CN114849716B - NiZn-LDH-based 1D/2D composite material and preparation method and application thereof - Google Patents
NiZn-LDH-based 1D/2D composite material and preparation method and application thereof Download PDFInfo
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- 238000004090 dissolution Methods 0.000 claims 1
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 abstract description 24
- 239000000463 material Substances 0.000 abstract description 18
- 239000002070 nanowire Substances 0.000 abstract description 15
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- 235000005074 zinc chloride Nutrition 0.000 abstract description 12
- 239000011592 zinc chloride Substances 0.000 abstract description 12
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 10
- 239000002086 nanomaterial Substances 0.000 abstract description 10
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 5
- 239000001569 carbon dioxide Substances 0.000 abstract description 5
- 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
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- 239000002064 nanoplatelet Substances 0.000 description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 14
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- 239000011941 photocatalyst Substances 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 5
- 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 4
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- 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
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- 229910052724 xenon Inorganic materials 0.000 description 3
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- 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
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- 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
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- 229910018661 Ni(OH) Inorganic materials 0.000 description 1
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- B01J35/39—
-
- 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
Abstract
The invention belongs to the technical field of nano material preparation, and discloses a preparation method of a 1D/2D composite material based on NiZn-LDH, which utilizes a hydrothermal method to prepare a nano composite material assembled by nanowires/nanosheets (1D/2D-NiZn-LDH); the method comprises the steps of taking nickel chloride hexahydrate and zinc chloride as raw materials, taking urea as a precipitator and deionized water as a solvent, performing constant-temperature reaction at a specific temperature, and obtaining the uniformly dispersed 1D/2D-NiZn-LDH nano material through centrifugal separation, sample washing and drying. The 1D/2D nano composite material prepared by the invention enhances the charge conversion on an interface through a one-dimensional nanowire array, and highly selectively reduces carbon dioxide light into carbon monoxide. The preparation method has the advantages of simple preparation process, short period and low cost, can realize large-scale industrial production, and has good economic and environmental benefits.
Description
Technical Field
The invention belongs to the technical field of nano material preparation, and particularly relates to a NiZn-LDH-based 1D/2D composite material, and a preparation method and application thereof.
Background
Both one-dimensional (1D) and two-dimensional (2D) nanomaterials belong to low-dimensional materials, and because of their inherent properties, they have attracted great attention as advanced photocatalysts for structural features. As for 1D nanostructured photocatalysts, well-defined 1D geometries facilitate fast and long-range electron transport and long-term photocatalytic stability, while their high aspect ratio and larger specific surface area significantly enhance light absorption properties. To date, various 1D nanostructured morphologies (ribbons, tubes, fibers, rods, and wires) of photocatalysts have been successfully prepared and applied to a variety of highly efficient photocatalytic reactions.
With respect to 2D nanomaterials, they are atomic scale sheets or layers that exhibit unique electronic and optical properties with significant potential for a variety of applications. In photocatalyst design, 2D nanomaterials also have many advantages, making them excellent candidates for photocatalytic applications. First, since 2D nanomaterial has a large specific surface area, there are a large number of active sites on its surface. Second, a shorter diffusion path may accelerate dissociation of excitons and transfer of free charges. Third, most 2D materials have good conductivity and superior electron mobility, which can promote the transfer and separation of photogenerated electrons and holes. Fourth, the 2D nanomaterial is an excellent catalyst support, facilitating construction of heterogeneous photocatalysts.
Inspired by the vigorous development of 1D and 2D photocatalysts, the reasonable design of the 1D/2D multidimensional heterojunction photocatalyst integrates the advantages of 1D and 2D nanometer geometric structures, and the photocatalytic performance is greatly improved. Conventionally, in order to prepare a one-dimensional/two-dimensional hybrid structure, a two-dimensional template is usually prepared to guide one-dimensional nanowires to deposit on a two-dimensional plane. However, a few successful cases of directional deposition are severely dependent on the use of organic surfactants or polymers. Even so, directed assembly of one dimension on a two-dimensional substrate remains a great challenge, especially long-scale nanowires are rarely reported. Therefore, the design of the preparation method for synthesizing the high-dispersion 1D/2D nano material by one step has important significance.
Disclosure of Invention
In order to achieve the above 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; transferring the reaction precursor liquid into a stainless steel autoclave with a polytetrafluoroethylene lining, and carrying out constant-temperature reaction in a drying oven; after the reaction is finished, cooling, centrifugal separation, washing and drying are carried out until the moisture is completely volatilized, thus obtaining the green solid 1D/2D-NiZn-LDH nanocomposite material with uniform and highly dispersed powder size.
The 1D/2D-NiZn-LDH nanocomposite material with uniform size and high dispersion comprises the following steps:
(1) Adding divalent nickel salt, divalent zinc salt and a precipitator into deionized water, and fully mixing and dissolving to prepare uniformly dispersed reaction precursor liquid;
(2) Transferring the reaction precursor liquid into a stainless steel autoclave with a polytetrafluoroethylene lining, and carrying out constant-temperature reaction in a drying oven;
(3) After the reaction is finished, cooling, centrifugal separation, washing and drying are carried out until the moisture is completely volatilized, thus obtaining the green solid powdery 1D/2D-NiZn-LDH nanocomposite.
Further, the divalent nickel salt in the step (1) is nontoxic nickel chloride hexahydrate NiCl 2 ·6H 2 O; the divalent aluminum salt is nontoxic zinc chloride ZnCl 2 The method comprises the steps of carrying out a first treatment on the surface of the The precipitant 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 dosage of deionized water is 50 mL.
Further, the mixing and dissolving in the step (1) specifically comprises the following steps: ultrasonic dispersion and magnetic stirring, wherein the ultrasonic dispersion time is 10 min; the stirring speed was 500 rpm; the stirring time was 10 min.
Further, the constant temperature reaction in the step (2) specifically comprises the following steps: reaction 4 h was carried out at a constant temperature of 120 ℃.
Further, the cooling in the step (3) specifically includes: cooling the mixture to room temperature along with the furnace.
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 freeze drying at-53 ℃ for 12 hours.
The invention has the beneficial effects that:
(1) The invention adopts a one-step hydrothermal synthesis method to synchronously generate the 1D/2D-NiZn-LDH nanocomposite material with uniform high dispersion in situ, and the nanowires of the 1D/2D-NiZn-LDH are uniformly dispersed on the nanosheets. Enriches the method for compounding one-dimensional and two-dimensional nano materials and provides a new idea for directional assembly and functionalization of nanowires and nanoplates.
(2) The 1D/2D-NiZn-LDH nanocomposite material prepared by the invention has the advantages that a lattice matching initiation synergistic effect is generated between the nanowires and the nanoplatelets, the surface area is increased, the charge migration rate is increased, the charge conversion on the interface is enhanced through the one-dimensional nanowire array, and the carbon dioxide is reduced to carbon monoxide in a highly selective way.
(3) The preparation method has the advantages of easy acquisition of equipment and materials, simple process operation, simple process conditions, low cost, safety and high efficiency, and can realize 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 obtained in example 1 of the present invention and a 2D-NiZn-LDH nanosheet obtained in comparative example 1;
FIG. 2 is a microscopic morphology and EDS spectrum of the 2D-NiZn-LDH nanoplatelets prepared in comparative example 1 of the present invention;
FIG. 3 is Ni (OH) obtained in comparative example 2 of the present invention 2 Micro morphology of the nano sheet and EDS energy spectrum;
FIG. 4 is a microscopic morphology and EDS spectrum of the 1D/2D-NiZn-LDH nanocomposite prepared in example 1 of the present invention;
FIG. 5 shows the micro-morphology of 1D/2D-NiZn-LDH nanocomposite materials prepared by different hydrothermal times according to the invention;
FIG. 6 is a graph showing the comparison of the properties of 1D/2D-NiZn-LDH nanocomposite materials produced by different hydrothermal times according to the present invention;
FIG. 7 is a transmission electron microscope image of the 1D/2D-NiZn-LDH nanocomposite material prepared in example 1 of the present invention;
FIG. 8 is a transmission electron microscope image of the 1D/2D-NiZn-LDH nanocomposite material prepared in example 1 of the present invention;
FIG. 9 is a diagram of1D/2D-NiZn-LDH nanocomposite obtained in example 1 of the present invention, 2D-NiZn-LDH nanosheets obtained in comparative example 1, and Ni (OH) obtained in comparative example 2 2 Performance contrast graph of nano-sheet;
FIG. 10 is a graph showing the cycle performance of the 1D/2D-NiZn-LDH nanocomposite material prepared in example 1 of the present invention;
FIGS. 11 and 12 are a 1D/2D-NiZn-LDH nanocomposite obtained in example 1, a 2D-NiZn-LDH nanoplatelet obtained in comparative example 1, and Ni (OH) obtained in comparative example 2 according to the present invention 2 A nanosheet impedance spectrum and photocurrent comparison chart;
FIG. 13 shows a 1D/2D-NiZn-LDH nanocomposite obtained in example 1 of the present invention, 2D-NiZn-LDH nanoplatelets obtained in comparative example 1, and Ni (OH) obtained in comparative example 2 2 BET plot 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 further described in detail below with reference to the accompanying drawings, i.e., embodiments. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention. In addition, the technical features of the embodiments of the present invention described below may be combined as long as they do not collide with each other.
Example 1
Preparation of 1D/2D-NiZn-LDH nanocomposite:
(1) Nickel chloride hexahydrate (NiCl) 5.94 g was weighed out using an electronic balance 2 ·6H 2 O), 0.68. 0.68 g zinc chloride (ZnCl) 2 ) Nickel chloride hexahydrate and ZnCl 2 Adding the mixture into 50 mL deionized water according to a molar ratio of 5:1, and performing ultrasonic dispersion for 10 minutes to obtain a solution A;
(2) Urea (CH) 1.8. 1.8 g was weighed out with an electronic balance 4 N 2 O), adding the mixture into the solution A, magnetically stirring for 10 min at a stirring speed of 500 rpm to obtain uniformly dispersed reaction precursor liquid;
(3) Transferring the reaction precursor liquid into a stainless steel autoclave lined with polytetrafluoroethylene, and reacting at a constant temperature of 120 ℃ in a drying oven for 4 h, and cooling to room temperature along with a furnace after the reaction is finished;
(4) Centrifuging the sample by using a centrifuge to obtain white solid powder, wherein the rotating speed is 8000 rpm; washing with deionized water for three times;
(5) The 1D/2D-NiZn-LDH nanocomposite was obtained by freeze-drying overnight until the moisture was completely volatilized.
Comparative example 1
Preparation of 2D-NiZn-LDH nanosheets:
(1) Nickel chloride hexahydrate (NiCl) 5.94 g was weighed out using an electronic balance 2 ·6H 2 O), 0.68. 0.68 g zinc chloride (ZnCl) 2 ) Nickel chloride hexahydrate and ZnCl 2 Adding the mixture into 50 mL deionized water according to a molar ratio of 5:1, and performing ultrasonic dispersion for 10 minutes to obtain a solution A;
(2) Urea (CH) 1.8. 1.8 g was weighed out with an electronic balance 4 N 2 O), adding the mixture into the solution A, magnetically stirring for 10 min at a stirring speed of 500 rpm to obtain uniformly dispersed reaction precursor liquid;
(3) Transferring the reaction precursor liquid into a stainless steel autoclave lined with polytetrafluoroethylene, and reacting at a constant temperature of 120 ℃ in a drying oven for 1 h, and cooling to room temperature along with a furnace after the reaction is finished;
(4) Centrifuging the sample by using a centrifuge to obtain white solid powder, wherein the rotating speed is 8000 rpm; washing with deionized water for three times;
(5) And (3) obtaining the 2D-NiZn-LDH nanocomposite material with uniform size and high dispersion by freeze drying overnight until the moisture is completely volatilized.
Comparative example 2
Ni(OH) 2 Preparation of nanosheets:
(1) 10 mmol Ni (OH) was weighed out 2 It was dissolved in a mixed solution of formic acid and water (10 ml of HCOOH, 70 ml of H 2 O), 2H is heated at 70 ℃.
(2) Evaporating most of the liquid by rotary evaporation after heating, and lyophilizing the rest small solid-liquid mixture overnight until the water is completely volatilized to obtain nickel formate (C) 2 H 2 NiO 4 ）。
(3) Nickel formate (C) of 0.184. 0.184 g was weighed out by an electronic balance 2 H 2 NiO 4 ) Adding the mixture into 50 mL methanol, and performing ultrasonic dispersion for 10 minutes to obtain uniformly dispersed reaction precursor liquid;
(4) Transferring the reaction precursor liquid into a stainless steel autoclave lined with polytetrafluoroethylene, and reacting at a constant temperature of 160 ℃ in a drying oven for 18 h, and cooling to room temperature along with a 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; washing with deionized water for three times;
(6) Ni (OH) was obtained by freeze drying overnight until the moisture was completely evaporated 2 Nanocomposite material
Application example 1
The 1D/2D-NiZn-LDH nanocomposite obtained in example 1 was used for photocatalytic carbon dioxide reduction, and the specific steps were as follows:
(1) Taking 1 mg of 1D/2D-NiZn-LDH powder; 8 mg of 2' -bipyridine is taken as a cocatalyst; 1 mL triethanolamine is an electron donor; 2 mL deionized water and 3 mL acetonitrile as solvents are added into a quartz glass reactor of 25 mL;
(2) Sealing the reactor, pumping air in the reactor by a vacuum pump, and then introducing CO 2 The gas, pumping-aeration was repeated three times to ensure that the reactor was full of CO 2 A gas;
(3) The reactor was illuminated under a poisehead xenon lamp with 400 nm cut-off filter 300W and kept under constant temperature stirring, the temperature being controlled at 30 ℃.
(4) Every 1 h, the gas in the 500 uL reactor was withdrawn by a sampling needle and quantitatively analyzed by gas chromatography (Agilent 7890B GC).
Comparative example 1 was used
The 2D-NiZn-LDH nanosheets obtained in comparative example 1 were used for photocatalytic carbon dioxide reduction, and the specific steps were as follows:
(1) Taking 1 mg of 2D-NiZn-LDH powder; 8 mg of 2' -bipyridine is taken as a cocatalyst; 1 mL triethanolamine is an electron donor; 2 mL deionized water and 3 mL acetonitrile as solvents are added into a quartz glass reactor of 25 mL;
(2) Sealing the reactor, pumping air in the reactor by a vacuum pump, and then introducing CO 2 The gas, pumping-aeration was repeated three times to ensure that the reactor was full of CO 2 A gas;
(3) The reactor was illuminated under a poisehead xenon lamp with 400 nm cut-off filter 300W and kept under constant temperature stirring, the temperature being controlled at 30 ℃.
(4) Every 1 h, the gas in the 500 uL reactor was withdrawn by a sampling needle and quantitatively analyzed by gas chromatography (Agilent 7890B GC).
Comparative example 2 was used
Ni (OH) obtained in comparative example 2 2 The nano-sheet is used for reduction of p-nitrophenol, and comprises the following specific steps:
(1) 1 mg Ni (OH) 2 A powder; 8 mg of 2' -bipyridine is taken as a cocatalyst; 1 mL triethanolamine is an electron donor; 2 mL deionized water and 3 mL acetonitrile as solvents are added into a quartz glass reactor of 25 mL;
(2) Sealing the reactor, pumping air in the reactor by a vacuum pump, and then introducing CO 2 The gas, pumping-aeration was repeated three times to ensure that the reactor was full of CO 2 A gas;
(3) The reactor was illuminated under a poisehead xenon lamp with 400 nm cut-off filter 300W and kept under constant temperature stirring, the temperature being controlled at 30 ℃.
(4) Every 1 h, the gas in the 500 uL reactor was withdrawn by a sampling needle and quantitatively analyzed by gas chromatography (Agilent 7890B GC).
FIG. 1 is an X-ray diffraction (XRD) pattern of the 1D/2D-NiZn-LDH nanocomposite obtained in example 1 of the present invention and the 2D-NiZn-LDH nanoplatelets obtained in comparative example 1, in which XRD did not change significantly after various times of reaction.
Comparison of FIGS. 2 and 3 2D-NiZn-LDH and Ni (OH) prepared in comparative examples 1 and 2 of the present invention 2 Microcosmic morphology of nanoplatelets, scanning electron microscope image of 1D/2D-NiZn-LDH nanocomposite obtained in example 1 of the present invention from FIG. 4It can be seen that nanowires are tightly packed with nanoplatelets.
FIG. 2 shows that 2D-NiZn-LDH was obtained within 1 hour of growth time, and the original 2D-NiZn-LDH was a microsphere assembled from crosslinked thin nanoplatelets. The generation of 1D/2D-NiZn-LDH and the assembly of 1D, 2D occurs over a 2-4 hour growth time, with a large number of 1D nanowires present and decorated at the surface and edges of the nanoplatelets (fig. 4). From the EDS spectra of fig. 2 and 4, we can find that the ratio of Ni to Zn increases from original 2.3 to 3.0, which is a spontaneous Ni enrichment process in which nanowires are grown in situ on original two-dimensional nanoplates. At the same time we studied a longer time series of 1D and 2D assembly (fig. 5), the nanowires were uniformly distributed on the nanoplatelets, and the highest photocatalytic reduction of CO was achieved at 4 hours 2 Performance (figure 6).
From the transmission electron microscope images of the 1D/2D-NiZn-LDH prepared in the embodiment 1 of the invention 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 are all attributed to the [010] crystal orientation of the LDH. The simultaneous presence of Ni and Zn elements on the Mapping image on the nanowires indicates successful synthesis of 1D/2D-NiZn-LDH.
FIG. 9 is a schematic diagram of a 1D/2D-NiZn-LDH nanocomposite obtained in example 1 of the present invention, comparative example 1 2D-NiZn-LDH nanoplatelets, and Ni (OH) obtained in comparative example 2 2 The performance of the nanoplatelets is compared to the graph showing that the 1D/2D-NiZn-LDH nanocomposite performance is superior to comparative example 1 and comparative example 2.
From fig. 10, it can be seen that the 1D/2D-NiZn-LDH nanocomposite prepared by the present invention has excellent cycle performance, and still maintains excellent catalytic reduction performance on carbon dioxide after 4 cycles.
FIGS. 11 and 12 are a 1D/2D-NiZn-LDH obtained in example 1, a 2D-NiZn-LDH nanosheet of comparative example 1 and Ni (OH) obtained in comparative example 2 according to the present invention 2 The impedance spectrum and the photoelectric spectrum of the nanoplatelets indicate that the presence of nanowires and nanoplatelet assemblies in the 1D/2D-NiZn-LDH accelerates the electron-hole separation efficiency, as well as being demonstrated in comparison with the performance of fig. 9. In addition, as can be seen from FIG. 13, the 1D/2D-NiZn-LDH has a larger specific surface area, which is advantageousIn its catalytic properties.
It will be readily appreciated 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, but any modifications, equivalents and improvements made within the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (5)
1. A 1D/2D composite material based on a NiZn-LDH, characterized in that: the preparation method of the composite material comprises the following steps:
(1) Adding divalent nickel salt, divalent zinc salt and a precipitator into deionized water, and fully mixing and dissolving to prepare uniformly dispersed reaction precursor liquid;
(2) Transferring the reaction precursor liquid into a stainless steel autoclave with a polytetrafluoroethylene lining, and carrying out constant-temperature reaction in a drying oven;
(3) After the reaction is finished, cooling, centrifugal separation, washing and drying are carried out until the moisture is completely volatilized, thus obtaining the green solid powdery 1D/2D-NiZn-LDH nanocomposite;
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 dosage of deionized water is 50 mL; the mixed dissolution in the step (1) is 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 was 500 rpm; stirring for 10 min; the constant temperature reaction in the step (2) is specifically as follows: reacting at constant temperature of 120 ℃ for 4 h; and (3) the drying mode is vacuum freeze drying at-53 ℃ and the drying time is 12 hours.
2. The NiZn-LDH based 1D/2D composite material according to claim 1, wherein: the divalent nickel salt in the step (1) is NiCl 2 ·6H 2 O; the bivalent zinc salt is ZnCl 2 The method comprises the steps of carrying out a first treatment on the surface of the The precipitant is urea.
3. The NiZn-LDH based 1D/2D composite material according to claim 1, wherein: the cooling in the step (3) is specifically as follows: cooling the mixture to room temperature along with the furnace.
4. The NiZn-LDH based 1D/2D composite material according to claim 1, wherein: the solvent for washing in the step (3) is deionized water, and the washing times are 3 times.
5. A 1D/2D composite material based on NiZn-LDH as claimed in any one of claims 1 to 4 for photocatalytic reduction of CO 2 Application to the above.
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