CN102874747A - Method for preparing multilevel structural material by performing epitaxial growth of layered double hydroxide (LDH) based on guiding of electric field of metallic oxide nano array - Google Patents
Method for preparing multilevel structural material by performing epitaxial growth of layered double hydroxide (LDH) based on guiding of electric field of metallic oxide nano array Download PDFInfo
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- CN102874747A CN102874747A CN2012103852042A CN201210385204A CN102874747A CN 102874747 A CN102874747 A CN 102874747A CN 2012103852042 A CN2012103852042 A CN 2012103852042A CN 201210385204 A CN201210385204 A CN 201210385204A CN 102874747 A CN102874747 A CN 102874747A
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Abstract
The invention belongs to the field of synthesis of inorganic nano materials, and discloses a method for preparing a multilevel structural material by performing epitaxial growth of layered double hydroxide (LDH) based on guiding of an electric field of a metallic oxide nano array. The synthesis method comprises the following steps of: preparing a nano array material which grows vertical to a conducting substrate; and directly growing an ordered LDH nano sheet on the nano array by an electrochemical synthesis method to finally obtain the multilevel structural material. The multilevel structural material can fully exert the photoresponse performance of the metallic oxide nano array and the electrochemical performance and the photoresponse performance of LDH simultaneously, and has significance to realization of high-efficiency photoelectrochemistry energy conversion and important research and application value in the aspects of photoelectrochemistry devices, sensing and the like. The ordered array composite material is obtained, the variety of the preparation method and the application field of the LDH materials are widened, and the multilevel structural material can be used for water decomposition in photoelectrochemistry.
Description
Technical field
The invention belongs to the synthetic field of inorganic nano material, particularly a kind of method for preparing multilevel structure material based on metal oxide nano array electric field guiding epitaxial growth hydrotalcite.
Background technology
Because the continuous aggravation of global environment and energy crisis, the development and utilization of new cleaning fuel faces unprecedented opportunities and challenge.At the solar energy conversion aspect, conductor photocatalysis material has been played the part of the key player.Such material can convert solar energy into chemical energy (photocatalysis, photoelectrocatalysis hydrogen manufacturing) or electric energy (solar cell) effectively.But the research of conductor photocatalysis material is faced with two big science difficult problems: the one, quantum yield is low, photo-generated carrier to the migration of catalyst surface and Mixed Circumscription the redox reaction of catalyst surface, thereby reduced the efficient of solar energy conversion; The 2nd, the photoresponse scope is narrow because most of semi-conducting material energy gap is larger so that these materials can only response wave length less than the ultraviolet light of 400nm, and this part light only accounts for about 4% of whole solar energies.In addition, the chemical stability of conductor photocatalysis material and active stability also are problem demanding prompt solutions.In order to utilize more efficiently sunshine, people were carrying out pilot study aspect visible light-responded photochemical catalyst, the efficient composite Nano photochemical catalyst in recent years.Although make some progress, visible light-responded, efficient decomposition water photochemical catalyst still is a challenge.
Layered double hydroxide (LDHs, claim again hydrotalcite) be the anionic type laminated material of a quasi-representative, because the divalence in the main body laminate and kind, ratio and the distribution of trivalent metal ion and interlayer object can artificial adjustments, and its design is synthetic and the diversity of assembling, has caused thus broad interest and the great attention of international functional material research field.Because layer structure and the body layer strip electrical feature of LDHs make it be easy to realize the several functions composite manufacture, so prepare inorganic-organic based on LDHs, the design of inorganic-inorganic composite and application have become the focus of functional material research field.But such composite mainly concentrates on the thin-film material, report for the hydrotalcite composite material of other structure and pattern is relative less, and hydrotalcite itself is a kind of semiconductor material with wide forbidden band, band gap can form by the laminate metallic element, ratio is regulated and control, use it for Optical Electro-Chemistry decomposition water field and will have the performance advantages such as quantum yield height, spectral response range is adjustable, in addition, the compound of hydrotalcite and other optical function material has important advantage equally to its raising photoelectrochemical behaviour.Therefore, the present invention proposes to construct the hydrotalcite of multilevel hierarchy/nano-array ordered composite material, regulates and control its band structure by structure, composition, the pattern of optimizing material, suppresses the compound of electronics and hole, strengthen carrier transport speed, develop the efficient Optical Electro-Chemistry decomposition water of class material.Such material has great importance at the Efficient Conversion of new forms of energy with aspect utilizing.
Summary of the invention
The objective of the invention is to prepare multilevel structure material based on metal oxide nano array electric field guiding epitaxial growth hydrotalcite.
Its synthesis step comprises two parts: at first prepare the nano-array material perpendicular to the conductive substrates growth; Then utilize the synthetic orderly LDH nanometer sheet of method direct growth on nano-array of electrochemistry, finally obtain multilevel structure material.
Of the present inventionly prepare the method for multilevel structure material based on metal oxide nano array electric field guiding epitaxial growth hydrotalcite, its concrete operation step is as follows:
1). preparation 20-50ml concentration is two kinds of different divalent metal nitrate mixed solutions of 0.005-0.01mol/L, and the molar ratio of these two kinds of different divalent metal nitrate is (2:1)-(1:2);
2). the metal oxide nano array is immersed in the mixed solution of step 1) preparation, utilize potentiostatic method at the metal oxide nano array hydrotalcite of growing, take Ag/AgCl as reference electrode, Pt is to electrode, the synthetic current potential of electrochemistry is made as (0.8)-(1.2) V, generated time is 10-400s, and synthesis temperature is 10-50 ℃.
Described divalent metal nitrate is selected from Mg (NO
3)
2, Co (NO
3)
2, Ni (NO
3)
2, Ca (NO
3)
2, Cu (NO
3)
2, Fe (NO
3)
2, Mn (NO
3)
2In any two kinds.
Described metal oxide nano array is ZnO, TiO
2, Co
3O
4, Fe
2O
3, SnO
2A kind of in the nano-array.
The synthetic method of described zinc oxide nano array is:
A: in the 60-80mL deionized water, add the zinc acetate of 0.4-0.6g and the 20-35wt% ammoniacal liquor of 2-5mL, then transfer in the polytetrafluoroethylene (PTFE) reactor;
B: pure zinc metal sheet is put into ultrasonic clean in the ethanol solution, then puts into the solution of step a preparation, deionized water rinsing is used in 60-90 ℃ of lower reaction 6-12 hour, 50-80 ℃ dry 2-5 hour, obtain the zinc oxide nano array perpendicular to substrate grown.
The synthetic method of described nano titania array:
A: adding 20-60mL deionized water, 20-60mL concentration are the concentrated hydrochloric acid of 36.5-38wt% and the butyl titanate of 1mL in 100mL polytetrafluoroethylene (PTFE) reactor, stir 5-10min;
B: electro-conductive glass FTO is put into the solution of step a preparation, and conducting surface down, 80-200 ℃ of lower reaction 6-24h takes out behind the cool to room temperature, fully washes with deionized water, and air drying namely obtains the nano titania array of vertical substrate grown.
The invention has the advantages that: the present invention has realized preparing multilevel structure material based on metal oxide nano array electric field guiding epitaxial growth hydrotalcite first, this multilevel structure material can be given full play to the photoresponse performance of metal oxide nano array and electrochemistry and the photoresponse performance of hydrotalcite simultaneously, for realizing that efficient Optical Electro-Chemistry power conversion has great importance.It has important researching value and using value at aspects such as photoelectrochemicalcell cell, sensings.The present invention has not only obtained a kind of orderly array composite material, and has widened the preparation method and application field of hydrotalcite-like material, and this multilevel structure material can be used for the Optical Electro-Chemistry decomposition water.
Description of drawings
Fig. 1 is that metal oxide nano array electric field guiding epitaxial growth hydrotalcite of the present invention prepares multilevel structure material method schematic diagram.
Fig. 2 is the stereoscan photograph of the multilevel structure material that obtains of embodiment 1; A is zinc oxide nano array; B is the front elevation of multilevel structure material; C is the side view of multilevel structure material.
Fig. 3 is the transmission electron microscope photo of the multilevel structure material that obtains of embodiment 1.
Fig. 4 is the XRD spectra of the multilevel structure material that obtains of embodiment 1; Abscissa is 2 θ, unit: degree; Ordinate is intensity.
Fig. 5 is the Optical Electro-Chemistry decomposition water performance characterization of the multilevel structure material that obtains of embodiment 1.
The specific embodiment
[embodiment 1]
1). synthesizing of zinc oxide nano array:
A: in the 70mL deionized water, add the zinc acetate of 0.6g and the 28wt% ammoniacal liquor of 2.5mL,, then transfer in the polytetrafluoroethylene (PTFE) reactor;
B: pure zinc metal sheet is put into ultrasonic clean in the ethanol solution, then puts into the solution of step a preparation, deionized water rinsing is used in 80 ℃ of lower reactions 10 hours, and 60 ℃ of dryings 3 hours obtain the zinc oxide nano array perpendicular to substrate grown;
2). preparation 50ml concentration is the Co (NO of 0.01mol/L
3)
2And Ni (NO
3)
2Mixed solution, Co (NO
3)
2And Ni (NO
3)
2Molar ratio be 1:1;
3). the zinc oxide nano array that obtains in the step 1) is immersed in step 2) preparation mixed solution in, utilize potentiostatic method at the zinc oxide nano array hydrotalcite of growing, take AgAgCl as reference electrode, Pt is to electrode, the synthetic current potential of electrochemistry is made as-1.0V, generated time is 200s, and synthesis temperature is 25 ℃.
[embodiment 2]
1). synthesizing of nano titania array:
A: adding 50mL deionized water, 10mL concentration are the concentrated hydrochloric acid of 38wt% and the butyl titanate of 1mL in 100mL polytetrafluoroethylene (PTFE) reactor, stir 5min;
B: electro-conductive glass FTO is put into the solution of step a preparation, and conducting surface down, 150 ℃ of lower reaction 24h take out behind the cool to room temperature, fully wash with deionized water, and air drying namely obtains the nano titania array of vertical substrate grown;
2). preparation 50ml concentration is the Co (NO of 0.005mol/L
3)
2And Ni (NO
3)
2Mixed solution, Co (NO
3)
2And Ni (NO
3)
2Molar ratio be 1:1;
3). the nano titania array that obtains in the step 1) is immersed in step 2) preparation mixed solution in, utilize potentiostatic method at the nano titania array hydrotalcite of growing, take Ag/AgCl as reference electrode, Pt is to electrode, the synthetic current potential of electrochemistry is made as-1.0V, generated time is 200s, and synthesis temperature is 25 ℃.
Claims (5)
1. one kind prepares the method for multilevel structure material based on metal oxide nano array electric field guiding epitaxial growth hydrotalcite, it is characterized in that its concrete operation step is as follows:
1). preparation 20-50ml concentration is two kinds of different divalent metal nitrate mixed solutions of 0.005-0.01mol/L, and the molar ratio of these two kinds of different divalent metal nitrate is (2:1)-(1:2);
2). the metal oxide nano array is immersed in the mixed solution of step 1) preparation, utilize potentiostatic method at the metal oxide nano array hydrotalcite of growing, take AgAgCl as reference electrode, Pt is to electrode, the synthetic current potential of electrochemistry is made as (0.8)-(1.2) V, generated time is 10-400s, and synthesis temperature is 10-50 ℃.
2. method according to claim 1 is characterized in that, described divalent metal nitrate is selected from Mg (NO
3)
2, Co (NO
3)
2, Ni (NO
3)
2, Ca (NO
3)
2, Cu (NO
3)
2, Fe (NO
3)
2, Mn (NO
3)
2In any two kinds.
3. method according to claim 1 is characterized in that, described metal oxide nano array is ZnO, TiO
2, Co
3O
4, Fe
2O
3, SnO
2A kind of in the nano-array.
4. method according to claim 3 is characterized in that, the synthetic method of described zinc oxide nano array is:
A: in the 60-80mL deionized water, add the zinc acetate of 0.4-0.6g and the 20-35wt% ammoniacal liquor of 2-5mL, then transfer in the polytetrafluoroethylene (PTFE) reactor;
B: pure zinc metal sheet is put into ultrasonic clean in the ethanol solution, then puts into the solution of step a preparation, deionized water rinsing is used in 60-90 ℃ of lower reaction 6-12 hour, 50-80 ℃ dry 2-5 hour, obtain the zinc oxide nano array perpendicular to substrate grown.
5. method according to claim 3 is characterized in that, the synthetic method of described nano titania array is:
A: adding 20-60mL deionized water, 20-60mL concentration are the concentrated hydrochloric acid of 36.5-38wt% and the butyl titanate of 1mL in 100mL polytetrafluoroethylene (PTFE) reactor, stir 5-10min;
B: electro-conductive glass FTO is put into the solution of step a preparation, and conducting surface down, 80-200 ℃ of lower reaction 6-24h takes out behind the cool to room temperature, fully washes with deionized water, and air drying namely obtains the nano titania array of vertical substrate grown.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103952717A (en) * | 2014-05-07 | 2014-07-30 | 北京化工大学 | Photoelectrochemical decomposition water and organic synthesis coupled cascade reaction design method |
| CN104037398A (en) * | 2014-03-12 | 2014-09-10 | 华中师范大学 | TiO2@Fe2O3 layered multistage composite nanometer array material and preparation method and applications thereof |
| CN105154950A (en) * | 2015-08-18 | 2015-12-16 | 上海交通大学 | Preparation method for laminated metal complex hydroxide |
| CN106149025A (en) * | 2016-06-26 | 2016-11-23 | 北京化工大学 | An a kind of step electrosynthesis method of ferrum acrylic/hydrotalcite-like nano chip arrays |
| CN110323071A (en) * | 2019-05-10 | 2019-10-11 | 北京化工大学 | A kind of titanium dioxide and cobalt aluminum hydrotalcite hetero-junctions inorganic composite materials and its application as light charge super capacitors |
| CN112921350A (en) * | 2021-01-25 | 2021-06-08 | 北京化工大学 | Preparation method of multi-stage structure layered double-metal hydroxide integrated electrode for electrocatalysis organic matter oxidation |
| CN115233254A (en) * | 2022-06-20 | 2022-10-25 | 厦门大学 | Core-shell structure of TiO 2 Composite electrode of/NiCoAl-LDH nanorod array and preparation method and application thereof |
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| CN1948159A (en) * | 2006-10-12 | 2007-04-18 | 北京化工大学 | Manganese dioxide/hydrotalcite inorganic nanometer piece composite superthin film and its preparation method |
| CN101140257A (en) * | 2007-10-18 | 2008-03-12 | 北京化工大学 | Biologic sensor enzyme functional susceptivity film containing nickel and aluminum hydrotalcite nano piece and method of producing the same |
| US20080293849A1 (en) * | 2005-12-06 | 2008-11-27 | Velperweg 76 | Nanocomposite Material Comprising Rubber and Modified Layered Double Hydroxide, Process for Its Preparation and Use Thereof |
| CN101393160A (en) * | 2008-10-29 | 2009-03-25 | 北京化工大学 | Biological functional multilayer film modified electrode and method for making same |
| CN102504802A (en) * | 2011-10-08 | 2012-06-20 | 北京化工大学 | Metallic organic luminescent molecule and hydrotalcite compounded electrochemiluminiscent ultrathin film and method of preparing same |
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2012
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080293849A1 (en) * | 2005-12-06 | 2008-11-27 | Velperweg 76 | Nanocomposite Material Comprising Rubber and Modified Layered Double Hydroxide, Process for Its Preparation and Use Thereof |
| CN1948159A (en) * | 2006-10-12 | 2007-04-18 | 北京化工大学 | Manganese dioxide/hydrotalcite inorganic nanometer piece composite superthin film and its preparation method |
| CN101140257A (en) * | 2007-10-18 | 2008-03-12 | 北京化工大学 | Biologic sensor enzyme functional susceptivity film containing nickel and aluminum hydrotalcite nano piece and method of producing the same |
| CN101393160A (en) * | 2008-10-29 | 2009-03-25 | 北京化工大学 | Biological functional multilayer film modified electrode and method for making same |
| CN102504802A (en) * | 2011-10-08 | 2012-06-20 | 北京化工大学 | Metallic organic luminescent molecule and hydrotalcite compounded electrochemiluminiscent ultrathin film and method of preparing same |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104037398A (en) * | 2014-03-12 | 2014-09-10 | 华中师范大学 | TiO2@Fe2O3 layered multistage composite nanometer array material and preparation method and applications thereof |
| CN103952717A (en) * | 2014-05-07 | 2014-07-30 | 北京化工大学 | Photoelectrochemical decomposition water and organic synthesis coupled cascade reaction design method |
| CN105154950A (en) * | 2015-08-18 | 2015-12-16 | 上海交通大学 | Preparation method for laminated metal complex hydroxide |
| CN105154950B (en) * | 2015-08-18 | 2018-06-26 | 上海交通大学 | A kind of preparation method of laminated metal complex hydroxide |
| CN106149025A (en) * | 2016-06-26 | 2016-11-23 | 北京化工大学 | An a kind of step electrosynthesis method of ferrum acrylic/hydrotalcite-like nano chip arrays |
| CN110323071A (en) * | 2019-05-10 | 2019-10-11 | 北京化工大学 | A kind of titanium dioxide and cobalt aluminum hydrotalcite hetero-junctions inorganic composite materials and its application as light charge super capacitors |
| CN112921350A (en) * | 2021-01-25 | 2021-06-08 | 北京化工大学 | Preparation method of multi-stage structure layered double-metal hydroxide integrated electrode for electrocatalysis organic matter oxidation |
| CN115233254A (en) * | 2022-06-20 | 2022-10-25 | 厦门大学 | Core-shell structure of TiO 2 Composite electrode of/NiCoAl-LDH nanorod array and preparation method and application thereof |
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