic acid trialkyl tin chloride coordination compound as well as preparation method and application thereof |
| CN102424693A (en) * | 2011-10-10 | 2012-04-25 | 聊城大学 | Tetra-2,6-dipicolinic acid-di-(ferrocenedicarboxylic acid)triphenyl tin complex, and its preparation method and application |
Non-Patent Citations (1)
| Title |
|---|
| Chiral Phosphinooxazolines with a Pentamethylferrocene Backbone-Synthesis and Use as Ligands in Asymmetric Catalysis;Felix M Geisler et al.;《The Journal of Organic Chemistry》;20060223;第71卷(第6期);2486-2492 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103435813A (en) | 2013-12-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103435813B (en) | A kind of ligand polymer microballoon and preparation method and use for storing hydrogen | |
| Li et al. | Tailored necklace-like Ag@ ZIF-8 core/shell heterostructure nanowires for high-performance plasmonic SERS detection | |
| Molavi et al. | Evaluation of UiO‐66 metal organic framework as an effective sorbent for Curcumin's overdose | |
| CN105879895B (en) | Porous carbon nanosheet load non-precious metal catalyst of N doping and preparation method thereof | |
| Chen et al. | Size-controlled synthesis and magnetic properties of NiFe2O4 hollow nanospheres via a gel-assistant hydrothermal route | |
| Shao et al. | Enhanced hydrogen storage capacity and reversibility of LiBH4 nanoconfined in the densified zeolite-templated carbon with high mechanical stability | |
| CN101794652B (en) | Method for preparing carbon-coated superparamagnetic ferroferric colloidal spheres | |
| Butt et al. | Synthesis, evolution and hydrogen storage properties of ZnV2O4 glomerulus nano/microspheres: a prospective material for energy storage | |
| Wu et al. | A humidity sensor based on ionic liquid modified metal organic frameworks for low humidity detection | |
| Choi et al. | Nanocrystalline MOFs embedded in the crystals of other MOFs and their multifunctional performance for molecular encapsulation and energy-carrier storage | |
| Wang et al. | One-pot synthesis of Co-based coordination polymer nanowire for Li-ion batteries with great capacity and stable cycling stability | |
| CN103274456A (en) | Doped Ti4O7 powder and preparation methods thereof | |
| Liu et al. | Simple solvothermal synthesis of hydrophobic magnetic monodispersed Fe3O4 nanoparticles | |
| Cheng et al. | Microstructure controlling and dielectric relaxation dynamic of ZIF-8 synthesized in different solvents | |
| Zhou et al. | Synthesis of porous Bi@ Cs networks by a one-step hydrothermal method and their superior catalytic activity for the reduction of 4-nitrophenol | |
| CN102259935B (en) | Auxiliary hydro-thermal method for preparing bird-nest-shaped Co3O4 surfactant | |
| Saemian et al. | Synthesis of CoFe2O4@ Cu3 (BTC) 2 nanocomposite as a magnetic metal–organic framework | |
| CN108658038A (en) | One kind being based on LiAlH4Hydrogen storage material and preparation method thereof | |
| Karami et al. | Novel UiO‐66‐NH2/Gly/GO Nanocomposite Adsorbent for Ultra‐trace Analyzing of Chlorpyrifos Pesticide by Ion Mobility Spectrometry | |
| Lee et al. | Synthesis, characterizations and kinetics of MOF‐5 as herbicide vehicle and its controlled release in PVA/ST biodegradable composite membranes | |
| CN105289456B (en) | A kind of superparamagnetic Fe3O4The preparation method and application of nano material | |
| Tong et al. | Preparation and characterization of Co-B flowers with mesoporous structure | |
| Luzan et al. | Hydrogen storage in Co-and Zn-based metal-organic frameworks at ambient temperature | |
| Wen et al. | Synthesis of size-controllable urchin-like covalent organic frameworks for adsorption of nitrophenols | |
| CN102897722A (en) | Alpha-In2Se3 nano-grade flower-ball solvothermal synthesizing method |
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 |