CN114849716A - 1D/2D composite material based on NiZn-LDH and preparation method and application thereof - Google Patents
1D/2D composite material based on NiZn-LDH and preparation method and application thereof Download PDFInfo
- Publication number
- CN114849716A CN114849716A CN202210537777.6A CN202210537777A CN114849716A CN 114849716 A CN114849716 A CN 114849716A CN 202210537777 A CN202210537777 A CN 202210537777A CN 114849716 A CN114849716 A CN 114849716A
- Authority
- CN
- China
- Prior art keywords
- nizn
- ldh
- composite material
- material based
- nano
- 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.)
- Granted
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- 239000002114 nanocomposite Substances 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000000463 material Substances 0.000 claims abstract description 22
- 239000008367 deionised water Substances 0.000 claims abstract description 16
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 14
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 10
- 239000004202 carbamide Substances 0.000 claims abstract description 7
- 239000012716 precipitator Substances 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 12
- 239000002243 precursor Substances 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 230000001699 photocatalysis Effects 0.000 claims description 7
- -1 polytetrafluoroethylene Polymers 0.000 claims description 7
- 238000004108 freeze drying Methods 0.000 claims description 6
- 150000002815 nickel Chemical class 0.000 claims description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 229910001220 stainless steel Inorganic materials 0.000 claims description 6
- 239000010935 stainless steel Substances 0.000 claims description 6
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 230000009467 reduction Effects 0.000 claims description 5
- 150000003751 zinc Chemical class 0.000 claims description 5
- 238000003760 magnetic stirring Methods 0.000 claims description 2
- 239000002135 nanosheet Substances 0.000 abstract description 25
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 abstract description 24
- 239000002070 nanowire Substances 0.000 abstract description 15
- 235000005074 zinc chloride Nutrition 0.000 abstract description 12
- 239000011592 zinc chloride Substances 0.000 abstract description 12
- 239000002086 nanomaterial Substances 0.000 abstract description 11
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 10
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 abstract description 10
- 230000008901 benefit Effects 0.000 abstract description 7
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 5
- 239000001569 carbon dioxide Substances 0.000 abstract description 5
- 238000000926 separation method Methods 0.000 abstract description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 abstract description 2
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 23
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 15
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- 239000011941 photocatalyst Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000000843 powder Substances 0.000 description 6
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 238000001000 micrograph Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 3
- 238000005086 pumping Methods 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 229910052724 xenon Inorganic materials 0.000 description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 3
- 230000008021 deposition Effects 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 238000001453 impedance spectrum Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000002055 nanoplate Substances 0.000 description 2
- 239000002064 nanoplatelet Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- HZPNKQREYVVATQ-UHFFFAOYSA-L nickel(2+);diformate Chemical compound [Ni+2].[O-]C=O.[O-]C=O HZPNKQREYVVATQ-UHFFFAOYSA-L 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 description 1
- 241000668842 Lepidosaphes gloverii Species 0.000 description 1
- 229910018661 Ni(OH) Inorganic materials 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000000724 energy-dispersive X-ray spectrum Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/40—Carbon monoxide
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to the technical field of preparation of nano materials, and discloses a preparation method of a 1D/2D composite material based on NiZn-LDH, which is characterized in that a hydrothermal method is utilized to prepare a nano composite material of nano wire/nano sheet assembly (1D/2D-NiZn-LDH); taking nickel chloride hexahydrate and zinc chloride as raw materials, urea as a precipitator and deionized water as a solvent, carrying out constant-temperature reaction at a specific temperature, and carrying out centrifugal separation, sample washing and drying to obtain the uniformly dispersed 1D/2D-NiZn-LDH nano material. The 1D/2D nano composite material prepared by the invention enhances charge conversion on the interface through the one-dimensional nano wire array, and highly selectively reduces carbon dioxide into carbon monoxide. The preparation method has the advantages of simple preparation process, short period, low cost, large-scale industrial production and good economic benefit and environmental benefit.
Description
Technical Field
The invention belongs to the technical field of nano material preparation, and particularly relates to a 1D/2D composite material based on NiZn-LDH, and a preparation method and application thereof.
Background
One-dimensional (1D) and two-dimensional (2D) nanomaterials are low-dimensional materials, and due to their inherent properties, they have attracted considerable attention as advanced photocatalysts for their structural features. As for 1D nanostructured photocatalysts, the well-defined 1D geometry facilitates fast and long distance electron transport and long-term photocatalytic stability, while their high aspect ratio and larger specific surface area significantly enhance the light absorption properties. To date, photocatalysts of various 1D nanostructure morphologies (ribbons, tubes, fibers, rods and wires) have been successfully prepared and applied to various highly efficient photocatalytic reactions.
With respect to 2D nanomaterials, they are atomically thin sheets or layers, exhibiting unique electronic and optical properties, with significant potential for a variety of applications. 2D nanomaterials also have many advantages in photocatalyst design, making them excellent candidates for photocatalytic applications. First, since the 2D nanomaterial has a large specific surface area, a large number of active sites exist on the surface thereof. Second, shorter diffusion paths can accelerate exciton dissociation and free charge transfer. Third, most 2D materials have good conductivity and excellent electron mobility, which can facilitate the transfer and separation of photogenerated electrons and holes. Fourthly, the 2D nano material is an excellent catalyst carrier, and is beneficial to constructing a heterogeneous photocatalyst.
Inspired by the vigorous development of 1D and 2D photocatalysts, the reasonable design of the 1D/2D multi-dimensional heterojunction photocatalyst integrates the advantages of 1D and 2D nano geometric structures, and the photocatalytic performance is greatly improved. Conventionally, to produce a one-dimensional/two-dimensional hybrid structure, a two-dimensional template is typically prepared to direct the deposition of one-dimensional nanowires onto a two-dimensional plane. However, a few successful cases of directional deposition rely heavily on the use of organic surfactants or polymers. Even so, the directional assembly of one dimension on a two-dimensional substrate remains a huge challenge, especially long-scale nanowires are rarely reported. Therefore, the design of the preparation method which has simple process and can synthesize the high-dispersion 1D/2D nano material in one step has important significance.
Disclosure of Invention
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a 1D/2D composite material based on NiZn-LDH comprises the following raw materials: nickel chloride hexahydrate (NiCl) 2 ·6H 2 O), zinc chloride (ZnCl) 2 ) Urea (CH) 4 N 2 O）。
A preparation method of a 1D/2D composite material based on NiZn-LDH comprises the following steps: mixing and dissolving nickel chloride hexahydrate, zinc chloride and precipitator urea in deionized water to prepare uniformly dispersed reaction precursor liquid; then transferring the reaction precursor liquid into a stainless steel high-pressure autoclave with a polytetrafluoroethylene lining, and carrying out constant-temperature reaction in a drying oven; after the reaction is finished, cooling, centrifugally separating, washing and drying until the water is completely volatilized to obtain the green solid powdery 1D/2D-NiZn-LDH nano composite material with uniform size and high dispersion.
The 1D/2D-NiZn-LDH nanocomposite material with uniform size and high dispersion specifically comprises the following steps:
(1) adding a divalent nickel salt, a divalent zinc salt and a precipitator into deionized water, and fully mixing and dissolving to prepare uniformly dispersed reaction precursor liquid;
(2) then transferring the reaction precursor liquid into a stainless steel high-pressure autoclave with a polytetrafluoroethylene lining, and carrying out constant-temperature reaction in a drying oven;
(3) after the reaction is finished, cooling, centrifugally separating, washing and drying until the water is completely volatilized to obtain the green solid powdery 1D/2D-NiZn-LDH nano composite material.
Further, the divalent nickel salt in the step (1) is nontoxic nickel chloride NiCl hexahydrate 2 ·6H 2 O; the divalent aluminum salt is nontoxic zinc chloride ZnCl 2 (ii) a The precipitator is urea.
Further, in the step (1), the molar ratio of the divalent nickel salt to the divalent zinc salt to the precipitant is 5:1:6, and the amount of deionized water is 50 mL.
Further, the mixing and dissolving in the step (1) specifically comprises: ultrasonic dispersion and magnetic stirring are carried out, and the ultrasonic dispersion time is 10 min; the stirring speed is 500 rpm; the stirring time was 10 min.
Further, the isothermal reaction in the step (2) is specifically as follows: the reaction is carried out for 4 h at a constant temperature of 120 ℃.
Further, the cooling in the step (3) is specifically as follows: and cooling the mixture along with the furnace to room temperature.
Further, the washing solvent in the step (3) is deionized water, and the washing times are 3 times.
Further, the drying mode in the step (3) is vacuum-53 ℃ freeze drying, and the drying time is 12 h.
The invention has the beneficial effects that:
(1) the invention adopts a one-step hydrothermal synthesis method, synchronously generates a uniform and high-dispersion 1D/2D-NiZn-LDH nano composite material in situ, and 1D/2D-NiZn-LDH nano wires are uniformly dispersed on a nano sheet. Enriches the method for compounding the one-dimensional and two-dimensional nano materials and provides a new idea for directional assembly and functionalization of the nano wires and the nano sheets.
(2) According to the 1D/2D-NiZn-LDH nano composite material prepared by the invention, a synergistic effect is caused by lattice matching between the nano wires and the nano sheets, the surface area is increased, the charge transfer rate is increased, the charge conversion on the interface is enhanced through the one-dimensional nano wire array, and carbon dioxide is photo-reduced into carbon monoxide with high selectivity.
(3) The preparation method has the advantages of easily available equipment and materials, simple process operation, concise process conditions, low cost, safety and high efficiency, and can be used for large-scale industrial production; compared with other noble metal elements, the material has less environmental pollution, is an ecological environment-friendly material, and has good popularization and application values.
Drawings
FIG. 1 is an X-ray diffraction (XRD) pattern of a 1D/2D-NiZn-LDH nanocomposite material prepared in example 1 of the present invention and a 2D-NiZn-LDH nanosheet prepared in comparative example 1;
FIG. 2 is the microstructure and EDS energy spectrum of the 2D-NiZn-LDH nanosheet prepared in comparative example 1 of the present invention;
FIG. 3 shows Ni (OH) produced in comparative example 2 of the present invention 2 The micro morphology of the nanosheets and an EDS energy spectrum;
FIG. 4 is the micro-morphology and EDS energy spectrum of the 1D/2D-NiZn-LDH nanocomposite material prepared in example 1 of the present invention;
FIG. 5 is the micro-morphology of 1D/2D-NiZn-LDH nanocomposite prepared by different hydrothermal times according to the invention;
FIG. 6 is a graph comparing the performance of 1D/2D-NiZn-LDH nanocomposite materials prepared by different hydrothermal times according to the present invention;
FIG. 7 is a transmission electron microscope image of the 1D/2D-NiZn-LDH nanocomposite prepared in example 1 of the present invention;
FIG. 8 is a transmission electron microscope image of the 1D/2D-NiZn-LDH nanocomposite prepared in example 1 of the present invention;
FIG. 9 is a 1D/2D-NiZn-LDH nanocomposite prepared in example 1 of the present invention, 2D-NiZn-LDH nanosheets prepared in comparative example 1, and Ni (OH) prepared in comparative example 2 2 A graph comparing the properties of the nanoplates;
FIG. 10 is a graph of the cycle performance of the 1D/2D-NiZn-LDH nanocomposite prepared in example 1 of the present invention;
FIGS. 11 and 12 are 1D/2D-NiZn-LDH nanocomposite prepared in example 1 of the present invention, 2D-NiZn-LDH nanosheets prepared in comparative example 1, and Ni (OH) prepared in comparative example 2 2 Nano-sheet impedance spectrum and photocurrent contrast diagram;
FIG. 13 is a 1D/2D-NiZn-LDH nanocomposite prepared in example 1 of the present invention, 2D-NiZn-LDH nanosheets prepared in comparative example 1, and Ni (OH) prepared in comparative example 2 2 BET pattern of nanoplatelets.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail below with reference to the accompanying drawings, which are examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features mentioned in the embodiments of the present invention described below may be combined as long as they do not conflict with each other.
Example 1
Preparing a 1D/2D-NiZn-LDH nano composite material:
(1) 5.94 g of nickel chloride hexahydrate (NiCl) was weighed using an electronic balance 2 ·6H 2 O), 0.68 g of zinc chloride (ZnCl) 2 ) Nickel chloride hexahydrate and ZnCl 2 Adding the mixture into 50 mL of deionized water according to the molar ratio of 5:1, and performing ultrasonic dispersion for 10 minutes to obtain a solution A;
(2) 1.8 g of urea (CH) was weighed using an electronic balance 4 N 2 O), adding the mixture into the solution A, and magnetically stirring for 10 min at the stirring speed of 500 rpm to prepare uniformly dispersed reaction precursor solution;
(3) then transferring the reaction precursor liquid into a stainless steel autoclave with a polytetrafluoroethylene lining, carrying out constant-temperature reaction for 4 hours in a drying oven at 120 ℃, and cooling to room temperature along with the furnace after the reaction is finished;
(4) centrifuging the sample by a centrifuge to obtain white solid powder, wherein the rotating speed is 8000 rpm; and washing with deionized water for three times;
(5) and (4) freeze-drying overnight until the water is completely volatilized to obtain the 1D/2D-NiZn-LDH nano composite material.
Comparative example 1
Preparation of 2D-NiZn-LDH nanosheets:
(1) 5.94 g of nickel chloride hexahydrate (NiCl) was weighed using an electronic balance 2 ·6H 2 O), 0.68 g of zinc chloride (ZnCl) 2 ) Nickel chloride hexahydrate and ZnCl 2 Adding the mixture into 50 mL of deionized water according to the molar ratio of 5:1, and performing ultrasonic dispersion for 10 minutes to obtain a solution A;
(2) 1.8 g of urea (CH) was weighed using an electronic balance 4 N 2 O), adding the mixture into the solution A, and magnetically stirring for 10 min at the stirring speed of 500 rpm to prepare uniformly dispersed reaction precursor solution;
(3) then transferring the reaction precursor liquid into a stainless steel autoclave with a polytetrafluoroethylene lining, carrying out constant temperature reaction for 1 h in a drying oven at 120 ℃, and cooling to room temperature along with the furnace after the reaction is finished;
(4) centrifuging the sample by a centrifuge to obtain white solid powder, wherein the rotating speed is 8000 rpm; and washing with deionized water for three times;
(5) and (3) freeze-drying overnight until the water is completely volatilized, thus obtaining the 2D-NiZn-LDH nano composite material with uniform size and high dispersion.
Comparative example 2
Ni(OH) 2 Preparing a nano sheet:
(1) weighing 10 mmol Ni (OH) 2 It was dissolved in a mixed solution of formic acid and water (10 ml of HCOOH, 70 ml of H) 2 O), 2H was heated at 70 ℃.
(2) Evaporating most of liquid by rotary evaporation after heating, freeze drying the rest part of solid-liquid mixture overnight until water is completely volatilized, and obtaining the product nickel formate (C) 2 H 2 NiO 4 ）。
(3) 0.184 g of nickel formate (C) was weighed out on an electronic balance 2 H 2 NiO 4 ) Adding the mixture into 50 mL of methanol, and ultrasonically dispersing for 10 minutes to obtain uniformly dispersed reaction precursor liquid;
(4) then transferring the reaction precursor liquid into a stainless steel autoclave with a polytetrafluoroethylene lining, carrying out constant temperature reaction at 160 ℃ in a drying box for 18 h, and cooling to room temperature along with the furnace after the reaction is finished;
(5) centrifuging the sample by using a centrifugal machine to obtain green solid powder, wherein the rotating speed is 8000 rpm; and washing with deionized water for three times;
(6) freeze drying overnight until the water is completely evaporated to obtain Ni (OH) 2 Nanocomposite material
Application example 1
The 1D/2D-NiZn-LDH nanocomposite obtained in the example 1 is used for photocatalytic carbon dioxide reduction, and the specific steps are as follows:
(1) 1 mg of 1D/2D-NiZn-LDH powder is taken; 8 mg of 2 ', 2' -bipyridine as a cocatalyst; 1 mL of triethanolamine is used as an electron donor; 2 mL of deionized water and 3 mL of acetonitrile are taken as solvents and added into a 25 mL quartz glass reactor;
(2) sealing the reactor, pumping out air from the reactor by vacuum pump, and introducing CO 2 Gas, bleed-vent was repeated three times to ensure that the reactor was filled with CO 2 A gas;
(3) the reactor was placed under a 300W Porphy xenon lamp with a 400 nm cut-off filter for illumination and stirred at constant temperature, the temperature being controlled at 30 ℃.
(4) At 1 h intervals, 500 uL of reactor gas was withdrawn with a sampling needle and quantitatively analyzed by gas chromatography (Agilent 7890B GC).
Application comparative example 1
The 2D-NiZn-LDH nanosheet obtained in the comparative example 1 is used for photocatalytic carbon dioxide reduction, and the specific steps are as follows:
(1) taking 1 mg of 2D-NiZn-LDH powder; 8 mg of 2 ', 2' -bipyridine as a cocatalyst; 1 mL of triethanolamine is used as an electron donor; 2 mL of deionized water and 3 mL of acetonitrile are taken as solvents and added into a 25 mL quartz glass reactor;
(2) sealing the reactor, pumping out air from the reactor by vacuum pump, and introducing CO 2 Gas, bleed-vent was repeated three times to ensure that the reactor was filled with CO 2 A gas;
(3) the reactor was placed under a 300W Porphy xenon lamp with a 400 nm cut-off filter for illumination and stirred at constant temperature, the temperature being controlled at 30 ℃.
(4) At 1 h intervals, 500 uL of reactor gas was withdrawn with a sampling needle and quantitatively analyzed by gas chromatography (Agilent 7890B GC).
Comparative application example 2
The Ni (OH) obtained in comparative example 2 was added 2 The nanosheet is used for p-nitrophenol reduction, and the specific steps are as follows:
(1) taking 1 mg of Ni (OH) 2 Powder; 8 mg of 2 ', 2' -bipyridine as a cocatalyst; 1 mL of triethanolamine is used as an electron donor; 2 mL of deionized water and 3 mL of acetonitrile are taken as solvents and added into a 25 mL quartz glass reactor;
(2) sealing the reactor, pumping out air from the reactor by vacuum pump, and introducing CO 2 Gas (es)Pumping-aerating is repeated three times to ensure that the reactor is filled with CO 2 A gas;
(3) the reactor was placed under a 300W Porphy xenon lamp with a 400 nm cut-off filter for illumination and stirred at constant temperature, the temperature being controlled at 30 ℃.
(4) At 1 h intervals, 500 uL of reactor gas was withdrawn with a sampling needle and quantitatively analyzed by gas chromatography (Agilent 7890B GC).
FIG. 1 is an X-ray diffraction (XRD) pattern of 1D/2D-NiZn-LDH nanocomposite prepared in example 1 of the present invention and 2D-NiZn-LDH nanosheets prepared in comparative example 1, wherein XRD does not change significantly after different times of reaction.
Comparison of FIGS. 2 and 3 2D-NiZn-LDH and Ni (OH) produced in comparative examples 1 and 2 of the present invention 2 The microscopic morphology of the nanosheets, as can be seen from the scanning electron microscope image of the 1D/2D-NiZn-LDH nanocomposite material prepared in example 1 of the invention in FIG. 4, the nanowires and the nanosheets are tightly assembled together.
FIG. 2 shows that 2D-NiZn-LDH is obtained within 1 hour of growth time, and original 2D-NiZn-LDH is microspheres assembled by cross-linked thin nanosheets. The generation of 1D/2D-NiZn-LDH and the assembly of 1D, 2D occurred at growth times of 2-4 hours, with a large amount of 1D nanowires appearing and decorating on the surface and edges of the nanoplates (fig. 4). From the EDS spectra of fig. 2 and 4, we can find that the ratio of Ni and Zn is increased from 2.3 to 3.0, which is a spontaneous Ni enrichment process, and nanowires are grown in situ on the original two-dimensional nanosheets in the Ni enrichment process. At the same time we studied longer time series of 1D and 2D assembly (fig. 5), with nanowires evenly distributed on the nanoplatelets and the highest photocatalytic reduction of CO achieved at hour 4 2 Performance (fig. 6).
From the transmission electron microscope images of the 1D/2D-NiZn-LDH prepared in the embodiment 1 of the invention shown in FIG. 7 and FIG. 8, it can be seen that two kinds of stripes exist on the nanowire at the same time, and 0.20 nm and 0.23 nm both belong to the [010] crystal orientation of the LDH. The simultaneous presence of Ni and Zn elements on Mapping patterns on nanowires indicates the successful synthesis of 1D/2D-NiZn-LDH.
FIG. 9 shows 1D/2D-N prepared in example 1 of the present inventioniZn-LDH nanocomposite, comparative example 12D-NiZn-LDH nanosheets, and Ni (OH) prepared in comparative example 2 2 The performance of the nanosheets is compared, and it can be seen that the 1D/2D-NiZn-LDH nanocomposite material has better performance than that of comparative example 1 and comparative example 2.
As can be seen from FIG. 10, the 1D/2D-NiZn-LDH nanocomposite prepared by the invention has excellent cycle performance, and still maintains excellent catalytic reduction performance on carbon dioxide after 4 cycles.
FIGS. 11 and 12 are 1D/2D-NiZn-LDH prepared in example 1 of the present invention, comparative example 12D-NiZn-LDH nanosheets, and Ni (OH) prepared in comparative example 2 2 The impedance spectrum and the photo-current spectrum of the nano-sheet show that the existence of the assembly of the nano-wire and the nano-sheet in the 1D/2D-NiZn-LDH accelerates the electron-hole separation efficiency, and simultaneously compare with the performance of the graph in FIG. 9. In addition, as can be seen from FIG. 13, 1D/2D-NiZn-LDH has a large specific surface area, which is beneficial to the catalytic performance.
It will be understood by those skilled in the art that the foregoing is merely a preferred embodiment of the invention, and is not intended to limit the invention, and that any modification, equivalent replacement or improvement made within the spirit and principle of the invention should be included within the scope of protection of the invention.
Claims (10)
1. A preparation method of a 1D/2D composite material based on NiZn-LDH is characterized by comprising the following steps: the method comprises the following steps:
(1) adding a divalent nickel salt, a divalent zinc salt and a precipitator into deionized water, and fully mixing and dissolving to prepare uniformly dispersed reaction precursor liquid;
(2) then transferring the reaction precursor liquid into a stainless steel high-pressure autoclave with a polytetrafluoroethylene lining, and carrying out constant-temperature reaction in a drying oven;
(3) after the reaction is finished, cooling, centrifugally separating, washing and drying until the water is completely volatilized to obtain the green solid powdery 1D/2D-NiZn-LDH nano composite material.
2. Preparation of a 1D/2D composite material based on NiZn-LDH according to claim 1The method is characterized in that: the divalent nickel salt in the step (1) is NiCl 2 ·6H 2 O; the divalent zinc salt is ZnCl 2 (ii) a The precipitator is urea.
3. The method for preparing a 1D/2D composite material based on NiZn-LDH according to claim 1, characterized in that: in the step (1), the molar ratio of the divalent nickel salt to the divalent zinc salt to the precipitator is 5:1:6, and the amount of deionized water is 50 mL.
4. The method for preparing a 1D/2D composite material based on NiZn-LDH according to claim 1, characterized in that: the mixing and dissolving in the step (1) are specifically as follows: firstly, ultrasonic dispersion is carried out, and then magnetic stirring is carried out; the ultrasonic dispersion time is 10 min; the stirring speed is 500 rpm; the stirring time was 10 min.
5. The method for preparing a 1D/2D composite material based on NiZn-LDH according to claim 1, characterized in that: the constant-temperature reaction in the step (2) is specifically as follows: the reaction is carried out for 4 h at a constant temperature of 120 ℃.
6. The method for preparing a 1D/2D composite material based on NiZn-LDH according to claim 1, characterized in that: the cooling in the step (3) is specifically as follows: and cooling the mixture along with the furnace to room temperature.
7. The method for preparing a 1D/2D composite material based on NiZn-LDH according to claim 1, characterized in that: and (4) washing the solvent in the step (3) by deionized water for 3 times.
8. The method for preparing a 1D/2D composite material based on NiZn-LDH according to claim 1, characterized in that: the drying mode in the step (3) is vacuum-53 ℃ freeze drying, and the drying time is 12 h.
9. A 1D/2D composite material based on NiZn-LDH prepared by the preparation process as claimed in any one of claims 1-8.
10. Use of the NiZn-LDH-based 1D/2D composite material as defined in claim 9 in photocatalytic reduction of CO 2 The application of (1).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210537777.6A CN114849716B (en) | 2022-05-18 | 2022-05-18 | NiZn-LDH-based 1D/2D composite material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210537777.6A CN114849716B (en) | 2022-05-18 | 2022-05-18 | NiZn-LDH-based 1D/2D composite material and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114849716A true CN114849716A (en) | 2022-08-05 |
| CN114849716B CN114849716B (en) | 2023-06-23 |
Family
ID=82638794
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210537777.6A Active CN114849716B (en) | 2022-05-18 | 2022-05-18 | NiZn-LDH-based 1D/2D composite material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114849716B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115739099A (en) * | 2022-12-07 | 2023-03-07 | 广东工业大学 | Zinc-ion-rich ZnNi LDHs nanosheet material as well as preparation method and application thereof |
| CN115999549A (en) * | 2022-12-30 | 2023-04-25 | 福州大学 | Two-dimensional/two-dimensional calcium silicate/LDH composite material and preparation method and application thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104291386A (en) * | 2014-10-10 | 2015-01-21 | 九江学院 | Preparation method of two-dimensional nickel hydroxide ultrathin nano-film |
| CN108993513A (en) * | 2018-07-18 | 2018-12-14 | 大连理工大学 | A kind of doping different metal ions regulate and control the preparation method of Ni-based double-metal hydroxide |
| CN109174104A (en) * | 2018-09-29 | 2019-01-11 | 陕西科技大学 | A kind of carbon cloth zinc supported nickel bimetal hydroxide water-splitting method for preparing catalyst |
| CN110379639A (en) * | 2019-07-02 | 2019-10-25 | 安徽师范大学 | NiCo double hydroxide nano line@NiCo double hydroxide nano piece composite material and preparation method and application |
| CN111530459A (en) * | 2020-05-19 | 2020-08-14 | 福州大学 | Preparation method and application of 0D/2D composite material based on AlOOH nanosheets |
| CN112390293A (en) * | 2020-11-24 | 2021-02-23 | 福州大学 | Ultrathin two-dimensional mangano-manganic oxide and two-dimensional Ni-Mn LDH nano composite material as well as preparation method and application thereof |
| CN113967475A (en) * | 2021-09-15 | 2022-01-25 | 江苏大学 | Preparation method and application of plasma-induced layered nickel-cobalt bimetallic hydroxide photocatalytic material |
-
2022
- 2022-05-18 CN CN202210537777.6A patent/CN114849716B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104291386A (en) * | 2014-10-10 | 2015-01-21 | 九江学院 | Preparation method of two-dimensional nickel hydroxide ultrathin nano-film |
| CN108993513A (en) * | 2018-07-18 | 2018-12-14 | 大连理工大学 | A kind of doping different metal ions regulate and control the preparation method of Ni-based double-metal hydroxide |
| CN109174104A (en) * | 2018-09-29 | 2019-01-11 | 陕西科技大学 | A kind of carbon cloth zinc supported nickel bimetal hydroxide water-splitting method for preparing catalyst |
| CN110379639A (en) * | 2019-07-02 | 2019-10-25 | 安徽师范大学 | NiCo double hydroxide nano line@NiCo double hydroxide nano piece composite material and preparation method and application |
| CN111530459A (en) * | 2020-05-19 | 2020-08-14 | 福州大学 | Preparation method and application of 0D/2D composite material based on AlOOH nanosheets |
| CN112390293A (en) * | 2020-11-24 | 2021-02-23 | 福州大学 | Ultrathin two-dimensional mangano-manganic oxide and two-dimensional Ni-Mn LDH nano composite material as well as preparation method and application thereof |
| CN113967475A (en) * | 2021-09-15 | 2022-01-25 | 江苏大学 | Preparation method and application of plasma-induced layered nickel-cobalt bimetallic hydroxide photocatalytic material |
Non-Patent Citations (3)
| Title |
|---|
| CHENGWEI WANG等: ""Rational design of 2D/1D ZnCo-LDH hierarchical structure with high rate performance as advanced symmetric supercapacitors"", 《JOURNAL OF COLLOID AND INTERFACE SCIENCE》 * |
| O.GUELLATI等: ""Electrochemical measurements of 1D/2D/3DNi-Co bi-phase mesoporous nanohybrids synthesized using free-template hydrothermal method"", 《ELECTROCHIMICA ACTA》 * |
| S.MEGALA等: ""Enhanced photocatalytic dye degradation activity of carbonate intercalated layered Zn, ZnNi and ZnCu hydroxides"", 《APPLIED SURFACE SCIENCE》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115739099A (en) * | 2022-12-07 | 2023-03-07 | 广东工业大学 | Zinc-ion-rich ZnNi LDHs nanosheet material as well as preparation method and application thereof |
| CN115999549A (en) * | 2022-12-30 | 2023-04-25 | 福州大学 | Two-dimensional/two-dimensional calcium silicate/LDH composite material and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114849716B (en) | 2023-06-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111437834B (en) | Method for constructing in-situ heterojunction based on sulfur indium zinc nanosheets and application | |
| CN114849716B (en) | NiZn-LDH-based 1D/2D composite material and preparation method and application thereof | |
| CN102580716B (en) | Method for synthesizing zinc oxide/graphene composite by solvothermal method | |
| CN106975489B (en) | Preparation method of nickel oxide in-situ coated graphene nanocomposite | |
| CN114588888B (en) | Photocatalyst, and preparation method and application thereof | |
| CN103877966A (en) | Preparation method of heterostructure photocatalyst | |
| CN109663611B (en) | Preparation method and nitrogen fixation application of single-layer carbon nitride composite zinc ferrite Z-type catalyst | |
| CN110745784B (en) | Metal oxide nano-particles and preparation method and application thereof | |
| CN111530459B (en) | Preparation method and application of 0D/2D composite material based on AlOOH nanosheets | |
| CN110665484A (en) | Preparation method of self-supporting mesoporous metal organic framework material with cooperative growth | |
| CN108126728B (en) | Preparation method of g-C3N4/g-C3N4 metal-free isomeric structure, obtained product and application | |
| CN113562760B (en) | Phase-state-controllable preparation method and application of CdS nano-materials in different phase states | |
| CN109174143B (en) | Perovskite-based composite nano photocatalytic material and preparation method and application thereof | |
| CN112958096B (en) | Preparation method and application of flower-ball-shaped nickel-aluminum hydrotalcite/titanium dioxide in-situ growth in sheet-shaped tri-titanium carbide composite photocatalyst | |
| CN112844413A (en) | Preparation method and application of photocatalyst with sphalerite/wurtzite junction | |
| CN115920929B (en) | MoO3-x/Cu0.5Cd0.5S composite photocatalyst, preparation method and application | |
| CN115779929B (en) | Modified ZnIn 2 S 4 Photocatalyst, preparation method and application thereof | |
| CN115400792B (en) | Modified PDI photocatalyst and preparation method and application thereof | |
| CN113101952B (en) | Bi 4 O 5 I 2 /Bi 5 O 7 I composite photocatalyst and preparation method and application thereof | |
| CN112390293B (en) | Ultrathin two-dimensional mangano-manganic oxide and two-dimensional Ni-Mn LDH nano composite material as well as preparation method and application thereof | |
| CN110252349B (en) | CdS @ MoS prepared by in-situ photo-deposition2Preparation method of composite photocatalyst | |
| CN111957334A (en) | Preparation method of composite ternary heterojunction photocatalyst | |
| CN112058289A (en) | Strontium titanate/strontium carbonate heterojunction photocatalyst and preparation method and application thereof | |
| CN115893487B (en) | Bismuth sulfide nano material with controllable morphology and preparation method and application thereof | |
| CN109772365B (en) | Zinc sulfide-cadmium sulfide double-layer porous nanotube composite material and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |