CN114272861B - Hydrogel and aerogel of three-dimensional layered and porous structure metal nano sheet/graphene composite, preparation method and application - Google Patents
Hydrogel and aerogel of three-dimensional layered and porous structure metal nano sheet/graphene composite, preparation method and application Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 152
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 148
- 239000002131 composite material Substances 0.000 title claims abstract description 129
- 239000002135 nanosheet Substances 0.000 title claims abstract description 125
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 98
- 239000002184 metal Substances 0.000 title claims abstract description 98
- 239000004964 aerogel Substances 0.000 title claims abstract description 89
- 239000000017 hydrogel Substances 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 41
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- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 38
- 238000000034 method Methods 0.000 claims description 18
- JKDRQYIYVJVOPF-FDGPNNRMSA-L palladium(ii) acetylacetonate Chemical compound [Pd+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O JKDRQYIYVJVOPF-FDGPNNRMSA-L 0.000 claims description 17
- 238000004729 solvothermal method Methods 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 14
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- 238000010438 heat treatment Methods 0.000 claims description 10
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 8
- 229910052750 molybdenum Inorganic materials 0.000 claims description 8
- 239000011733 molybdenum Substances 0.000 claims description 8
- FQNHWXHRAUXLFU-UHFFFAOYSA-N carbon monoxide;tungsten Chemical group [W].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-] FQNHWXHRAUXLFU-UHFFFAOYSA-N 0.000 claims description 7
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- KLFRPGNCEJNEKU-FDGPNNRMSA-L (z)-4-oxopent-2-en-2-olate;platinum(2+) Chemical compound [Pt+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O KLFRPGNCEJNEKU-FDGPNNRMSA-L 0.000 claims description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052804 chromium Inorganic materials 0.000 claims description 5
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
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- 229910052700 potassium Inorganic materials 0.000 claims description 4
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- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 claims description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 3
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- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 3
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 claims description 3
- 238000001338 self-assembly Methods 0.000 claims description 3
- FSJSYDFBTIVUFD-SUKNRPLKSA-N (z)-4-hydroxypent-3-en-2-one;oxovanadium Chemical compound [V]=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FSJSYDFBTIVUFD-SUKNRPLKSA-N 0.000 claims description 2
- MBVAQOHBPXKYMF-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;rhodium Chemical compound [Rh].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O MBVAQOHBPXKYMF-LNTINUHCSA-N 0.000 claims description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 2
- ZKXWKVVCCTZOLD-UHFFFAOYSA-N copper;4-hydroxypent-3-en-2-one Chemical compound [Cu].CC(O)=CC(C)=O.CC(O)=CC(C)=O ZKXWKVVCCTZOLD-UHFFFAOYSA-N 0.000 claims description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 2
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
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- 206010021143 Hypoxia Diseases 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
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- OYJSZRRJQJAOFK-UHFFFAOYSA-N palladium ruthenium Chemical compound [Ru].[Pd] OYJSZRRJQJAOFK-UHFFFAOYSA-N 0.000 description 13
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- 229910001080 W alloy Inorganic materials 0.000 description 11
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- LZKLAOYSENRNKR-LNTINUHCSA-N iron;(z)-4-oxoniumylidenepent-2-en-2-olate Chemical compound [Fe].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O LZKLAOYSENRNKR-LNTINUHCSA-N 0.000 description 4
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- 239000000463 material Substances 0.000 description 3
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
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- 239000000084 colloidal system Substances 0.000 description 2
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
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- SHWZFQPXYGHRKT-FDGPNNRMSA-N (z)-4-hydroxypent-3-en-2-one;nickel Chemical compound [Ni].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O SHWZFQPXYGHRKT-FDGPNNRMSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
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- HLYTZTFNIRBLNA-LNTINUHCSA-K iridium(3+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ir+3].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O HLYTZTFNIRBLNA-LNTINUHCSA-K 0.000 description 1
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- Carbon And Carbon Compounds (AREA)
Abstract
The invention relates to a novel three-dimensional lamellar and porous metal nano sheet/graphene composite hydrogel and aerogel, a preparation method and application thereof. Preparing hydrogel with a metal nano sheet/graphene composite structure by adopting an optimized solvothermal technology, and rapidly drying to prepare the three-dimensional layered and porous metal nano sheet/graphene composite aerogel. The three-dimensional composite aerogel contains abundant defective oxygen and oxygen-containing functional groups, has a porous layered structure, provides a large specific surface area and reaction sites, can be used in the fields of gas sensing, electrochemical sensing and biological sensing, and has potential application value.
Description
Technical Field
The invention relates to the field of design and preparation of novel nano composite materials with layered porous structures and application thereof, in particular to a three-dimensional layered and porous metal nano sheet/graphene composite hydrogel and aerogel, a preparation method and application thereof.
Background
Aerogel is a colloid with solid characteristics formed by dispersing nano materials with a dispersed phase of 1-100 nm size into a gas dispersion medium. Similarly, hydrogels are colloids of solid character consisting of nanomaterial of 1-100 nm size dispersed into an aqueous medium. Aerogel and hydrogel have high porosity and high specific surface area, and provide a new idea for developing high-performance gas-sensitive, electrochemical and biological sensing materials and sensing components. Graphene and graphite oxide are two-dimensional materials, have large surface areas, and are convenient to modify a large number of oxygen-containing functional groups such as hydroxyl groups, carboxyl groups, epoxy groups and the like, if the graphene and the graphite oxide can be used as aerogel and a disperse phase of the hydrogel or form a part of the disperse phase, the novel hydrogel and aerogel sensing material can be obtained. However, pure graphene or graphite oxide is either too small or unfavorable for desorption due to its adsorption capacity for target gases, targeted biomolecules, etc. The conductive channels of graphene can be regulated by gas molecules adsorbed on the surface of graphene as donor or acceptor, however, the original graphene without any functionalization is hardly soluble in any solvent, is difficult to disperse, and its large specific surface area is not effectively exposed and utilized (Ref: nano lett.,2009,9,1472-1475). The study shows that the pure graphene surface can not be combined with specific target molecules or ions in the bioelectrochemical detection, the high-sensitivity detection mainly comes from defects on graphene sheets, oxygen-containing groups are utilized to serve as binding sites of protons, and the detection sensitivity is improved (Ref: nano Lett.,2011,11,3597-3600). For this reason, the design preparation of hydrogel and aerogel formed by compounding three-dimensional graphene and metal nano-sheets provides possibility for solving the above-mentioned key problems, but has not been reported yet.
Disclosure of Invention
The invention aims to provide hydrogel and aerogel of a three-dimensional layered and porous structure metal nano sheet/graphene compound, a preparation method and application thereof. Firstly preparing the metal nano-sheet/graphene composite hydrogel by a solvothermal method, then preparing the metal nano-sheet/graphene composite aerogel by a rapid drying technology, and finally obtaining the layered porous three-dimensional structure. The three-dimensional composite aerogel is rich in defective oxygen and oxygen-containing functional groups, has an ultra-large porous layered structure, provides a large specific surface area and reaction sites, and finally obtains enhanced sensing performance.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a three-dimensional lamellar porous structure metal nano sheet/graphene composite hydrogel and aerogel, which comprise three-dimensional graphene hydrogel, aerogel, metal nano sheets and an organic solvent, wherein the metal nano sheets and the organic solvent are dispersed in the three-dimensional graphene hydrogel; wherein the density of the metal nano sheet/graphene composite hydrogel is 0.5-2 g/cm 3 The density of the aerogel is 10-30 mg/cm 3 。
Preferably, the metal nano-sheet includes one or two or more alloys of metallic palladium (Pd), metallic platinum (Pt), metallic ruthenium (Ru), metallic rhodium (Rh), metallic tungsten (W), metallic tungsten (Cr) and metallic molybdenum (Mo).
The mass of the metal nano sheet and the graphene is (2-20) mg and (0.1-40) mg respectively.
The hydrogel solvent is one or more mixed solvents of water, ethanol, N-Dimethylformamide (DMF) and toluene.
The metal nano sheet is characterized by being in a curled sheet shape, wherein the diameter of the sheet is 10 nm-1 um, and the thickness of the sheet is 0.5-2 nm.
The metal nano-sheet/graphene composite hydrogel and aerogel have the chemical structural characteristics that: contains abundant defective oxygen and oxygen-containing functional groups, and accounts for 20% -90%.
The invention provides a preparation method of three-dimensional graphene/carbon nano tube hydrogel and aerogel, which comprises the following steps:
(1) Method for preparing metal nano-sheet/graphene composite hydrogel by solvothermal method
Dissolving 0.0003-0.2M palladium acetylacetonate, 0-0.2M ruthenium acetylacetonate and 0.0005-0.2M carbonyl compound in 2-80 mL of organic solvent, and performing ultrasonic dispersion for 10-60 min; adding the graphene oxide solution with the concentration of 5-80 mL and the concentration of 0.5-3 mg/mL into a reaction kettle; adding 0-10 mL of acetic acid, magnetically stirring for 10-60 min to obtain a uniform solution, and then performing solvothermal self-assembly reaction to obtain the metal nano sheet/graphene composite hydrogel;
(2) Rapidly drying to obtain metal nano sheet/graphene composite aerogel
And (3) rapidly drying the metal nano sheet/graphene composite hydrogel to obtain the metal nano sheet/graphene composite aerogel.
Preferably, the palladium acetylacetonate can be replaced by palladium chloride, potassium chloropalladate, potassium chloroplatinate, palladium acetate and platinum acetylacetonate; ruthenium acetylacetonate may be replaced with one or more of rhodium acetylacetonate, iridium acetylacetonate, nickel acetylacetonate, iron acetylacetonate, copper acetylacetonate, vanadyl acetylacetonate.
Preferably, the carbonyl compound comprises: chromium hexacarbonyl, molybdenum hexacarbonyl, tungsten hexacarbonyl and formaldehyde.
Preferably, the organic solvent comprises: n, N-dimethylformamide, toluene and oleylamine.
Preferably, the solvothermal self-assembly reaction temperature is 150-200 ℃ and the time is 6-24h.
Preferably, the vacuum degree in the rapid drying process is 0.1-100 Pa, the temperature is-50-100 ℃, and the drying rate is 0.05-0.5L/(m) 2 ·h)。
The three-dimensional metal nano sheet/graphene composite hydrogel and the application of the hydrogel are used for gas sensing such as hydrogen, carbon monoxide, nitrogen dioxide, hydrogen sulfide, ammonia and the like, electrochemical sensing and biological sensing. Taking the application of the three-dimensional metal nano-plate/graphene composite aerogel in gas sensing as an example, the following is explained:
(1) Composition of test system
The block three-dimensional metal nano sheet/graphene composite aerogel is used as an electrode to be tested to be directly connected with a test gold electrode clamp or smashed and dispersed in ethanol, and is integrated into interdigital electrodes with the interdigital distance of 10-200 uM, MEMS (micro electro mechanical system) electrodes and ceramic tube electrode surfaces to construct sensors with different structures. Here we take gas sensing as an example;
(2) Sensing applications
The three-dimensional metal nano sheet/graphene composite aerogel sensing material has good sensing performance on ammonia and hydrogen. The reason is attributed to the layered porous three-dimensional structure bearing a large number of reaction sites, having a large specific surface area and rich gas diffusion paths. Meanwhile, the metal nano sheet/graphene composite aerogel is rich in oxygen-containing functional groups and oxygen-containing functional groups, so that the metal nano sheet/graphene composite aerogel has good gas-sensitive performance on ammonia gas and hydrogen gas, and has important application prospects in the aspects of environment monitoring, safety monitoring of large-concentration gas leakage of factories and the like.
Drawings
Fig. 1 is a physical diagram of a metal nano-sheet/graphene composite hydrogel.
Fig. 2 is a physical diagram of a metal nano-sheet/graphene composite aerogel.
Fig. 3 is a scanning electron micrograph of a metal nano-sheet/graphene composite aerogel, showing that the prepared metal nano-sheet/graphene aerogel is rich in a rich pore layered structure.
Fig. 4 is a graph of the metal nano-sheet/graphene composite aerogel O1s X ray photoelectron spectrum, and a peak fitting result shows that the ratio of defective oxygen is 23%, and the ratio of oxygen-containing functional groups such as hydroxyl groups is 52%, which indicates that the prepared composite aerogel is rich in defective oxygen and oxygen-containing functional groups.
Fig. 5 is an elemental distribution diagram of a metal nano-sheet/graphene composite aerogel.
FIG. 6 is a graph of the sensing response of metal nano-sheet/graphene composite aerogel to hydrogen at different concentrations at room temperature.
FIG. 7 is a graph of the sensing response of metal nano-sheet/graphene composite aerogel to ammonia gas of different concentrations at room temperature.
Detailed Description
The invention is described below by means of specific embodiments. The technical means used in the present invention are methods well known to those skilled in the art unless specifically stated. Further, the embodiments should be construed as illustrative, and not limiting the scope of the invention, which is defined solely by the claims. Various changes or modifications to the materials ingredients and amounts used in these embodiments will be apparent to those skilled in the art without departing from the spirit and scope of the invention. The raw materials and reagents used in the invention are all commercially available.
The graphene oxide solution in the following examples is prepared by adopting a modified Hummer method, and the specific steps are as follows: 1) 3g of graphite powder was added to 70mL of concentrated sulfuric acid and stirred at room temperature for 5 hours. 2) 1.5g of sodium nitrate was added to the above solution and vigorous stirring was continued. 3) Simultaneously, the mixed liquid is ice-bathed to 0 ℃, 9g of potassium permanganate is slowly added, and the ice-bath temperature is kept to be less than 20 ℃. 4) Then the temperature of the water bath is adjusted to 35-40 ℃ and stirring is continued for 1h. 5) 140mL of water is added, and stirring is continued for 15-30 min. 6) 500mL of water is added for further dilution, and then 20mL of hydrogen peroxide (30%) is added for stirring and mixing for 30-60 min. 7) And (3) filtering and washing the mixed solution with 10% hydrochloric acid for 2 times, centrifuging and washing the mixed solution with water until the pH is between= 6, and dispersing the mixed solution in the aqueous solution to obtain the final graphene oxide solution.
Example 1
(1) Method for preparing metal nano-sheet/graphene composite hydrogel by solvothermal method
Adding 0.003M palladium acetylacetonate, 0.0025M ruthenium acetylacetonate and 0.005M tungsten hexacarbonyl into 24mL of N, N-dimethylformamide, performing ultrasonic dispersion for 30min, adding the mixture and 10mL of graphene oxide solution into a reaction kettle, adding 6mL of acetic acid, performing mechanical stirring for 30min to obtain a uniform solution, placing the uniform solution at 180 ℃ for heat preservation for 20h, and naturally cooling to obtain the palladium ruthenium tungsten alloy nano-sheet/reduced graphene composite hydrogel, thereby obtaining the composite hydrogel with the appearance similar to that shown in figure 1.
(2) Heating and drying to prepare metal nano sheet/graphene composite aerogel
And (3) heating and drying the metal nano sheet/graphene composite hydrogel at 50 ℃ to obtain palladium ruthenium tungsten alloy nano sheet/reduced graphene composite aerogel, wherein the appearance is similar to that shown in fig. 2, the internal abundant pore layering nano structure is similar to that shown in fig. 3, and the composite aerogel contains abundant defective oxygen and oxygen-containing functional groups as shown in fig. 4.
Example 2
(1) Method for preparing metal nano-sheet/graphene composite hydrogel by solvothermal method
Adding 0.003M palladium acetylacetonate, 0.0025M iron acetylacetonate and 0.005M tungsten hexacarbonyl into 24mL of N, N-dimethylformamide, performing ultrasonic dispersion for 30min, adding the mixture and 10mL of graphene oxide solution into a reaction kettle, adding 6mL of acetic acid, magnetically stirring for 30min to obtain a uniform solution, placing the uniform solution at 200 ℃, preserving the temperature for 20h, and naturally cooling to obtain the palladium-iron-tungsten alloy nano-sheet/reduced graphene composite hydrogel, thereby obtaining the product with the appearance similar to that shown in figure 1.
(2) Vacuum drying to prepare metal nano sheet/graphene composite aerogel
And (3) drying the metal nano sheet/graphene composite hydrogel under reduced pressure to obtain palladium-iron-tungsten alloy nano sheet/reduced graphene composite aerogel, wherein the appearance is similar to that shown in fig. 2, the internal abundant pore layering nano structure is similar to that shown in fig. 3, and the composite aerogel contains abundant defective oxygen and oxygen-containing functional groups as shown in fig. 4.
Example 3
(1) Method for preparing metal nano-sheet/graphene composite hydrogel by solvothermal method
Adding 0.003M palladium acetylacetonate, 0.0025M platinum acetylacetonate and 0.005M tungsten hexacarbonyl into 24mL of N, N-dimethylformamide, performing ultrasonic dispersion for 30min, adding the mixture and 10mL of graphene oxide solution into a reaction kettle, adding 6mL of acetic acid, performing mechanical stirring for 30min to obtain a uniform solution, performing heat preservation at 150 ℃ for 20h, and naturally cooling to obtain palladium-platinum-tungsten alloy nano-sheet/reduced graphene composite hydrogel, thereby obtaining the product with the appearance similar to that shown in figure 1.
(2) Preparation of metal nano sheet/graphene composite aerogel by vacuum freeze drying technology
And carrying out vacuum freeze drying on the metal nano sheet/graphene composite hydrogel at the temperature of minus 50 ℃ to obtain palladium-platinum-tungsten alloy nano sheet/reduced graphene composite aerogel, wherein the appearance is similar to that shown in figure 2, the internal abundant hole layering nano structure is similar to that shown in figure 3, and the composite aerogel contains abundant defective oxygen and oxygen-containing functional groups as shown in figure 4.
Example 4
(1) Method for preparing metal nano-sheet/graphene composite hydrogel by solvothermal method
Adding 0.003M palladium acetylacetonate, 0.0025M ruthenium acetylacetonate and 0.005M tungsten hexacarbonyl into 24mL of N, N-dimethylformamide, performing ultrasonic dispersion for 30min, adding the mixture and 10mL of graphene oxide solution into a reaction kettle, adding 6mL of acetic acid, stirring for 30min to obtain a uniform solution, placing the uniform solution at 120 ℃ for heat preservation for 24h, and naturally cooling to obtain the palladium ruthenium tungsten alloy nano-sheet/reduced graphene composite hydrogel, thereby obtaining the product with the appearance similar to that shown in figure 1.
(2) Preparation of metal nano sheet/graphene composite aerogel by microwave drying technology
And carrying out microwave drying on the metal nano sheet/graphene composite hydrogel at the temperature of minus 30 ℃ to obtain palladium ruthenium tungsten alloy nano sheet/reduced graphene composite aerogel, wherein the appearance is similar to that shown in figure 2, the internal abundant hole layering nano structure is similar to that shown in figure 3, and the composite aerogel contains abundant defective oxygen and oxygen-containing functional groups as shown in figure 4.
Example 5
(1) Method for preparing metal nano-sheet/graphene composite hydrogel by solvothermal method
Adding 0.003M palladium acetylacetonate, 0.0025M ruthenium acetylacetonate and 0.005M molybdenum hexacarbonyl into 24mL of N, N-dimethylformamide, performing ultrasonic dispersion for 30min, adding the mixture and 10mL of graphene oxide solution into a reaction kettle, adding 6mL of acetic acid, magnetically stirring for 30min to obtain a uniform solution, placing the uniform solution at 180 ℃ for heat preservation for 10h, and naturally cooling to obtain the palladium ruthenium molybdenum alloy nano-sheet/reduced graphene composite hydrogel, thereby obtaining the product with the appearance similar to that shown in figure 1.
(2) Preparation of metal nano sheet/graphene composite aerogel by decompression freeze drying technology
And performing reduced pressure freeze drying on the metal nano sheet/graphene composite hydrogel to obtain palladium ruthenium molybdenum alloy nano sheet/reduced graphene composite aerogel, wherein the appearance is similar to that shown in fig. 2, the internal abundant hole layering nano structure is similar to that shown in fig. 3, and the composite aerogel contains abundant defective oxygen and oxygen-containing functional groups as shown in fig. 4.
Example 6
(1) Method for preparing metal nano-sheet/graphene composite hydrogel by solvothermal method
Adding 0.003M palladium acetylacetonate, 0.0025M platinum acetylacetonate and 0.005M molybdenum hexacarbonyl into 24mL of N, N-dimethylformamide, performing ultrasonic dispersion for 30min, adding the mixture and 10mL of graphene oxide solution into a reaction kettle, adding 6mL of acetic acid, performing mechanical stirring for 30min to obtain a uniform solution, placing the uniform solution at 180 ℃ for heat preservation for 10h, and naturally cooling to obtain the palladium-platinum-molybdenum alloy nano-sheet/reduced graphene composite hydrogel, thereby obtaining the product with the appearance similar to that shown in figure 1.
(2) Heating and drying to prepare metal nano sheet/graphene composite aerogel
And (3) heating and drying the metal nano sheet/graphene composite hydrogel at 80 ℃ to obtain palladium-platinum-molybdenum alloy nano sheet/reduced graphene composite aerogel, wherein the appearance is similar to that shown in fig. 2, the internal abundant hole layering nano structure is similar to that shown in fig. 3, and the composite aerogel contains abundant defective oxygen and oxygen-containing functional groups as shown in fig. 4.
Example 7
(1) Method for preparing metal nano-sheet/graphene composite hydrogel by solvothermal method
Adding 0.003M palladium acetylacetonate, 0.0025M iron acetylacetonate and 0.005M molybdenum hexacarbonyl into 24mL of N, N-dimethylformamide, performing ultrasonic dispersion for 30min, adding the mixture and 10mL of graphene oxide solution into a reaction kettle, adding 6mL of acetic acid, performing mechanical stirring for 30min to obtain a uniform solution, placing the uniform solution at 180 ℃ for heat preservation for 10h, and naturally cooling to obtain palladium-iron-molybdenum alloy nano-sheet/reduced graphene composite hydrogel, thereby obtaining the product with the appearance similar to that shown in figure 1.
(2) Preparation of metal nano sheet/graphene composite aerogel by decompression freeze drying technology
The metal nano sheet/graphene composite hydrogel is decompressed to 0.1Pa and dried, so that palladium-iron-molybdenum alloy nano sheet/reduced graphene composite aerogel is obtained, the appearance is similar to that shown in fig. 2, the internal abundant hole layering nano structure is similar to that shown in fig. 3, and the composite aerogel contains abundant defective oxygen and oxygen-containing functional groups as shown in fig. 4.
Example 8
(1) Method for preparing metal nano-sheet/graphene composite hydrogel by solvothermal method
Adding 0.003M palladium acetylacetonate, 0.0025M ruthenium acetylacetonate and 0.005M chromium hexacarbonyl into 24mL of N, N-dimethylformamide, performing ultrasonic dispersion for 30min, adding the mixture and 10mL of graphene oxide solution into a reaction kettle, adding 6mL of acetic acid, performing mechanical stirring for 30min to obtain a uniform solution, placing the uniform solution at 180 ℃ for heat preservation for 12h, and naturally cooling to obtain the palladium ruthenium chromium alloy nano-sheet/reduced graphene composite hydrogel, thereby obtaining the composite hydrogel with the appearance similar to that shown in figure 1.
(2) Preparation of metal nano sheet/graphene composite aerogel by microwave drying technology
And carrying out microwave freeze drying on the metal nano sheet/graphene composite hydrogel to obtain palladium ruthenium chromium alloy nano sheet/reduced graphene composite aerogel, wherein the appearance is similar to that shown in fig. 2, the internal abundant pore layering nano structure is similar to that shown in fig. 3, and the composite aerogel contains abundant defective oxygen and oxygen-containing functional groups as shown in fig. 4.
Example 9
(1) Method for preparing metal nano-sheet/graphene composite hydrogel by solvothermal method
Adding 0.003M palladium acetylacetonate, 0.0025M platinum acetylacetonate and 0.005M chromium hexacarbonyl into 24mL of N, N-dimethylformamide, performing ultrasonic dispersion for 30min, adding the mixture and 10mL of graphene oxide solution into a reaction kettle, adding 6mL of acetic acid, stirring for 30min to obtain a uniform solution, placing the uniform solution at 180 ℃ for heat preservation for 10h, and naturally cooling to obtain the palladium-platinum-chromium alloy nano sheet/reduced graphene composite hydrogel, thereby obtaining the nano sheet/reduced graphene composite hydrogel with the appearance similar to that shown in figure 1.
(2) Heating and drying to prepare metal nano sheet/graphene composite aerogel
And heating and drying the metal nano sheet/graphene composite hydrogel at 100 ℃ to obtain palladium-platinum-chromium alloy nano sheet/reduced graphene composite aerogel, wherein the appearance is similar to that shown in fig. 2, the internal abundant hole layering nano structure is similar to that shown in fig. 3, and the composite aerogel contains abundant defective oxygen and oxygen-containing functional groups as shown in fig. 4.
Example 10
(1) Method for preparing metal nano-sheet/graphene composite hydrogel by solvothermal method
Adding 0.003M palladium acetylacetonate, 0.0025M ruthenium acetylacetonate and 0.005M molybdenum hexacarbonyl into 20mL of toluene, performing ultrasonic dispersion for 30min, adding the mixture and 10mL of graphene oxide solution into a reaction kettle, adding 6mL of acetic acid, magnetically stirring for 30min to obtain a uniform solution, placing the uniform solution at 180 ℃ for heat preservation for 10h, and naturally cooling to obtain the palladium ruthenium molybdenum alloy nano sheet/reduced graphene composite hydrogel, thereby obtaining the product with the appearance similar to that shown in figure 1.
(2) Preparation of metal nano sheet/graphene composite aerogel by vacuum freeze drying technology
And freeze-drying the metal nano sheet/graphene composite hydrogel at the temperature of minus 30 ℃ to obtain palladium ruthenium molybdenum alloy nano sheet/reduced graphene composite aerogel, wherein the appearance is similar to that shown in figure 2, the internal abundant hole layering nano structure is similar to that shown in figure 3, and the composite aerogel contains abundant defective oxygen and oxygen-containing functional groups as shown in figure 4.
Example 11
(1) Method for preparing metal nano-sheet/graphene composite hydrogel by solvothermal method
Adding 0.003M palladium acetylacetonate, 0.0025M iron acetylacetonate and 0.005M chromium hexacarbonyl into 24mL of N, N-dimethylformamide, performing ultrasonic dispersion for 30min, adding the mixture and 10mL of graphene oxide solution into a reaction kettle, adding 6mL of acetic acid, performing mechanical stirring for 30min to obtain a uniform solution, placing the uniform solution at 200 ℃, preserving the temperature for 10h, and naturally cooling to obtain the palladium-iron-chromium alloy nano sheet/reduced graphene composite hydrogel, thereby obtaining the product with the appearance similar to that shown in figure 1.
(2) Preparation of metal nano sheet/graphene composite aerogel by decompression drying technology
And (3) performing reduced pressure heating drying on the metal nano sheet/graphene composite hydrogel to obtain palladium-iron-chromium alloy nano sheet/reduced graphene composite aerogel, wherein the appearance is similar to that shown in fig. 2, the internal abundant hole layering nano structure is similar to that shown in fig. 3, and the composite aerogel contains abundant defective oxygen and oxygen-containing functional groups as shown in fig. 4.
Example 12
(1) Method for preparing metal nano-sheet/graphene composite hydrogel by solvothermal method
Adding 0.003M palladium acetylacetonate, 0.0025M ruthenium acetylacetonate and 0.005M tungsten hexacarbonyl into 20mL of oleylamine, performing ultrasonic dispersion for 30min, adding the obtained solution and 10mL of graphene oxide solution into a reaction kettle, adding 6mL of acetic acid, stirring for 30min to obtain a uniform solution, placing the uniform solution at 180 ℃ for heat preservation for 10h, and naturally cooling to obtain the palladium ruthenium tungsten alloy nano-sheet/reduced graphene composite hydrogel, thereby obtaining the product with the appearance similar to that shown in figure 1.
(2) Heating and drying to prepare metal nano sheet/graphene composite aerogel
And carrying out vacuum heating drying on the metal nano sheet/graphene composite hydrogel at 60 ℃ to obtain palladium ruthenium tungsten alloy nano sheet/reduced graphene composite aerogel, wherein the appearance is similar to that shown in fig. 2, the internal abundant pore layering nano structure is similar to that shown in fig. 3, and the composite aerogel contains abundant defective oxygen and oxygen-containing functional groups as shown in fig. 4.
Example 13
(1) Method for preparing metal nano-sheet/graphene composite hydrogel by solvothermal method
Adding 0.003M palladium acetylacetonate and 0.005M molybdenum hexacarbonyl into 20mL of oleylamine, performing ultrasonic dispersion for 30min, adding the solution and 10mL of graphene oxide solution into a reaction kettle, adding 6mL of acetic acid, magnetically stirring for 30min to obtain a uniform solution, placing the uniform solution at 180 ℃ for heat preservation for 10h, and obtaining the palladium-molybdenum alloy nano sheet/reduced graphene composite hydrogel after natural cooling, wherein the appearance is similar to that shown in figure 1.
(2) Preparation of metal nano sheet/graphene composite aerogel by microwave drying technology
And carrying out microwave drying on the metal nano sheet/graphene composite hydrogel to obtain palladium-molybdenum alloy nano sheet/reduced graphene composite aerogel, wherein the appearance is similar to that shown in fig. 2, the internal abundant pore layering nano structure is similar to that shown in fig. 3, the composite aerogel contains abundant defective oxygen and oxygen-containing functional groups as shown in fig. 4, and the distribution of the component elements is shown in fig. 5.
Example 14
(1) Composition of the gas sensing test system:
integrating the block three-dimensional palladium ruthenium tungsten alloy nano sheet/graphene composite aerogel onto an electrode with an interdigital distance of 50um, and collecting electric signals (resistance, current, voltage and the like) by using a Keithley 2400 multifunctional power supply ammeter;
(2) Hydrogen sensing applications
As shown in fig. 6, the three-dimensional metal nano-sheet/graphene composite aerogel sensing material has good sensing response to hydrogen with different concentrations at room temperature. The layered porous three-dimensional structure carries a large number of reaction sites, has a large specific surface area and rich gas diffusion paths. Meanwhile, a large contact area is formed between the metal nano-sheet and the graphene, which is favorable for electron transmission, so that the metal nano-sheet has good gas sensitivity to hydrogen, and has important application prospects in the aspects of environment monitoring, safety monitoring of large-concentration gas leakage of factories and the like.
Example 15
(1) Composition of the gas sensing test system:
directly connecting a block three-dimensional palladium-platinum-molybdenum alloy nanosheet/graphene composite aerogel serving as an electrode to be tested with a test gold electrode clamp, and collecting electric signals (resistance, current, voltage and the like) by using a Keithley 2400 multifunctional power supply ammeter;
(2) Ammonia gas sensing application
As shown in fig. 7, the three-dimensional metal nano sheet/graphene composite aerogel sensing material has good sensing response to ammonia gas with different concentrations at room temperature. The layered porous three-dimensional structure carries a large number of reaction sites, has a large specific surface area and rich gas diffusion paths. Meanwhile, a large contact area is formed between the metal nano-sheet and the graphene, which is favorable for electron transmission, so that the metal nano-sheet has good gas sensitivity to ammonia gas, and has important application prospects in the aspects of environmental monitoring, safety monitoring of large-concentration gas leakage of factories and the like.
Claims (6)
1. A three-dimensional layered and porous metal nano sheet/graphene composite aerogel is characterized in that: the preparation method of the metal nano sheet/graphene composite aerogel comprises the following steps of:
(1) Hydrogel of metal nano-sheet/graphene composite prepared by solvothermal method
Dissolving 0.0003-0.2M palladium acetylacetonate, 0-0.2M ruthenium acetylacetonate and 0.0005-0.2M carbonyl compound in 2-80 mL of organic solvent, stirring and dispersing for 10-120 min, then mixing with 5-80 mL of graphene oxide solution with 0.5-3 mg/mL, finally adding 0-10 mL of acetic acid, stirring for 10-60 min, and heating for 150-220 o C, fully reacting to obtain the metal nano sheet/graphene composite hydrogel; the density of the metal nano sheet/graphene composite hydrogel is 0.5-2 g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The mass ratio of the metal nano sheet to the graphene is 2-20 mg: 0.1-40 mg;
(2) Aerogel for preparing metal nano sheet/graphene composite by rapid drying technology
Carrying out quick drying on the metal nano sheet/graphene composite hydrogel to obtain metal nano sheet/graphene composite aerogel; the density of the metal nano sheet/graphene composite aerogel is 10-30mg/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The palladium acetylacetonate can be replaced by palladium chloride, potassium chloropalladate, potassium chloroplatinate, palladium acetate and platinum acetylacetonate; the ruthenium acetylacetonate can be replaced by one or more of rhodium acetylacetonate, ferric acetylacetonate, copper acetylacetonate and vanadyl acetylacetonate; the carbonyl compound is chromium hexacarbonyl, molybdenum hexacarbonyl, tungsten hexacarbonyl or formaldehyde; the organic solvent is N, N-dimethylformamide, toluene or oleylamine.
2. The three-dimensional layered, porous structured metal nano-sheet/graphene composite aerogel of claim 1, wherein: the geometric characteristic of the metal nano sheet is a highly curled sheet, the diameter of the sheet is 10 nm-1 um, and the thickness is 0.5-2 nm.
3. The three-dimensional layered, porous structured metal nano-sheet/graphene composite aerogel of claim 1, wherein: the aerogel has a chemical structure rich in oxygen deficiency and oxygen-containing functional groups, wherein the functional groups account for 20% -90%.
4. The three-dimensional layered, porous structured metal nano-sheet/graphene composite aerogel of claim 1, wherein: the solvothermal self-assembly reaction temperature is 150-220 o And C, the time is 6-24h.
5. The three-dimensional layered, porous structured metal nano-sheet/graphene composite aerogel of claim 1, wherein: in the rapid drying process, the drying rate is 0.05 to 0.5L/(m) 2 ·h)。
6. Use of the three-dimensional layered, porous structured metal nanoplatelet/graphene composite aerogel according to any of claims 1 to 5, characterized in that: the aerogel is used for hydrogen (H) 2 ) Carbon monoxide (CO), nitrogen dioxide (NO) 2 ) Hydrogen sulfide (H) 2 S), ammonia (NH) 3 ) Gas sensing, electrochemical sensing and biosensing.
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| CN105253879A (en) * | 2015-11-23 | 2016-01-20 | 国家纳米科学中心 | High-porosity functional graphene material as well as preparation method and applications thereof |
| CN107399735A (en) * | 2017-08-25 | 2017-11-28 | 南京航空航天大学 | A kind of preparation method and applications of graphene composite aerogel absorbing material |
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| CN105253879A (en) * | 2015-11-23 | 2016-01-20 | 国家纳米科学中心 | High-porosity functional graphene material as well as preparation method and applications thereof |
| CN107399735A (en) * | 2017-08-25 | 2017-11-28 | 南京航空航天大学 | A kind of preparation method and applications of graphene composite aerogel absorbing material |
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